JP2006191002A - Remover composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a remover composition, low in an environmental load and excellent in removing the residue of resist generated after ashing and metal oxide products coming from the metal wirings (aluminum, copper and titanium based oxide products, for example) and especially prominent for removing aluminum based oxide products while being excellent in anticorrosive property with respect to metal wirings (especially metal wirings containing aluminum) even under cleaning conditions at low temperatures within a short period of time. <P>SOLUTION: The remover composition employed for cleaning a semiconductor substrate or a semiconductor element contains (1) 65 wt% or more of water and has (2) pH of more than 2 or more and 6 or less at 20°C, while containing (3) (I) at least one kind, selected from a group consisting of saccharide, an amino acid compound, an organic acid salt and an inorganic acid salt, and 0.01-1 wt.% of ammonium silicofluoride, or (II) an organic phosphonic acid and a compound containing fluorine. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resist residue remaining after removing a resist used in a step of forming a semiconductor element on a semiconductor substrate such as a silicon wafer by ashing and a metal oxidation product derived from metal wiring (hereinafter referred to as resist residue and metal wiring). A release agent composition used for peeling off the metal oxidation products derived from the substrate (sometimes referred to as an ashing residue), and a semiconductor substrate or semiconductor including a step of cleaning a semiconductor substrate or semiconductor element using the release agent composition The present invention relates to a method for manufacturing an element.

  In manufacturing a semiconductor element on a semiconductor substrate such as a silicon wafer, a thin film is formed by a method such as sputtering, and a predetermined pattern is formed on the thin film by lithography using a resist. Using this as an etching resist, the thin film in the lower layer is selectively removed by etching to form wirings, via holes, etc., and then the resist is removed by ashing. These series of steps are repeated to manufacture a semiconductor device product.

  Residues generated after the above-described etching or ashing can cause defects such as poor contact, and therefore require a high degree of peeling.

Conventionally, various cleaning liquids containing a fluorine-containing compound have been proposed (see, for example, Patent Documents 1 to 4) because they are effective for peeling off such residues.
Japanese Patent Laid-Open No. 9-279189 Japanese Patent Laid-Open No. 11-67632 JP 2004-94203 A JP 2003-68699 A

  The present invention has a low environmental impact, and even under low-temperature and short-time cleaning conditions, resist residues and metal oxide products derived from metal wiring (for example, aluminum, copper and titanium-based oxidation products) generated after ashing. In particular, a release agent composition having excellent peelability for aluminum-based oxidation products and excellent corrosion resistance to metal wiring (particularly metal wiring containing aluminum), and cleaning a semiconductor substrate or a semiconductor element using the composition It is an object of the present invention to provide a method for manufacturing a semiconductor substrate or a semiconductor element including the step of:

That is, the gist of the present invention is as follows.
[1] A release agent composition used for cleaning a semiconductor substrate or a semiconductor element,
(1) The release agent composition contains 65% by weight or more of water,
(2) The release agent composition has a pH of 2 or more and 6 or less at 20 ° C.,
(3) The release agent composition is
(I) containing at least one selected from the group consisting of sugars, amino acid compounds, organic acid salts and inorganic acid salts and 0.01 to 1% by weight of ammonium silicofluoride, or (II) containing organic phosphonic acids and fluorine-containing compounds It is related with the manufacturing method of a semiconductor substrate or a semiconductor element including the process of wash | cleaning a semiconductor substrate or a semiconductor element using the peeling agent composition to perform and [2] said release agent composition of said [1].

  According to the present invention, a resist residue and a metal oxidation product (for example, aluminum, copper and titanium-based oxidation products) generated after ashing, particularly an aluminum-based material, which have a low environmental load and are washed at low temperature for a short time. A release agent composition that is excellent in the releasability of the oxidation product and has excellent corrosion resistance to metal wiring (particularly metal wiring containing aluminum), and a step of cleaning a semiconductor substrate or a semiconductor element using the composition A method for manufacturing a semiconductor substrate or a semiconductor element can be provided.

  The conventional cleaning agents containing a fluorine-containing compound disclosed in Patent Documents 1 to 3 have a low moisture content in order to suppress corrosion on metal wiring. However, if a large amount of water is used in the rinsing process or the like, the metal wiring is corroded. Therefore, it is necessary to perform rinsing using a solvent such as isopropanol in order to suppress corrosion on the metal wiring, and in recent years, demands for environmental compatibility (workability, wastewater treatment property, etc.) are increasing.

  On the other hand, a system containing a fluorine-containing compound and having a large water content, that is, an aqueous detergent has been proposed (for example, Patent Document 4).

  However, conventional water-based cleaning agents containing fluorine-containing compounds are difficult to adjust the peelability and anticorrosion properties, especially in semiconductor devices with fine wiring widths and single wafer cleaning methods described below. It has been found that a product with sufficient performance has not been proposed in response to a request for a cleaning process in a short time at a low temperature from the viewpoint of improving the efficiency of the cleaning process.

  The recent manufacture of semiconductor devices tends to produce a variety of products in small quantities. For this reason, the diameter of the silicon wafer is increased, and the number of semiconductor elements obtained by one manufacturing is increased to reduce the cost.

  However, the batch-type cleaning method (a method of cleaning about 25 silicon wafers at a time) that has been conventionally used for cleaning semiconductor substrates or semiconductor elements is difficult to handle high-mix low-volume production. Increasing the size of the transport equipment accompanying the increase in diameter has become a new issue.

  In order to solve such a problem, a single-wafer cleaning method (a method of cleaning silicon wafers one by one) is increasingly used in cleaning semiconductor substrates or semiconductor elements. However, since the single wafer cleaning method cleans silicon wafers one by one, how to maintain and improve production efficiency is a problem.

  As one of the means to maintain and improve production efficiency in single wafer cleaning method, while maintaining sufficient cleaning performance, lower cleaning temperature than batch cleaning method and further shortening cleaning time Is mentioned.

  Therefore, in order to maintain and improve the production efficiency, it is preferable that the single wafer cleaning method can sufficiently remove the ashing residue even under cleaning conditions at a low temperature and in a short time as compared with the batch cleaning method.

  However, designing the releasability under low temperature and short time cleaning conditions as in the single wafer cleaning method has not been made in the past, and the techniques specifically disclosed in the documents 1 to 4 have been introduced. It has been found that the above-mentioned problem cannot be solved by just doing.

  Accordingly, the present inventors have found that, by combining a fluorine-containing compound such as ammonium silicofluoride with a specific agent, extremely excellent peelability and corrosion resistance are expressed even in an aqueous system, and the present invention is completed. It came.

The release agent composition of the present invention is a release agent composition used for cleaning a semiconductor substrate or a semiconductor element,
(1) The release agent composition contains 65% by weight or more of water,
(2) The release agent composition has a pH of 2 or more and 6 or less at 20 ° C.,
(3) The release agent composition is
(I) containing at least one selected from the group consisting of sugars, amino acid compounds, organic acid salts and inorganic acid salts and 0.01 to 1% by weight of ammonium silicofluoride, or (II) containing organic phosphonic acids and fluorine-containing compounds One feature is to do.
Here, the release agent composition of the present invention containing (I) is the release agent composition of embodiment 1, and the release agent composition of the present invention containing (II) is the release agent composition of embodiment 2.

(Release composition of embodiment 1)
The release agent composition of Embodiment 1 of the present invention will be described below.

"water"
Examples of the water in the release agent composition of Embodiment 1 include ultrapure water, pure water, ion exchange water, distilled water, and the like. Ultrapure water, pure water, and ion exchange water are preferable, and ultrapure water is preferable. Water and pure water are more preferable, and ultrapure water is more preferable. Pure water and ultrapure water refer to those obtained by passing tap water through activated carbon, subjecting it to ion exchange treatment, and further distilling it, irradiating a predetermined ultraviolet germicidal lamp as necessary, or passing it through a filter. For example, the electrical conductivity at 25 ° C. is often 1 μS / cm or less for pure water and 0.1 μS / cm or less for ultrapure water. The water content is 65% by weight or more, preferably 65 to 99.94% by weight, preferably 70 to 99.94% by weight in the release agent composition from the viewpoint of chemical stability, workability, and environmental properties such as waste liquid treatment. More preferably, 80 to 99.94% by weight is further preferable, and 90 to 99.94% by weight is even more preferable.

<Ammonium silicofluoride>
The content of ammonium silicofluoride is 0.01 to 1% by weight in the release agent composition from the viewpoint of compatibility between peelability to ashing residue at low temperature and short time and corrosion resistance to metal wiring during water rinsing and product stability. 0.01 to 0.5% by weight is more preferable, 0.01 to 0.3% by weight is further preferable, and 0.01 to 0.2% by weight is particularly preferable.

  The release agent composition of Embodiment 1 also contains at least one selected from the group consisting of sugars, amino acid compounds, organic acid salts, and inorganic acid salts. The total content of at least one selected from the group consisting of saccharides, amino acid compounds, organic acid salts, and inorganic acid salts is peelable from the viewpoint of maintaining releasability against ashing residues and improving corrosion resistance against metal wiring. In the agent composition, it is preferable not to exceed 30% by weight, more preferably not to exceed 20% by weight, even more preferably not to exceed 10% by weight, and still more preferably not to exceed 5% by weight.

<Sugar>
The saccharide in the release agent composition of aspect 1 is at least one selected from the group consisting of pentoses such as xylose, pentose sugar alcohols such as xylitol, hexoses such as glucose, and hexose sugar alcohols such as sorbitol and mannitol. Preferably, at least one selected from the group consisting of xylitol, glucose, sorbitol and mannitol is more preferable. When contained in the release agent composition, the content of the saccharide is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, and further preferably 0.5 to 5% by weight in the release agent composition.

《Amino acid compound》
Examples of the amino acid compound in the release agent composition of Embodiment 1 include glycine, dihydroxyethyl glycine, alanine, glycylglycine, cysteine, glutamine and the like. When the content of the amino acid compound is contained in the release agent composition, the content of the release agent composition is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight, and still more preferably 0.05 to 1% by weight.

《Organic acid salt》
Examples of the organic acid salt in the release agent composition of Aspect 1 include an ammonium salt of an organic acid, and preferably an organic ammonium phosphonate, ammonium acetate, ammonium oxalate, ammonium citrate, ammonium gluconate, and sulfosuccinic acid. Ammonium. When the organic acid salt is contained in the release agent composition, the content of the release agent composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, and further preferably 0.5 to 5% by weight.

《Inorganic acid salt》
Examples of the inorganic acid salt in the release agent composition of Aspect 1 include ammonium salts of inorganic acids, and preferably ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium borate, and ammonium chloride. The content of the inorganic acid salt, when contained in the release agent composition, is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, and further preferably 0.5 to 5% by weight in the release agent composition.

  In the release agent composition of aspect 1, the total content of at least one selected from the group consisting of saccharides, amino acid compounds, organic acid salts and inorganic acid salts and ammonium silicofluoride is determined by the release property against ashing residues and metal From the viewpoint of coexistence with corrosion resistance to wiring, the upper limit of the release agent composition is preferably 31% by weight or less, more preferably 15.5% by weight or less, and further preferably 10.5% by weight or less. , 5.3% by weight or less, even more preferably 1.2% by weight or less, still more preferably 0.06% by weight or more, more preferably 0.11% by weight or more, From this viewpoint, it is preferably 0.06 to 31% by weight, more preferably 0.06 to 15.5% by weight, further preferably 0.06 to 10.5% by weight, and 0.11 to 5%. More preferably, it is .3% by weight, even more preferably 0.11 to 1.2% by weight.

  Further, the weight ratio of ammonium silicofluoride / (at least one selected from the group consisting of saccharides, amino acid compounds, organic acid salts and inorganic acid salts) is preferably 1/50 to 20/1, and preferably 1/20 to 20 / 1 is more preferable, 1/1/10 to 10/1 is more preferable, and 1/5 to 5/1 is still more preferable.

《Water-soluble organic solvent》
It is preferable that the release agent composition of Embodiment 1 further contains a water-soluble organic solvent from the viewpoint of enhancing the permeability to ashing residues, the wettability to the wafer and the water solubility, and improving the peelability. Examples of water-soluble organic solvents include γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, polyhydric alcohols such as ethylene glycol and propylene glycol, and glycol ethers such as ethylene glycol monobutyl ether and diethylene glycol monobutyl ether. Can be mentioned. Among these, ethylene glycol and diethylene glycol monobutyl ether are preferable, and diethylene glycol monobutyl ether is more preferable from the viewpoint of further increasing the permeability to ashing residues, the wettability to the wafer, and the water solubility.

  The content of the water-soluble organic solvent is preferably 1 to 10% by weight, preferably 1 to 5% by weight in the release agent composition from the viewpoint of imparting sufficient permeability and wettability without reducing product stability. More preferably, 1 to 3% by weight is further preferable, and 1 to 2% by weight is even more preferable.

"Oxidant"
It is preferable that the release agent composition of Embodiment 1 further contains an oxidizing agent from the viewpoint of improving the release property against the ashing residue derived from titanium nitride. Examples of the oxidizing agent include inorganic peroxides such as hydrogen peroxide, ozone, hypochlorous acid, and perchloric acid. Among these, hydrogen peroxide is preferable from the viewpoint of further improving the peelability of ashing residues derived from titanium nitride.

  The content of the oxidizing agent is preferably 0.5 to 5% by weight, more preferably 0.5 to 3% by weight, and more preferably 1 to 2% by weight in the release agent composition from the viewpoint of obtaining sufficient peelability for ashing residues derived from titanium nitride. Is more preferable.

<Ammonium fluoride>
The release agent composition of Embodiment 1 may further contain ammonium fluoride from the viewpoint of improving the peelability for the ashing residue derived from the interlayer film. The content of ammonium fluoride is preferably 0.01 to 1% by weight and more preferably 0.1 to 1% by weight in the release agent composition from the viewpoint of obtaining sufficient peelability from the ashing residue derived from the interlayer film.

  In addition, the release agent composition of Embodiment 1 may contain an organic phosphonic acid from the viewpoint of exhibiting excellent anticorrosive properties against metal wiring under a wide range of use conditions such as temperature and time. The content of the organic phosphonic acid in the release agent composition is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight, further preferably 0.1 to 3% by weight, still more preferably 0.1 to 1% by weight, Even more preferred is 0.1-0.5 wt%. Specific examples of the organic phosphonic acid include organic phosphonic acids that can be used in the release agent composition of Aspect 2 described later.

  In addition, the release agent composition of aspect 1 includes ammonium silicofluoride and ammonium fluoride from the viewpoint of compatibility between releasability against ashing residues at low temperature and short time and anticorrosion against metal wiring during water rinsing, and product stability. Other fluorine-containing compounds may be included. The content of the fluorine-containing compound in the release agent composition is preferably 0.01 to 1% by weight, more preferably 0.01 to 0.5% by weight, further preferably 0.01 to 0.3% by weight, and still more preferably 0.01 to 0.2% by weight. . Specific examples of the fluorine-containing compound include hydrofluoric acid, ammonium hexafluorophosphate, alkylamine hydrofluoride, alkanolamine hydrofluoride, and tetraalkylammonium fluoride.

<Surfactant>
The release agent composition of aspect 1 may further contain a surfactant as long as the effects of the present invention are not impaired. Surfactants include anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, dialkylsulfosuccinic acids, alkylamine acetates, quaternary ammonium salts, and the like. Nonionics such as cationic surfactants, amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene ether Surfactants and the like.

  The content of the surfactant is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and further preferably 0.5 to 3% by weight in the release agent composition from the viewpoint of improving the peelability to ashing residues. .

<PH>
The pH at 20 ° C. of the release agent composition of Embodiment 1 is preferably 2 or more and 6 or less, more preferably 2 or more and less than 6 from the viewpoint of coexistence of releasability with respect to ashing residues at a low temperature for a short time and corrosion resistance with respect to metal wiring. Preferably, it is 2 or more and 5.7 or less. The pH can be adjusted, for example, by adding organic acids such as acetic acid and oxalic acid, inorganic acids such as sulfuric acid and nitric acid, amines such as amino alcohol and alkylamine, ammonia and the like. The pH at 20 ° C. can be measured by a method known in the art.

<Preparation method>
The release agent composition of aspect 1 is produced by mixing the water with at least one selected from the group consisting of saccharides, amino acid compounds, organic acid salts and inorganic acid salts and ammonium silicofluoride by a known method. be able to. The thus obtained release agent composition of the present invention can not only substantially remove the ashing residue even by low-temperature and short-time cleaning such as single wafer cleaning, but also contains metal wiring, particularly aluminum. Excellent corrosion resistance against metal wiring.

[The Release Agent Composition of Aspect 2]
The release agent composition of aspect 2 of the present invention will be described below.

"water"
The water in the release agent composition of aspect 2 may be the same as that used for the release agent composition of aspect 1. The content of water is 65% by weight or more, preferably 65 to 99.89% by weight, and preferably 70 to 99.89% by weight in the release agent composition from the viewpoints of chemical stability, workability and environmental performance such as waste liquid treatment. More preferably, 85 to 99.89% by weight is still more preferable, and 90 to 99.89% by weight is even more preferable.

<Fluorine-containing compound>
In the release agent composition of aspect 2, the fluorine-containing compound has an action of dissolving the ashing residue in a short time at a low temperature. Examples of the fluorine-containing compound include hydrofluoric acid, ammonium silicofluoride, ammonium fluoride, ammonium hexafluorophosphate, alkylamine hydrofluoride, alkanolamine hydrofluoride, and tetraalkylammonium fluoride. be able to. Among these, ammonium silicofluoride and ammonium fluoride are preferable from the viewpoint of coexistence of releasability to ashing residues at low temperature and short time and corrosion resistance to metal wiring. These fluorine-containing compounds can be used alone or in admixture of two or more.

  The content of the fluorine-containing compound is 0.01 to 1% by weight in the release agent composition from the viewpoints of coexistence of releasability to ashing residues at low temperature and short time and anticorrosion to metal wiring during water rinsing and product stability. Is preferred, 0.01 to 0.5% by weight is more preferred, 0.01 to 0.3% by weight is more preferred, and 0.01 to 0.2% by weight is even more preferred.

《Organic phosphonic acid》
In the release agent composition of aspect 2, the organic phosphonic acid has a peelability improving action against ashing residues and an anticorrosive action against metal wiring. Among them, when used in combination with ammonium silicofluoride, it exhibits an excellent anticorrosive action on metal wiring, and when used in combination with ammonium fluoride, it has an excellent action of improving peelability against ashing residues. Examples of the organic phosphonic acid include methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, Hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediamine Examples thereof include bis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and cyclohexanediaminetetra (methylenephosphonic acid). Of these, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediaminetetra (methylenephosphonic acid) are preferable from the viewpoint of having excellent anticorrosive properties for metal wiring. These organic phosphonic acids can be used alone or in admixture of two or more.

  The content of the organic phosphonic acid is preferably 0.05 to 10% by weight in the release agent composition from the viewpoint of exhibiting excellent anticorrosive properties against metal wiring under a wide range of use conditions (temperature, time, etc.). -5% by weight is more preferred, 0.1-3% by weight is more preferred, 0.1-1% by weight is even more preferred, and 0.1-0.5% by weight is even more preferred.

  In the release agent composition of Aspect 2, the total content of the fluorine-containing compound and the organic phosphonic acid has an upper limit in the release agent composition from the viewpoint of coexistence of release properties for ashing residues and anticorrosive properties for metal wiring. It is preferably 11% by weight or less, more preferably 5.5% by weight or less, further preferably 3.3% by weight or less, still more preferably 1.2% by weight or less, and the lower limit is 0.06% by weight or more. It is preferably 0.11% by weight or more, more preferably 0.06 to 11% by weight, more preferably 0.06 to 5.5% by weight, more preferably 0.11 to 3.3% by weight from a comprehensive viewpoint. % Is more preferable, and 0.11 to 1.2% by weight is even more preferable.

  The weight ratio of fluorine-containing compound / organic phosphonic acid is preferably 1/20 to 20/1, more preferably 1/110 to 10/1, and further preferably 1/5 to 5/1.

《Water-soluble organic solvent》
It is preferable that the release agent composition of aspect 2 further contains a water-soluble organic solvent from the viewpoint of improving the permeability to ashing residues, the wettability to the wafer and the water solubility, and improving the peelability. The water-soluble organic solvent and the content thereof may be the same as those used for the release agent composition of Embodiment 1 and the content thereof.

"Oxidant"
It is preferable that the release agent composition of aspect 2 further contains an oxidizing agent from the viewpoint of improving the release property against the ashing residue derived from titanium nitride. As an oxidizing agent and its content, what is necessary is just the same as what is used about the peeling agent composition of aspect 1, and its content.

<Surfactant>
The release agent composition of aspect 2 may further contain a surfactant as long as the effects of the present invention are not impaired. The surfactant and the content thereof may be the same as those used for the release agent composition of Embodiment 1 and the content thereof.

  The release agent composition of aspect 2 comprises a saccharide, an amino acid compound, an organic acid salt and an inorganic acid salt from the viewpoint of exhibiting excellent anticorrosive properties against metal wiring under a wide range of use conditions such as temperature and time. At least one selected from the group may be included. The content of the component in the release agent composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, still more preferably 0.5 to 5% by weight, and an amino acid compound. Is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight, still more preferably 0.05 to 1% by weight, and the organic acid salt is preferably 0.1 to 30% by weight, and 0.5 to 15% by weight. Is more preferable, 0.5 to 5% by weight is further preferable, and the inorganic acid salt is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, and further preferably 0.5 to 5% by weight. The total content of at least one selected from the group consisting of saccharides, amino acid compounds, organic acid salts, and inorganic acid salts is peelable from the viewpoint of maintaining releasability against ashing residues and improving corrosion resistance against metal wiring. In the agent composition, it is preferable not to exceed 30% by weight, more preferably not to exceed 20% by weight, even more preferably not to exceed 10% by weight, and still more preferably not to exceed 5% by weight. Specific examples of the saccharide, amino acid compound, organic acid salt or inorganic acid salt include saccharide, amino acid compound, organic acid salt or inorganic acid salt that can be used in the release agent composition of the first aspect.

<PH>
The pH at 20 ° C. of the release agent composition of aspect 2 is also the same as that of the release agent composition of aspect 1 from the viewpoint of coexistence of releasability against ashing residues at a low temperature for a short time and corrosion resistance to metal wiring. The adjustment method is also as described above.

<Preparation method>
The release agent composition of aspect 2 can be produced by mixing the organic phosphonic acid, the fluorine-containing compound and the like with the water by a known method. The release agent composition of the present invention thus obtained can not only substantially peel off ashing residues, particularly aluminum-based oxidation products, even with low temperature and short time cleaning such as single wafer cleaning. It has excellent anticorrosive properties for metal wiring, particularly metal wiring containing aluminum.

〔Production method〕
The present invention also provides a method for producing a semiconductor substrate or a semiconductor element, comprising the step of cleaning the semiconductor substrate or the semiconductor element using the release agent composition of the aspect 1 or the aspect 2. For the cleaning process, an immersion cleaning method, a rocking cleaning method, a paddle cleaning method, a cleaning method using air or liquid spray, a cleaning method using ultrasonic waves, and the like can be applied. As a cleaning method of a semiconductor substrate or a semiconductor element, typically, a batch type cleaning method for cleaning about 25 silicon wafers at a time, a single wafer cleaning method for cleaning silicon wafers one by one, and the like, The release agent composition of the present invention is particularly preferably used for cleaning by a single wafer cleaning method. On the other hand, when the release agent composition of the present invention is used for cleaning in a batch type cleaning method, sufficient releasability can be obtained at a low temperature in a short time, so that long time cleaning as in the prior art is unnecessary, energy saving and production There is an effect of improving efficiency.

  Although a good peeling property can be obtained even at a low temperature of about 20 ° C., the cleaning temperature is preferably 20 to 50 ° C. from the viewpoints of peeling properties against ashing residues, corrosion resistance to metal wiring, safety and operability. 20 to 40 ° C. is more preferable.

  The cleaning time is preferably 10 seconds to 5 minutes, more preferably 0.5 to 3 minutes, further preferably 0.5 to 2 minutes, from the viewpoints of peelability to ashing residues, corrosion resistance to metal wiring, safety and operability. Even more preferred is ˜1 minute.

  In the rinsing after washing, rinsing with water is possible. Conventional amine-based release agents such as ammonium fluoride-based release agents and hydroxylamine are solvent-based release agents, so they are difficult to rinse with water, and when mixed with water, metal wiring, especially metal wiring containing aluminum In general, a method of rinsing with a solvent such as isopropanol has been used. However, the release agent composition of the present invention is selected from the group consisting of saccharides, amino acid compounds, organic acid salts and inorganic acid salts that have an anticorrosive action on metal wirings, particularly metal wirings containing aluminum. In view of the fact that it contains at least one kind of organic phosphonic acid, the metal wiring, particularly the metal wiring containing aluminum, has high resistance to corrosion even when water is excessive. Thereby, in the washing | cleaning process included in the manufacturing method of this invention, water rinse becomes possible and the effect that the load with respect to an environment is very small and there exists an effect is show | played.

  The semiconductor substrate or semiconductor element manufactured in this manner has almost no ashing residue, and corrosion of metal wiring, particularly metal wiring containing aluminum is extremely small.

  The release agent composition according to aspect 1 or aspect 2 of the present invention is suitable for manufacturing a semiconductor substrate or semiconductor element having a metal wiring containing aluminum, copper, tungsten, titanium, etc., and particularly aluminum, copper, and titanium. It is suitable for the production of a semiconductor substrate or a semiconductor element having a metal wiring containing aluminum because it has excellent releasability with respect to the oxidation product of the system and excellent corrosion resistance to metal wiring containing aluminum. Especially, since the release agent composition of aspect 2 is further excellent in the corrosion resistance with respect to the metal wiring containing aluminum, it is more suitable for manufacture of the semiconductor substrate or semiconductor element which has the metal wiring containing aluminum.

  From the viewpoint of excellent corrosion resistance for metal wiring, particularly metal wiring containing aluminum, the release agent composition of Embodiment 1 or Embodiment 2 of the present invention preferably has a metal wiring width of preferably 0.25 μm or less, more preferably 0.18 μm or less. More preferably, it can also be suitably used for the production of a semiconductor substrate or a semiconductor element of 0.13 μm or less.

1. Preparation of evaluation wafer Uncleaned patterned wafer A (Al wiring) having an aluminum (Al) wiring with a wiring width of 0.25 μm having the following structure and an uncleaned patterned wafer B with a via hole having a diameter of 0.25 μm ( The wafer for evaluation was divided into 1 cm square.
<Structure of patterned wafer A>
TiN / Al-Cu / TiN / SiO _{2 /} underlayer <structure of patterned wafer B>
SiO _{2 (insulating layer) /} TiN (barrier layer) / Al—Cu (conductive layer) / TiN / underlayer The barrier layer is etched in the via hole.

2. Preparation of Release Agent Composition Each component was added and mixed so as to have the composition shown in Tables 1 and 2 (numerical value is% by weight), and Examples I-1 to I-10 and II-1 to II-9 and comparison The release agent compositions of Examples I-1 to I-5 were prepared respectively.

3. Cleaning test In 30 ml of the release agent composition prepared in 1. The wafer for evaluation prepared in the above was immersed at 25 ° C. for 1 minute. Thereafter, the evaluation wafer was taken out of the release agent composition, and the evaluation wafer was immersed in 30 ml of ultrapure water at 25 ° C. for 30 seconds. This immersion in ultrapure water was repeated twice, and then the evaluation wafer was dried by blowing nitrogen gas to obtain an observation sample.

[Peelability and corrosion resistance]
Using an FE-SEM (scanning electron microscope), observe the observed sample under a magnification of 50000 to 100000 times, and the Al wiring and ashing residue of the wafer for evaluation and the ashing residue in the via hole before being subjected to the cleaning test In comparison, peelability and corrosion resistance were evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2. In addition, an acceptable product shall be (double-circle) or (circle) in both peelability and corrosion resistance.
〔Evaluation criteria〕
(Removability against ashing residue)
◎: Residual residue is not confirmed at all ○: Residue partially remains Δ: Residue remains mostly ×: Residue cannot be removed (corrosion resistance against Al wiring)
◎: Al wiring corrosion is not confirmed at all. ○: Al wiring corrosion is partially generated. △: Al wiring corrosion is mostly generated. ×: Al wiring corrosion is generated as a whole.

  From the results of Tables 1 and 2, the release agent compositions obtained in Examples I-1 to I-10 and II-1 to II-9 are all obtained in Comparative Examples I-1 to I-5. It can be seen that, compared to the above, it has excellent peelability against ashing residue and corrosion resistance against Al wiring even at low temperature and short time.

  The release agent composition of the present invention has excellent releasability at a low temperature in a short time with respect to a resist residue generated during the formation of a semiconductor element and a metal oxidation product derived from metal wiring, particularly an aluminum-based oxidation product, and Excellent corrosion resistance to metal wiring, particularly metal wiring containing aluminum. Therefore, by using the release agent composition of the present invention, it is possible to meet the recent demands for high-mix low-volume production of semiconductor devices, enabling high-speed and high-integration of semiconductor devices, and high-quality LCDs and memories. An effect that an electronic component such as a CPU can be manufactured is exhibited.

Claims (6)

A release agent composition used for cleaning a semiconductor substrate or a semiconductor element,
(1) The release agent composition contains 65% by weight or more of water,
(2) The release agent composition has a pH of 2 or more and 6 or less at 20 ° C.,
(3) The release agent composition is
(I) containing at least one selected from the group consisting of sugars, amino acid compounds, organic acid salts and inorganic acid salts and 0.01 to 1% by weight of ammonium silicofluoride, or (II) containing organic phosphonic acids and fluorine-containing compounds Release agent composition.   2. The release agent composition according to claim 1, further comprising a water-soluble organic solvent.   The stripping composition according to claim 1 or 2, further comprising an oxidizing agent.   The release agent composition according to any one of claims 1 to 3, which is used for cleaning a semiconductor substrate or a semiconductor element having a metal wiring containing aluminum.   The manufacturing method of a semiconductor substrate or a semiconductor element including the process of wash | cleaning a semiconductor substrate or a semiconductor element using the peeling agent composition in any one of Claims 1-4.   The manufacturing method according to claim 5, wherein the step of cleaning the semiconductor substrate or the semiconductor element is performed by a single wafer cleaning method.