CN109075052A - The manufacturing method of composition, composition host body and composition - Google Patents

Abstract

It can be used in manufacturing semiconductor devices and containing the composition of hydrogen peroxide the subject of the invention is to provide a kind of, and excellent storage stability and the composition small to the defective effect of semiconductor substrate.Also, another project of the invention is to provide a kind of manufacturing method of the composition containing above-mentioned hydrogen peroxide and keeping has the composition host body of above-mentioned composition.Composition of the invention contains hydrogen peroxide, acid and Fe ingredient, and content of the content of above-mentioned Fe ingredient relative to above-mentioned acid, is by quality ratio 10^‑5~10²。

Description

The manufacturing method of composition, composition host body and composition

Technical field

The present invention relates to a kind of constituent containing hydrogen peroxide and its manufacturing method and composition host bodies.

Background technique

In the manufacturing process of semiconductor devices including the cleaning process of semiconductor silicon wafer, photo-mask process, etching work procedure, The various processes such as ion injecting process or stripping process.Here, after each process terminates or before being moved to subsequent processing, one As include the process handled using treatment fluid unwanted organic matter and inorganic matter.

As the treatment fluid, the treatment fluid containing hydrogen peroxide is used sometimes.

Hydrogen peroxide using anthraquinone analog compound as the so-called of raw material generally by anthraquinone synthesizing (referring for example to special Sharp document 1).

It is required that using the treatment fluid of high-purity in the manufacturing process of semiconductor devices." high-purity " said here is table Show, as impurity comprising metal component or particle (particle) each concentration it is low.

If being mixed into the impurity (for example, metal ion or metallic) of metal component in treatment fluid, processed When processing, metal can be caused to be spread in the phenomenon that being known as migration of subject material.Migration hinders the transmitting of electric signal and becomes short The bad reason such as road.Also, moreover, there is also the impurity of metal, and its metal itself is become coarse as core Grain, and the case where remained on a semiconductor substrate as residue after treatment.Residue is other than deteriorating lithography performance, also The reason of as defect is generated, baneful influence can be brought to the formation of fine corrosion-resisting pattern or semiconductor element.

Conventional art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2014-108903 bulletin

Summary of the invention

The invention technical task to be solved

The inventors of the present invention utilize through the anthraquinone aquae hydrogenii dioxidi being fabricated as recorded in Patent Document 1, right The applicability of semiconductor devices manufacture is studied, so that recognize the sky in the presence of the storage stability for improving aquae hydrogenii dioxidi Between.The reason low as the storage stability, mixed Fe ingredient is in acidic region derived from solvent or derived from raw material etc. The middle reaction that catalytic occurs, so that hydroxyl free radical (so-called Fenton's reaction) is carried out to hydrogen peroxide, as a result, by recognizing It is decomposed for hydrogen peroxide.

On the other hand, it is known that when use the metal absorbents such as acid and using above-mentioned Fe ingredient as metal adsorption body (for example, acid Be chelate complexes when for polydonita (polydentate) structure) when inhibit Fenton's reaction.The inventors of the present invention want using Fe at Point and as metal absorbent acid and improve the storage stability of aquae hydrogenii dioxidi, result recognize Fe ingredient relative to When hypoacidity, there are aquae hydrogenii dioxidis to be unable to satisfy the case where semiconductor devices manufactures the high-purity required by using on the way.That is, So that recognizing when using above-mentioned aquae hydrogenii dioxidi cleaning semiconductor substrate, there is the particle of attachment on a semiconductor substrate Number (also referred to as " defect number ".) increase and can not be suitable for the situation semiconductor devices manufacturing process.In particular, the problem can be with Semiconductor devices high product bodyization and miniaturization (for example, below 30nm node) and it is more obvious.And in recent years, also right The manufacture of 10nm node semiconductor devices below is studied, and the problem becomes further obvious.

It can be used in semiconductor devices manufacture and combination containing hydrogen peroxide the subject of the invention is to provide a kind of Object, and excellent storage stability and the composition small to the defective effect of semiconductor substrate.

Also, project of the invention is also to provide the manufacturing method and keeping of a kind of composition containing above-mentioned hydrogen peroxide There is the composition host body of above-mentioned composition.

For solving the means of technical task

The inventors of the present invention in order to realize the above subject and carried out sharp study as a result, it has been found that, according to containing hydrogen peroxide And Fe ingredient and the acid as metal absorbent are controlled in the composition of specific ratios, are able to solve the above subject, so that it is complete At the present invention.

I.e., it was found that can be realized above-mentioned purpose and with flowering structure.

(1) a kind of composition, containing hydrogen peroxide, acid and Fe ingredient,

Content of the content of above-mentioned Fe ingredient relative to above-mentioned acid, is by quality ratio 10^-5~10²。

(2) composition according to (1), also contains anthraquinone analog compound.

(3) composition according to (1) or (2), wherein the content of above-mentioned anthraquinone analog compound is total relative to composition Quality is 0.01 mass of mass ppb~1000 ppb.

(4) composition according to any one of (1) to (3), wherein the content of above-mentioned acid is relative to the total matter of composition Amount is 0.01 mass of mass ppb~1000 ppb.

(5) composition according to any one of (1) to (4), wherein the total content of above-mentioned Fe ingredient is relative to combination Object gross mass is 0.1 mass of mass ppt~1 ppb.

(6) composition according to any one of (1) to (5), wherein Fe particle contained in above-mentioned Fe ingredient contains Amount is 0.01 mass of mass ppt~0.1 ppb relative to composition gross mass.

(7) composition according to any one of (1) to (6) should also containing the metal component of at least one or more Metal component contains the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al,

The content of above-mentioned metal component is respectively relative to composition gross mass according to each specific atoms, is 0.01 mass ppt ~10 mass ppb.

(8) composition according to any one of (1) to (6) should also containing the metal component of at least one or more Metal component contains the specific atoms in the group including Ni, Pt, Pd and Al,

The content of above-mentioned metal component is 0.01 mass of mass ppt~1 ppb relative to composition gross mass.

(9) composition according to any one of (2) to (8), wherein above-mentioned anthraquinone analog compound is selected from including alkane At least one or more in the group of base anthraquinone and alkyl tetrahydro anthraquinone.

(10) composition according to (9), wherein abovementioned alkyl anthraquinone is ethyl hydrazine or amyl anthraquinone, above-mentioned alkane Base tetrahydro-anthraquinone is ethyl tetrahydro-anthraquinone or amyl tetrahydro-anthraquinone.

(11) composition according to any one of (1) to (10), wherein above-mentioned acid is selected to spread out including phosphoric acid and phosphoric acid 1 kind in the group of biology.

(12) composition according to any one of (1) to (11), is used as the treatment fluid of semiconductor substrate.

(13) a kind of composition host body, with storage container and (1) that is contained in above-mentioned storage container to (12) Any one of described in composition,

The region of above-mentioned storage container contacted with above-mentioned composition is by being formed with nonmetallic for the material of principal component 's.

(14) the composition host body according to (13), wherein it is above-mentioned with the nonmetallic material for principal component, it is to be selected from 1 kind in group including high density polyethylene (HDPE), tetrafluoroethene perfluoroalkyl vinyl ether copolymer and polytetrafluoroethylene (PTFE).

(15) the composition host body according to (13) or (14), wherein above-mentioned with the nonmetallic material for principal component Be 60 °~120 ° with the contact angle of water.

(16) a kind of manufacturing method of composition is the manufacturing method of composition described in any one of (1) to (12), It is included

Feed purification process carries out any a kind or more selected from solvent and the material composition comprising anthraquinone analog compound Purifying；

Hydrogen peroxide synthesis procedure restores above-mentioned anthraquinone analog compound and elbs reaction hydroquinones chemical combination in the presence of a catalyst Object further aoxidizes above-mentioned anthrahydroquinone class compound and synthesizes hydrogen peroxide；

Hydrogen peroxide separation process is taken out from reaction system by extracting resulting hydrogen peroxide；And

Hydrogen peroxide composition purification procedures, further to the peroxide containing the hydrogen peroxide isolated from reaction system Change hydrogen composition to be purified.

Invention effect

In accordance with the invention it is possible to provide a kind of can use in semiconductor devices manufacture and the combination containing hydrogen peroxide Object, and excellent storage stability and the composition being inhibited to the defective effect of semiconductor substrate.

Also, in accordance with the invention it is possible to provide the manufacturing method and keeping of a kind of composition containing above-mentioned hydrogen peroxide There is the composition host body of above-mentioned composition.

In addition, in accordance with the invention it is possible to provide it is a kind of especially in recent years submicroscopic patterns (for example, 10nm node with Under) semiconductor devices formed in be also able to suppress the generation of defect and the treatment fluid of excellent storage stability and receiving a combination thereof The host body of object.

Detailed description of the invention

Fig. 1 be indicate to be capable of the purification devices used in the manufacturing method of composition of the invention a kind of mode it is general Sketch map.

Fig. 2 be indicate to be capable of the purification devices used in the manufacturing method of composition of the invention another way it is general Sketch map.

Specific embodiment

Hereinafter, being described in detail to the present invention.

The explanation for the constitutive requirements recorded below is completed sometimes based upon representative embodiments of the invention, but this hair It is bright to be not limited to this embodiment.

In addition, in the present specification, being to indicate with the numberical range that "~" indicates, the numerical value of the front and back of "~" will be recorded in As lower limit value and upper limit value comprising range.

In the label of group (atomic group) in the present specification, do not describe substitution and it is unsubstituted label be without detriment to It together include the group (atomic group) without substituent group and the group (atom with substituent group in the range of effect of the invention Group).For example, " alkyl " refers to not only comprising the alkyl (unsubstituted alkyl) without substituent group, also comprising having substituent group Alkyl (replaces alkyl).This is synonymous for each compound.

Also, when in the present specification, referred to as " preparing ", in addition to indicating the feelings as synthesizing or concocted certain material and have Other than condition, it is also represented by the case where regulation article is buied by purchase etc..

Also, in the present specification, " ppm " expression " hundred a ten thousandths (parts-per-million) (10^-6) ", " ppb " Indicate " part per billion (parts-per-billion) (10^-9) ", " ppt " expression " part per trillion (parts-per- trillion)(10^-12)”。

Also, in the present specification, " semiconductor substrate " if can be used for semiconductor devices manufacture in substrate, It is not particularly limited, for example, silicon substrate (Si substrate), silicon oxide layer substrate (SiO substrate), silicon nitride board can be enumerated (SiN substrate) etc..Also, substrate is not only limited in wafer, is also possible to include the substrate for being implemented with circuit structure on wafer Entire structure.

(composition)

Composition of the invention contains hydrogen peroxide, acid and Fe ingredient, and the content of above-mentioned Fe ingredient is relative to above-mentioned acid Content is by quality ratio 10^-5~10²。

Composition of the invention is by being set as above structure, thus excellent storage stability, and it is suitable for semiconductor devices It is smaller to the defective effect of semiconductor substrate when manufacturing process.That is, composition of the invention through when save after, hydrogen peroxide Resolution ratio is also smaller.Also, for example, when composition of the invention is suitable for semiconductor devices manufacturing process as treatment fluid When, as the semiconductor substrate of process object, the attachment of particle is less (in other words, defect number is less), therefore is able to suppress The reduction of semiconductor substrate yield rate.

Its detailed content is simultaneously indefinite, but can be speculated as follows.

Composition of the invention preferably in a manner of it can be suitable for semiconductor devices manufacturing process, by filtering or from Son exchange etc. removes made of the impurity such as organic pollutant, metal pollutant and grease micro contained in simultaneously purification of liquid Composition.The feature of composition of the invention is excessively to carry out the removal when being prepared and purify, but not fully remove Above-mentioned impurity, but the Fe ingredient of at least residual minim degree.Additionally, it is believed that Fe ingredient the raw material containing solvent or anthraquinone at Exist to a certain degree in point, and is mixed into composition by these solvents or raw material.In the present specification, Fe ingredient include from The Fe atom of sub- state and the Fe atom of non-ionic state, for example, the shape of the metallic (Fe particle) comprising Fe ion and Fe State.That is, Fe ingredient is to indicate the ingredient (Fe ion, Fe particle) derived from Fe atom whole contained in composition, Fe at The content divided is to indicate total amount of metal (total Fe atomic weight).

In addition, being also possible in the preparation process of the present composition in purifying removal Fe ingredient to less than above-mentioned regulation After the lower limit of numberical range, Fe ingredient is added in the form of becoming specified value range.

Also, above-mentioned impurity remove and purify both can to synthesis hydrogen peroxide during the solvent that uses or raw material at Divide and implements, it can also be to the composition implementation containing hydrogen peroxide after synthesis hydrogen peroxide.

As described above, in composition of the invention, it is believed that acid plays a role as metal absorbent.Fe ingredient is especially in acid Property region in by Fenton's reaction peroxynitrite decomposition hydrogen (pH is higher, and decomposition rate is faster), but by by acid be used as metal Adsorbent and make Fe ingredient complexingization, so as to inhibit Fenton's reaction.If content of the content of Fe ingredient relative to acid, with matter Amount is than meter more than 10², then it is difficult to inhibit Fenton's reaction, the storage stability of composition is insufficient.On the other hand, Fe ingredient contains The content relative to acid is measured, by quality ratio less than 10^-5, then form colloidal particle in a liquid, become be attached to it is semiconductor-based The reason of defect number on plate increases.In composition, when content of the content relative to above-mentioned acid of Fe ingredient, by quality ratio for 10^-5~10²When, excellent storage stability and when being suitable for semiconductor devices manufacturing process to the defective effect of semiconductor substrate compared with It is small.

Also, in composition of the invention, the total content of above-mentioned Fe ingredient is preferably 0.1 matter relative to composition gross mass Measure the mass of ppt~1 ppb.By the way that the total content of above-mentioned Fe ingredient contained in composition is set as above range, make of the invention Effect is further excellent.The reason is not yet clear for it, but can be speculated as when the total content of above-mentioned Fe ingredient being low concentration region When domain, except the non-formation complex ion with ease of solubility, otherwise usually its major part becomes hydrogen made of the hydrate condensation of Fe Oxide colloid and disperse.If the total content of Fe ingredient is 0.1 mass ppt or more, the declines as positive colloid, it is difficult to The oxidation film more slightly higher than silicon face to negative Zeta potential adsorbs, and therefore, it is difficult to show the defect shadow to semiconductor substrate It rings.

Also, when the total content of Fe ingredient is 0.1 mass ppt or more relative to composition gross mass, further acknowledge group The oxidizing force for closing object is excellent.The reason is not yet clear for it, it is believed that being the total content due to Fe ingredient relative to composition When gross mass is 0.1 mass ppt or more, the amount of the hydroxyl free radical as reactivity kind is deposited in systems with amount appropriate ?.In other words, when the total content of Fe ingredient relative to composition gross mass less than 0.1 mass ppt when, as reactivity kind Hydroxyl free radical amount it is very few in systems, with oxidizing force reduce tendency.

On the other hand, if the total content of above-mentioned Fe ingredient relative to composition gross mass be 1 mass ppb hereinafter, if Fe at Point will not become particle, and be suitable for semiconductor devices manufacturing process when, not will increase the defect of double of conductor substrate.

In composition of the invention, sour content is preferably 0.01 matter of mass ppb~1000 relative to composition gross mass Measure ppb.Acid content relative to composition gross mass less than 0.01 mass ppb when, deposit the content of Fe ingredient in the composition It opposite can become excessive situation.As long as the content of acid is 0.01 mass ppb or more, Fe ingredient relative to composition gross mass Content be adjusted to range appropriate, therefore storage stability is more excellent or Fe ingredient will not become core and shape in a liquid At particle, and while being used in the manufacturing process of semiconductor devices, is able to suppress the defect to semiconductor substrate.

On the other hand, when sour content is more than 1000 mass ppb relative to composition gross mass, Fe in the composition is deposited The content of ingredient opposite can become very few situation.As long as acid content relative to composition gross mass be 1000 mass ppb with Under, then it is difficult to form colloidal particle in a liquid, and be suitable for being able to suppress when the manufacturing process of semiconductor devices to semiconductor The defect of substrate.

Also, hydrogen peroxide usually passes through anthraquinone synthesis.Containing pass through the anthraquinone hydrogen peroxide being synthesized into Composition in, although mostly exist be it is micro, still remain it is a degree of derived from raw material impurity (for example, derivative From anthraquinone analog compound or in reduction anthraquinone it can synthesize catalyst used in the process of anthrahydroquinone and containing selected from including The metal component of atom in the group of Ni, Pt, Pd and Al) the case where.These impurity are generally preferably removed, but in the present invention In not fully remove, but the preferably at least degree of residual minim in the composition.

In composition of the invention, the content of anthraquinone analog compound is preferably 0.01 mass relative to composition gross mass The mass of ppb~1000 ppb.As long as the content of anthraquinone analog compound is 0.01 mass ppb or more relative to composition gross mass, Have the effect of improving defect performance.On the other hand, as long as the content of anthraquinone analog compound is relative to composition gross mass 1000 mass ppb hereinafter, then be suitable for semiconductor devices manufacturing process when, it is smaller to the defective effect of semiconductor substrate.

Also, composition of the invention can also contain metal component, the metal component contain selected from including Ni, Pt, Pd, Atom in the group of Cr, Ti and Al is (hereinafter, also known as " specific atoms ".).

It is preferably 0.01 mass that the content of above-mentioned metal component, which is respectively relative to composition gross mass according to each specific atoms, The mass of ppt~10 ppb.

Here, metal component contains the specific atoms of ionic condition and the specific atoms of non-ionic state, for example, including spy The form of complexing metal ion and special metal particle (nonionic metal).That is, when composition of the invention for example only includes Pt It include all the components (Pt ion, Pt particle) that Pt atom is derived from contained in composition, Pt ingredient when ingredient, in Pt ingredient Content be to indicate that (total amount of metal is as above for total amount of metal (total Pt atomic weight) of Pt.).Also, " above-mentioned metal component contains It is to indicate that amount, which is respectively relative to composition gross mass according to each specific atoms as 0.01 mass of mass ppt~10 ppb ", when this hair Bright composition is for example comprising Pt ingredient and when this 2 kinds of Ni ingredient, according to each specific atoms difference (in other words, Pt ingredient Any one of content and the content of Ni ingredient) relative to composition gross mass, it is 0.01 mass of mass ppt~10 ppb.

As long as the content of the metal component containing the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al is pressed Being respectively relative to composition gross mass according to each specific atoms is 0.01 mass ppb or more, then the oxidizing force of composition is more excellent. On the other hand, as long as the content of the metal component containing the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al is pressed Being respectively relative to composition gross mass according to each specific atoms is 1000 mass ppb or less (preferably 10 mass ppb or less), then fits It is smaller to the defective effect of semiconductor substrate when manufacturing process for semiconductor devices.

In addition, as described above, containing being permitted by that can contain in the composition of the anthraquinone hydrogen peroxide being synthesized into More metal components, these metal components be derived from the process that reduction anthraquinone synthesizes anthrahydroquinone the catalyst that can be used and Contain Ni atom, Pt atom, Pd atom and/or Al atom.It also, is to exist much also to be mixed into other derivatives other than the above The case where from the metal component of material composition.In these metal components, above-mentioned model is set as particularly by by the content of metal component It encloses and confirms the case where obtaining said effect, which contains the original in the group including Ni, Pt, Pd, Cr, Ti and Al Son.

Also, in composition of the invention, containing the atom in the group including Ni, Pt, Pd and Al (hereinafter, also claiming For " specific atoms ".) the content of metal component relative to composition gross mass be preferably 0.01 mass of mass ppt~1 ppb. Here, the specific atoms of specific atoms and non-ionic state in metal component comprising ionic condition, for example, including special metal The form of ion and special metal particle (nonionic metal).That is, when composition of the invention only includes for example Pt ingredient, It include all the components (Pt ion, Pt particle) that Pt atom is derived from contained in composition, the content of Pt ingredient in Pt ingredient It is to indicate that (total amount of metal is as above for total amount of metal (total Pt atomic weight) of Pt.).As long as containing selected from including Ni, Pt, Pd and Al Group in the contents of metal component of specific atoms relative to composition gross mass be 0.01 mass ppb or more, then composition Oxidizing force it is more excellent.On the other hand, as long as the metal containing the specific atoms in the group including Ni, Pt, Pd and Al The content of ingredient is 1000 mass ppb or less (preferably 1 mass ppb or less) relative to composition gross mass, then is suitable for half It is smaller to the defective effect of semiconductor substrate when the manufacturing process of conductor device.

In addition, as described above, containing being permitted by that can contain in the composition of the anthraquinone hydrogen peroxide being synthesized into More metal components, these metal components be derived from the process that reduction anthraquinone synthesizes anthrahydroquinone the catalyst that can be used and Contain Ni atom, Pt atom, Pd atom and/or Al atom.Confirmed by the way that the content of the metal component is set as above range Said effect is obtained, which contains the atom in the group including Ni, Pt, Pd and Al.

Hereinafter, each ingredient to composition of the invention is described in detail.

< hydrogen peroxide >

In composition of the invention, the content of hydrogen peroxide is preferably 0.001~70 mass %, more preferably 10~60 matter Measure %, further preferably 15~60 mass %.

< acid >

Composition of the invention contains acid.In addition, not containing hydrogen peroxide in " acid " said here.

As acid, as long as can adsorb the metal ion being present in liquid (as absorption shape, can enumerate ionic bond Knot or coordination bond.), then it is not particularly limited, it is preferred that being aqueous acidic compound.

As aqueous acidic compound, it is dissolved in water as long as having and shows the acid functional group that can be dissociated, It is not particularly limited, can be organic compound, be also possible to inorganic compound.Also, water solubility said here refers to, At 25 DEG C, the situation of 5g or more is dissolved in water 100g.

As aqueous acidic compound and its salt, for example, can enumerate inorganic acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid and Nitric acid etc.) etc. acid compounds, carboxylic acid derivates, sulfonic acid and phosphoric acid derivatives etc..Also, these acid functional groups It can be the compound of forming salt.

Wherein, as above-mentioned aqueous acidic compound, from can effectively chelate impurity and remove the viewpoint of the impurity Consider, preferably phosphoric acid derivatives or phosphoric acid.

As phosphoric acid derivatives, for example, pyrophosphoric acid and polyphosphoric acid can be enumerated.

Also, as formed aqueous acidic compound and salt cation, can enumerate alkali metal, alkaline-earth metal, Level Four alkyl compound is (for example, tetramethylammonium hydroxide (TMAH), tetraethyl ammonium hydroxide (TEAH), first propyl ammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) etc.) etc..The cation for forming above-mentioned salt can be a kind, be also possible to two or more Combination.

Also, as aqueous acidic compound, in addition to above-mentioned aqueous acidic compound, it is so-called to use Chelating agent.It as chelating agent, is not particularly limited, it is preferred that being polyamine based polycarboxylic acid.

Polyamine based polycarboxylic acid is the compound with multiple amidos and multiple carboxylic acid groups, for example, can enumerate mono- or poly- stretch Alkylated polyamines polycarboxylic acids, polyamine group alkane polycarboxylic acids, polyamine group alkanol polycarboxylic acids and hydroxyalkyl ether polyamine polycarboxylic acids.

As suitable polyamine group polycarboxylate chelating agent, for example, butanediamine tetraacethyl, five second of diethylenetriamine can be enumerated Acid (DTPA), ethylenediamine tetrapropionic acid, triethylenetetramine hexaacetic acid, 1,3- bis- amido -2- hydroxy propane-N, N, N ', N '-tetrem Acid, trimethylen-edinitrilo-tetraacetic acid, ethylenediamine tetra-acetic acid (EDTA), anti-form-1,2- diamines butylcyclohexane tetraacethyl, ethylenediamine diacetic acid, Ethylene diamine dipropionic acid, 1,6- hexa-methylene-diamines-N, N, N ', N '-tetraacethyl, N, bis- (2- hydroxybenzyl) ethylenediamine-N, N- of N- Oxalic acid, two amido propane tetraacethyls, Cyclen-tetraacethyl, two aminopropanol tetraacethyls and (hydroxyl Ethyl) ethylenediamine triacetic acid.Wherein, preferably diethylene triamine pentacetic acid (DTPA) (DTPA), ethylenediamine tetra-acetic acid (EDTA) or anti-form-1, 2- diamines butylcyclohexane tetraacethyl.

In composition of the invention, acid can cooperate alone or in combination of two kinds or more.

As described above, the content of acid is preferably 0.01 mass of mass ppb~1000 ppb relative to composition gross mass.From Make effect of the invention further it is excellent from the viewpoint of, the more preferably 0.05 mass ppb of mass ppb~800, further it is excellent It is selected as 0.05 mass of mass ppb~500 ppb.

< Fe ingredient >

Composition of the invention contains Fe ingredient.

As described above, content of the content of Fe ingredient relative to acid, is by quality ratio 10 in composition of the invention^-5 ~10².From the viewpoint of keeping effect of the invention further excellent, the content of Fe ingredient relative to acid content with quality Than meter preferably 10^-3~10^-1。

Also, as described above, the content of above-mentioned Fe ingredient is preferred relative to composition gross mass in composition of the invention For 0.1 mass of mass ppt~1 ppb.From make effect of the invention further it is excellent from the viewpoint of, more preferably 0.1 mass The mass ppt of ppt~800, further preferably 0.1 mass of mass ppt~500 ppt.In addition, content in this is to indicate Fe original Total amount of metal of son.

< water >

Composition of the invention can contain water as solvent.

The content of water is not particularly limited, and is that 1~99.999 mass % can relative to composition gross mass.

As water, the ultrapure water that preferably uses in the manufacture of semiconductor devices.

As water, in particular, it is preferred that reducing the water of inorganic anion and metal ion etc., wherein be more preferably derived from Fe, The water that the ion concentration of the metallic atoms such as Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn is lowered, when for this hair When the tune liquid of bright composition, be further preferably adjusted to ppt grades or its following (in a kind of form, metal containing ratio is less than 0.001 mass ppt) water.As method of adjustment, it is preferable to use the purifying of filter membrane or amberplex or based on distillation Purifying.As method of adjustment, for example, Japanese Unexamined Patent Publication 2011-110515 bulletin [0074] section can be enumerated into [0084] section The method recorded in the method for record, Japanese Unexamined Patent Publication 2007-254168 bulletin.

In addition, the water that water used in embodiments of the present invention preferably obtains as described above.When by group of the invention It is above-mentioned from the viewpoint of it can obviously obtain the desired effect of the present invention when closing object as semiconductors manufacture treatment fluid Water is more preferably applied not only to composition of the invention, is also used to the cleaning of accepting container, in the tune liquid of aftermentioned kit.And And above-mentioned water is preferably also used to the manufacturing process of the present composition, the composition measurement of the present composition and for the present invention In measurement of the evaluation of composition etc..

< anthraquinone analog compound >

Composition of the invention can also contain anthraquinone analog compound.

As anthraquinone analog compound, for example, can enumerate makes in the synthesis process by the hydrogen peroxide of anthraquinone progress Anthraquinone analog compound.Specifically, it is preferable that be at least one kind of in the group including alkyl-anthraquinone and alkyl tetrahydro anthraquinone More than.

Alkyl contained in alkyl-anthraquinone and alkyl tetrahydro anthraquinone, such as preferably carbon atom number 1~8, more preferably carbon Atomicity 1~5.As alkyl-anthraquinone, wherein preferred ethyl hydrazine or amyl anthraquinone.Also, as alkyl tetrahydro anthraquinone, In, preferably ethyl tetrahydro-anthraquinone or amyl tetrahydro-anthraquinone.

In composition of the invention, anthraquinone analog compound can cooperate alone or in combination of two kinds or more.

When composition of the invention contains anthraquinone analog compound, as described above, its content is relative to composition gross mass Preferably 0.01 mass of mass ppb~1000 ppb.From make effect of the invention further it is excellent from the viewpoint of, more preferably For the 0.05 mass ppb of mass ppb~800, further preferably 0.05 mass of mass ppb~500 ppb.

< contains the metal component > of the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al

Composition of the invention can also contain to be selected from containing the metal component of at least one or more, the metal component Specific atoms in the group of Ni, Pt, Pd, Cr, Ti and Al.

When composition of the invention includes containing the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al When metal component, as described above, according to each specific atoms to be respectively relative to composition gross mass excellent for the content of above-mentioned metal component It is selected as 0.01 mass of mass ppt~10 ppb.From make effect of the invention further it is excellent from the viewpoint of, more preferably The 0.01 mass ppb of mass ppt~1, the further preferably 0.01 mass ppt of mass ppt~800, especially preferably 0.01 mass The mass of ppt~500 ppt.

< contains the metal component > of the specific atoms in the group including Ni, Pt, Pd and Al

Composition of the invention can also contain to be selected from containing the metal component of at least one or more, the metal component Specific atoms in the group of Ni, Pt, Pd and Al.

When composition of the invention include containing selected from including Ni, Pt, Pd and Al group in specific atoms metal at Timesharing, as described above, its content is preferably 0.01 mass of mass ppt~1 ppb relative to composition gross mass.From making the present invention Effect it is further excellent from the viewpoint of, more preferably 0.01 mass ppt~800 mass ppt, further preferably 0.01 The mass of quality ppt~500 ppt.

Composition of the invention in addition to the above ingredients, in the range of playing effect of the invention, can also contain Other additives.As other additives, for example, interfacial agent, defoaming agent, pH regulator and fluoride etc. can be enumerated.

(manufacturing method of composition)

The manufacturing method of composition of the invention, includes

Feed purification process (below also known as " the 1st process "), to selected from solvent and including the raw material of anthraquinone analog compound Any a kind or more of ingredient is purified；

Hydrogen peroxide synthesis procedure (below also known as " the 2nd process "), restores above-mentioned Anthraquinones in the presence of a catalyst Object and elbs reaction hydroquinone compound are closed, above-mentioned anthrahydroquinone class compound is further aoxidized and synthesizes hydrogen peroxide；

Hydrogen peroxide separation process (below also known as " the 3rd process "), by extracting resulting hydrogen peroxide from reaction It is taken out in system；And

Hydrogen peroxide composition purification procedures (below also known as " the 4th process "), further to containing from reaction system The hydrogen peroxide composition for the hydrogen peroxide isolated is purified.

Hereinafter, being described in detail to the 1st process to the 4th process.

(the 1st process: feed purification process)

The manufacturing method of composition of the invention be by so-called anthraquinone, use anthraquinone analog compound as raw material and The method for synthesizing hydrogen peroxide.

In this 1st process, it is selected from by the purifying such as distillation, ion exchange and filtering contains solvent and Anthraquinones in advance Any a kind or more for closing the material composition of object.As the degree of purifying, for example, being purified to material purity is preferably 99% or more, It is purified to purity and is more preferably 99.9% or more.In order to obtain based on apparent effect of the invention, this high-purity is used Raw material is important.

Described solvent refers in 1st process, in addition to the synthesis for being used in hydrogen peroxide comprising implementing in the 2nd process is anti- It also include to be used as the water of the extractant of hydrogen peroxide in the 3rd process or purify work in above-mentioned composition other than seasonable solvent Arbitrarily used solvent before sequence terminates.

Also, the described material composition containing anthraquinone analog compound refers in the 1st process, in addition to including abovementioned alkyl anthracene It also include the reducing catalyst of anthraquinone analog compound other than the anthraquinone analog compounds such as quinone and alkyl tetrahydro anthraquinone.

It as purification process, is not particularly limited, can enumerate in ion exchange resin or RO film (reverse osmosis membrane (Reverse Osmosis Membrane)) etc. in pass through method, distillation and it is aftermentioned filtering the methods of.Specifically, example Such as, it can enumerate after making liquid in reverse osmosis membrane etc. by implementing 1 purifying, making liquid is including cation exchange tree Method etc. in the purification devices of rouge, anion exchange resin or mixing bed-type ion exchange resin by implementing 2 purifying.

In addition, purification process can also combine multiple above-mentioned well known purification process and implement.

Also, purification process also can be implemented repeatedly.

(the 2nd process: hydrogen peroxide synthesis procedure)

This 2nd process can be applicable in using anthraquinone analog compound as the synthetic method of the well known hydrogen peroxide of raw material.Example Such as, the method recorded in Japanese Unexamined Patent Publication 2014-108903 bulletin can be enumerated.

(the 3rd process: hydrogen peroxide separation process)

This 3rd process is the process for extracting hydrogen peroxide obtained in above-mentioned 2nd process and taking out, and can be applicable in known Hydrogen peroxide extracting process.For example, the method recorded in Japanese Unexamined Patent Publication 2014-108903 bulletin can be enumerated.

In addition, it is preferable to use water carrys out extraction of hydrogen peroxide when being extracted.

" water " in 3rd process preferably via the 1st process, i.e. feed purification process, and derived from Fe, Co, Na, K, Ca, " water " that the ion concentration of the metallic atoms such as Cu, Mg, Mn, Li, Al, Cr, Ni and Zn is lowered, more preferable ion exchange water or half Ultrapure water used in the manufacture of conductor device.

(the 4th process: hydrogen peroxide composition purification procedures)

4th process is the process for purifying the hydrogen peroxide composition (aquae hydrogenii dioxidi) obtained in the 3rd process.

It as purification process, is not particularly limited, the method and decompression passed through in ion exchange resin can be enumerated The methods of distillation.

As the method passed through in ion exchange resin, for example, the method in addition to using acid cation exchange resin In addition, the method for the mixed bed using anion exchange resin and cation exchange resin can also be enumerated.

Also, filtering as described later can also be implemented to aquae hydrogenii dioxidi.

In addition, purification process can also combine multiple above-mentioned well known purification process and implement.

Also, purification process also can be implemented repeatedly.

< filters >

As filter, as long as the filter used in filtration applications etc. all the time, then without special limit Surely it uses.For example, can enumerate based on polytetrafluoroethylene (PTFE) (PTFE) and tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PFA) etc. the polyolefin resins such as polyamide resins and polyethylene and polypropylene (PP) such as fluororesin, nylon are (comprising highly dense Degree, super high molecular weight) etc. filter.Among these materials, it is preferably selected from (poly- comprising high density including polyethylene, polypropylene Propylene), the material in the group of the polyamide resins such as fluororesin and nylon such as PTFE and PTA, wherein more preferable polypropylene The filter of (including high density poly propylene) and nylon.By using the filter formed by these materials, can effectively go The high foreign matter of the polarity of the reason of except defect (residue defect or the grain defect) for easily becoming semiconductor substrate, in addition to this, The amount of the special metal ingredient of the present application can also be efficiently reduced.

In a kind of form, the aperture of filter is suitably for 0.001~1.0 μm or so, preferably 0.02~0.5 μm of left side The right side, more preferably 0.01~0.1 μm or so.By setting it as the range, it is able to suppress filtering blocking, and can certainly be removed Treated object (is the solution as filtering object, for example, solvent or material composition used in the 1st process and via the 3rd work The aquae hydrogenii dioxidi that sequence obtains) contained in the fine foreign matter such as impurity or condensation product.

When using filter, different filters can also be combined.

When the different filters of combination in use, for example, the method using the 1st filter and the 2nd filter can be enumerated. At this point, the filtering in the 1st filter can carry out 1 time, can also carry out 2 times or more.Also, it can also group within the above range Close the 1st filter of different pore size.It aperture in this can be referring to the nominal value of filter manufacturer's.As commercially available filtering Device, for example, can be from NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. are (old Japan Microlis Co., Ltd.) or KITZ MICRO FILTER CORPORATION etc. provided by various filters Selection.

2nd filter is able to use by the filter of the formation such as material identical with above-mentioned 1st filter.In a kind of form In, the aperture of the 2nd filter is suitably for 0.01~1.0 μm or so, preferably 0.1~0.5 μm or so.By setting it as the range, When containing component particle (for example, aftermentioned Fe particle) in treated object, it can be removed with the state for remaining the component particle The foreign matter being mixed into treated object.

Also, used filter is preferably handled before filtering treated object.Liquid used in the processing It is not particularly limited, but metal containing ratio is preferably less than 0.001 mass ppt, in addition to above-mentioned water, as long as to other Organic solvent purified and tenor become above range liquid or the present composition itself, dilution the present invention Composition made of liquid or the compound comprising making an addition in the present composition liquid, then can obviously obtain this hair Desired effect in bright.

Hereinafter, to can it is preferable to use in the purifying of treated object and the purification devices that have filter are illustrated.

Purification devices

Fig. 1 is the skeleton diagram for indicating a kind of form of purification devices.Purification devices 100 have tank 101, and tank 101 has use In the supply mouth 102 of supply treated object.Purification devices 100 have filter device 105, and tank 101 and filter device 105 pass through confession Link to pipeline 109, making being capable of trandfer fluid (treated object) between tank 101 and filter device 105.Match on feeding pipe 109 It is equipped with valve 103 and pump 104.In Fig. 1, purification devices 100 have tank 101 and filter device 105, but as in treated object The purification devices that can be used in filtering, however it is not limited to this.

In purification devices 100, the fluid supplied from supply mouth 102 inflow filter via valve 103 and pump 104 105.The fluid being discharged from filter device 105 is contained in tank 101 via circulation line 110.

Purification devices 100 have the discharge unit 111 that treated object is discharged to circulation line 110.Discharge unit 111 has valve 107 and container 108 treated object can be contained in by being set to the valve 106 of circulation line and the switching of above-mentioned valve 107 In container 108.Also, the pipeline 113 that can switch is connected on valve 107, it, can will be after wash cycles via the pipeline 113 Treated object be expelled to the outsides of purification devices 100.It is miscellaneous sometimes with particle and metal in treated object after wash cycles Matter etc. can not pollute container 108 according to the purification devices 100 for having the pipeline 113 being expelled to treated object outside device Fill part etc. and be effectively removed the foreign matter for easily becoming semiconductor substrate defect cause.

Moreover, purification devices 100 have treated object monitoring portion 112 in circulation line 110.In Fig. 1, purification devices 100 have treated object monitoring portion 112 in circulation line 110, but pure as can be used in the filtering of treated object Makeup is set, however it is not limited to this.Treated object monitoring portion 112 can also have in feeding pipe 109, can also have and supply In pipeline 109 and circulation line 110.In addition, treated object monitoring portion 112 is directly provided in circulation pipe in purification devices 100 In road 110, but as the purification devices that can be used in the filtering of treated object, however it is not limited to this.Treated object monitoring portion The interim receiving tank that can also have the fluid not shown having in pipeline is (different from tank 101.) in.

Fig. 2 is the skeleton diagram of another form for the purification devices that can be used in the filtering for indicate treated object.Purifying dress It sets 200 and has tank 101 and filter device 105, be also equipped with destilling tower 201, which passes through tank 101 and pipeline 202, pipe Road 204 and pipeline 203 connect, and be configured to by above-mentioned each pipeline can between the pipeline and tank 101 trandfer fluid.And And on the other hand, as the purification devices that can be used in the filtering of treated object, not necessarily to have filter device 105 And/or on the other hand destilling tower 201 can also be also equipped with the reaction vessel etc. connecting by pipeline 203 with destilling tower 201.Separately Outside, it when treated object is aquae hydrogenii dioxidi, may not possess by destilling tower 201 and by pipeline 203 and destilling tower 201 The reaction vessel etc. of connection.

In purification devices 200, it is distilled in destilling tower 201 via the fluid that pipeline 203 is supplied in destilling tower 201. Fluid through distilling is contained in tank 101 via pipeline 202.Have valve 103 and valve 206 in feeding pipe 109, by with pipe The switching for the valve 205 having in road 204 can make from the fluid inflow filter 105 that tank 101 is discharged.

Also, in purification devices 200, the fluid being discharged from tank 101 can also again flowed into destilling tower 201.It should In the case of, by the switching of above-mentioned valve 103, valve 206 and valve 205, fluid is flowed into from pipeline 204 via valve 207 and pipeline 203 In destilling tower 201.

As purification devices connect liquid portion (docking liquid portion definition will be aftermentioned.) material, be not particularly limited, from energy It is enough further reduced from the aspect of the foreign matter of treated object, preferably by selected from including nonmetallic materials and through the metal of electropolishing At least one kind of formation in the group of material.In addition, in the present specification, " meeting liquid portion " is to indicate, with fluid contact can be with Can property position (for example, inner surface of tank and the inner surface of pipeline etc.) and from its surface with a thickness of the region of 100nm.

It as above-mentioned nonmetallic materials, is not particularly limited, preferably polyvinyl resin, acrylic resin and poly- second The resin material containing fluorine such as the polyolefin resins such as alkene-acrylic resin and perfluorinated resin, the dissolution from metallic atom are less From the viewpoint of, preferably comprise the resin of fluorine.

As the resin containing fluorine, perfluorinated resin etc. can be enumerated, tetrafluoroethylene resin (PTFE), tetrafluoro second can be enumerated Alkene-perfluoroalkyl vinyl ether copolymer (PFA), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer resins (FEP), tetrafluoroethylene-Ethylene are total Copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), vinylidene difluoride resin (PVDF), chlorotrifluoroethylene Copolymer resins (PCTFE) and fluoroethylene resin (PVF) etc..

Wherein, as the resin containing fluorine, preferably tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether is total Polymers or hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer resins.

It as above-mentioned metal material, is not particularly limited, is able to use well known material.

As metal material, for example, can enumerate is that the total of chromium and nickel content is more than relative to metal material gross mass The metal material of 25 mass %, wherein preferably 30 mass % or more.Total as chromium and nickel content in metal material Upper limit value is not particularly limited, it is generally preferable to be 90 mass % or less.

As metal material, for example, stainless steel and nickel-chromium alloy etc. can be enumerated.

It as stainless steel, is not particularly limited, is able to use well known stainless steel.Wherein, preferably comprise 8 mass % with On nickel alloy, the further preferably austenitic stainless steel of the nickel of 8 mass % or more.As austenitic stainless steel, for example, can To enumerate SUS (steel use stainless steel (Steel Use Stainless)) 304 (8 mass %, Cr content of Ni content, 18 matter Measure %), SUS304L (9 mass %, Cr content of Ni content, 18 mass %), SUS316 (10 mass %, Cr content of Ni content, 16 matter Measure %) and SUS316L (12 mass %, Cr content of Ni content, 16 mass %) etc..

It as nickel-chromium alloy, is not particularly limited, is able to use well known nickel-chromium alloy.Wherein, preferred nickel content The nickel-chromium alloy for being 1~30 mass % for 40~75 mass %, chromium content.

As nickel-chromium alloy, for example, can enumerate Hastelloy (trade name, it is same as below.), Monel (trade name, It is same as below) and Inconel (trade name, same as below) etc..More specifically, HastelloyC-276 can be enumerated (Ni contains Measure 63 mass %, Cr content, 16 mass %), Hastelloy-C (60 mass %, Cr content of Ni content, 17 mass %), HastelloyC-22 (61 mass %, Cr content of Ni content, 22 mass %) etc..

Also, nickel-chromium alloy can also also contain boron, silicon, tungsten, molybdenum, copper and cobalt optionally and containing other than above-mentioned alloy Deng.

As the method for carrying out electropolishing to metal material, it is not particularly limited, is able to use well known method.Example Such as, 0011~0014 section and Japanese Unexamined Patent Publication 2008-264929 bulletin of Japanese Unexamined Patent Publication 2015-227501 bulletin are able to use 0036~0042 section it is equal in documented method.

Metal material can be speculated as being contained by chromium in electropolishing surface passivation layer (passivation layer) Metal material of the amount more than the content of chromium in parent phase.Therefore, the steaming that the metal material of electropolishing is formed has been carried out from by meeting liquid portion Evaporate be difficult in tower flow out treated object in the metal impurities containing metallic atom therefore can be speculated as, which can Obtain the treated object that the distillation of impurity content reduction finishes.

In addition, metal material can also be polished (buffing).Polishing method is not particularly limited, and is able to use public affairs The method known.The size of the abrasive grains (abrasive grain) used when polishing is not particularly limited, but calm From the aspect of easily the bumps of metal material surface being made to become smaller, preferably #400 or less.In addition, polishing preferably electropolishing it Preceding progress.

From the aspect of the foreign matter that can be further reduced treated object, liquid portion is preferably met by the stainless steel through electropolishing It is formed.In particular, in the case that purification devices have tank, more preferably by the stainless steel shape for meeting liquid portion and having carried out electropolishing of tank At.Content as the content and Fe for meeting the Cr in liquid portion containing mass ratio (hereinafter, also known as " Cr/Fe ".), there is no special It does not limit, it is generally preferable to be 0.5~4, wherein metal impurities and/or organic impurities are more difficult to dissolution from treated object From the aspect of, more preferably above 0.5 and less than 3.5, more preferable 0.7 or more and 3.0 or less.If Cr/Fe is more than 0.5, can Inhibit metal dissolving in tank, if Cr/Fe less than 3.5, be not susceptible to become granular raw because the removing etc. for meeting liquid portion.

As the method for adjusting the Cr/Fe in above-mentioned metal material, it is not particularly limited, adjustment metal material can be enumerated The method of Cr atom content in material, and make the content of chromium in polished surface passivation layer more than chromium in parent phase by electropolishing The method etc. of content.

Epithelium technology can also be applied in metal material.

Coating metal (various plating), inorganic coating (various chemical conversion treatments, glass can be roughly divided into epithelium technology Glass, concrete and ceramics etc.) and organic coating (antirust oil, coating, rubber and plastic cement etc.) this 3 seed type.

As preferred epithelium technology, can enumerate based on antirust oil, antirust agent, corrosion inhibitor, chelate compound, can The surface treatment carried out with fissility plastic cement or lining agent.

Wherein, the carboxylics such as preferably various chromate, nitrite, silicate, phosphate, oleic acid acid, dimeric dibasic acid, aphthenic acids The saprophages inhibitor, ethylenediamine such as acid, carboxylic acid metal's soap, sulfonate, amine salt, ester (glyceride and phosphate of higher fatty acids etc.) The chelate compounds such as tetraacethyl, gluconic acid, nitrilotriacetic acid, hydroxyethylethylene diamine tri-acetic acid, diethylene triamine pentacetic acid (DTPA) or fluorine Resin lining, particularly preferred phosphate treated or fluororesin lining.

Above-mentioned purification devices can be further reduced the foreign matter of treated object by having filter device 105.As filtering Filter element contained by device 105, is not particularly limited, it is preferred that for selected from including particle removal diameter (particle-eliminating diameter) is in the group of 20nm filter below and adsorption of metal ions filter At least one kind of, more preferably particle removal diameter is 20nm filter below and is adsorption of metal ions filter.

It is 20nm filter below that particle, which removes diameter,

Particle removal diameter be 20nm filter below have be effectively removed from treated object diameter be 20nm with On particle function.

In addition, the particle as filter removes diameter, preferably 1~15nm, more preferably 1~12nm.If particle is gone Except diameter is 15nm hereinafter, can then remove finer particle, if particle removal diameter is 1nm or more, filtering effect is improved Rate.

Here, particle removal diameter is the minimum dimension for the particle for indicating that filter can remove.For example, when filter When particle removal diameter is 20nm, the particle that diameter is 20nm or more can be removed.

As the material of filter, for example, 6- nylon and 6 can be enumerated, the nylon such as 6- nylon, polypropylene, gather polyethylene Styrene, polyimides, polyamidoimide and fluororesin etc..Polyimides and/or polyamidoimide, which can be, to be had At least one in the group including carboxyl, salt form carboxyl and-NH- key.About solvent resistance, fluororesin, polyimides and/ Or polyamidoimide is more excellent.Also, from the viewpoint of adsorbing metal ions, preferred 6- nylon and 6, the Buddhist nuns such as 6- nylon Dragon.

Filter device 105 also may include multiple above-mentioned filters.When filter device 105 includes multiple filters, make It for other other filters, is not particularly limited, preferred particle removal diameter is the filter of 50nm or more (for example, hole The particle removal secondary filter film that diameter is 50nm or more).When in treated object in addition to there is impurity through colloidization, especially There is also when particle other than the impurity through colloidization containing the metallic atoms such as iron or aluminium, diameter is being removed as 20nm using particle It the use of particle removal diameter is 50nm or more before filter (for example, aperture is 20nm secondary filter film below) below Filter (for example, the particle that aperture is 50nm or more removes secondary filter film) and implementation is purified the filtering of object, as a result, Improve the filtering effect that particle removal diameter is 20nm filter below (for example, aperture is 20nm secondary filter film below) Rate, to further increase the removal capacity of particle.

Adsorption of metal ions filter

Above-mentioned filter device 105 preferably comprises adsorption of metal ions filter.

It as adsorption of metal ions filter, is not particularly limited, well known adsorption of metal ions filtering can be enumerated Device.

Wherein, it as adsorption of metal ions filter, is preferably able to carry out the filter of ion exchange.It is inhaled here, becoming The metal ion of attached object is not particularly limited, for example, it is preferable to selected from including Fe ion, Ni ion, Pt ion, Pd ion, The metal ion of one or more of the group of Cr ion, Ti ion and Al ion, more preferably Fe ion, Ni ion, Pt ion, The whole metal ion such as Pd ion, Cr ion, Ti ion and Al ion.

From the viewpoint of the absorption property for improving metal ion, acid is contained on the preferred surface of adsorption of metal ions filter Base.As acidic group, sulfo group and carboxyl etc. can be enumerated.

As the substrate (material) for constituting adsorption of metal ions filter, cellulose can be enumerated, diatomite, nylon, gathered Ethylene, polypropylene, polystyrene and fluororesin etc..From the viewpoint of the efficiency of adsorbing metal ions, particularly preferred nylon.

Also, adsorption of metal ions filter can also be by the material structure containing polyimides and/or polyamidoimide At.As above-mentioned adsorption of metal ions filter, for example, Japanese Unexamined Patent Publication 2016-155121 bulletin (JP2016- can be enumerated 155121) documented polyimides and/or polyamidoimide multiple aperture plasma membrane in.

Above-mentioned polyimides and/or polyamidoimide multiple aperture plasma membrane are also possible to containing selected from including carboxyl, salt form carboxylic At least one in the group of base and-NH- key.If adsorption of metal ions filter includes fluororesin, polyimides and/or polyamide Acid imide then has more excellent solvent resistance.

Organic impurities adsorption filter

Filter device 105 can also include organic impurity absorption filter.

It as organic impurities adsorption filter, is not particularly limited, well known organic impurities adsorption filtration can be enumerated Device.

Wherein, preferably exist from the aspect of the absorption property for improving organic impurities as organic impurities adsorption filter Surface has the organic matter skeleton that can be interacted with organic impurities (in other words, by can be with organic impurities phase interaction Organic matter skeleton and surface is upgraded).As the organic matter skeleton that can be interacted with organic impurities, for example, can be with Enumerate the chemical structure for reacting with organic impurities and organic impurities capable of being made to be captured by organic impurities adsorption filter.More For body, as organic impurities, when including n- long-chain alkyl alcohol (structure when using 1- long-chain alkyl alcohol as organic solvent Isomeric compound) when, alkyl can be enumerated as organic matter skeleton.It also, include dibutyl hydroxy toluene as organic impurities (BHT) when, phenyl can be enumerated as organic matter skeleton.

As the substrate (material) for constituting organic impurities adsorption filter, cellulose, the silicon for carrying active carbon can be enumerated Diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene and fluororesin etc..

Also, it is also able to use Japanese Unexamined Patent Publication 2002-273123 bulletin in organic impurities adsorption filter and Japan is special Open recorded in 2013-150979 bulletin active carbon is fixed on to filter made of nonwoven fabric.

As organic impurities adsorption filter, in addition to be applicable in it is above-mentioned shown in chemisorption (having used has energy on surface The absorption of the organic impurities adsorption filter of the organic matter skeleton of enough and organic impurities interaction) other than, it can also be applicable in object Manage adsorption method.

For example, the structure of BHT is greater than 10 angstroms (=1nm) when including BHT as organic impurities.Therefore, by using Aperture is the organic impurities adsorption filter of 1nm, and BHT can not pass through the hole of filter.That is, BHT is by filter by physics It captures, therefore is removed from being purified in object.In this way, the removal of organic impurities can not only be applicable in interaction chemically, Physical removal methods can be applicable in.Wherein, in this case, the filter in the aperture 3nm or more is used as " particle removal filter ", It is used as " organic impurities adsorption filter " less than the filter in the aperture 3nm.

Repeated explanation again, using different filters can also be combined when filter.As the side for combining different filters Formula, for example, the method for combining the 1st filter and the 2nd filter as described above can be enumerated.At this point, the mistake in the 1st filter Filter can only carry out 1 time, can also carry out 2 times or more.It is each to filter when the different filters of combination, which carry out 2 times or more, to be filtered Device can be mutually the same type, be also possible to type different from each other, it is preferred that for diverse filter each other. Typically, at least one of the 1st filter and the preferred aperture of the 2nd filter and composition raw material are different.

2nd later pore size filter is preferably identical or smaller as the 1st pore size filter.Also, it can also be upper State the 1st filter of combination different pore size in range.It aperture in this can be referring to the nominal value of filter manufacturer's.As city The filter sold, for example, can be from NIHON PALL LTD., Toyo Ro shi Kaisha, Ltd., Nihon Entegris K.K. various provided by (old Japan Microlis Co., Ltd.) or KITZ MICRO FILTER CORPORATION etc. It is selected in filter.Also, also it is able to use " P- nylon filter-(0.02 μm of the aperture, critical surface tension of polyamide 77mN/m)"；" PE clean filter (0.02 μm of the aperture) " of (NIHON PALL LTD. system), high density polyethylene (HDPE)； " PE clean filter (0.01 μm of the aperture) " of (NIHON PALL LTD. system) and high density polyethylene (HDPE)；(NIHON PALL LTD. it makes).

From the aspect of the foreign matter that can be further reduced treated object, purification devices are preferably pre- by cleaning solution First clean.In this method, cleaning solution is supplied from the supply mouth 102 of tank 101.Supply amount as cleaning solution is limited there is no special System, is preferably capable the amount for connecing liquid portion degree of abundant purge tank 101, as the capacity of the cleaning solution supplied, relative to tank 101 capacity is preferably 30 volume % or more.When supplying cleaning solution from supply mouth 102, valve 103 can be closed, and can also open It opens, but in terms of more easily purge tank 101, when supplying cleaning solution from supply mouth 102, preferably is off valve 103.

The cleaning solution supplied to tank 101 can also be conveyed directly in purification devices, can also be carried out in tank 101 After cleaning, (for example, passing through feeding pipe 109) is conveyed in purification devices.As using in cleaning solution purge tank 101 Method be not particularly limited, for example, can enumerate the diagram that do not disappear for having tank 101 stirring blade rotation and carry out The method of cleaning.As using the time of cleaning solution purge tank to be not particularly limited, according to the material for meeting liquid portion of tank 101 and Pollution can property etc. and suitably select can.It is generally preferred to 0.1 second~48 hours or so.In addition, ought only purge tank 101 When, for example, the cleaning solution after cleaning can be discharged from the outlet (not shown) for being set to pot bottom.

As the method for using the feeding pipe 109 of cleaning solution cleaning purification devices 100 to wait, it is not particularly limited, it is excellent It is selected in and opens valve 103 and valve 106 and close operation pump 104 on the basis of valve 107, so that cleaning solution be made to pass through feeding pipe 109 And circulation line 110 and recycled in purification devices method (hereinafter, also known as " wash cycles ".).By be set as it is above-mentioned that As, while cleaning solution can be conveyed, the different of liquid portion is connect by be attached to tank 101, filter device 105 and feeding pipe 109 etc. Object etc. is effectively dispersed by cleaning solution and/or is more efficiently made it dissolve in the cleaning solution.

In particular, when purification devices have filter device, as cleaning method, preferred cycle cleaning.It is followed using Fig. 1 explanation The example of ring cleaning.Firstly, supplying from tank 101 via valve 103 to the cleaning solution in purification devices, pass through feeding pipe 109 (via filter device 105, circulation line 110 and valve 106) and return again to tank 101 (circulation).At this point, cleaning solution quilt Filter device 105 filters, and dissolves the particle etc. being scattered in cleaning solution and is removed, can further increase cleaning effect.

As the other modes of cleaning method, for example, it is also possible to using opening valve 103 and valve 107 and closing valve 106 On the basis of operation pump 104, make from the supply mouth 102 of tank 101 supply to the cleaning solution in purification devices by valve 103 and pump 104 And in inflow filter 105, then, cleaning solution is not made to be recycled and be expelled to the method outside purification devices via valve 107 (this method in the present specification, is also known as " batch cleaning " below.).In this case, cleaning solution can be as described above, make one It is quantitative intermittently to supply to purification devices, it can also be continuously supplied into purification devices.

Filtering in 4th process

When implementing filtering in the 4th process, in addition to the method described above, preferably also implement hydrogen peroxide by following methods The filtering of composition.In addition, the filtering carried out by following methods also can be implemented in the 1st process.

As filter, as long as the filter used in filtration applications etc. all the time, then without special limit Surely it uses.For example, being based on polytetrafluoroethylene (PTFE) (PTFE) and tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PFA) etc. the polyolefin resins such as polyamide resins and polyethylene and polypropylene (PP) such as fluororesin, nylon are (comprising highly dense Degree, super high molecular weight) etc. filter.In these materials, it is preferably selected from including polyethylene, polypropylene (comprising high density poly- third Alkene), the material in the group of the polyamide resins such as fluororesin and nylon such as PTFE and PTA, wherein more preferable PTFE and PTA Equal fluororesin filter.By using the filter formed by these materials, can be effectively removed easily become it is semiconductor-based The high foreign matter of the polarity of the reason of defect (residue defect or grain defect) of plate, in addition to this, additionally it is possible to efficiently reduce this Apply for the amount of the special metal ingredient of invention.

It is as the critical surface tension of filter, preferably 70mN/m or more, more preferably 95mN/m hereinafter, further excellent It is selected as 75mN/m or more and 85mN/m or less.In addition, the value of critical surface tension is the nominal value of manufacturer.By using critical Surface tension be above range filter, can be effectively removed easily become semiconductor substrate defect (residue defect and Grain defect) the reason of the high foreign matter of polarity, in addition to this, additionally it is possible to efficiently reduce the special metal of the present application at The amount divided.

In a kind of form, the aperture of filter is preferably 2~20nm or so, more preferably 2~15nm.By being set as this Range is able to suppress filtering blocking, and can certainly remove impurity or condensation product contained in hydrogen peroxide composition etc. Fine foreign matter, in addition to this, additionally it is possible to efficiently reduce the amount of the special metal ingredient of the present application.

When using filter, different filters can also be combined.At this point, the filtering in the 1st filter can only carry out 1 It is secondary, it can also carry out 2 times or more.When the different filters of combination, which carry out 2 times or more, to be filtered, preferably the 2nd later filtering Aperture is identical or smaller as the 1st pore size filter.Also, the 1st mistake of different pore size can also be combined within the above range Filter.It aperture in this can be referring to the nominal value of filter manufacturer's.As commercially available filter, for example, can be from NIHON PALL LTD., Toyo Ro shi Kaisha, Ltd., Nihon Entegris K.K. (old Japan Microlis Co., Ltd. it) or in various filters provided by KITZ MICRO FILTER CORPORATION etc. selects.Also, can also it make With " P- nylon filter-(0.02 μm of the aperture, critical surface tension 77mN/m) " of polyamide；(NIHON PALL LTD. System), " PE clean filter (0.02 μm of the aperture) " of high density polyethylene (HDPE)；(NIHON PALL LTD. system) and high density " PE clean filter (0.01 μm of the aperture) " of polyethylene；(NIHON PALL LTD. system).

2nd filter is able to use by the filter of the formation such as material identical as above-mentioned 1st filter.2nd filter Aperture is preferably 1~10nm or so.

Also, in the present invention, filter progress is preferably carried out in room temperature (25 DEG C) below.More preferably 23 DEG C hereinafter, into One step is preferably 20 DEG C or less.Also, preferably 0 DEG C or more, more preferably 5 DEG C or more, further preferably 10 DEG C or more.

The foreign matter and impurity that corpuscular property can be removed in filter progress are then dissolved in hydrogen peroxide group if above-mentioned temperature The amount of the foreign matter and/or impurity that close the above-mentioned corpuscular property in object is reduced, therefore is effectively removed by filtering.

In particular, when hydrogen peroxide composition contain have more than the desired amount of the application, containing selected from including Ni, Pt, Pd, When the metal component of the specific atoms in the group of Cr, Ti and Al, preferably it is filtered with above-mentioned temperature.Though mechanism is indefinite, That may be considered, when in hydrogen peroxide composition comprising containing selected from including Ni, Pt, Pd, Cr, Ti and Al group in spy When determining the metal component of atom, its most colloidal state with corpuscular property of metal component exist.It may be considered, if with above-mentioned temperature Degree is filtered, then a part cohesion of the metal component to be suspended with colloidal, therefore the condensation product is by filtering by effectively Removal, is easily tailored as the desired amount of the application.

Also, used filter is preferably handled before filtering hydrogen peroxide composition.Made in the processing Liquid is not particularly limited, it is preferred that metal containing ratio is less than 0.001 mass ppt (part per trillion (parts per Trillion)), for example, in addition to above-mentioned water, it can also enumerate and purify other organic solvents and tenor is made to become above-mentioned model The liquid that encloses, the present composition itself (liquid adjusted in advance) or liquid made of being diluted, or into one Walk liquid made of purifying composition of the invention and more reduce metal component, impurity or oversize grain etc..Using it is above-mentioned that Kind reduces the liquid of metal containing ratio and carries out pre-treatment to filter, thus obviously obtains the desired effect of the present invention.

The purification procedures of hydrogen peroxide composition in 4th process preferably combine above-mentioned each purification process and implement.

Via above-mentioned 1st process to the 4th process, it can obtain and realize high purity in the manufacture of semiconductor devices may be used With the composition of the invention of usage degree.

In addition, composition of the invention is as above.Also, acid contained by composition of the invention can be by it is anthraquinone into The acid such as secondary O-phthalic acids generated in the synthesis process of capable hydrogen peroxide, also, be also possible in above-mentioned 4th process Or the acid in addition added after above-mentioned 4th process.From the purity of composition and from the sight for keeping effect of the invention further excellent Point considers, adds sour component (preferably phosphoric acid or phosphoric acid derivatives) into composition preferably in the 4th process, is more preferably adding Add further progress purification procedures after the sour component.

< quantitative approach >

Also, sour component or anthraquinone analog compound contained in water or solvent, material composition or composition of the invention etc. It is various quantitative, can be analyzed by ion chromatography.

Also, Fe ingredient contained in water or solvent, material composition or composition of the invention etc. or metal component is each Kind is quantitative, can pass through ICP-MS method (inductively coupled plasma mass spectrometry (inductively coupled plasma Mass spectrometry), as measurement device, such as it is able to use Yokogawa Analytical Systems, Inc. System, Agilent 7500cs type.) etc. analyzed.Gross mass, that is, metal ion in ICP-MS method, as metallic atom The total quality (also known as " total amount of metal " of (cationic metal) and metallic (nonionic metal).) and quantified.

Also, according to the SNP-ICP-MS (single nanoparticle-inductively coupled plasma mass spectrometry developed recently (Single Nano Particle-Inductively Coupled Plasma-Mass Spectrometry)) measurement, it can The amount for the metallic atom that will be present in liquid is divided into metal ion (cationic metal) and metallic (nonionic metal) And it is measured.It is not dissolved in here, metallic (nonionic metal) refers in solution and as ingredient existing for solid.

So far, the amount of metallic atom contained in semiconductors manufacture treatment fluid etc. usually by ICP-MS method etc. come It is analyzed, and can not identify cationic metal and metallic derived from metallic atom by prior methods such as ICP-MS methods (nonionic metal), therefore, gross mass, that is, cationic metal and corpuscular property metal (the nonionic gold as metallic atom Belong to) total quality (hereinafter, also known as " total amount of metal " etc..) and quantified.

It uses in treatment fluid in semiconductors manufacture as impurity and the metallic atom that contains becomes in fine pattern and fine One of the main reason for defect is generated in semiconductor element.Therefore, think always contained in the semiconductors manufacture treatment fluid The fewer the amount of metallic atom the better.However, the inventors discovered that, the generation of the amount and defect of metallic atom contained in treatment fluid Rate may not be related, has in the generation rate of defect and generates deviation.

The present inventor has carried out sharp study to following influence, that is, can be by using the measurement of SNP-ICP-MS method And it is identified and quantitative cationic metal and metal derived from metallic atom contained in semiconductors manufacture treatment fluid Particle (nonionic metal) respectively influences defect bring.As a result, being discovery metallic (nonionic metal) amount The influence generated to defect is very big, has correlativity between metallic (nonionic metal) amount and defect generation.As The device of SNP-ICP-MS method, for example, being able to use Agilent Technologies Japan, Ltd. system, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, semiconductor analysis are used, Option (option) #200) and the method by being recorded in embodiment be measured.Than that described above, it can also enumerate PerkinElmer Co., Ltd. NexION350S and Agilent Tec hnologies Japan, Ltd. system Agilent 8900。

In the present compositions, from the viewpoint of improving defect performance and ensuring ageing stability, pass through SNP- The content of Fe particle (non-ionic metal) when ICP-MS method measures is relative to composition gross mass, preferably 0.01 mass ppt ~0.1 mass ppb.

Also, it ought be in the present compositions comprising containing the spy in the group including Ni, Pt, Pd, Cr, Ti and Al The metal component of atom is determined, and when above-mentioned metal component contains metallic (non-ionic metal), from improving defect performance and really It protects from the viewpoint of ageing stability, the content of the above-mentioned metallic in the present composition distinguishes phase according to each specific atoms For composition gross mass, the preferably 0.01 mass ppt of mass ppt~100, more preferably 0.01 mass of mass ppt~50 Ppt, further preferably 0.01 mass of mass ppt~10 ppt.That is, when composition of the invention for example only contains Pt particle, Pt particle becomes above-mentioned numberical range.On the other hand, when composition of the invention is for example containing Pt particle and when Ni particle, Pt Son and Ni particle respectively become above-mentioned numberical range.In addition, the content of above-mentioned metallic is by above-mentioned SNP-ICP-MS method And the value measured.

The opening of preparation, accepting container comprising the present composition and closing and/or cleaning, the filling of composition etc. exist Interior processing, processing analysis and measurement, preferably carries out at toilet (clean room).It is preferred that toilet meets 14644-1 Toilet's benchmark.Any one of 1 grade of ISO (International Standards Organization), 2 grades, ISO3 grades, ISO4 grades of ISO are preferably satisfied, it is more excellent Be full 1 grade of sufficient ISO, 2 grades of ISO, further preferably 1 grade of ISO.

< organic impurities >

In addition, gas chromatography-mass spectrometric apparatus (ProductName " GCMS- is also used in the measurement of organic impurity content sometimes 2020 ", SHIMADZU CORPORATION system).Though also, be not particularly limited, when organic impurities is molecular weight When closing object, Py-QTOF/MS (pyrolysis apparatus quadrupole time-of-flight type mass spectrum), Py-IT/MS (pyrolysis apparatus ion well-type matter can be passed through Spectrum), Py-Sector/MS (pyrolysis apparatus field type mass spectrum), Py-FTICR/MS (pyrolysis apparatus Fourier transform ion well-type mass spectrum), The methods of Py-Q/MS (four polar form mass spectrum of pyrolysis apparatus) and Py-IT-TOF/MS (pyrolysis apparatus ion trap time-of-flight type mass spectrum), from The identification of structure and quantifying for concentration are carried out in decomposition product.For example, Py-QTOF/MS is able to use such as SHIMADZU The device of CORPORATION.

< impurity and oversize grain >

Also, composition of the invention is preferably substantially free of oversize grain.

In addition, oversize grain contained in composition of the invention refers to, the dust that contains in the feed as impurity, The particles such as dirt, organic solid matter or inorganic solid material, the dust being had in the preparation of composition as pollutant, The particles such as dirt, organic solid matter or inorganic solid material are equivalent to and are finally not dissolved in composition of the invention and make For substance existing for particle.It is present in the amount of the oversize grain in composition of the invention, can utilizes using laser as light source Light scatters the commercially available measurement device in formula liquid particle mensuration mode, is measured in the liquid phase.

< kit and concentrate >

Composition of the invention can also be used as the kit in addition adding other raw materials.In this case, when as using In addition other raw materials added, other than water removal and organic solvent equal solvent, additionally it is possible to make according to other compounds of Function Mixture With.From the viewpoint of obviously obtaining effect of the invention, in the solvent that can be used at this time, if Fe ingredient contained in solvent Or the range of each containing ratio of metal component be it is identical as the range of the particular value in aforementioned present invention composition, then even try Agent box and concentrate can also obviously obtain the desired effect of the present invention.

< purposes >

Composition of the invention can be used preferably in the manufacture of semiconductor devices.Composition of the invention can It is used in any process of manufacturing semiconductor devices, specifically, can include photo-mask process, etching work procedure, ion note In the manufacturing process for entering the semiconductor devices of process or stripping process etc., after each process or before being moved to subsequent processing, It is used as the treatment fluid for handling organic matter or inorganic matter, specifically, can be used as cleaning solution, removal liquid or removing Liquid etc. and preferably used.

It when composition of the invention to be used in the manufacture of semiconductor devices, is not particularly limited, for example, can be excellent Selection of land is used to be mixed to remove the purpose of the inorganic metal ion on silicon substrate with hydrochloric acid, and by being referred to as SC-2 The case where medical fluid of (standard clean (Standard Clean) 2) handles and removes metal ion from silicon substrate.And it is possible to excellent Selection of land is used to be mixed to remove the purpose of the particle on silicon substrate with ammonia, and by being referred to as SC-1 (standard clean 1) Medical fluid processing and from silicon substrate remove silicon particle the case where.Furthermore, it is possible to be preferably used for remove the resist layer on substrate Purpose and mixed with sulfuric acid, and by being referred to as SPM (sulfuric acid hydrogen peroxide mixture (Sulfuric Acid Hydrogen Peroxide Mixture) medical fluid processing and from semiconductor substrate remove resist layer the case where.In addition, Removal of the removal of resist layer described in this also comprising etchant resist, etch residues, antireflection film and ash residue.Etching Residue is the residue generated when indicating to be etched resist layer, and ash residue is to indicate to carry out ash to resist layer Change the residue generated when processing.

Also, composition of the invention can also be preferably used for other use in addition to semiconductors manufacture is used on the way. For example, can also be as the cleaning solution of polyimides, sensor resist layer or lens resist layer etc., stripper or removal liquid And it uses.

Further, it is possible to be used in cleaning method other than the above, container, piping or substrate can be preferably used for The cleaning of (for example, wafer or glass etc.) etc..Also, the original of organic peroxide or inorganic peroxide can also be used in Material；The raw material of organic compound；The raw material of epoxide；The bleaching of paper, slurry and timber etc.；The raw material of fiber；Fiber Bleaching；The oxidant of metal in melting process；The raw material of food and medicine etc.；The cleaning agent of manufacturing equipment or container kills In the various uses such as microbial inoculum.

(composition host body)

Composition host body of the invention has storage container and the aforementioned present invention that is contained in above-mentioned storage container Composition, the region of above-mentioned storage container contacted with above-mentioned composition with nonmetallic for the material of principal component by being formed.In addition, Principal component in this is to indicate, constitutes the 80 mass % or more in the region that predetermined component is contacted.

As storage container, as long as the region contacted with composition of the invention is by with the nonmetallic material shape for principal component At then its form is not particularly limited, and can be filled in any vessel and be taken care of, carried and used.As container, For semiconductor applications it is preferred that the container that cleanliness in container is high, impurity dissolution is few.It, can as the container being able to use To enumerate " Clean bottle " series, the KODAMA PLASTICS Co. of AICELLO CORPORATION, Ltd.'s " Pure bottle " etc., but it is not limited to these.The region of the container contacted with the present composition, such as its receipts The inner wall in appearance portion or the flow path of the present composition with nonmetallic for the material of principal component by being formed, from the mistake prevented with container It spends from the viewpoint of the leachable pollution caused by compatibility from container, preferably by selected from including high density polyethylene (HDPE) (HDPE), the material in the group of tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PFA) and polytetrafluoroethylene (PTFE) (PTFE) is formed. Wherein, it is more preferably 60~120 ° by the contact angle with water and is formed with nonmetallic for the material of principal component, further preferred fluorine It is resin (perfluorinated resin).In particular, being fluorine resin by using the region as described above contacted with composition of the invention Storage container, and the region contacted with composition of the invention is used to be that polyvinyl resin, acrylic resin or polyethylene-are poly- It is compared when the storage container of allyl resin, is able to suppress the generation of such unfavorable condition of dissolution of ethylene or propylene oligomer, because This is preferably.

As the concrete example for the container that the region contacted with composition of the invention is fluorine resin, for example, can enumerate Entegris Co., Ltd. FluoroPurePFA compound barrel etc..Also, Japanese Kohyo 3-502677 can also be used Page 4 of bulletin etc., No. 99/46309 page 3 etc. of No. 2004/016526 pamphlet of International Publication No., International Publication No. brochure Page 9 and page 16 etc. of son, waits the container of middle record.These containers preferably before filling clean container inside.It should Liquid used in cleaning is not particularly limited, and preferably metal containing ratio is less than 0.001 mass ppt (part per trillion).

Also, according to purposes, for example, also making tenor by the way that other organic solvents will be purified in addition to above-mentioned water As the liquid of above range, composition of the invention itself or liquid made of being diluted, or this hair is further purified Bright composition and liquid made of more reducing metal component, impurity or oversize grain etc. for cleaning in, so as to bright Seem to the desired effect of the present invention.

Also, before cleaning container, as cleaned the lid of various containers with acid or organic solvent and remove and be attached to lid Thus foreign matter prevents being mixed into for the foreign matter from lid, therefore preferably.

Also, composition of the invention can bottle in the containers such as gallon bottle or coating bottles after fabrication and carry out defeated It send, keeping.Gallon bottle can be to be formed using glass material, is also possible to using forming in addition to this.

When keeping composition of the invention, can will hold for the purpose of the variation of ingredient in composition when preventing keeping It is replaced in device with the inert gas (nitrogen or argon gas etc.) of 99.99995 volume % of purity or more.In particular, it is preferred that moisture content is few Gas.Also, when being conveyed or being taken care of, temperature is not particularly limited, and is gone bad in order to prevent, temperature can be controlled In the range of -20 DEG C to 20 DEG C.

Embodiment

Hereinafter, being illustrated in more details according to embodiment to the present invention.Material shown in embodiment below uses Amount, ratio, process content, processing step etc. are then able to carry out and suitably change without departing from spirit of the invention.Therefore, originally The range of invention should not restrictively be explained by embodiment described below.

The purifying > of < raw material etc.

Each raw material used in each embodiment as shown below, each catalyst, the high-purity for the use of purity being 99% or more Grade, and then carry out purifying in advance by distillation, ion exchange and filtering etc..

Ultrapure water used in embodiment, be by documented method in Japanese Unexamined Patent Publication 2007-254168 bulletin into The respective atom containing ratio of Na, Ca and Fe is set as small by the aftermentioned measurement carried out by common ICP-MS method by row purifying In 10 mass ppt.

The preparation of the composition (hereinafter, also known as " hydrogen peroxide composition ") of Examples and Comparative Examples, filling, keeping and Analysis measurement is meeting 2 grades of ISO to carry out in lower horizontal toilet.Also, used container is utilizing the present invention Composition cleaned in advance after use.Measurement and water content in order to improve measurement accuracy, in metal component content In measurement, the measurement below for detectable limit in usual measurement is concentrated to the 1 of 100 points with volume conversion to be measured, And it is converted into the concentration that preceding composition is concentrated and has carried out content calculating.

1 > > of < < embodiment

(preparation of hydrogen peroxide composition)

By implement it is following shown in the 1st process~the 4th process, prepare hydrogen peroxide composition.(the 1st process: raw material Purification procedures)

In 1st process, the 2- ethyl hydrazine for becoming raw material passes through in the cation exchange resin for being filled in tubing string, weight It is multiple to carry out until concentration of metal ions contained in raw material becomes 1 mass ppm.Then, isolated 2- ethyl hydrazine out.

(the 2nd process: hydrogen peroxide synthesis procedure)

It is dissolved in addition Pt catalyst in solution obtained from benzene to 2- ethyl hydrazine, to obtain suspension.Then, lead to Crossing makes hydrogen contact with resulting suspension and hydrogenate 2- ethyl hydrazine under Pt catalyst, to generate 2- ethyl anthrahydroquinone. In addition, eliminating catalyst by filtering resulting composition.

Then, 2- ethyl anthrahydroquinone is aoxidized and contacting the oxygen in air with resulting composition, to generate 2- ethyl hydrazine and hydrogen peroxide.

(the 3rd process: hydrogen peroxide separation process)

With water extract the hydrogen peroxide generated in above-mentioned 2nd process and by its it is isolated, to obtain aqueous hydrogen peroxide solution (hydrogen peroxide composition).

(the 4th process: hydrogen peroxide composition purification procedures)

After stating the 3rd process on the implementation, with cation exchange resin purifying hydrogen peroxide water solution.It eliminates as a result, Contain aluminium, potassium contained in aqueous hydrogen peroxide solution, magnesium, the equiatomic metal component of sodium.It is used in cation exchange resin By sulfonic group (- SO₃H) as the storng-acid cation exchange resin of ion-exchange group.In process so far, peroxidating Concentration of metal ions contained in aqueous solution of hydrogen is 1 mass ppb or so.Then, using average pore size be 0.001~0.01 μm with Under PTFE (polytetrafluoroethylene (PTFE)) filter filter resulting aqueous hydrogen peroxide solution, and it is dense to further reduced metallic atom Degree.Then, phosphoric acid is added into the aqueous hydrogen peroxide solution.Then, make aqueous hydrogen peroxide solution and anion exchange resin and The mixed bed of cation exchange resin contacts.Confirming the concentration of metal ions in aqueous hydrogen peroxide solution as a result, is ppt grades.

(evaluation)

Then, to resulting aqueous hydrogen peroxide solution (hydrogen peroxide composition) implement it is following shown in various evaluations.

(measurement of the Fe ingredient in composition)

In ICP-MS analysis (indicating common ICP-MS analysis, rather than SNP-ICP-MS is analyzed), analysis software is replaced On behalf of the analysis software as aftermentioned ICP-MS analytical equipment, in addition to this, with identical as aftermentioned SNP-ICP-MS analysis Method determine the concentration of each atom.

In addition, the amount of Fe particle is analyzed by aftermentioned SNP-ICP-MS to be measured, the amount energy of Fe ion in Fe ingredient It is enough to pass through calculating of such as getting off, that is, from the amount (total amount of metal) of the Fe ingredient by ICP-MS analysis measurement, to subtract and pass through SNP- ICP-MS is analyzed and the amount of the Fe particle of measurement.

(SNP-ICP-MS (single nanoparticle-inductively coupled plasma mass spectrometry) measurement)

" measurement of Fe particle containing ratio "

About the containing ratio of Fe particle, it is determined using Perkinelmer Co., Ltd. system " Nexion350S ".

1) preparation of standard substance

For standard substance, the metering investment ultrapure water into clean glass container, so that median particle diameter is 50nm's After the mode that measure object metallic becomes 10000/ml concentration is added, supersonic cleaner processing 30 will be utilized Dispersion liquid obtained by minute has been used as the standard substance of transfer efficiency measurement.

2) determination condition

Using PFA coaxial type atomizer (in addition, " PFA " refers to the copolymerization of tetrafluoroethene and perfluoroalkyl vinyl ether Object.), quartz cyclone-like type spray chamber, quartz internal diameter 1mm torch injector (Torch Injector), with about 0.2mL/min has aspirated measure object liquid.Oxygen additive amount is 0.1L/min, plasma-based output is 1600W, has carried out unit with ammonia Cleaning.It is analyzed with 50 μ s of temporal analytical density (time resolution).

3) containing ratio of the Fe particle following analysis software attached used as manufacturer is measured.

The containing ratio of Fe particle: nanoparticle analyzes " SNP-ICP-MS " dedicated Syngistix nano application mould group

4) containing ratio of the Fe atom following analysis software attached used as manufacturer is measured (ICP-MS points Analysis).

The containing ratio of Fe atom: ICP-MS software Syngistix.

(measurement of the metal component of other specific atoms (Ni, Pt, Pd, Cr, Ti and Al) in derived from compositions)

8800 triple quadrupole ICP-MS of Agilent has been used when measurement (semiconductor analysis is used, option #200).According to upper Measurement device is stated, each cationic metal measured in sample and nonionic metal can be classified, and measure respective Content.In addition, the summation of the content of the content and nonionic metal of cationic metal is equivalent to total amount of metal.

Determination condition

Sample introduction system used quartz torch and coaxial type PFA (perfluoroalkoxyalkanes) atomizer (smoking certainly) and Platinum interface cone (Platinum interface cone).The location parameter of cold plasma-based condition is as follows.

RF (radio frequency (Radio Frequency)) exports (W): 600

Carrier gas flow (L/min): 0.7

Make-up gas (Make-up gas) flow (L/min): 1

Depth selection (mm): 18

(measurement of acid, anthraquinone analog compound in composition)

Acid or anthraquinone analog compound in composition are determined by following methods.

By using the middle liquid level using electrolyte aqueous solution of ion exchange resin, mobile phase (eluat) in stationary phase Analysis method (ion-exchange chromatography mass spectrography) is determined.Ion chromatography mass spectrography (IC-MS) is connected as IC detector There is mass spectrometric method.It is separated in mass spectrograph according to mass/charge number (m/z), therefore has used electricity to spill in ionization method Free (electrospray ionization) method (ESI) has used tandem mass spectrometer in mass spectrograph.Moreover, making separated Molecular ion cracking in collision cell (Collision cell), and have detected product ion generated (reflection molecular ion Structure).

(storage stability of hydrogen peroxide composition is evaluated)

By having made the hydrogen peroxide composition with potassium iodide and the titration of the well known method of thio-acid sodium just immediately after preparation, And determine the amount of hydrogen peroxide of hydrogen peroxide composition just immediately after preparation.Also, by hydrogen peroxide composition at 25 DEG C 1 week is stood after being saved, by method same as described above, the amount of hydrogen peroxide found out in hydrogen peroxide composition is (residual Allowance).

Then, resolution ratio is calculated by following formula, and storage stability is evaluated.

(resolution ratio)=((the just amount of hydrogen peroxide of hydrogen peroxide composition immediately after preparation)-(and through when save after peroxide Change the residual quantity of the hydrogen peroxide of hydrogen composition))/(the just amount of hydrogen peroxide of hydrogen peroxide composition immediately after preparation) × 100

Evaluation criteria is as follows.In following benchmark, as long as being evaluated as " D " or more, meet storage stability in practical Requirement, preferably more than " C ".

" A ": the resolution ratio of hydrogen peroxide is less than 5%

" B ": the resolution ratio of hydrogen peroxide is 5% more than and less than 10%

" C ": the resolution ratio of hydrogen peroxide is 10% more than and less than 20%

" D ": the resolution ratio of hydrogen peroxide is 20% more than and less than 30%

" E ": the resolution ratio of hydrogen peroxide is 30% or more

(oxidizing force of hydrogen peroxide composition is evaluated)

The oxidizing potential (oxidizing force) of hydrogen peroxide composition is found out by the method for electrochemistry.Using hydrogen electrode as reference Electrode simultaneously finds out OCP (open circuit potential (Open Cirkit Potential)) at this time.

Evaluation criteria is as follows.

" A ": oxidizing force is 1.8mV or more

" B ": oxidizing force is 1.6mV more than and less than 1.8mV

" C ": oxidizing force is less than 1.6mV

(the defect performance (measurement for being attached to the defect number of semiconductor substrate) of hydrogen peroxide composition)

Surface examining device (SP-5 is utilized on wafer；KLA Tencor system), it measures and is present in diameter for 300mm's The diameter of silicon oxide layer substrate surface is the particle of 32nm or more (hereinafter, also this will be referred to as " defect ".) number.Then, by the silicon Oxidation ilm substrate is set to rotating spray device, rotates it on one side, on one side to the surface of the silicon oxide layer substrate with 1.5L/ The flow velocity of min sprays resulting hydrogen peroxide composition.Then, it is rinsed processing and is dried.For resulting examination Sample reuses above-mentioned apparatus (SP-5) measurement and is present in the defect number of silicon oxide layer substrate surface, and by the difference with initial value Amount is used as defect number.Result obtained by being evaluated according to following benchmark resulting defect number is shown in table 1.In following benchmark In, as long as being evaluated as " C " or more, it can realize the inhibition energy as defect required by semiconductor devices manufacture treatment fluid Power.

" A ": defect number is 0 or more and 50 or less

" B ": defect number is more than 50 and is 100 or less

" C ": defect number is more than 100 and is 500 or less

" D ": defect number is more than 500 and is 1000 or less

" E ": defect number is more than 1000

< < embodiment 2~23, comparative example 1,2 > > of comparative example

To obtain the form of the hydrogen peroxide composition formed shown in following table 1, change the peroxidating of above-described embodiment 1 The preparation method of hydrogen composition and the hydrogen peroxide group that embodiment 2~23, comparative example 1 and comparative example 2 are prepared using material Object is closed, and has carried out identical evaluation.Show the result in table 1.

In addition, in table 1, such as 10^ (- 1) indicates " 10-1 powers " (0.1).Also, for example, 10^1 indicates " 10 1 power " (10).

Also, " acid " in table 1 further comprises as the decomposition of anthraquinone other than the phosphoric acid added in comprising the 4th process Product and the phthalic acid derivatives generated.

Also, about the various metal components on column (D) and (E) in the 1st table, indicate total amount of metal.

Also, table 2 indicate table 1 metal component composition, specifically, be displayed separately metal ion (ionic metal) and Metallic (non-ionic metal).In addition, metallic (non-ionic metal) is carried out by " SNP-ICP-MS " in table 2 The various metallics of measurement.

It confirms, hydrogen peroxide composition according to the embodiment, excellent storage stability and is suitable for according to the result of table 1 It is smaller to the defective effect of semiconductor substrate when the manufacturing process of semiconductor devices.

Also, it is confirmed according to the comparison of embodiment 1, embodiment 9,10,11 and comparative example 2, if above-mentioned Fe ingredient contains Amount relative to composition gross mass be 0.1 mass of mass ppt~1 ppb (preferably 0.1 mass of mass ppt~800 ppt, it is more excellent It is selected as the 0.1 mass ppt of mass ppt~500), then excellent storage stability can be taken into account with excellent level and is suitable for partly leading To the lesser effect of the defective effect of semiconductor substrate when the manufacturing process of body device, also, oxidizing force is also more excellent.

Also, it is confirmed according to the comparison of embodiment 1, embodiment 6,7,8 and comparative example 1, if the content of acid is relative to group Conjunction object gross mass be 0.01 mass of mass ppb~1000 ppb (the preferably 0.05 mass ppb of mass ppb~800, more preferably The 0.05 mass ppb of mass ppb~500), then excellent storage stability can be taken into account with excellent level and is suitable for semiconductor device To the lesser effect of the defective effect of semiconductor substrate when the manufacturing process of part.

Also, it is confirmed according to the comparison of embodiment 1, embodiment 2~5, when containing anthraquinone analog compound, if Anthraquinones The content of compound relative to composition gross mass be 0.01 mass of mass ppb~1000 ppb (preferably 0.05 mass ppb~ 800 mass ppb, the more preferably 0.05 mass ppb of mass ppb~500), then be suitable for semiconductor devices manufacturing process when pair The defective effect of semiconductor substrate is further smaller.

Also, confirmed according to the comparison of embodiment 1, embodiment 12, embodiment 13, when comprising containing selected from including Ni, When the metal component of the specific atoms in the group of Pt, Pd, Cr, Ti and Al, if the content of above-mentioned metal component is according to each specific original Son be respectively relative to total composition be 0.01 mass of mass ppt~1 ppb (the preferably 0.01 mass ppt of mass ppt~800, The more preferably 0.01 mass ppt of mass ppt~500), then be suitable for semiconductor devices manufacturing process when to semiconductor substrate Defective effect is further smaller.

Also, result according to the embodiment confirms, when the content of Fe ingredient is by quality ratio relative to the content of acid 10^-3~10^-1When, excellent storage stability and when being suitable for the manufacturing process of semiconductor devices to the defect shadow of semiconductor substrate Sound is smaller, and oxidizing force is also further excellent.

Also, result according to the embodiment confirms, when comprising selected from former including Ni atom, Pt atom, Pd atom, Cr When the metal component of special metal atom in the group of son, Ti atom and Al atom contains metallic, if metallic contains Amount is separately 0.01 (preferably 0.01 mass ppt~100 the mass of mass ppt~500 ppt relative to total composition Quality ppt, the more preferably 0.01 mass ppt of mass ppt~50), then it is suitable for half-and-half leading when the manufacturing process of semiconductor devices The defective effect of structure base board is further smaller.

On the other hand, in the hydrogen peroxide composition of comparative example, become and cannot be considered in terms of storage stability and to semiconductor-based The result of the defective effect of plate.

< < embodiment A1~A3 > >

Embodiment is added into the storage container for the ingredient that the region contacted with hydrogen peroxide composition is set as to following Table 3 1 hydrogen peroxide composition has carried out the measurement of SNP-ICP-MS and commenting for defect performance after taking care of 1 month at 25 DEG C Valence.The evaluation measuring method of SNP-ICP-MS and defect performance is same as Example 1.Show the result in table 3.In addition, following The concentration of each metal component shown in the column embodiment A1~A3 of table 3 indicates the concentration after keeping.Also, in table 3, Measure object in " SNP-ICP-MS " is Fe particle.

In addition, with the contact angle of container by contact angle instrument DM-901 (Kyowa Interface Science Co., Ltd. make) it is determined.

In addition, PFA indicates that tetrafluoroethene perfluoroalkyl vinyl ether copolymer, PTFE indicate polytetrafluoroethylene (PTFE) in table.

[table 3]

It confirms according to the result of table 3, by the way that hydrogen peroxide composition to be stored in storage container, even if being protected for a long time Guan Hou, defect performance is also excellent, the storage container be the region that is contacted with hydrogen peroxide composition by with nonmetallic for principal component Material formed.

< < embodiment B1~B7 > >

Aquae hydrogenii dioxidi (hydrogen peroxide composition of embodiment 1 has been used into embodiment B1~B7.Embodiment B5, B6 And it is used in B7 and the concentration of hydrogen peroxide is only changed into the mistake recorded in table 4 in the hydrogen peroxide composition of embodiment 1 Hydrogen peroxide composition made of hydrogen peroxide concentration (quality %).) and sulfuric acid water (sulfuric acid concentration (quality %): being recorded in table 4) It is mixed with blending ratio shown in table 4 (mass ratio), and resist layer removing examination has been carried out by condition shown in following table 4 It tests.The resist layer of subjects described below.

(resist layer disbonded test)

Test wafer: being made the film of 10 μm of PMER P-CA1000PM (TOK eurymeric resist layer) on Silicon Wafer, and The stripping ability relative to the resist layer is evaluated under the following conditions.

Liquid volume: 200ml.

Wafer size: 3cm × 3cm

Processing method: wafer is immersed in medical fluid

Handle time 1min

In addition, in table 4, about embodiment B1~B4, sulfuric acid water is heated in advance to make itself and peroxidating after 90 DEG C Hydrogen composition is mixed.Also, about embodiment B5~B7, sulfuric acid water is heated in advance to make itself and peroxidating after 65 DEG C Hydrogen composition is mixed.For any embodiment, after mixing hydrogen peroxide composition and sulfuric acid water, and then added After heat is until become " treatment temperature ", it is used in the disbonded test of resist layer.

About resist layer fissility, determined according to following evaluation criteria.

" A ": the resist layer removal of lower display 100% is visually observed.

" B ": lower 90% or more~resist layer removal less than 100% of display is visually observed.

" C ": lower resist layer removal of the display less than 90% is visually observed.

[table 4]

	Aquae hydrogenii dioxidi	Sulfuric acid water	Mixed proportion	Treatment temperature (DEG C)	Photoresist fissility
						Embodiment B1	30%	98%	1:1	> 150	A
Embodiment B2	30%	98%	2:1	> 150	A
						Embodiment B3	30%	98%	3:1	> 150	A
Embodiment B4	30%	98%	1:1	> 100	A
						Embodiment B5	15%	50%	1:1	60	B
Embodiment B6	10%	50%	1:1	60	C
						Embodiment B7	3%	50%	1:1	60	C

It is confirmed according to the result of above-mentioned table 4, hydrogen peroxide composition of the invention can be preferably used for SPM processing In.

< < embodiment C1~C5,3 > > of comparative example

Aquae hydrogenii dioxidi (hydrogen peroxide composition of embodiment 1 has been used into embodiment C1~C3.Embodiment C4~C5 The concentration of hydrogen peroxide is only changed into the peroxidating recorded in table 5 in the hydrogen peroxide composition of embodiment 1 by middle used Hydrogen peroxide composition made of hydrogen concentration (quality %).) and ammonium hydroxide (ammonia density (quality %): being recorded in table 5) shown in table 5 Blending ratio (mass ratio) mixed, and following conditions carried out the particle on Si substrate removal test.The present embodiment Used in ammonium hydroxide be confirm total metal concentration be 10 mass ppt high-purity ammonium hydroxide below.In addition, being used in comparative example 3 Hydrogen peroxide composition be table 1 in comparative example 2 hydrogen peroxide composition.

In addition, for any embodiment, after mixing hydrogen peroxide composition and ammonium hydroxide, and carry out heating until at After " treatment temperature ", it is used in particle removal processing.

Particle removal test

It is coated with each medical fluid on TEOS (tetraethyl orthosilicate) substrate, then with UVison5 (Applied Materials, Inc. system) bright field (brightfield) mode determination, defect number before and after the processing is counted.? Defect evaluation of classification EDAX (elemental analysis) is carried out in the counting, the defect number containing Si is set as total particle.In addition, before measurement TEOS substrate on total particle number be 200.

For particle removal, determined according to following evaluation criteria.

" A ": total particle number is 50 or less

" B ": total particle number is more than 50~100 or less

" C ": total particle number is more than 100~200 or less

" D ": total particle number is more than 200

[table 5]

	Aquae hydrogenii dioxidi	Ammonium hydroxide	Mixed proportion	Treatment temperature (DEG C)	Particle removal
						Embodiment C1	30%	30%	1:1	60	A
Embodiment C2	30%	30%	2:1	60	A
						Embodiment C3	30%	30%	3:1	60	A
Embodiment C4	10%	10%	1:1	45	B
						Embodiment C5	3%	3%	1:1	35	C
Comparative example 3	30%	30%	1:1	60	D

It is confirmed according to the result of above-mentioned table 5, uses particle when hydrogen peroxide composition implementation SC-1 processing of the invention Removal is excellent.

< < embodiment D1~D6,4 > > of comparative example

Aquae hydrogenii dioxidi (hydrogen peroxide composition of embodiment 1 has been used into embodiment D1~D6.Embodiment D5~D6 The concentration of hydrogen peroxide is only changed into the peroxidating recorded in table 6 in the hydrogen peroxide composition of embodiment 1 by middle used Hydrogen peroxide composition made of hydrogen concentration (quality %).) and hydrochloric acid water (concentration of hydrochloric acid (quality %): being recorded in table 6) with table 6 Shown in blending ratio (mass ratio) mixed, and carried out under the following conditions the metal removal on Si substrate test.

Hydrochloric acid water used in the present embodiment is to confirm total metal concentration as 10 mass ppt high-purity hydrochloric acids below Water.In addition, hydrogen peroxide composition used in comparative example 4 is the hydrogen peroxide composition of the comparative example 2 in table 1.

In addition, for any embodiment, after mixing hydrogen peroxide composition and ammonium hydroxide, and carry out heating until at After " treatment temperature ", treatment fluid is removed as metal ion and is used.

Metal ion removal test

Each medical fluid is coated on TEOS substrate, then with the bright field of UVison5 (Applied Materials, Inc. system) Mode determination, defect number before and after the processing is counted.Defect evaluation of classification EDAX (element point is carried out in the counting Analysis), and the defect number containing metallic atom other than si is set as total metal cation component number.In addition, the TEOS before measurement Metal cation component number on substrate is 50.

About metal ion removal, determined according to following evaluation criteria.

" A ": metal cation component is 20 or less

" B ": metal cation component is more than 20~30 or less

" C ": metal cation component is more than 30~50 or less

" D ": metal cation component is more than 50

[table 6]

	Aquae hydrogenii dioxidi	Hydrochloric acid water	Mixed proportion	Treatment temperature (DEG C)	Metal ion removal
						Embodiment D1	30%	37%	1:1	> 150	A
Embodiment D2	30%	37%	2:1	> 150	A
						Embodiment D3	30%	37%	3:1	> 150	A
Embodiment D4	30%	37%	1:1	> 100	A
						Embodiment D5	15%	10%	1:1	60	B
Embodiment D6	3%	3%	1:1	60	C
						Comparative example 4	30%	30%	1:1	60	D

It is confirmed according to the result of above-mentioned table 6, uses metal when hydrogen peroxide composition implementation SC-2 processing of the invention Ion remaval is excellent.

< < embodiment E1~E4 > >

(liquid before purification of " before the processing " in table 7 is comparable to benchmark liquid.) carry out filtering examination shown in following table 7 Test, and confirmed filtered various metals (Fe ingredient, Pt ingredient) total metal concentration and by SNP-ICP-MS measurement Fe particle weight.In addition, benchmark liquid is the side to obtain the hydrogen peroxide composition formed shown in following table 7 " before processing " Formula changes the preparation method of the hydrogen peroxide composition of above-described embodiment 1 to be prepared benchmark liquid.Also, in each embodiment In, documented each composition indicates to form via made of filter progress documented in table 7 purifying.That is, such as embodiment E1 In, expression with the nylon (aperture 5nm) recorded in table 7 filtered processing before hydrogen peroxide composition the case where, the result table Show that the content for being purified to (B) anthraquinone analog compound is 0.1 mass ppb, (C) acid concentration is 0.1 mass ppb, (D) Fe constituent concentration The case where for 31 mass ppt and (E) Pt constituent concentration being 8 mass ppt.Show the result in table 7.

[table 7]

It is confirmed according to the result of above-mentioned table 7, by using the filter formed by fluorine resins such as PTFE and PTA, energy Enough efficiently reduce the amount of metal component.

Symbol description

100,200- manufacturing device, 101- tank, 102- supply mouth, 103,106,107- valve, 104- pump, 105- filtering dress It sets, 108- container, 109- feeding pipe, 110- circulation line, 111- discharge unit, 112- cleaning solution monitoring portion, 113- pipeline, 201- destilling tower, 202,203,204- pipeline, 205,206,207- valve.

Claims (16)

1. a kind of composition, containing hydrogen peroxide, acid and Fe ingredient,

Content of the content of the Fe ingredient relative to the acid, is by quality ratio 10^-5~10²。

2. composition according to claim 1, also contains anthraquinone analog compound.

3. composition according to claim 1 or 2, wherein

The content of the anthraquinone analog compound is 0.01 mass of mass ppb~1000 ppb relative to composition gross mass.

4. composition according to any one of claim 1 to 3, wherein

The content of the acid is 0.01 mass of mass ppb~1000 ppb relative to composition gross mass.

5. composition according to any one of claim 1 to 4, wherein

The total content of the Fe ingredient is 0.1 mass of mass ppt~1 ppb relative to composition gross mass.

6. composition according to any one of claim 1 to 5, wherein

The content of Fe particle contained in the Fe ingredient is 0.01 mass of mass ppt~0.1 relative to composition gross mass ppb。

7. composition according to any one of claim 1 to 6, also containing the metal component of at least one or more, the gold Belong to ingredient and contain the specific atoms in the group including Ni, Pt, Pd, Cr, Ti and Al,

The content of the metal component is respectively relative to composition gross mass according to each specific atoms, is 0.01 mass ppt~10 Quality ppb.

8. composition according to any one of claim 1 to 6, also containing the metal component of at least one or more, the gold Belong to ingredient and contain the specific atoms in the group including Ni, Pt, Pd and Al,

The content of the metal component is 0.01 mass of mass ppt~1 ppb relative to composition gross mass.

9. the composition according to any one of claim 2 to 8, wherein

The anthraquinone analog compound is at least one or more in the group including alkyl-anthraquinone and alkyl tetrahydro anthraquinone.

10. composition according to claim 9, wherein

The alkyl-anthraquinone is ethyl hydrazine or amyl anthraquinone, and the alkyl tetrahydro anthraquinone is ethyl tetrahydro-anthraquinone or amyl tetrahydro Anthraquinone.

11. composition according to any one of claim 1 to 10, wherein

Sour a kind in the group including phosphoric acid and phosphoric acid derivatives.

12. composition according to any one of claim 1 to 11 is used as the treatment fluid of semiconductor substrate.

13. a kind of composition host body, in storage container and the claim 1 to 12 being contained in the storage container Described in any item compositions,

The region of the storage container contacted with the composition is by being formed with nonmetallic for the material of principal component.

14. composition host body according to claim 13, wherein

It is described with the nonmetallic material for principal component, be selected from include high density polyethylene (HDPE), tetrafluoroethene perfluoroalkyl vinyl 1 kind in the group of ether copolymer and polytetrafluoroethylene (PTFE).

15. composition host body described in 3 or 14 according to claim 1, wherein

The contact angle with the nonmetallic material for principal component and water is 60 °~120 °.

16. a kind of manufacturing method of composition is the manufacturing method of composition described in any one of claims 1 to 12, It is included

Feed purification process purifies any a kind or more selected from solvent and the material composition comprising anthraquinone analog compound；

Hydrogen peroxide synthesis procedure restores the anthraquinone analog compound and elbs reaction hydroquinone compound in the presence of a catalyst, It further aoxidizes the anthrahydroquinone class compound and synthesizes hydrogen peroxide；

Hydrogen peroxide separation process is taken out from reaction system by extracting resulting hydrogen peroxide；And

Hydrogen peroxide composition purification procedures, further to the hydrogen peroxide containing the hydrogen peroxide isolated from reaction system Composition is purified.