JP2009206301A - Rinse liquid, and processing method for base - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rinse liquid which has high safety, can suppress corrosion of metal wiring, and is suitable for recycling use, and to provide a processing method for a base which uses the rinse liquid. <P>SOLUTION: The rinse liquid containing an anticorrosive and water is used to clean the base having the metal wiring after resist film peeling. The content of the anticorrosive is preferably 1 to 30% by mass and the content of the water is preferably 20 to 99% by mass. The rinse liquid may contain a water-soluble organic solvent and is thereby more suitable for recycling use. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a rinsing liquid used for cleaning a substrate having a metal wiring after peeling a resist film, and a substrate processing method using the rinsing solution.

  For semiconductor elements such as IC and LSI, a resist composition is formed on a conductive metal film or insulating film formed on a substrate to form a resist film, and this resist film is selectively exposed and developed to form a resist film. The conductive metal film and the insulating film are selectively etched using the resist pattern as a mask to form a metal wiring and the like, and then the unnecessary resist film is removed with a stripping solution. The stripping solution adhering to the substrate after removing the resist film is usually washed away with a rinse solution.

Conventionally, isopropyl alcohol is generally used as a rinsing liquid for removing the stripping liquid in order to suppress corrosion of metal wiring (see Patent Document 1, etc.). For the purpose of removing the alkaline stripping solution while suppressing the corrosion of the metal wiring, a rinsing solution in which carbon dioxide gas is introduced into water and a rinsing solution in which organic acid / inorganic acid is contained in water or alcohol are also proposed. (Refer to patent document 2 etc.).
JP 2002-151394 A JP 7-37846 A

  However, isopropyl alcohol is volatile and highly flammable, and has a problem in terms of safety. In addition, a rinsing liquid in which carbon dioxide gas is introduced into water is not suitable for recycle use (recycling use), and a rinsing liquid containing an organic acid / inorganic acid in water or alcohol can also be treated with a stripping solution. When neutralized, corrosion of metal wiring cannot be suppressed.

  The present invention has been made in view of the above problems, and uses a rinsing liquid that is highly safe, can suppress corrosion of metal wiring, and is also suitable for recirculation use, and the rinsing liquid. An object is to provide a method for treating a substrate.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, it has been found that the above-mentioned problems can be solved by using a specific rinsing liquid, and the present invention has been completed. Specifically, the present invention provides the following.

  A first aspect of the present invention is a rinsing liquid used for cleaning a substrate having a metal wiring after stripping a resist film, which contains an anticorrosive and water.

  A second aspect of the present invention is characterized in that a resist film formed on a substrate having metal wiring is stripped with a stripping solution, and the substrate after stripping the resist film is washed with a rinse solution according to the present invention. A substrate processing method.

  According to the present invention, it is possible to provide a rinsing liquid that is highly safe, can suppress corrosion of metal wiring, and is also suitable for use in circulation regeneration, and a substrate processing method using the rinsing liquid. .

[Rinse solution]
The rinse liquid according to the present invention contains at least an anticorrosive and water, and is used for cleaning a substrate having a metal wiring after the resist film is peeled off. Hereinafter, each component contained in the rinse liquid will be described.

<Anticorrosive>
The rinse liquid according to the present invention contains an anticorrosive agent. By containing the anticorrosive agent, corrosion of the metal wiring can be effectively prevented when cleaning the substrate having the metal wiring after the resist film is peeled off. As such an anticorrosive agent, it is preferable to use at least one selected from sugar alcohol compounds and aromatic hydroxy compounds.

  Examples of the sugar alcohol compound include D-sorbitol, xylitol, arabitol, mannitol and the like. Among these, D-sorbitol and xylitol are preferable. A sugar alcohol compound may use only 1 type and may use 2 or more types together.

  As aromatic hydroxy compounds, phenol, cresol, xylenol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl Alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4- Examples include dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid. Among these, pyrocatechol is preferable. An aromatic hydroxy compound may use only 1 type and may use 2 or more types together.

  The content of the anticorrosive is preferably 1 to 30% by mass and more preferably 5 to 20% by mass in the rinse solution. By setting the content of the anticorrosive to the above range, excellent anticorrosion performance can be obtained. Other anticorrosive agents may be added, and a water-soluble anticorrosive agent can be preferably used.

<Water>
The rinse liquid according to the present invention contains water. The water content is preferably 20 to 99% by mass and more preferably 30 to 70% by mass in the rinse liquid. By setting the water content in the above range, excellent cleaning performance can be obtained.

<Water-soluble organic solvent>
The rinse liquid according to the present invention may contain a water-soluble organic solvent. By containing the water-soluble organic solvent, the resist film component contained in the stripping solution can be prevented from precipitating in the rinsing solution.
The water-soluble organic solvent is not particularly limited as long as it is miscible with water. Sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, and tetramethylene sulfone Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-methylpyrrolidone, N-ethylpyrrolidone, N-propyl Lactams such as pyrrolidone, N-hydroxymethylpyrrolidone, N-hydroxyethylpyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2- Imidazolidinones such as imidazolidinone; Polyhydric alcohols such as lenglycol, propylene glycol, glycerin; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether Ethers and the like can be used. Among these, glycol ethers are preferable. Only one type of water-soluble organic solvent may be used, or two or more types may be used in combination.

  When the water-soluble organic solvent is contained, the content thereof is preferably 50% by mass or less, more preferably 5 to 30% by mass in the rinse liquid. By setting the content of the water-soluble organic solvent in the above range, it is possible to effectively prevent the resist film component from being precipitated in the rinse liquid while maintaining the cleaning performance.

<Antimicrobial agent>
The rinse liquid according to the present invention may contain an antibacterial agent. By containing an antibacterial agent, generation | occurrence | production of bacteria etc. can be suppressed and a preservability can be improved.
The antibacterial agent is not limited to a conventionally known antibacterial agent, and any antibacterial agent can be used without particular limitation as long as it has an antibacterial action. For example, alkylamine oxides such as laurylamine oxide, octylamine oxide, mistyrylamine oxide, and tridecylamine oxide, and peracids such as performic acid, peracetic acid, and perpropionic acid can be used. Alkylamine oxide is particularly preferable because it has a surface active action and can improve cleaning performance. Further, as the peracid, peracetic acid is preferable.

  When the antibacterial agent is contained, the content thereof is preferably 5% by mass or less, and more preferably 0.01 to 3% by mass in the rinse liquid. By making content of an antibacterial agent into the said range, an antibacterial action can be obtained effectively, maintaining cleaning performance.

[Substrate treatment method]
The substrate processing method according to the present invention is a method in which a resist film formed on a substrate having a metal wiring is stripped with a stripping solution, and the substrate after the resist film is stripped is washed with a rinse solution according to the present invention.

  Examples of the metal wiring material formed on the substrate include aluminum (Al); aluminum alloys such as aluminum-silicon (Al-Si) and aluminum-silicon-copper (Al-Si-Cu). The rinsing liquid according to the present invention is particularly effective when an Al wiring is formed on the substrate.

The resist film formed on the substrate is not particularly limited, and may be either a negative type or a positive type, and may be either a chemical amplification type or a non-chemical amplification type.
Further, the stripping solution for stripping the resist film is not particularly limited, but an organic sulfonic acid-based stripping solution containing alkylbenzene sulfonic acid as a main component and an organic amine such as alkanolamine as a main component. Organic amine stripping solution, hydrofluoric acid stripping solution containing hydrofluoric acid as a main component, hydrofluoric acid stripping solution containing a salt of hydrofluoric acid and a base not containing metal ions as a main component Etc. The rinsing liquid according to the present invention is particularly effective when cleaning and removing a stripping solution containing an alkaline substance. Examples of the alkaline substance include organic amines such as alkanolamine.

  Any of a dipping method, a spray method, a shower method, a paddle method and the like can be used for cleaning the substrate with the rinse liquid.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

<Examples 1-4, Comparative Examples 1-3>
A glass substrate on which an aluminum film of about 300 μm is deposited is immersed in a stripping solution (trade name: ST-105, manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C. for 2 minutes, and then rinsed in each composition shown in Table 1. It was immersed for 10 minutes and further washed with running water with pure water. And the film reduction amount (corrosion amount) of the aluminum film was calculated | required by measuring the sheet resistance value (surface resistance value) before and behind the immersion treatment when using the rinse liquid of each composition. The results are shown in Table 1. In Table 1, the numbers in parentheses represent mass%.

  Moreover, in order to confirm the aging effect of the rinse solution, the glass substrate with aluminum film (2 × 4 cm) was immersed in a stripping solution (trade name: ST-105, manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C. for 2 minutes. Then, the step of immersing in 100 ml of the rinsing solution of each composition shown in Table 1 for 10 minutes was repeated every day. Ten glass substrates with aluminum films were prepared every day, and the same stripping solution and each rinsing solution were continuously used. Then, by measuring the sheet resistance value (surface resistance value) before and after the immersion treatment when using the rinse liquid of each composition, the amount of reduction (corrosion amount) of the aluminum film was obtained, and the anticorrosive efficacy period was obtained. .

Ｘｙｌ：キシリトール
ＩＰＡ：イソプロピルアルコール
ＢＤＧ：ジエチレングリコールモノブチルエーテル

Xyl: Xylitol IPA: Isopropyl alcohol BDG: Diethylene glycol monobutyl ether

  As can be seen from Table 1, when the rinsing liquids of Examples 1 to 4 were used for cleaning, corrosion of the aluminum film could be suppressed to the same extent as in Comparative Example 1 using isopropyl alcohol. . Moreover, since the anticorrosive efficacy period is as long as 5 days or more, it is considered that it is suitable for the recycling use. In addition, these rinse solutions are highly flammable because of their low flammability, and there are no problems with the Fire Service Law. On the other hand, the rinsing liquid of Comparative Example 1 is excellent in the corrosion resistance of the aluminum film and its effective period, but has high flammability and has a problem in the Fire Service Law. Further, it is considered that the rinsing liquid of Comparative Example 2 cannot suppress the corrosion of the metal wiring because the corrosion resistance of the aluminum film is low, and the rinsing liquid of Comparative Example 3 has an anticorrosive effect period of half a day for the aluminum film. It is considered to be unsuitable for recycle use because it is short as follows.

Claims (9)

A rinsing liquid used for cleaning a substrate having a metal wiring after peeling a resist film,
A rinse liquid characterized by containing an anticorrosive and water.   The rinsing solution according to claim 1, wherein the content of the anticorrosive is 1 to 30% by mass and the content of water is 20 to 99% by mass.   The rinse solution according to claim 1 or 2, wherein the anticorrosive is at least one selected from a sugar alcohol compound and an aromatic hydroxy compound.   Furthermore, the rinse liquid of any one of Claim 1 to 3 containing a water-soluble organic solvent.   The rinse liquid according to claim 4, wherein the content of the water-soluble organic solvent is 50% by mass or less.   Furthermore, the rinse liquid of any one of Claim 1 to 5 containing an antibacterial agent.   The rinse liquid according to claim 6, wherein the content of the antibacterial agent is 5% by mass or less.   8. A substrate comprising: a resist film formed on a substrate having metal wiring stripped with a stripping solution; and the substrate after stripping the resist film is washed with a rinsing solution according to any one of claims 1 to 7. Processing method.   9. The substrate processing method according to claim 8, wherein the metal wiring is aluminum wiring.