TWI522753B - Photoresist stripper composition and method of manufacturing electronic device - Google Patents

Description

Photoresist removal composition and method of manufacturing electronic component

The present invention relates to a photoresist removal composition, and more particularly to a photoresist removal composition containing an alcohol amine compound and a method of producing an electronic component using the photoresist removal composition for a lithography process.

Generally, the process of the semiconductor integrated circuit is basically performed by: forming a material layer on the substrate; coating the photoresist on the material layer; exposing and developing the photoresist to form a photoresist pattern; The photoresist pattern acts as a mask, and the material layer is etched to transfer a specific microcircuit pattern to the lower photoresist layer; finally, the photoresist layer is removed using an photoresist stripper.

For photoresist strippers, their high stripping capacity and low corrosivity are two basic requirements. The high stripping ability ensures that no photoresist material remains on the material layer after rinsing; while low corrosivity is to avoid damage to the underlying metal or dielectric material of the photoresist. In addition, photoresist strippers may additionally require high temperature stability, low volatility, storage stability, low toxicity, and the like.

The present invention provides a photoresist removal composition which can maintain low corrosion resistance to the underlying material of the photoresist while removing the photoresist. The present invention further provides a method of fabricating an electronic component using such a photoresist removal composition to remove photoresist on a substrate.

The photoresist removal composition of the present invention comprises an alcohol amine compound and a solvent in an amount of from 55 to 90% by weight based on the total of the photoresist removal composition. The solvent is represented by HO-X-OH wherein X is C ₁ -C ₄ alkylene, C ₂ -C ₄ extended alkenyl, >R _x -COOH or >R _y -OH, and R _x is C ₁ -C ₃ a hydrocarbon group, R _y is a C ₁ -C ₄ hydrocarbon group.

In one embodiment, the photoresist removal composition further comprises less than 30% by weight water, based on the total of the photoresist removal composition.

In one embodiment, the aforementioned photoresist removal composition further comprises a corrosion inhibitor.

In one embodiment, the alcohol amine compound comprises a primary alcohol amine.

In one embodiment, the primary alcohol amine is present in the photoresist removal composition in an amount of 40% by weight or more based on the total of the photoresist removal composition.

In one embodiment, the alkanolamine compound is present in an amount of from 65 to 75% by weight based on the total of the photoresist removal composition.

In one embodiment, the primary alcohol amine comprises ethanolamine, aminoethylethanolamine or a mixture thereof.

In one embodiment, the solvent is propylene glycol.

The method of manufacturing an electronic component of the present invention includes removing the photoresist formed on the element substrate using the aforementioned photoresist removal composition.

Based on the above, the present invention provides a photoresist removal composition and a method of applying the photoresist removal composition to the manufacture of electronic components. Containing 55 weights in the photoresist removal composition The amount of the alcoholamine compound is more than %, whereby the photoresist removal composition of the present invention has both excellent photoresist removal ability and low corrosion resistance.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, a particular numerical range is recited and is equivalent to the disclosure of any numerical value in the range of the value and the numerical range defined by any value in the numerical range, as the The smaller value range is the same. For example, the description of the range of "content of 10 to 80% by weight" is equivalent to the disclosure of the range of "20% by weight to 50% by weight", regardless of whether other values are listed in the specification.

Herein, if a group is not specifically indicated to be substituted, the group may represent a substituted or unsubstituted group. For example, "alkylene" can mean a substituted or unsubstituted alkylene group. Further, when a group crown is described by "C _X ", it means that the group has X carbon atoms.

A first embodiment of the present invention relates to a photoresist removal composition comprising an alkanolamine compound and a solvent in an amount of from 55% by weight to 90% by weight based on the total of the photoresist removal composition. When the photoresist is removed using the photoresist removal composition, the alcohol amine compound reacts with the photoresist material, and the reacted photoresist material is removed by the solvent. These two components will be separately described below.

The alcohol amine compound may be a primary alcohol amine, a secondary alcohol amine, a tertiary alcohol amine or any combination thereof; wherein the tertiary alcohol amine may be triethanolamine (TEA), dimethylethanolamine (DMEA), or Ethylethanolamine, methyldiethanolamine, N-methyldiethanolamine or 1-(2-hydroxyethyl)piperazine, but is not limited thereto; the secondary alcoholamine may be N - N-methylethanol amine, N-ethylethanolamine or diethanolamine; the primary alcohol amine may be monoethanolamine (MEA) or N-(2-aminoethyl)ethanolamine, AEEA) .

In one embodiment, the alcohol amine compound comprises a primary alcohol amine.

In one embodiment, the alcohol amine compound consists of a primary alcohol amine.

In one embodiment, the primary alcohol amine is present in an amount of 40% by weight or more, preferably 65% by weight to 75% by weight based on the total of the photoresist removal composition.

The solvent may be represented by the general formula "HO-X-OH"; X is a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ alkylene group, a >R _x -COOH or >R _y -OH, wherein R _x is C _{a 1-} C ₃ trivalent hydrocarbon group, and R _y is a C ₁ -C ₄ trivalent hydrocarbon group. For example, the solvent can be 1,2 propanediol, 1,3 propanediol, or a mixture thereof.

In principle, when the above-mentioned alcohol amine compound and solvent are contained in the photoresist removal composition, the effect of removing the photoresist while maintaining low corrosion resistance to the underlying material of the photoresist can be achieved. Of course, other ingredients may also be added to the photoresist removal composition to modulate or optimize the performance of the photoresist removal composition.

For example, when the photoresist removal composition contains a small amount of water, the rate of removal of the photoresist can be increased, and the rate of corrosion of the underlying material can also be reduced. However, it should be noted that if the water content is too high, the rate of removal of the photoresist will be reduced. In this regard, the photoresist removal composition may further comprise less than 30% by weight water, based on the total amount.

Further, the photoresist removal composition may also contain a corrosion inhibitor to further suppress corrosion of the underlying material of the photoresist. The corrosion inhibitor may include, but is not limited to, an organic carboxylic acid corrosion inhibitor, a sugar or sugar alcohol inhibitor, an azole inhibitor, or an organic phenolic inhibitor. An example of an organic carboxylic acid corrosion inhibitor is lactic acid. Examples of sugar or sugar alcohol inhibitors may be monosaccharides, polysaccharides or sugar alcohols. Monosaccharides such as C ₃ -C ₆ monosaccharides such as glyceraldehyde, threose, arabinose, xylose, ribose, ribulose, xylulose, glucose, mannose, galactose, tagatose, ar Loose sugar, altrose, gulose, idose, tarotose, sorbose, psicose, fructose. Polysaccharides such as sucrose, maltose, cellobiose, lactose, sucrose, kelp disaccharide, trimeric mannose, arabinic pentose, xylan, mannan, starch. Sugar alcohols such as threitol, butanol, adonitol, arabitol, xylitol, talitol, sorbitol, mannitol, iditol, galactitol. Examples of azole inhibitors are benzotriazole, methylbenzotriazole or 3-amino-1,2,4-triazole and the like. Examples of organic phenolic inhibitors are phthalic acid, pyrocatechol, benzopyridylamine, o-hydroxyaniline, 1,2-hydroxycyclohexane, citric acid and decanoic acid esters.

A second embodiment of the present invention relates to a method of manufacturing an electronic component, and also to an electronic component manufactured by the manufacturing method. The electronic component is not particularly limited, and an important point is that, in the manufacturing process, after the formation of a certain material layer, the photoresist removal composition of the first embodiment is used to remove the residual photoresist of the upper layer of the material layer. In one embodiment, the method is applicable to the case where the material layer contains copper, molybdenum, aluminum or an indium containing oxide.

<Example>

The examples are hereinafter described to more specifically describe the present invention. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.

In the following various examples and comparative examples, the inventors formulated various photoresist removal compositions according to the composition and content (% by weight) of Table 1, and tested these photoresist removals. The photoresist removal capabilities of the compositions and their rate of corrosion to different materials were summarized in Table 2. Among them, the evaluation criteria of the photoresist removal ability is: after cleaning the substrate with the photoresist removal composition, the substrate is observed by an optical microscope, and a significant photoresist residue is observed to be x at a magnification of 500 times; observed at a magnification of 500 times. The residue was judged to be Δ; a significant residual was not observed at 500 times magnification. In addition, the photoresist removal capability is tested under relatively stringent conditions, that is, when the test is performed, 2 or 4% by weight of the photoresist component is added to the photoresist removal composition (without photoresist). The total amount of the photoresist removal composition of the component was 100% by weight based on the performance of the photoresist removal composition when the photoresist was removed.

As for the measurement of the corrosion rate of the material, the glass substrate with the metal wiring (material Cu or Mo) was immersed in the photoresist removal composition for 20 minutes at a fixed temperature of 50 °C. The concentration of metal ions in the liquid to be tested was measured by ICP-MS method as a basis for comparison. Among them, Cu corrosion rate is less than 50 ppb / min; medium is between 50 and 80 ppb / min; greater than 80 ppb / min is poor.

In addition, the full abbreviations used in the table are detailed below.

Referring to Tables 1 and 2, the photoresist removal compositions of Comparative Examples 1 and 2 have an alkanolamine content of greater than or equal to 55% by weight, but the solvent used is diethylene glycol monobutyl ether or dimethyl carbonate, Consistent with the limitations of the general formula HO-X-OH (as defined above), the result is a poor ability to remove photoresist. Further, comparing Example 1 and Example 2, or Comparative Example 6 and Example 2, it is understood that if a small amount of water is added to the photoresist removal composition, the photoresist removal composition can be further inhibited against copper. Corrosion ability. However, it should also be noted that as the amount of water added gradually increases, the photoresist removal ability of the photoresist removal composition will gradually deteriorate. Referring to Tables 1 and 3, the content of water in the photoresist removal composition is known. When it reaches 30% by weight, the photoresist removal ability of the photoresist removal composition can no longer meet the demand.

Further, by observing Comparative Examples 3 to 6, it is understood that if the amount of the alcohol amine compound is less than 55% by weight, the corrosion resistance of the photoresist removal composition to copper will increase. This result is quite different from the teachings given by the prior art in the art. For example, Taiwan Patent Publication No. 201308031 describes "Comparative Examples 2 to 8 are samples in which the main component of the mixed solution is replaced with MEA (monoethanolamine). The MEA of the primary [alcohol] amine is highly corrosive, even if a considerable amount is added. BTA or pyrocatechol, vitamin C, and sorbitol, which are corrosion inhibitors, still cannot suppress the corrosive power." That is, the conventional art in the art has consistently regarded the alcohol amine compound as a highly corrosive component, and its content should be strictly controlled. However, as shown by the results of the foregoing experiments, the inventors have found that although the alcohol amine compound is extremely corrosive in the presence of a low content in the photoresist removal composition, it is unexpected once the content thereof is more than 55% by weight. The ground exhibits the effect of inhibiting corrosion.

In summary, the present invention provides a photoresist removal composition and a method of applying the photoresist removal composition to the manufacture of electronic components. The photoresist removal composition contains 55% by weight or more of the alcohol amine compound, whereby the photoresist removal composition of the present invention exhibits, in addition to being effective in removing the photoresist, exhibits unpredictability by conventional techniques. The effect of inhibiting corrosion.

Although the present invention has been described above by way of examples, it is not intended to be limiting this invention. Any changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, the scope of protection of this application is subject to the definition of the scope of the patent application attached.

Claims (10)

A photoresist removal composition comprising: an alcohol amine compound in an amount of 55 to 90% by weight based on the total of the photoresist removal composition; and a solvent, the content of which is removed by the photoresist The amount is 3 to 45% by weight, represented by HO-X-OH, wherein X is a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ -extended alkenyl group, >R _x -COOH or >R _y -OH, R _x is a C ₁ -C ₃ hydrocarbon group, and R _y is a C ₁ -C ₄ hydrocarbon group. The photoresist removal composition of claim 1, further comprising less than 30% by weight of water based on the total amount of the photoresist removal composition. The photoresist removal composition of claim 1, further comprising a corrosion inhibitor. The photoresist removal composition of claim 1, wherein the alcohol amine compound comprises a primary alcohol amine. The photoresist removal composition according to claim 4, wherein the primary alcohol amine is contained in an amount of 40% by weight or more based on the total of the photoresist removal composition. The photoresist removal composition according to claim 1, wherein the content of the alcohol amine compound is 65 to 75% by weight based on the total amount of the photoresist removal composition. The photoresist removal composition according to claim 6, wherein the alcohol amine compound comprises a primary alcohol amine, wherein the primary alcohol amine is contained in an amount of 40 or more by weight based on the total of the photoresist removal composition. %. The photoresist removal composition of claim 6, wherein the primary alcohol amine comprises ethanolamine, aminoethylethanolamine or a mixture thereof. The photoresist removal composition of claim 1, wherein the solvent is propylene glycol. A method of manufacturing an electronic component, comprising using the photoresist removal composition according to any one of claims 1 to 9 to remove a photoresist formed on a substrate of the component.