TWI608311B - A photoresist stripper composition and a photolithography process for manufacturing a electronic device utilizing the same - Google Patents

Description

Photoresist removal composition and method for manufacturing electronic component using the photoresist to remove composition for lithography process

[001] The present invention relates to a photoresist removal composition and a method of manufacturing an electronic component using the photoresist removal composition to perform a lithography process.

[002] lithography is a process technology commonly used in the semiconductor and panel industries. Its main processes include the deposition of a metal or dielectric film on a substrate, photoresist coating, baking, exposure, development, etching, and light. Removal, cleaning, etc. The main component of the photoresist is an organic compound. Under high-energy plasma bombardment or high-temperature baking after etching, the organic compound is easily removed due to carbonization, drying and gelation in the subsequent photoresist removal process. Clean, which in turn affects subsequent processes. [003] In view of this, a novel photoresist removal composition that can remove the photoresist pattern is highly anticipated by the industry.

[004] An object of the present invention is to provide a photoresist removal composition comprising an organic solvent having the structure shown in the following formula I: (Formula I) wherein R ₁ is alkoxy or alkyl, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently hydrogen or hydroxy, and n is greater than 0; The content is 10-65% by weight; and water. Another object of the present invention is to provide a photoresist removal composition as described above, wherein the content of the organic solvent of the above formula (I) is 5% by weight or more. Another object of the present invention is to provide a photoresist removal composition as described above, and the content of the above water is 30% by weight or less. Another object of the present invention is to provide a photoresist removal composition as described above, and the above amine compound is a primary amine or a secondary amine. Another object of the present invention is to provide a photoresist removal composition as described above, and the above amine compound is an alcohol amine compound. Another object of the present invention is to provide a photoresist removal composition as described above, wherein the content of the above alcohol amine compound is 45 wt% or more.

Another object of the present invention is to provide a photoresist removal composition as described above, and the above alcohol amine compound is selected from the group consisting of monoethanolamine (MEA), N-methylethanolamine (NMEA), isobutanolamine, and dimethyl Aminoethoxyethanethiol, dimethylaminoethoxypropane, dipropylaminoethoxybutanol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanol, diethyl Aminoethoxyethanol, dipropylaminoethoxyethanol, N-(2-methoxyethanol)morpholine, N-(2-ethoxyethanol)morpholine or N-(2-butoxyethanol) Morpholine, 1-aminoisopropanol (AIP), 2-amino-1-propanol, 3-amino-1-propanol, 2-(2-aminoethylamino)-1-ethanol (2-(2-aminoethylamino)-1-ethanol), diethanolamine (DEA), and hydroxyethylpiperazine (HEP), or a combination thereof.

Another object of the present invention is to provide a photoresist removal composition as described above, wherein R ₁ is a C ₂ -C ₆ alkoxy group or a C ₁ -C ₆ alkyl group, preferably an ethoxylated group. And a propoxy group or a methyl group, and R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently hydrogen, and n is from 1 to 4. When further herein, labeled "C _X" on a group is described, X represents a group having the carbon atoms.

Another object of the present invention is to provide a photoresist removal composition as described above, and further comprising a metal corrosion inhibitor.

Another object of the present invention is to provide a photoresist removal composition as described above, and the metal corrosion inhibitor is one selected from the group consisting of organic carboxylic acids, organic phenols, azoles or sugar alcohol compounds or a combination thereof.

Another object of the present invention is to provide a photoresist removal composition as described above, and the content of the metal corrosion inhibitor is at least 1 weight percent.

Another object of the present invention is to provide a method for fabricating an electronic component of a lithography process, the method comprising: providing a substrate, and forming a film on the surface of the substrate; forming a photoresist pattern on the film to make the film a part a masking region whose surface is shielded by the photoresist pattern, and an exposed portion where the other portion of the surface is not shielded by the photoresist pattern; using the photoresist pattern as an etching mask to etch away the film located in the exposed region; Any of the photoresist removal compositions described above, and removing the photoresist pattern using the photoresist removal composition, forms a patterned film on the substrate.

Another object of the present invention is to provide a method of manufacturing an electronic component of a lithography process as described above, wherein the film is a metal film or an insulating film.

An embodiment of the present invention provides a photoresist removal composition comprising an organic solvent having a structure as shown in the following formula I: (Formula I) wherein R ₁ is alkoxy or alkyl, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently hydrogen or hydroxy, and n is greater than 0; The content is 10-65% by weight; and water.

In some embodiments according to the present invention, R ₁ is C ₂ -C ₆ alkoxy or C ₁ -C ₆ alkyl, preferably ethoxy, propenoxy or methyl. And R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently hydrogen, and n is from 1 to 4.

In some embodiments according to the present invention, the above amine compound is a primary or secondary amine, and may be, for example, one selected from the group consisting of monoethanolamine (MEA), N-methylethanolamine (NMEA), isobutanolamine, and dimethyl. Aminoethoxyethanethiol, dimethylaminoethoxypropane, dipropylaminoethoxybutanol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanol, diethyl Aminoethoxyethanol, dipropylaminoethoxyethanol, N-(2-methoxyethanol)morpholine, N-(2-ethoxyethanol)morpholine or N-(2-butoxyethanol) Morpholine, 1-aminoisopropanol (AIP), 2-amino-1-propanol, 3-amino-1-propanol, 2-(2-aminoethylamino)-1-ethanol An alcohol amine compound of one or a combination of (2-(2-aminoethylamino)-1-ethanol), diethanolamine (DEA), and hydroxyethylpiperazine (HEP).

In some embodiments according to the present invention, the photoresist removal composition provided by the present invention further comprises a metal selected from one or a combination of organic carboxylic acids, organic phenols, azoles or sugar alcohol compounds. Corrosion inhibitors, etc., but not limited to this. Examples of organic carboxylic acid corrosion inhibitors are lactic acid, citric acid or a salt thereof. 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.

Other types of organic solvents may be added as needed without affecting the photoresist removal effect of the photoresist removal composition provided by the present invention, but are not limited thereto. Examples of other types of organic solvents may be diethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol tert-butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, dipropylene glycol uncle Butyl ether, dipropylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol butyl ether, ethylene glycol tert-butyl ether and the like.

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.

Hereinafter, in the processes of forming a patterned copper thin film pattern on a glass substrate by using Examples 1 to 9 and Comparative Examples 1 to 3, respectively, the photoresist removal composition according to the present invention is used (Examples 1 to 9). And using a conventional photoresist removal composition (Comparative Examples 1 to 3), the photoresist pattern was removed and a patterned copper film was formed on the glass substrate.

First, please refer to FIG. 1A to provide a glass substrate 100. Next, referring to FIG. 1B, a copper film 200 having a thickness of about 3,000 Å to 5,000 Å is formed on the glass substrate 100 by sputtering, plating, physical vapor deposition (PVD) or printing. Then, a positive photoresist layer 300 is coated on the copper film 200 described above.

Next, referring to FIG. 1C, the photoresist layer 300 is converted into a predetermined photoresist pattern 300' by using a lithography technique, so that the copper film 200 becomes a masking region 200A in which a part of the surface is shielded by the photoresist pattern 300', and another portion of the surface. Exposed area 200B that is not obscured by the photoresist pattern.

Next, referring to FIG. 1D, the photoresist pattern 300' is used as an etching mask to etch away the copper film 200 located in the exposed region 200B, and a patterned copper is formed in the mask region 200A blocked by the photoresist pattern 300'. Film 200'.

Next, referring to FIG. 1E, the glass substrate 100 including the photoresist pattern 300' is immersed in the photoresist removal compositions of Examples 1 to 9 or Comparative Examples 1 to 3 at a Celsius temperature of about 40 C, and 40 is maintained. In seconds, the photoresist pattern 300' described above is removed. Finally, a patterned copper film 200' is formed on the glass substrate 100 by washing with deionized water. The photoresist pattern 300' removal ability and copper corrosion rate of Examples 1 to 9 and Comparative Examples 1 to 3 were compared by the following detection methods, and the results are shown in Table 1 below.

The method for detecting the photoresist pattern removal ability: the glass substrate 100 containing the photoresist pattern 300' is immersed in the photoresist removal compositions of Examples 1 to 9 or Comparative Examples 1 to 3 at a temperature of about 40 ° C. After maintaining for 40 seconds, the photoresist pattern 300' was removed, and then washed with deionized water, and an optical microscope (OM) at a magnification of 500 and a scanning electron microscope (SEM) at a magnification of 5000 were used to observe the removal of the photoresist. The surface of the patterned copper film 200' after the pattern 300'. Among them, the obvious hindrance of the photoresist observed under OM and SEM was judged as X; no photoresist residue was observed under OM, and Δ was observed as slight photoresist residue under SEM; it was observed under OM and SEM. If it does not remain in the photoresist, it is judged as O.

Method for detecting copper corrosion rate : The glass substrate 100 containing the photoresist pattern 300' is immersed in the photoresist removal compositions of Examples 1 to 9 at a temperature of about 40 ° C for 20 minutes to maintain the above-mentioned photoresist The pattern 300' was removed, and after washing with deionized water, the copper ion content dissolved in the photoresist removal compositions of Examples 1 to 9 was examined by ICP-MS to calculate the photoresists of Examples 1 to 9. The copper corrosion rate of the composition is removed.

Table I         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> </td><td><b>Example 1< /b></td><td><b>Example 2</b></td><td><b>Example 3</b></td><td><b>Example 4 </b></td><td><b>Example 5</b></td><td><b>Example 6</b></td><td><b>Example 7</b></td><td><b>Example 8</b></td><td><b>Example 9</b></td><td><b>Comparative Example 1</b></td><td><b>Comparative Example 2</b></td><td><b>Comparative Example</b><b>3</b></td ></tr><tr><td><b>Formula (I)</b><b>Organic solvent (wt/%)</b></td><td><b>BDG</b ></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td> <td><b>-</b></td><td><b>20</b></td><td><b>10</b></td><td><b >-</b></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b ></td><td><b>-</b></td><td><b>-</b></td></tr><tr><td><b>PH1< /b></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></ Td><td><b>5</b></td><td><b>5</b></td><td><b>20</b></td><td> <b>-</b></td><td><b>5</b></td><td><b>-</b></td><td><b>-< /b></td><td><b>-</b></td><td><b>-</b></td></tr><tr><td><b> PH2</b></td><td><b>5</b></td><td><b>20</b></td><td><b>60< /b></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></ Td><td><b>20</b></td><td><b>-</b></td><td><b>-</b></td><td> <b>67</b></td><td><b>92</b></td><td><b>0.5</b></td></tr><tr>< Td><b>Benzyl alcohol</b></td><td><b>-</b></td><td><b>-</b></td><td><b >-</b></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b ></td><td><b>-</b></td><td></td><td><b>38</b></td><td><b>-< /b></td><td><b>-</b></td><td><b>-</b></td></tr><tr><td><b> Amines (wt%)</b></td><td><b>MEA</b></td><td><b>-</b></td><td><b >-</b></td><td><b>-</b></td><td><b>65</b></td><td><b>45</b ></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td> <td><b>55</b></td><td><b>-</b></td><td><b>-</b></td><td><b >-</b></td></tr><tr><td><b>NMEA</b></td><td><b>65</b></td><td> <b>50</b></td><td><b>10</b></td><td><b>-</b></td><td><b>-< /b></td><td><b>40</b></td><td><b>-</b></td><td><b>62</b></ Td><td><b>-</b></td><td><b>3</b></td><td><b>3</b></td><td> <b>9.5</b></td></tr><tr><td><b>AMP95</b></td><td><b>-</b></td>< Td><b>-</b></td><td><b>-</b></td><td><b >-</b></td><td><b>-</b></td><td><b>-</b></td><td><b>65</b ></td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td> <td><b>-</b></td><td><b>-</b></td></tr><tr><td><b>Metal corrosion inhibitor (wt% )</b></td><td><b>CA</b></td><td><b>-</b></td><td><b>-</b> </td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td>< Td><b>-</b></td><td><b>-</b></td><td><b>1</b></td><td></td ><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td></tr> <tr><td><b>BzI</b></td><td><b>-</b></td><td><b>-</b></td><td ><b>-</b></td><td><b>-</b></td><td><b>-</b></td><td><b>- </b></td><td><b>-</b></td><td><b>2</b></td><td><b>2</b>< /td><td><b>-</b></td><td><b>-</b></td><td><b>-</b></td></ Tr><tr><td><b>water (wt%)</b></td><td><b>30</b></td><td><b>30</b> </td><td><b>30</b></td><td><b>30</b></td><td><b>30</b></td>< Td><b>30</b></td><td><b>30</b></td><td><b>30</b></td><td><b> 5</b></td><td><b>30</b></td><td><b>5</b></td><td><b>90</b> </td></tr><tr><td><b>Resistance of photoresist pattern</b></td><td><b>O</b></td><td>< b>O</b></td><td><b>O</b></td><td><b>O </b></td><td><b>O</b></td><td><b>△</b></td><td><b>O</b>< /td><td><b>O</b></td><td><b>O</b></td><td><b>X</b></td><td ><b>X</b></td><td><b>X</b></td></tr><tr><td><b>copper corrosion rate (ppb/min)< /b></td><td><b>51.87</b></td><td><b>79.95</b></td><td><b>102.15</b></ Td><td><b>34.31</b></td><td><b>58.42</b></td><td><b>43.01</b></td><td> <b>63.18</b></td><td><b>51.07</b></td><td><b>75.00</b></td><td><b>Photoresist Not removed, </b><b>cannot be measured</b></td><td><b>The photoresist is not removed,</b><b>cannot be measured</b></td> <td><b>The photoresist is not removed,</b><b>cannot be measured</b></td></tr></TBODY></TABLE>BDG: diethylene glycol monobutyl ether PH1: Ethylene glycol phenyl ether PH2: Diethylene glycol phenyl ether Benzyl alcohol: Phenylmethanol MEA: monoethanolamine NMEA: N-methylethanolamine AMP95 : Isobutanolamine CA: Citric Acid BzI: Benzimidazole       

As shown in Table 1, the photoresist removal compositions of Examples 1 to 9 contain 5 to 60% by weight of the organic solvent of the formula (I) (PH1, PH2 or Benzyl alcohol), and 10 to 65 weight percent of the amine compound. (MEA, NMEA or AMP95) and water, and Examples 5 and 6 each contain 20 and 10% by weight of BDG; and the photoresist removal compositions of Comparative Examples 1 and 2 respectively contain 67 or more than 92% by weight of the formula ( I) an organic solvent (PH2) and 3 parts by weight of an amine compound (NMEA) and water, and the photoresist removal composition of Comparative Example 3 contains 0.5% by weight of an organic solvent of the formula (I) (PH2) and 9.5. Weight percent of amines (NMEA) and water. As shown in Table 1, the photoresist removal pattern 300' removal ability of the photoresist removal compositions of Examples 1 to 9 was superior to the photoresist removal compositions of Comparative Examples 1 to 3.

In addition, as shown in Table 1, the photoresist removal compositions of Examples 1 to 7 were not added with a conventional metal corrosion inhibitor: citric acid (CA) or benzimidazole (BzI), and the copper corrosion rate was removed. The photoresist removal rate of the photoresist removal compositions of the other Examples 1, 2, and 4-7 was higher than that of the photoresist removal composition of Example 3, which was between 34.31 and 79.95 ppb/min. Corrosion rate. Among them, the photoresist removal compositions of Examples 1 and 6 have a copper etching rate (51.87 ppb/min; 58.42 ppb/min), which corresponds to the addition of 1% by weight of citric acid (CA) and 2% by weight of benzimidazole. (BzI) Copper corrosion rate (51.07 ppb/min) of the photoresist removal composition of Example 8 as a metal corrosion inhibitor; and the photoresist removal rate of the photoresist removal example of Example 2 (79.95 ppb/min) ), which corresponds to the copper corrosion rate (75.00 ppb/min) of the photoresist removal composition of Example 9 to which 2% by weight of benzimidazole (BzI) was added as a metal corrosion inhibitor; Examples 4, 5, and 7 The photoresist removal composition had a copper corrosion rate (41.86 ppb/min; 34.31 ppb/min; 43.01 ppb/min) which was lower than the photoresist removal compositions of Examples 8 and 9. In contrast, in the photoresist removal compositions of Comparative Examples 1 to 3, since the photoresist could not be removed, it was impossible to follow the paragraph.

The method for detecting the corrosion rate of copper is used to measure the copper corrosion rate of the photoresist removal composition of Comparative Examples 1 to 3.

In summary, the photoresist removal composition (Examples 1 to 9) provided by the present invention has a photoresist pattern 300' removal ability superior to the conventional photoresist removal composition (Comparative Example 1~) 3), and the photoresist removal composition disclosed in Embodiments 1 and 4-7 of the present invention, the corrosion rate of the metal film is still equivalent to or better than the addition of the conventional metal corrosion inhibitor. The metal film corrosion rate of the photoresist removal composition of Example 8 or Example 9 of the known metal corrosion inhibitor.

Further, in other embodiments according to the present invention, the glass substrate 100 may be replaced with other semiconductor substrates, such as a germanium substrate, a sapphire substrate, a gallium arsenide substrate, or the like. In addition, the copper thin film 200 may be replaced by another metal having a high conductivity, such as aluminum, or a metal oxide or an insulator such as indium tin oxide (ITO) or indium zinc oxide (IZO), and will not be described herein. .

While the invention has been described above in terms of the preferred embodiments thereof, which are not intended to limit the invention, the invention may be modified and combined with the various embodiments described above without departing from the spirit and scope of the invention. example.

<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 100 </td><td> glass substrate</td><td> 200' </ Td><td> patterned copper film</td></tr><tr><td> 200 </td><td> copper film</td><td> 300 </td><td> photoresist Layer</td></tr><tr><td> 200A </td><td> masking area</td><td> 300' </td><td> photoresist pattern</td></ Tr><tr><td> 200B </td><td> exposed area</td><td> </td><td> </td></tr></TBODY></TABLE>

Figures 1A-1E show a thin film patterned cross-section process in accordance with an embodiment of the present invention.

<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 100 </td><td> glass substrate</td><td> 200' </ Td><td> patterned copper film</td></tr><tr><td> 200A </td><td> masked area</td><td> 300' </td><td> light Resistance pattern</td></tr><tr><td> 200B </td><td> exposed area</td><td> </td><td> </td></tr><tr ><td> </td><td> </td><td> </td><td> </td></tr></TBODY></TABLE>

Claims (13)

A photoresist removal composition comprising: an organic solvent having the structure shown in the following formula I: (Formula I) wherein R ₁ is alkoxy or alkyl, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently hydrogen or hydroxy, and n is greater than 0; The content is 10-65% by weight; and water. The photoresist removal composition according to claim 1, wherein the organic compound is contained in an amount of greater than or equal to 5% by weight. The photoresist removal composition according to claim 1, wherein the water content is 30% by weight or less. The photoresist removal composition according to claim 2, wherein the amine compound is a primary amine or a secondary amine. The photoresist removal composition as described in claim 4, wherein the amine compound is an alcohol amine compound. The photoresist removal composition according to claim 5, wherein the content of the alcohol amine compound is greater than or equal to 45 weight percent. The photoresist removal composition according to claim 5, wherein the alcohol amine compound is selected from the group consisting of monoethanolamine (MEA), N-methylethanolamine (NMEA), isobutanolamine, dimethylaminoethoxylate. Ethyl ethane thiol, dimethylamino ethoxy propyl thiol, dipropylamino ethoxy butyl thiol, dibutyl ethoxy ethoxyethanol, dimethylamino ethoxyethanol, diethyl ethoxy ethoxy Ethyl alcohol, dipropylaminoethoxyethanol, N-(2-methoxyethanol)morpholine, N-(2-ethoxyethanol)morpholine or N-(2-butoxyethanol)morpholine, 1-aminoisopropanol (AIP), 2-amino-1-propanol, 3-amino-1-propanol, 2-(2-aminoethylamino)-1-ethanol (2-( 2-aminoethylamino)-1-ethanol), diethanolamine (DEA), and hydroxyethylpiperazine (HEP), or a combination thereof. The photoresist removal composition according to claim 1, wherein R ₁ is C ₂ -C ₆ alkoxy or C ₁ -C ₆ alkyl, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ is a respective independent hydrogen, and n is between 1 and 4. The photoresist removal composition according to item 8 of the patent application, wherein R ₁ is an exoethoxy group, a propenoxy group or a methyl group. The photoresist removal composition as described in claim 1 further includes a metal corrosion inhibitor. The photoresist removal inhibitor according to claim 10, wherein the metal corrosion inhibitor is one selected from the group consisting of an organic carboxylic acid, an organic phenol, an azole or a sugar alcohol compound, or a combination thereof. A method for manufacturing an electronic component of a lithography process, comprising the steps of: providing a substrate, and forming a film on the surface of the substrate; forming a photoresist pattern on the film, so that the film becomes a part of the surface by the photoresist a masking region of the pattern masking, and an exposed portion of the other portion of the surface not obscured by the photoresist pattern; using the photoresist pattern as an etching mask to etch away the film located in the exposed region; and providing a patent application scope The photoresist removal composition according to any one of items 1 to 11, wherein the photoresist pattern is removed using the photoresist removal composition, and a patterned film is formed on the substrate. A method of manufacturing an electronic component of a lithography process according to claim 12, wherein the film is a metal film or an insulating film.