JP6421197B2 - Removal liquid, removal method using the same, and method for manufacturing semiconductor substrate product - Google Patents

Description

  The present invention relates to a removing liquid, a removing method using the same, and a method for manufacturing a semiconductor substrate product.

  The manufacturing process of a semiconductor element includes various processes such as a lithography process, an etching process, and an ion implantation process. This includes a step of treating organic matter after the end of each step or before moving to the next step. For example, a process of removing and removing the resist remaining on the substrate surface is performed. As a stripping solution for organic residues and residual resist, for example, a mixed solution of concentrated sulfuric acid and hydrogen peroxide (SPM), a mixed solution of ammonia and hydrogen peroxide (APM), or the like. It has been adopted (see Patent Documents 1 to 3). As an example different from the strong acid / strong alkali, there is an example in which an amine, an organic solvent, and a cosolvent are used (see Patent Document 4). In addition, there is disclosed a cleaning agent in which potassium hydroxide and / or sodium hydroxide, a water-soluble organic solvent, and a group 9 or 11 metal corrosion inhibitor are blended (see Patent Document 5).

JP 2005-268308 A JP 2005-189660 A JP 2012-043991 A Special table 2013-500503 gazette JP 2007-1119783 A

In addition to the removal of the resist necessary for the processing of the semiconductor substrate described above, there is a need to remove a permanent resin film after it is formed on the semiconductor substrate. For example, in the manufacture of a solid-state image sensor or an image display element, a finely processed color filter, a transparent insulating film, or a resin lens may be formed on a semiconductor substrate. When there is a manufacturing defect or the like in a part of this, it is considered that these resins are washed out from the entire substrate, regenerated and processed again.
Alternatively, in the processing of a through silicon via (Through-silicon via, hereinafter simply referred to as “TSV”), the resist may be removed after the etching. At this time, in the TSV, rather than simply may be removed resist, narrow openings, entered into the via hole with a depth resist residue and the etching residue (hereinafter, the residue derived from the resist this is found simply May be referred to as “residue”). Therefore, it is desirable to remove not only the resist on the substrate surface but also the residue in the via hole.
On the other hand, when peeling or removing a resist or the like, an electrode material or the like formed on a semiconductor substrate is often exposed. If possible, it is desirable to remove the resist preferentially without corroding such an electrode material.

  An object of the present invention is to provide a removing solution suitable for removing at least one of various resists and residues (hereinafter referred to as a resist), a removing method using the removing solution, and a method for producing a semiconductor substrate product. An object of the present invention is to provide a removing liquid capable of suppressing damage to an electrode material such as aluminum, a removing method using the same, and a method for manufacturing a semiconductor substrate product, when peeling or removing the resist or the like, as required. . Furthermore, the present invention aims to provide a removal liquid that can be applied to peeling and removal of permanent films such as color filter materials and the like, resists for creating TSVs and residues, and removal methods, and methods for manufacturing semiconductor substrate products. .

式（１）、（２）において、Ｒ ^１１ 、Ｒ ^１２ 、Ｒ ^２１ およびＲ ^２２ は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、、アリール基、アラルキル基、カルボキシル基もしくはその塩を含有する基またはアミノ基もしくはその塩を含有する基を表す。Ｒ ^Ｎ は、水素原子、アルキル基、アルケニル基、アルキニル基、、アリール基、アラルキル基を表す。ここで、Ｒ ^１１ とＲ ^１２ 、Ｒ ^１２ とＲ ^Ｎ 、Ｒ ^２２ とＲ ^Ｎ は互いに連結して環を形成していてもよい。
ただし、式（１）中、Ｒ ^１１ 、Ｒ ^１２ およびＲ ^Ｎ のいずれかはカルボキシル基もしくはその塩を含有する基であり、式（２）中、Ｒ ^２１ 、Ｒ ^２２ およびＲ ^Ｎ のいずれかは、カルボキシル基もしくはその塩を含有する基である。
（３）レジストおよびエッチング残渣の少なくとも一種を除去する除去液であって、
カルボキシル基またはその塩を有する環状化合物、第四級アンモニウム化合物、および有機溶媒を含有し、
上記第四級アンモニウム化合物が、水酸化テトラメチルアンモニウムと水酸化テトラブチルアンモニウムの混合物である除去液。
（４）レジストおよびエッチング残渣の少なくとも一種を除去する除去液であって、
カルボキシル基またはその塩を有する環状化合物、第四級アンモニウム化合物、および有機溶媒を含有し、かつ、
アルコキシシラン化合物および水を含有する除去液。

（５）上記環状化合物が芳香族複素環化合物である（３）または（４）に記載の除去液。
（６）上記環状化合物がテトラゾール−５−酢酸、ベンゾトリアゾール−５−カルボン酸、イミダゾール−４，５−ジカルボン酸、または３−アミノ−１，２，４−トリアゾール−５−カルボン酸である（５）に記載の除去液。
（７）上記第四級アンモニウム化合物が水酸化テトラメチルアンモニウム、水酸化テトラブチルアンモニウム、またはこの両者の組合せである（１）、（２）または（４）のいずれか１つに記載の除去液。
（８）上記有機溶媒が極性非プロトン性の有機溶媒である（１）、（３）または（４）のいずれか１つに記載の除去液。
（９）上記有機溶媒がジメチルスルホキシドである（１）〜（４）のいずれか１つに記載の除去液。
（１０）上記有機溶媒の含有率が７０質量％以上９９．５質量％以下である（１）、（３）または（４）のいずれか１つに記載の除去液。
（１１）アルコキシシラン化合物を含有する（１）〜（３）のいずれか１つに記載の除去液。
（１２）水を含有する（１）〜（３）のいずれか１つに記載の除去液。
（１３）レジストおよびエッチング残渣の少なくとも一種を除去する除去液であって、
ジメチルスルホキシド、水酸化テトラメチルアンモニウム、および水酸化テトラブチルアンモニウムを含有する除去液。
（１４）上記ジメチルスルホキシドを８０質量％以上９９質量％以下、上記水酸化テトラメチルアンモニウムおよび水酸化テトラブチルアンモニウムを合計で０．１質量％以上１０質量％以下含有する（１３）に記載の除去液。
（１５）水を含有し、その水の含有率が０．１質量％以上１０質量％以下である（１３）または（１４）に記載の除去液。
（１６）水酸化テトラブチルアンモニウムの含有率を水酸化テトラメチルアンモニウムの含有率で除した値が５以上である（１３）〜（１５）のいずれか１つに記載の除去液。
（１７）上記レジストが樹脂製の永久膜である（１）〜（１６）のいずれか１つに記載の除去液。
（１８）上記レジストがＴＳＶ作成用のレジストである（１）〜（１６）のいずれか１つに記載の除去液。
（１９）除去液をレジストおよびエッチング残渣の少なくとも一種に適用してこのレジストおよびエッチング残渣の少なくとも１種を除去する除去方法であって、
上記除去液が、（１）〜（１６）のいずれか１つに記載の除去液である除去方法。
（２０）上記レジストが、アルカリ可溶性樹脂、重合性化合物、重合開始剤、および着色剤を含む着色硬化性樹脂組成物の硬化物である（１９）に記載の除去方法。
（２１）除去液をレジストに４０℃以上１００℃以下で適用する（１９）または（２０）に記載の除去方法。
（２２） （１９）〜（２１）のいずれか１つに記載の除去方法を介して、半導体基板製品を製造する半導体基板製品の製造方法。
The above problem has been solved by the following means.
(1) A removing solution for removing at least one of a resist and an etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent ,
The removal liquid whose cyclic compound which has the said carboxyl group or its salt is a 1,2,4-triazole compound or a tetrazole compound .
(2) A removing solution for removing at least one of resist and etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent,
The cyclic compound having the carboxyl group or a salt thereof is a compound represented by the following formula (1) or (2):
The removal liquid whose said organic solvent is a sulfoxide compound, and content is 90 mass% or more .

In the formulas (1) and (2), R ¹¹ , R ¹² , R ²¹ and R ²² are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, carboxyl group or its It represents a group containing a salt or an amino group or a group containing a salt thereof. R ^N represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group ,, an aryl group, an aralkyl group. Here, R ¹¹ and R ¹² , R ¹² and R ^N , R ²² and ^RN may be connected to each other to form a ring.
In the formula ^(1), one of R ^{11, R 12} and ^{R N} is a group containing a carboxyl group or a salt thereof, wherein ^(2), one of R ^{21, R 22} and ^{R N} are , A group containing a carboxyl group or a salt thereof.
(3) A removing solution for removing at least one of resist and etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent,
A removal solution in which the quaternary ammonium compound is a mixture of tetramethylammonium hydroxide and tetrabutylammonium hydroxide .
(4) A removing solution for removing at least one of resist and etching residue,
A cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent, and
A removal solution containing an alkoxysilane compound and water.

( 5 ) The removal liquid according to ( 3 ) or (4) , wherein the cyclic compound is an aromatic heterocyclic compound.
( 6 ) The cyclic compound is tetrazole-5-acetic acid, benzotriazole-5-carboxylic acid, imidazole-4,5-dicarboxylic acid, or 3-amino-1,2,4-triazole-5-carboxylic acid ( The removal liquid as described in 5) .
( 7 ) The removal solution according to any one of (1) , (2), and ( 4 ), wherein the quaternary ammonium compound is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, or a combination of both. .
( 8 ) The removal liquid according to any one of (1) , (3), and ( 4 ), wherein the organic solvent is a polar aprotic organic solvent.
( 9 ) The removal liquid according to any one of (1) to ( 4 ), wherein the organic solvent is dimethyl sulfoxide.
( 10 ) The removal liquid according to any one of (1 ), (3), and ( 4 ), wherein the content of the organic solvent is 70% by mass or more and 99.5% by mass or less.
( 11 ) The removal liquid according to any one of (1) to ( 3 ), which contains an alkoxysilane compound.
( 12 ) The removal liquid according to any one of (1) to ( 3 ), containing water.
( 13 ) A removal liquid for removing at least one of a resist and an etching residue,
A removal solution containing dimethyl sulfoxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide.
( 14 ) The removal according to ( 13 ), containing 80% by mass to 99% by mass of the dimethyl sulfoxide and a total of 0.1% by mass to 10% by mass of the tetramethylammonium hydroxide and tetrabutylammonium hydroxide. liquid.
( 15 ) The removal liquid according to ( 13 ) or ( 14 ), which contains water and has a water content of 0.1% by mass or more and 10% by mass or less.
( 16 ) The removal liquid according to any one of ( 13 ) to ( 15 ), wherein a value obtained by dividing the content of tetrabutylammonium hydroxide by the content of tetramethylammonium hydroxide is 5 or more.
( 17 ) The removing liquid according to any one of (1) to ( 16 ), wherein the resist is a permanent film made of a resin.
( 18 ) The removal liquid according to any one of (1) to ( 16 ), wherein the resist is a resist for creating TSV.
( 19 ) A removal method in which a removing liquid is applied to at least one of a resist and an etching residue to remove at least one of the resist and the etching residue,
The removal liquid, (1) to remove how a removing solution according to any one of (16).
( 20 ) The removal method according to ( 19 ), wherein the resist is a cured product of a colored curable resin composition containing an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a colorant.
(21) removing how according to remove liquid applying 100 ° C. below 40 ° C. above the resist (19) or (20).
( 22 ) A method for manufacturing a semiconductor substrate product, wherein the semiconductor substrate product is manufactured through the removal method according to any one of ( 19 ) to ( 21 ).

In the description of the group (atom group) in this specification, the description that does not indicate substitution and non-substitution includes those not having a substituent and those having a substituent, as long as the effects of the present invention are not impaired. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous also about each compound.
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. A monomer in the present specification is distinguished from an oligomer and a polymer, and unless otherwise specified, refers to a compound having a molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, the weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

The removing liquid of the present invention is suitable for removing various resists and exhibits excellent removability / removability of resists and the like. When peeling or removing the resist or the like, damage to an electrode material such as aluminum can be suppressed as required. Furthermore, if necessary, it can also be applied to the removal and removal of permanent films such as color filter materials, resists and residues for TSV creation, and exhibits its excellent characteristics.
In the removing method and the method for producing a semiconductor substrate product of the present invention, the above-described removing liquid is used, and the above-described excellent effects derived therefrom are exhibited.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is a side view schematically showing a test substrate used in Examples. (A) shows a state before the peeling treatment and (b) after the peeling treatment. FIG. 2 is a side view schematically showing another test substrate (TSV substrate) used in the example. (A) shows a state before the peeling treatment and (b) after the peeling treatment.

The removal liquid of the present invention contains a quaternary ammonium compound and an organic solvent. In the first embodiment, it further contains a cyclic compound having a carboxyl group or a salt thereof. In the second embodiment, dimethyl sulfoxide is contained as the organic solvent. Hereinafter, the present invention will be described in detail focusing on preferred embodiments of the present invention.
Hereinafter, the “carboxyl salt” is included in the “group containing a carboxyl salt”.

<Removal solution>
(Quaternary ammonium compounds)
The quaternary ammonium compound used in the first embodiment of the present invention is not particularly limited, but is preferably a quaternary ammonium hydroxide. As quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), trimethylhydroxyethylammonium hydroxide (Choline), methyl tri (hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH) and the like. Among these, TMAH, TEAH, TPAH, TBAH, and choline are more preferable, and TMAH and TBAH are particularly preferable. In terms of the number of carbon atoms excluding the counter anion, a quaternary ammonium hydroxide compound having 4 to 36 carbon atoms is preferable, and a quaternary ammonium hydroxide compound having 4 to 24 carbon atoms is more preferable.

  The counter ion (anion) of the quaternary ammonium compound is not particularly limited and may be a hydroxide ion as described above, but can be appropriately selected and combined within a range not impairing the effects of the present invention. For example, quaternary ammonium halides (chlorides, fluorides, bromides) and various acid anions such as carboxylic acid, phosphoric acid, sulfuric acid, phosphonic acid, and nitric acid may be used as counter ions. Or the anion of the compound which has said acid as a functional group is also mentioned. In addition, a specific cyclic compound having a carboxyl group or a salt thereof described later may be used as a counter anion.

  In the first embodiment of the present invention, the content of the quaternary ammonium compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass or more in the removal liquid. Further preferred is 2% by mass or more. The upper limit is particularly preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. Especially, in the removal liquid using TMAH, it is preferable to finely adjust the content of TMAH, and the lower limit is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. The content is preferably 0.1% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1% by mass or less, 0.5 It is particularly preferable that the content is not more than mass%. By making the content rate of a quaternary ammonium compound into said range, since peeling / removability of a suitable resist etc. and protection of electrode materials (aluminum etc.) are compatible, it is preferable. In 1st embodiment, a quaternary ammonium compound may be used independently, or 2 or more types may be used in combination.

  In the second embodiment of the present invention, tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH) are used as the quaternary ammonium compounds. The use of other quaternary ammonium compounds is not hindered, but it is preferable in the present embodiment that only the above two types are used as the quaternary ammonium compounds.

  The total content of TMAH and TBAH is the same as that in the first embodiment as a preferable range in the removal liquid. The ratio of TMAH to TBAH is preferably a value obtained by dividing the amount of TBAH by the amount of TMAH (TBAH / TMAH), preferably 5 or more, more preferably 8 or more. 10 or more is particularly preferable. The upper limit is preferably 100 or less, more preferably 50 or less, further preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. In addition, the ratio of TMAH and TBAH is synonymous as a preferable range also in the first embodiment. By setting TMAH and TBAH to the above ratios, it is possible to exhibit particularly good electrode material (aluminum or the like) damage prevention properties while maintaining a high resist or other peeling / removal effect. The reason for this is not clear, but it is expected that the balance between hydrophilicity and hydrophobicity of these compounds is optimized and an effective protective film is formed on the surface of the electrode material (aluminum or the like).

(Organic solvent)
Although the organic solvent applied to 1st embodiment of this invention is not specifically limited, It is preferable that it is a polar aprotic solvent. Examples of such organic solvents include halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, and the like. Typical examples are shown below, among which organic solvents composed of sulfoxide compounds are preferred, and dimethyl sulfoxide is particularly preferred. In the second embodiment of the present invention, dimethyl sulfoxide is used as the organic solvent.
Alcohol compounds: methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentane Diol, 1,3-butanediol, 1,4-butanediol, etc.-Ether compounds (including hydroxyl group-containing ether compounds)
Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), ester compounds, ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol monomethyl ether acetate, etc., ketone compounds Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc., nitrile compounds, acetonitrile, etc. Amide compounds N, N-dimethylformamide, 1- Methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Propanamide, hexamethylphosphoric triamide, etc. ・ Sulphoxide compounds, Dimethyl sulfoxide, etc.

  The content of the organic solvent in the removal liquid is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. As an upper limit, 99.8 mass% or less is preferable, 99.5 mass% or less is more preferable, 99 mass% or less is more preferable, 98 mass% or less is further more preferable, 97 mass% or less is especially preferable. It is preferable to set the organic solvent in the above range because high removability of a resist or the like can be exhibited while maintaining the protection of the electrode material (aluminum or the like). As for the said organic solvent, only 1 type may be used and 2 or more types may be used together. When using 2 or more types together, the combined use ratio is not particularly limited, but the total use amount is preferably within the above-mentioned concentration range as a total of 2 or more types.

(Specific cyclic compounds)
In the first embodiment of the present invention, a cyclic compound having a carboxyl group or a salt thereof (hereinafter sometimes referred to as a specific cyclic compound) is used. The cyclic structure part of the specific cyclic compound may be a heterocyclic ring or a hydrocarbon ring. Alternatively, it may be an aromatic ring or a non-aromatic ring (aliphatic ring). In particular, the specific cyclic compound is preferably a compound having a carboxyl group or a salt thereof and containing a heterocyclic ring (hereinafter sometimes referred to as a specific heterocyclic compound). When the specific cyclic compound contains a heterocyclic ring, the heterocyclic compound constituting the mother nucleus may be an aliphatic heterocyclic compound or an aromatic heterocyclic compound, but may be an aromatic heterocyclic compound. preferable. The heterocyclic compound is preferably a compound having a 5- to 7-membered skeleton, and more preferably a compound having a 5- or 6-membered skeleton. Therefore, a 5- or 6-membered aromatic heterocyclic compound is particularly preferable. At this time, the heterocyclic compound may be monocyclic or bicyclic. Therefore, a compound having a 5- or 6-membered ring skeleton may further have a multi-ring structure accompanied by a benzene ring or the like, and these multi-ring compounds are also included in a compound having a 5- or 6-membered ring skeleton. Is done. Specifically, indole, carbazole, purine and the like are also included.

  The heterocyclic compound that forms the mother nucleus of the specific heterocyclic compound is preferably a 5-membered azole compound. Examples of the 5-membered azole compound include pyrrole, 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, and tetrazole.

  Among the specific heterocyclic compounds, compounds represented by any of the following formulas (1) to (6) are preferable.

R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁶¹ , R ⁶² , R ⁶³ are each independently A hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group (C2-C12 is preferable, C2-C6 is more preferable), Aryl group (C6-C22 is preferable, C6-C14 is more preferable, C6-C10 is particularly preferable), Aralkyl group (C7 To 23, more preferably 7 to 15 and particularly preferably 7 to 11), a group containing a carboxyl group or a salt thereof (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3). Like There), or an amino group (0-6 carbon atoms preferably 0-3 and more preferably) or a group of a salt thereof (ammonio group). When a group containing a carboxyl group or a salt thereof or a group containing an amino group or a salt thereof has a linking group, the linking group is preferably an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 3 is particularly preferable), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), O, CO, NR ^N , S, or a combination thereof. The number of atoms constituting the linking group is preferably 1-12, more preferably 1-6, particularly preferably 1-3, excluding hydrogen atoms. The number of linking atoms in the linking group is preferably 6 or less, and more preferably 3 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH ₂ —C (═O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3. The linking group defined here is called a linking group L.

R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁶¹ , R ⁶² , R ⁶³ are a hydrogen atom, carboxyl When it is a group other than a group or an amino group, it may have an arbitrary substituent T. Examples of the optional substituent T include a carboxyl group, an amino group (preferably having 0 to 6 carbon atoms, more preferably 0 to 3), and a hydroxyl group. Among the linking groups L, the linking groups other than O, S, and CO may have a substituent T as well.

^RN is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). ), An alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (C7-23 is preferred, 7-15 is more preferred, and 7-11 is particularly preferred). ^RN may have the above optional substituent T.

The compound represented by any one of formulas (1) to (6) has at least one carboxyl group or salt thereof in the molecule. The upper limit is the number that can be substituted in the molecule in each compound, but the number of carboxyl groups or salts thereof in the molecule is preferably 1 to 4, more preferably 1 or 2. Each formula is specifically shown as follows.
In the formula ^(1), one of R ^{11, R 12,} and ^{R N} is a group containing a carboxyl group or a salt thereof. Especially, it is preferable that any of R ¹¹ and R ¹² is a group containing a carboxyl group or a salt thereof.
In the formula ^(2), either of R ^{21, R 22,} and ^{R N,} is a group containing a carboxyl group or a salt thereof. Of these, any of R ²¹ and R ²² is preferably a group containing a carboxyl group or a salt thereof.
In the formula (3), either of R ³¹ and R ^N, is a group containing a carboxyl group or a salt thereof. Of these, R ³¹ is preferably a carboxyl group or a group containing a salt thereof.
In the formula ^(4), any of ^{R 41, R 42, R 43} , and ^{R N,} is a group containing a carboxyl group or a salt thereof. Especially, it is preferable that any of R ⁴¹ , R ⁴² , and R ⁴³ is a group containing a carboxyl group or a salt thereof.
In the formula ^(5), any of ^{R 51, R 52, R 53} , R 54, and ^{R N,} is a group containing a carboxyl group or a salt thereof. Of these, any of R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ is preferably a group containing a carboxyl group or a salt thereof.
In the formula ^(6), any of ^{R 61, R 62, R 63} , and ^{R N,} is a group containing a carboxyl group or a salt thereof. Of these, any of R ⁶¹ , R ⁶² , and R ⁶³ is preferably a group containing a carboxyl group or a salt thereof.

R ¹¹ and R ¹² , R ¹² and R ^N , R ²² and R ^N , R ⁴¹ and R ^N , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁵¹ and R ^N , R ⁵¹ and R ⁵² , R ⁵² And R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁴ and R ^N , R ⁶¹ and R ^N , R ⁶¹ and R ⁶² , and R ⁶³ and ^RN may be linked to each other to form a ring. The ring formed is preferably a 5-membered ring or a 6-membered ring. Specific examples include a benzene ring, a cyclohexane ring, a cyclopentane ring, a cyclobutane ring, and a cyclopropane ring. The formed ring may be further optionally substituted with a group as an option for R ¹¹ .

  Examples in which the compound represented by any one of the above formulas (1), (4), (5) and (6) is a bicyclic ring with a benzene ring are shown below. In the formula, substituents denoted by the same reference numerals have the same meaning.

R ¹⁷ , R ⁴⁷ , R ⁵⁷ , R ⁵⁸ , and R ⁶⁷ are groups having the same options as R ¹¹ , respectively. n is an integer of 0-4. At this time, the compound of each formula has one or more carboxyl groups or salts thereof in the molecule. The upper limit is the number that can be substituted in the molecule in each compound, but the number of carboxyl groups or salts thereof is preferably 1 to 4, more preferably 1 or 2. Among these, for formula (1a), it is preferable that at least one of R ¹⁷ is a carboxyl group or a salt thereof. In the formula (4a), it is preferable that at least one of R ⁴⁷ and R ⁴¹ is a carboxyl group or a salt thereof. In the formula (5a), it is preferable that at least one of R ⁵⁷ , R ⁵¹ and R ⁵² is a carboxyl group or a salt thereof. In the formula (5b), it is preferable that at least one of R ⁵¹ , R ⁵⁴ and R ⁵⁸ is a carboxyl group or a salt thereof. Regarding formula (6a), it is preferable that at least one of R ⁶³ and R ⁶⁷ is a carboxyl group or a salt thereof.

  Specific examples of the specific cyclic compound include tetrazole-5-acetic acid, benzotriazole-5-carboxylic acid, imidazole-4,5-dicarboxylic acid, and 3-amino-1,2,4-triazole-5-carboxylic acid. Is mentioned.

  The content of the specific cyclic compound is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more as a lower limit in the removal liquid. As an upper limit, 5 mass% or less is preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is especially preferable. By applying the specific cyclic compound to the removal liquid within this range, it is preferable in that corrosion of an electrode material such as Al can be effectively prevented while achieving sufficient removal and stripping of a resist and the like. A specific cyclic compound may be used independently or may be used in combination of 2 or more type.

(water)
The removal liquid of the present invention may contain water. The applied water is not particularly limited, but may be an aqueous medium containing a dissolved component as long as the effects of the present invention are not impaired. Or the inevitable trace amount mixing component may be included. Among these, water that has been subjected to purification treatment such as distilled water, ion-exchanged water, or ultrapure water is preferable, and ultrapure water that is used for semiconductor manufacturing is particularly preferable. The amount of water in the removal solution is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. As a lower limit, it is preferable that it is 0.01 mass% or more, 0.05 mass% or more is more preferable, 0.1 mass% or more is further more preferable, and 0.4 mass% or more is especially preferable. In the present invention, it is preferable that water is not substantially contained, but it is preferably contained at the lower limit value or more. This is because the corrosivity of the electrode is increased due to the presence of water, and its concentration is preferably reduced, but a trace amount is included to effectively exhibit the removal and stripping properties of the resist, etc. possessed by the quaternary ammonium compound. It is preferable that

(Silane compound)
The removal liquid according to the present invention may contain a silane compound. A silane compound broadly means a compound having a silicon atom in the compound. The silane compound preferably has a molecular weight of 80 or more, more preferably 100 or more. The upper limit is preferably 1000 or less, and more preferably 500 or less. As the silane compound, an alkoxysilane compound having an alkoxy group in the molecule is preferable. Among these, a compound represented by the following formula (S1) is more preferable.

(R ¹ ) _a Si (OR ² ) _4-a (S1)

R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl. Group (C2-C12 is preferable, C2-C6 is more preferable), aryl group (C6-C22 is preferable, C6-C14 is more preferable, C6-C10 is particularly preferable), aralkyl group (C7 -23 are preferable, 7-15 are more preferable, and 7-11 are particularly preferable), and an alkyl group, an aryl group, or an alkenyl group is more preferable.
a is 0, 1 or 2.

  The content of the silane compound is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more as a lower limit in the removal liquid. As an upper limit, 5 mass% or less is preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is especially preferable. By applying the silane compound to the removal liquid within this range, it is preferable in that corrosion of an electrode material such as Al can be effectively prevented while achieving sufficient removal and stripping of a resist and the like. A silane compound may be used independently or may be used in combination of 2 or more type.

(Other additives)
The removal liquid of the present invention does not prevent other additives from being included within the range where the effects of the present invention are exhibited. For example, a pH adjuster, a surfactant, an antifoaming agent, an organic acid other than the specific cyclic compound, or the like may be added as appropriate.

  The removal liquid of the present invention, as an embodiment thereof, consists essentially of (Ia) a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, an organic solvent, and water, or (Ib) It preferably comprises only a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, an organic solvent, a silane compound, and water. Or (IIa) consisting essentially of (IIa) dimethyl sulfoxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and water, or (IIa) dimethyl sulfoxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide It is preferable that it consists only of a silane compound and water. Here, “substantially” means that an unavoidable impurity or a trace amount mixture may be contained within a range where the effects of the present invention are exhibited.

<Container>
The removal liquid of the present invention can be stored, transported and used by filling it in any container as long as corrosion resistance or the like does not matter (whether it is a kit or not). For semiconductor applications, a container having a high cleanliness and a low impurity elution is preferable. Examples of containers that can be used include the “Clean Bottle (trade name)” series manufactured by Aicero Chemical Co., Ltd., and the “Pure Bottle (trade name)” manufactured by Kodama Plastic Industry Co., Ltd. It is not something. The container or the inner wall of the container is subjected to a resin different from at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust prevention and metal elution prevention treatment. Preferably, it is formed from a finished metal. About such container preservation | save, it is the same also about the preservation | save of a resist mentioned later about the preferable embodiment.

<Filtering>
The removal liquid of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore size of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it as this range, it becomes possible to remove fine foreign matters, such as impurities and aggregates contained in the removal liquid, while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or larger than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm. By setting it as this range, the foreign material mixed in the removal liquid can be removed while the component particles contained in the mixed liquid remain.
For example, after filtering with the first filter, the second filtering may be performed after mixing other components with the removal liquid.

<Metal concentration, etc.>
The concentration of the metal (Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn metal elements) that can be contained in the removing liquid of the present invention is 5 ppm or less. It is preferable. About the reduction of such metal concentration, it is the same also about the resist (coloring curable resin composition) of a postscript about the preferable embodiment. Further, in the removing solution and the resist, the number of coarse particles having an average particle size of 0.5 μm or more is preferably in the range of 100 / cm ³ or less, and in the range of 50 / cm ³ or less. preferable.

<Removal method>
The method of applying the removing liquid is not particularly limited, but it is preferable that the removing liquid is circulated through the flow path, the removing liquid is discharged or ejected from the discharge port, and is brought into contact with the semiconductor substrate. If it demonstrates with a specific example, the prepared removal liquid will be introduce | transduced from an inlet, will move to a discharge outlet, will be ejected from there, and will be applied to the upper surface of the semiconductor substrate in a processing container (processing tank). In this embodiment, the removal liquid is transferred to the discharge port via the flow path. The flow path indicates a return path for reusing the chemical solution. It is preferable that the semiconductor substrate is on a rotary table and is rotated together with the rotary table by a rotary drive unit.

  In the present invention, it is preferable to use a single wafer apparatus. Specifically, the single wafer type apparatus has a processing tank, and the semiconductor substrate is transported or rotated in the processing tank, and an upper removing liquid is applied (discharge, jetting, flowing down, dropping, etc.) into the processing tank. It is preferable that the removal liquid is brought into contact with the semiconductor substrate. Advantages of the single-wafer apparatus include (i) a fresh removal liquid is always supplied, so that reproducibility is good, and (ii) in-plane uniform processability is high. The single-wafer apparatus preferably includes a nozzle in its processing tank, and a method of discharging the removal liquid onto the semiconductor substrate by swinging the nozzle in the surface direction of the semiconductor substrate is preferable. By doing so, the deterioration of the liquid can be prevented, which is preferable.

The treatment temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. As an upper limit, it is preferable that it is 100 degrees C or less, and it is more preferable that it is 90 degrees C or less.
The processing temperature is measured under the following conditions in a single wafer type apparatus. A radiation thermometer IT-550F (trade name) manufactured by HORIBA, Ltd. is fixed to a height of 30 cm above the wafer in the single wafer type apparatus. A thermometer is directed onto the wafer surface 2 cm outside from the center of the wafer, and the temperature is measured while flowing a chemical solution. The temperature is digitally output from the radiation thermometer and recorded continuously by a personal computer. Among these, the value obtained by averaging the temperature for 10 seconds at which the temperature was stabilized was defined as the temperature on the wafer. When managing by storage temperature or batch processing, the temperature in the tank can be held and set until it is stabilized for a predetermined time (for example, 1 minute). When managing in the circulation system, the temperature may be maintained and set until the temperature in the circulation channel is stabilized for a predetermined time (for example, 1 minute).

  The supply rate of the removal liquid in the case of the single wafer type is not particularly limited, but is preferably 0.05 to 5 L / min, and more preferably 0.1 to 3 L / min. By setting it as said range, the uniformity in the surface of a process can be ensured more favorably, On the other hand, the stable performance at the time of continuous processing can be ensured, and it is preferable. When the semiconductor substrate is rotated, although it depends on its size and the like, it is preferably rotated at 50 to 1000 rpm from the same viewpoint as described above. The moving speed of the discharge port (nozzle) is not particularly limited, but is preferably 0.1 cm / s or more, and more preferably 1 cm / s or more. On the other hand, the upper limit is preferably 30 cm / s or less, and more preferably 15 cm / s or less. The movement trajectory line may be a straight line or a curved line (for example, an arc shape). In either case, the moving speed can be calculated from the actual distance of the trajectory line and the time spent for the movement. The time required for processing one substrate is preferably in the range of 10 to 1200 seconds.

<Resist>
(Pattern for patterning)
The resist peeled off by the removing liquid of the present invention is not particularly limited, and a normal resist material can be used as a target. For example, a positive type, a negative type, and a positive / negative type photoresist can be mentioned. Specific examples of the positive resist include vinyl cinnamate, cyclized polyisobutylene, azo-novolak resin, and diazoketone-novolak resin. Specific examples of the negative resist include azide-cyclized polyisoprene, azide-phenol resin, and chloromethyl polystyrene. Furthermore, specific examples of the positive / negative resist include poly (p-butoxycarbonyloxystyrene) type. Examples of the positive resist include a positive resist containing at least one of a novolac resin and a polyhydroxystyrene resin. Other examples of resists include those disclosed in Japanese Patent Nos. 5222804, 5244740, 5244933, 5286236, 5210755, 5277128, 5303604, 5321589, 5553139, 5553178, and 5155803. Which is incorporated herein by reference.

(Color filter resist)
The removing liquid of the present invention can be applied to a permanent film made of a resin incorporated in various elements such as a color filter, a microlens, and an insulating film, and used for the peeling. In the present specification, these permanent films are also included in the term “resist”.
Specifically, RGB 5000 series / 6000 series (trade name) and CMY 3000 series (trade name) manufactured by FUJIFILM Corporation can be suitably used as the color resist. Also disclosed in the following publications: Patent 5274680, Patent 5283747, Patent 0533624, Patent 05339781, Patent 0534040, Patent 0534484, Patent 5355069, Patent 5367060, Patent 5371313, Patent 5371449, Patent 5374189, Patent 5398586, Patent 5448352, Patent 5448416. Can be referred to and are incorporated herein by reference.
The details of one embodiment of the color filter forming material and forming method will be described below.

  Each pixel of the color filter according to the present embodiment can be formed by curing the following colored curable resin composition (hereinafter also simply referred to as “composition”). Examples of the colored curable resin composition include an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a colorant.

-Alkali-soluble resin As an alkali-soluble resin, what has at least 1 group which promotes alkali solubility in a molecule | numerator is preferable. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. From the viewpoint of development control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acidic group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Those which are soluble in a solvent and can be developed with a weak alkaline aqueous solution are preferred, and (meth) acrylic acid is particularly preferred. These acidic groups may be only one type or two or more types.
The alkali-soluble resin is preferably a polymer having a carboxyl group in the main chain or side chain. Specifically, alkalis such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolak resin Examples include soluble phenol resins and the like, acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group to which an acid anhydride is added. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonite As an N-substituted maleimide monomer described in JP-A-10-300922, such as ruthenium, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, jN-phenylmaleimide, N- Examples thereof include cyclohexylmaleimide.
The alkali-soluble resin preferably has a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond group. Specifically, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from one or more of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide.

  The synthesis of the polymerizable alkali-soluble resin can be performed based on the synthesis method described in paragraph Nos. 0027 to 0057 of JP-A No. 2003-262958. Of these, the synthesis method 1) in the publication is preferred. As the exemplified compounds, the compounds described in paragraph Nos. 0058 to 0061 of JP-A No. 2003-262958 can be referred to, and are incorporated herein. Specific examples of the alkali-soluble resin having a specific structural unit include the following compounds (resins). In the following compound P-1, MMA represents a methyl methacrylate component, and AA represents an acrylic acid component.

  The alkali-soluble resin is also preferably a polymer represented by the following formula.

L ^X1 represents a single bond or a linking group. Examples of the linking group include the linking group L described above. Of these, a single bond is preferable.
R ^X1 and R ^Y1 are a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a cyano group, preferably a hydrogen atom or a methyl group.
R ^A is an acidic group. The preferable thing is synonymous with the above.
R ^Y2 represents a substituent, and among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, and 6 to 6 carbon atoms). 14 is more preferable, and 6 to 10 is particularly preferable), and an aralkyl group (C7 to C23 is preferable, 7 to 15 is more preferable, and 7 to 11 is particularly preferable). These groups may further have a substituent, and examples of the further substituent include a hydroxyl group and a carboxyl group.
nx and ny are mole fractions, and nx + ny may be less than 1 (meaning that it may have other repeating units), and is preferably 1. The lower limit of nx is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.2 or more. As an upper limit, 0.7 or less is preferable, 0.6 or less is more preferable, and 0.5 or less is especially preferable. As a lower limit, ny is preferably 0.3 or more, more preferably 0.4 or more, and particularly preferably 0.6 or more. As an upper limit, 0.9 or less is preferable and 0.8 or less is more preferable.

  The alkali-soluble resin is preferably one that is soluble in a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.1% by mass or more at 23 ° C. Further, it is preferably soluble in 1% by mass or more of TMAH aqueous solution, and more preferably soluble in 2% by mass or more of TMAH aqueous solution.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, particularly preferably from 7,000 to 20,000.
As content rate of alkali-soluble resin, 10-50 mass% is preferable with respect to the total solid of a composition, More preferably, it is 15-40 mass%, Most preferably, it is 20-35 mass%. A soluble resin may be used individually by 1 type, or may be used in combination of 2 or more type.

Polymerizable compound The polymerizable compound may be a compound having a polymerizable group in the molecule, and among them, a monomer having an ethylenically unsaturated double bond (hereinafter sometimes referred to as “specific monomer”) is preferable. . The specific monomer is preferably a polyfunctional monomer. A specific monomer may be used individually by 1 type, and may use 2 or more types together. The specific monomer is preferably a (meth) acrylate monomer. As these specific compounds, the compounds described in JP-A 2009-288705, paragraphs 0095 to 0108 can also be suitably used in this embodiment. The specific monomer is preferably further represented by the following formulas (MO-1) to (MO-6).

  In the formula, n is 0 to 14 respectively, and m is 1 to 8 respectively. A plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.

n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
Specific examples of the polymerizable compound represented by any one of the above formulas (MO-1) to (MO-6) include the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. It can be suitably used also in the embodiment.

Among them, as a polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company), and the structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by Toa Gosei) ) ( Shift trade names) are preferred. These oligomer types can also be used.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.
The content of the polymerizable compound with respect to the total solid content in the composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, More preferably, it is in the range of 5% by mass to 30% by mass. Within this range, the curability is good and preferable without excessively reducing the refractive index and transparency. A polymeric compound may be used individually by 1 type, or may be used in combination of 2 or more type.

-Polymerization initiator The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. For example, organic halogen compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds , Disulfonic acid compound, oxime compound, onium salt compound, hydroxyacetophenone compound, aminoacetophenone compound, acylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, Phosphine oxide compound, metallocene compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzothiol Examples include enone compounds, cyclopentadiene-benzene-iron complex compounds, halomethyloxadiazole compounds, 3-aryl-substituted coumarin compounds, α-aminoalkylphenone compounds, and benzoate compounds.
As specific examples of these, the description after paragraph [0135] of JP 2010-106268 A (corresponding US Patent Application Publication No. 2011/0124824 [0163]) can be referred to. Incorporated into.

  In the present invention, it is preferable to use an oxime compound. Among these, commercially available products (both trade names, manufactured by BASF) such as IRGACURE OXE01 (lower formula) and IRGACURE OXE02 (lower formula) can be preferably used. Further, NCl-831 (trade name, manufactured by ADEKA) represented by the following chemical formula (A) and a compound represented by the following chemical formula (B) are also preferable. Two or more of these oxime compounds may be used in combination.

  The polymerization initiator is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 8% by mass in the solid content of the composition. You may use a polymerization initiator in combination of 2 or more type as needed.

Colorant The colorant is not particularly limited, and various dyes and pigments can be used. For example, chromatic colorants (chromatic colorants) such as red, magenta, yellow, blue, cyan, and green that form color pixels of color filters, and black that is commonly used for black matrix formation Any of the above colorants (black colorants) can be used. In the present embodiment, the colorant is preferably at least one selected from red, magenta, yellow, blue, cyan, and green.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Examples thereof include metal oxides such as silver and complex oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.
Organic pigments include perylene pigment, perinone pigment, quinacridone pigment, quinacridone quinone pigment, anthraquinone pigment, anthanthrone pigment, benzimidazolone pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triarylcarbonium pigment, dioxazine Examples include pigments, aminoanthraquinone pigments, diketopyrrolopyrrole pigments, indigo pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, pyranthrone pigments, or isoviolanthrone pigments.
Examples of the dye include triarylmethane, pyrazoleazo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, phenothiazine Azomethine, pyrrolopyrazole, azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes.

The following can be mentioned as an example of a chromatic colorant. However, the present invention is not limited to these.
Color index (CI) pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
These chromatic colorants can be used alone or in various combinations in order to increase color purity.
Various known black pigments can be used as examples of the black colorant. In particular, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite and the like are preferable from the viewpoint of realizing a high optical density in a small amount, and in particular, at least one of carbon black and titanium black is included. In particular, titanium black is preferred from the viewpoint of low absorption in the light absorption wavelength region of the initiator related to the curing efficiency by exposure. Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include, but are not limited to, inorganic pigments such as CI Pigment Black 7. Moreover, a black coloring agent may be used independently and may be used together 2 or more types. In addition, you may use together with a chromatic color agent.

When the colorant is in the form of particles, the average primary particle size is preferably 5 nm or more, particularly preferably 30 nm or more. As an upper limit, 1 micrometer or less is preferable, 500 nm or less is more preferable, and 100 nm or less is especially preferable.
As used herein, “average particle size” means the average particle size of secondary particles in which primary particles are aggregated, unless otherwise specified. The particle size is measured by using a dynamic light scattering particle size distribution measuring device (Nanotrac Wave-EX150 [trade name] manufactured by Nikkiso, LB-500 [trade name] manufactured by Horiba, Ltd.). Do it. The procedure is as follows. The sample dispersion is dispensed into a 20 ml sample bottle and diluted with an insoluble solvent (eg water) to a solid component concentration of 0.2% by weight. Data acquisition was performed 50 times using a 2 ml measuring quartz cell at a temperature of 25 ° C., and the obtained “number average” was defined as the average particle diameter. For other detailed conditions, the description of JISZ8828: 2013 “Particle size analysis—dynamic light scattering method” can be referred to if necessary.

  As content rate of a coloring agent, it is preferable that it is 10 mass% or more in solid content of a composition, 20 mass% or more is more preferable, and 30 mass% or more is still more preferable. Although there is no restriction | limiting in particular about an upper limit, Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less. According to the removing liquid of the present invention, the resist can be sufficiently peeled even when the composition contains a large amount of the colorant.

-Dispersant You may make a coloring curable resin composition contain a dispersing agent. As the dispersant, a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
Specific examples of the pigment dispersant include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162 manufactured by BYK Chemie. , 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ”,“ EFKA 4047, 4050, 4010, 4165 (manufactured by EFKA) Polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative). , 6750 (Azo Pigment derivatives) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetami 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24,000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. (all trade names) Is mentioned.

  As a density | concentration of a dispersing agent, it is preferable that it is 1-100 mass parts with respect to 1 mass part of coloring agents, 3-100 mass parts is more preferable, and 5-80 mass parts is further more preferable. Moreover, it is preferable that it is 5-30 mass% with respect to the total solid of a composition (in total solid). These dispersants may be used alone or in combination of two or more.

-Surfactant You may add various surfactant to a colored curable resin composition from a viewpoint of improving applicability | paintability more. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The amount of the surfactant added is preferably in the range of 1% by mass to 40% by mass with respect to the total solid content of the composition (in total mass of the solid content), preferably 5% by mass to 20% by mass. % Is more preferable.

  The colored curable resin composition can also contain other components as appropriate. As other components, solvents (such as those described in the above-mentioned “organic solvent” section can be used as appropriate), ultraviolet absorbers, adhesion improvers, sensitizing dyes, co-sensitizers, diluents, Examples include plasticizers and oil sensitizers.

Color filter formation Preparation of the colored curable resin composition and formation of the cured film may be performed by a general method, but in the following, formation of a color filter using the colored curable resin composition is taken as an example. Further details will be described. As a support for forming the color filter, for example, an image pickup device (light receiving device) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate). A substrate for a solid-state image sensor can be used. The coloring pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface). A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. As a method for applying the colored curable resin composition on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The colored curable resin composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

In the exposure step, the colored curable resin composition layer formed in the colored curable resin composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example. As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, and most preferably 80~500mJ / cm ^2.

Next, by performing development such as alkali development treatment, the colored curable resin composition of the light non-irradiated portion in the exposure step is eluted into the alkaline aqueous solution, and only the photocured portion remains. As the developer, an organic alkali developer that hardly damages the underlying image sensor or circuit is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
Examples of methods and materials for manufacturing color filters that can be preferably applied in the present invention include Japanese Patent Application Laid-Open No. 2014-199272, Japanese Patent Application Laid-Open No. 2013-064999, Japanese Patent Application Laid-Open No. 2013-064993, Japanese Patent Application Laid-Open No. 2013-064083, Japanese Patent Application Laid-Open No. 2013-040881, Japanese Patent Application Laid-Open No. 2013-2013. 040240, JP 2012-136669, JP 2012-012498, JP 2011-252046, JP 2011-252045, JP 2011-252044, JP 2011-162781, JP 2011-144299, JP 2011-144298, JP2011-127044, JP2011-127043, JP2011-084726, JP2010-244028, JP2010-159409, JP2010-155983, JP2010-085779, JP 010-084135, JP 2009-244320, JP 2006-058821, it is possible to refer to the description of such JP 2004-117856 captures by reference herein.

  Next, it is preferable to perform heat treatment (post-bake) after drying. At this time, it is preferable to form a multicolored colored pattern, and the cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained. Post-baking is a heat treatment after development for complete curing. The heating temperature is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 220 ° C. or lower. Although there is no particular lower limit, in view of efficient and effective treatment, it is preferable to perform a thermosetting treatment of 50 ° C. or higher, and more preferably 100 ° C. or higher. Instead of post-baking by heating, the pixels of the color filter may be cured by UV (ultraviolet) irradiation.

  The film thickness of the cured film (color filter) is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.5 μm or more. As an upper limit, 10 micrometers or less are preferable, 5 micrometers or less are more preferable, 4 micrometers or less are more preferable, and 3 micrometers or less are especially preferable. The size (pattern width) of the colored pattern (colored pixel) is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less. As a lower limit, 0.1 μm or more is practical. Such a film thickness is common as a color filter, and according to the removing liquid of the present invention, a sufficient peeling effect can be obtained even with the above color filter.

<TSV>
The removal liquid according to a preferred embodiment of the present invention is also effective for stripping a resist for TSV creation (for digging TSV holes). In addition to removing the resist remaining on the substrate surface after processing the TSV, it is possible to effectively remove resist residues, etching residues, and the like remaining inside the narrow TSV (via hole).
Three-dimensional (3D) technology such as TSV and its structures are becoming increasingly important in IC technology. This is because there is a high possibility of further improving the performance of the system and reducing its size. For such 3D applications, photoresist is applied. For example, patterning of TSV or processing of a combination of plating and bumps (3D stacked integration: 3D-SIC, 3D wafer level packaging: 3D-WLP).
For 3D-WLP TSV, a positive photoresist having a thickness of several μm is usually applied. Silicon dry etching and photoresist wet etching (peeling) are generally performed. Negative photoresists are also applied for copper plating and microbump applications.

  Often, it becomes difficult to remove photoresist damaged by etching or plasma ashing, that is, post etching residue (PER). Additional physical processing may be required to remove such PER.

  The removal liquid according to a preferred embodiment of the present invention can be suitably used for stripping a positive resist or a negative resist applied to the above-described TSV or the like. Moreover, it is preferable that the removal of PER is also effective. On the other hand, it is preferable to maintain an electrode material such as a silicon wafer (blanket wafer) or aluminum without being damaged. The removal liquid according to a preferred embodiment of the present invention is preferable because both of them can be achieved simultaneously.

As the negative resist, the above-mentioned color filter resist formulation is helpful. Examples include photopolymerization initiators, photocuring materials (monofunctional or polyfunctional monomers, oligomers, or crosslinkable group-containing polymers), binders, fillers, sensitizers, polymerization inhibitors, dyes, pigments, surfactants, Additives such as thickeners, leveling agents, crosslinking agents, adhesion improvers, solvents, etc. can optionally be included. As the photopolymerization initiator, known compounds and mixtures thereof can be appropriately selected and used as a photoinitiator for photoradical polymerization. Although there is no restriction | limiting in particular in the kind of said photoinitiator, For example, an alkylphenone type compound (For example, a benzyldimethyl ketal compound, an alpha-hydroxyalkylphenone compound, an alpha-aminoalkylphenone compound etc.), an oxime type compound (for example, Oxime ester compounds) and the like can be used. Moreover, a photoinitiator may be used independently or may be used in combination of 2 or more type.
Positive resists include, for example, photoacid generators and curing agents, binders, fillers, sensitizers, polymerization inhibitors, dyes, pigments, surfactants, thickeners, leveling agents, crosslinking agents, and adhesion improvers. Additives such as agents and solvents can optionally be included.

  From the viewpoint of suitably exhibiting the effect of the removing liquid of the present invention, the width of the TSV opening is preferably 15 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is practically 1 μm or more. The aspect ratio (depth / opening width) of the TSV via hole is preferably 5 or more, more preferably 10 or more, and particularly preferably 15 or more. The upper limit is practically 30 or less.

<Electrode material>
Although electrode material is not specifically limited, Copper or aluminum etc. are mentioned as what is used widely. The etching rate [R1] of the electrode material (aluminum or the like) is not particularly limited, but it is preferable that the electrode material (aluminum or the like) is not excessively removed by application of a removing liquid. Specifically, it is preferably 500 Å / min or less, more preferably 200 Å / min or less, and particularly preferably 100 Å / min or less. There is no particular lower limit, but considering the measurement limit, it is practical that it is 1 と / min or more. In this specification, unless otherwise specified, the etching rate depends on the conditions measured in the examples described later.

<Manufacture of semiconductor substrate products>
The wafer size in the semiconductor substrate is not particularly limited, but those having a diameter of 8 inches, a diameter of 12 inches, or a diameter of 14 inches can be suitably used (1 inch = 25.4 mm). As described above, various processes such as a lithography process, an etching process, and an ion implantation process are applied to the semiconductor element manufacturing process. In the present invention, a semiconductor substrate product or a semiconductor element can be manufactured by an appropriate method. Among them, it is preferable to apply the removing solution of the present invention in order to peel and remove the resist applied for patterning the substrate.
Alternatively, the removing liquid of the present invention may be used to remove a permanent resin film from a semiconductor substrate. For example, when a portion of the semiconductor substrate product that is in the process of being manufactured needs to be repaired, it is conceivable to wash away this member and regenerate the substrate. According to the present invention, it is possible to suitably cope with the regeneration of such a substrate. Examples of the permanent film include the color filter described above, a transparent insulating film, a resin lens (microlens array), and the like. Unlike a resist film, such a permanent film remains undissolved by development and is not supposed to be peeled off or removed after processing, and it is expected that peeling will be difficult.

  On the other hand, the removal liquid according to the embodiment of the present invention exhibits a particularly high effect for peeling and removing the permanent film. Of these, application to peeling / removal of the color filter is preferable because a particularly remarkable effect is exhibited. Although this reason includes an unclear point, the color filter is expected to be difficult to peel because there are components such as a coloring material that are not included in a normal resist. On the other hand, the removal liquid containing the component according to the present invention exerts a high effect due to the interaction, and achieves both releasability of the resist (color filter) and damage suppression of the electrode material (aluminum, etc.). It is understood that.

  In this specification, the term “semiconductor substrate” is used to mean not only a wafer but also the entire substrate structure having a circuit structure formed thereon. A semiconductor substrate member refers to the member which comprises the semiconductor substrate defined above, and may consist of one material or may consist of several materials. A processed semiconductor substrate is sometimes referred to as a semiconductor substrate product, and is further distinguished as necessary, and a chip that has been processed and diced out and processed product thereof is referred to as a semiconductor element. That is, in a broad sense, a semiconductor element or a semiconductor product incorporating the semiconductor element belongs to a semiconductor substrate product.

In this specification, the term “preparation” means that a specific material is synthesized or blended, and a predetermined item is procured by purchase or the like. Further, in this specification, the use of the removing liquid to treat each material of the semiconductor substrate is referred to as “application”, but the embodiment is not particularly limited. For example, the method widely includes contacting the removal liquid with the substrate. Specifically, the removal liquid may be processed by being immersed in a batch type or may be processed by discharging with a single wafer type.
In the present specification, each step according to the method invention is allowed to be applied in a suitable order within the scope of the effects of the present invention. Similarly, it does not preclude that another step is appropriately interposed between the steps.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to a following example. In addition, unless otherwise indicated,% and part shown as prescription and compounding quantity in an Example are mass references | standards.

(Example 1 and Comparative Example 1)
<Preparation of Green pigment dispersion>
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 12.6 parts of a 100/55 (mass ratio) mixture with Pigment Yellow 139, 5.2 parts of a dispersing agent, BYK2001 (Disperbyk: manufactured by BYK Corporation, solid content concentration: 45.1% by mass), and dispersion A mixed solution consisting of 2.7 parts of benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as a resin and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent was obtained by a bead mill. Green pigment dispersion was prepared by mixing and dispersing for 15 hours.

<Preparation of Red pigment dispersion>
As a pigment and C.I. I. Pigment Red 254 12.1 parts, BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) as a dispersant, 10.4 parts, and benzyl methacrylate / methacrylic acid copolymer (as a dispersion resin) A mixed liquid consisting of 3.8 parts of acid value 134 mgKOH / g, Mw = 30,000) and 73.7 parts of propylene glycol monomethyl ether acetate as a solvent was mixed and dispersed for 15 hours by a bead mill, and the Red pigment was dispersed. A liquid was prepared.

<Preparation of Blue Pigment Dispersion>
As a pigment, C.I. I. Pigment blue 15: 6 and C.I. I. 14 parts of a 100/25 (mass ratio) mixture with CI Pigment Violet 23, 4.7 parts of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersant, and a dispersion resin A mixed solution composed of 3.5 parts of a benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) and 77.8 parts of propylene glycol monomethyl ether acetate as a solvent was mixed with a bead mill for 15 hours. A blue pigment dispersion was prepared by mixing and dispersing.

<Preparation of colored curable resin composition>
Using each of the above pigment dispersions, a colored photosensitive resin composition was prepared by mixing and stirring so as to have the following composition.

―――――――――――――――――――――――――――――――――
Each pigment dispersion 83.3 parts Resin P-1 2.05 parts Polymerization initiator 1.2 parts DPHA 1.4 parts M-305 1.4 parts p-methoxyphenol 0.001 part PGMEA 7.4 parts The following fluoropolymer surfactant (applied in 0.2% solution of PGMEA) 4.2 parts ―――――――――――――――――――――――――― ―――――――
Polymerization initiator: IRGACURE OXE01 [trade name] manufactured by BASF
DPHA: Nippon Kayaku Co., Ltd. KARAYAD DPHA [trade name]
Dipentaerythritol hexaacrylate M-305 [trade name]: Triacrylate manufactured by Toagosei Co., Ltd.
Mixture of pentaerythritol tetraacrylate PGMEA: Propylene glycol monomethyl ether acetate Fluoropolymer surfactant: Mixture of compounds represented by the following chemical formula

<Formation of color filter (CF)>
Each colored photosensitive composition prepared above was applied onto an 8-inch silicon wafer previously sprayed with hexamethyldisilazane to form a photocurable coating film. Heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100 ° C. so that the dry film thickness of this coating film was 1.0 μm. Next, using a stepper exposure apparatus FPA-3000i5 + (trade name, manufactured by Canon Inc.), i-line was irradiated at a wavelength of 365 nm through a 1.0 μm square Bayer pattern mask at 50 to 1000 mJ / cm ² . (The exposure amount is changed by 50 mJ / cm ² ). Thereafter, the silicon wafer on which the irradiated coating film was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; trade name, manufactured by Chemitronics). Paddle development was performed at 23 ° C. for 180 seconds using a 40% dilution of CD-2000 (trade name, manufactured by Fuji Film Electronics Materials Co., Ltd.) to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from a jet nozzle. And then rinsed and then spray dried. Next, it was heated on a hot plate at 200 ° C. for 5 minutes to obtain a color filter on which a pattern was formed.

<Preparation of aluminum electrode>
An aluminum (Al) electrode was formed on another silicon wafer by the CVD method. The thickness of the Al electrode was about 0.5 μm.

<Implementation of CF peeling test>
A wafer having the color filter and an Al blanket wafer were cut into 1 × 2 cm to obtain a test wafer. A chemical solution having the following composition was prepared, a stirrer and a chemical solution were placed in a beaker, and the mixture was heated to 70 ° C. while stirring the chemical solution at a rotation speed of 250 rpm. Thereafter, the test wafer was immersed for 5 minutes. After the immersion, ion exchange water (DIW) was ejected from the two-fluid nozzle and rinsed for 30 seconds. A schematic side view of the test wafer is shown in FIG. FIG. 1A is before the peeling process, and FIG. 1B is after the peeling process.

<Resist peelability evaluation [CF peelability]>
The wafer provided with the RGB color filter was observed with an optical microscope (magnification 50 times), and the peelability of the color filter layer was observed. The peelability of the color filter (CF) was evaluated by classification as follows.
A: Residue could not be confirmed with an optical microscope and 100% was removed B: Residue could be confirmed with an optical microscope, and more than 50% was removed less than 100% C: Residue could be confirmed with an optical microscope, More than 50% remains

<Evaluation of peelability of Al layer [Al EV]>
An Al test wafer was processed under the conditions of the CF peeling test. Before and after the treatment, the film thickness was calculated from the current value of the Al layer using a four-terminal ammeter (trade name VR200, manufactured by Kokusai Electric Alpha Co., Ltd.). The table below shows the amount of decrease in film thickness.

<Evaluation of changes over time>
The drug solution was allowed to stand at room temperature (25 ° C.) for 1 week. Thereafter, the change in the color of the chemical solution was confirmed visually.
A: No change with time B: Change with time

Formulation: parts by mass Al EV: etching amount of aluminum layer (reduced thickness)
DMSO: Dimethyl sulfoxide TMAH: Tetramethylammonium hydroxide TBAH: Tetrabutylammonium hydroxide TMS: Tetramethoxysilane TA: Quaternary ammonium compound 1Å = 0.1 nm
About said Example, it filtered all using DFA4201NXEY (brand name, 0.45 micrometer nylon filter) by Nippon Pole about each after the preparation of a sample liquid and after preparing a colored curable resin composition.

  From the above results, according to the removal liquid according to the first embodiment of the present invention and the removal liquid according to the second embodiment, both achieve good color filter (resist permanent film) peeling, Thus, it can be seen that the electrode material (aluminum) exhibits damage prevention properties.

  A test wafer having a color filter layer is prepared in the same manner by replacing the above colored curable resin composition by Fuji Film Co., Ltd., RGB 5000 series / 6000 series (trade name) and CMY 3000 series (trade name). did. Using the test wafer, the above peel test was performed. As a result, it was confirmed that good peelability was exhibited.

(Example 2 and Comparative Example 2)
<Creation of TSV board>
A TSV having an aspect ratio of 10: 1 having an opening diameter (diameter) of 5 μm and a depth of 50 μm was formed on a predetermined silicon substrate using a fluorine-based gas (see FIG. 2). A three-layer structure of Si layer, SiO ₂ layer (hard mask: thickness 500 nm), and positive photoresist (PR: thickness 3.5 μm) was adopted.
<Aluminum substrate>
On the other hand, a commercially available aluminum wafer (manufactured by Advanced Materials) was used for evaluation of damage to aluminum. The film thickness was 5000 mm.

<Execution of TSV cleaning test>
The wafer was processed using a single wafer apparatus (trade name wafer spin cleaning apparatus manufactured by ET System Engineering Co., Ltd.).
Chemical treatment: 3 minutes / 70 ° C
Flow rate: 1.5L / min
Rotation speed: 10rpm, DIW (distilled water)
Megasonic rinse: 1 minute Spin drying: 25 ° C 1 minute

<Evaluation of cleaning ability>
The above TSV wafer was observed with a scanning electron microscope (SEM), and the cleaning ability with respect to the surface of the wafer and the inside of the TSV was evaluated.
A: Residue cannot be confirmed on the wafer surface or inside the TSV, and 100% is removed B: Residue can be confirmed on the wafer surface or inside the TSV, and more than 50% is removed less than 100% C: Wafer surface or Residue can be confirmed inside TSV, and 50% or more remains

<Al damage evaluation [Al EV]>
The Al wafer was processed in the same manner as in Example 1 under the above conditions. Before and after the treatment, the film thickness was calculated from the current value of the Al layer using a four-terminal ammeter (trade name VR200, manufactured by Kokusai Electric Alpha Co., Ltd.). The table below shows the amount of decrease in film thickness.

  Table notes are the same as Table 1.

  From the above results, it can be seen that according to the removing liquid of the present invention, the resist for removing TSV can be effectively removed and the residue inside TSV (via hole) can be removed effectively.

  While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

  This application claims priority based on Japanese Patent Application No. 2014-240588 filed in Japan on November 27, 2014 and Japanese Patent Application No. 2015-030378 filed in Japan on February 19, 2015 Which are hereby incorporated by reference herein as part of their description.

Claims (22)

A removal solution for removing at least one of a resist and an etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent ,
The removal liquid whose cyclic compound which has the said carboxyl group or its salt is a 1,2,4-triazole compound or a tetrazole compound . A removal solution for removing at least one of a resist and an etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent,
The cyclic compound having the carboxyl group or a salt thereof is a compound represented by the following formula (1) or (2):
The removal liquid whose said organic solvent is a sulfoxide compound, and content is 90 mass% or more .

In the formulas (1) and (2), R ¹¹ , R ¹² , R ²¹ and R ²² are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, carboxyl group or its It represents a group containing a salt or an amino group or a group containing a salt thereof. R ^N represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group ,, an aryl group, an aralkyl group. Here, R ¹¹ and R ¹² , R ¹² and R ^N , R ²² and ^RN may be connected to each other to form a ring.
In the formula ^(1), one of R ^{11, R 12} and ^{R N} is a group containing a carboxyl group or a salt thereof, wherein ^(2), one of R ^{21, R 22} and ^{R N} are , A group containing a carboxyl group or a salt thereof. A removal solution for removing at least one of a resist and an etching residue,
Containing a cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent,
A removal liquid in which the quaternary ammonium compound is a mixture of tetramethylammonium hydroxide and tetrabutylammonium hydroxide . A removal solution for removing at least one of a resist and an etching residue,
A cyclic compound having a carboxyl group or a salt thereof, a quaternary ammonium compound, and an organic solvent, and
A removal solution containing an alkoxysilane compound and water. Removing solution according to claim 3 or 4 before Symbol cyclic compound is an aromatic heterocyclic compound. Before SL cyclic compound tetrazol-5-acetic acid, benzotriazole-5-carboxylic acid, imidazole-4,5-dicarboxylic acid according to claim 5 or 3-amino-1,2,4-triazole-5-carboxylic acid, The removing liquid described in 1. Before SL quaternary ammonium compound is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, or claim 1 which is a combination of both, 2 or removing solution according to any one of 4. Before Symbol claim 1 the organic solvent is a polar aprotic organic solvent, 3 or removing solution according to any one of 4. Removing solution according to any one of claims 1-4 before Symbol organic solvent is dimethyl sulfoxide. Before Symbol claim 1 the content of the organic solvent is 99.5% by mass or less to 70 wt%, 3 or removing solution according to any one of 4. The removal liquid according to any one of claims 1 to 3 , comprising an alkoxysilane compound. The removal liquid according to any one of claims 1 to 3 , comprising water. A removal solution for removing at least one of a resist and an etching residue,
A removal solution containing dimethyl sulfoxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide. Before SL dimethyl sulfoxide 80 wt% to 99 wt% or less, prior SL-removing solution according to claim 13 containing less than 10 wt% 0.1 wt% tetramethylammonium hydroxide and tetrabutylammonium hydroxide in total . The removal liquid according to claim 13 or 14 , which contains water, and the content of the water is 0.1 mass% or more and 10 mass% or less. The removal liquid according to any one of claims 13 to 15 , wherein a value obtained by dividing the content of tetrabutylammonium hydroxide by the content of tetramethylammonium hydroxide is 5 or more. Removing solution according to any one of claims 1-16 before Symbol resist is a permanent film made of resin. Removing solution according to any one of claims 1-16 before Symbol resist is a resist for creating TSV. A removal method in which a removing liquid is applied to at least one of a resist and an etching residue to remove at least one of the resist and the etching residue,
Before Symbol removal solution, removing method is removing solution according to any one of claims 1 to 16. Before Symbol resist, an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and method for removing of claim 19 which is a cured product of the colored curable resin composition containing a coloring agent. The removal method according to claim 19 or 20 , wherein the removing liquid is applied to the resist at 40 ° C or higher and 100 ° C or lower. Through the method of removing according to any one of claims 19-21, a method of manufacturing a semiconductor substrate product for manufacturing a semiconductor substrate product.

Images