TW200923597A - Photoresist remover and method for removing photoresist by using the same - Google Patents

Abstract

A photoresist remover comprises propylene glycol mono methyl ether propionate (PGMEP), cyclohexanone (Anone), and propylene glycol mono methyl ether (PGME). The photoresist remover, in which PGMEP, Anone, and PGME are mixed by any proportions, is capable of dissolving and removing all kinds of photoresist, including the positive photoresist and even the negative photoresist that could not be removed by the conventional reagent for cleaning photoresist. PGMEP comprises 20% to 80% by weight of the photoresist remover.

Description

200923597

-.^/[>TO7//L·* a vv ^ / 21PA IX. Description of the Invention: [Technical Field] The present invention relates to a cleaning agent and a method of using the same, and in particular to a light A cleaning agent and a photoresist cleaning method using the same. [Prior Art] U.S. Patent No. 4,983,490 discloses a photoresist cleaning agent, propylene glycol monomethyl ether (PMM E) and propylene glycol mono methyl ether acetate (propylene glycol mono methyl ether acetate). , PGMEA) is a mixture of ratios and has been widely used in the semiconductor industry and the optoelectronic industry to clean positive photoresists. However, such photoresist cleaners are highly undesirable for the cleaning of negative photoresists. SUMMARY OF THE INVENTION The present invention relates to a photoresist cleaning agent which has good dissolution and cleaning effects for all kinds of photoresists according to any ratio, including positive photoresist and conventional photoresist cleaning agents. Negative photoresist. According to an aspect of the present invention, there is provided a photoresist cleaning agent comprising monodecyl ether propylene glycol propionate (PGMEP), cyclohexanone, and monodecyl ether propylene glycol (PGME). According to another aspect of the invention, a method of cleaning a photoresist is provided, comprising: (a) providing a device with photoresist; and (b) a photoresist cleaning device, the photoresist cleaning agent comprising a monomethyl bond Propylene glycol propionate 200923597

__ 21 PA (PGMEP), cyclohexanone and monomethyl ether propylene glycol (PGME). In order to make the above-mentioned content of the present invention more comprehensible, a preferred embodiment will be described below in detail with reference to the accompanying drawings, which are described below as follows: [Embodiment] The present invention provides a photoresist cleaning agent including a single crucible. Propylene glycol monomethyl ether propionate ("PGMEP"), cyclohexanone (Anone), and propylene glycol monomethyl ether (PGME). The photoresist cleaning agent is mixed in any proportion and has good dissolution and cleaning effects for all kinds of photoresists, including positive photoresist and negative photoresist which cannot be processed by traditional photoresist cleaners, especially The pigment dispersion type resistor in the negative photoresist has a cleaning effect superior to that of the conventional lotion. The present invention further proposes four groups of preferred examples of the photoresist cleaning agent, wherein the mixing ratio of Ο PGMEP : Anone : PGME is respectively It is 20:20:60, 35:55:10, 60:30:10 and 80:10:10, and it is tested by J to test its negative photoresist. The negative photoresist used in the test includes Red photoresist, green Pigment-dispersed photoresist used in color filter processes such as photoresist, blue photoresist, and black photoresist. In addition, six sets of conventional photoresist cleaners S1 to S6 were used in the test to achieve better implementation. For example, the photo-resistance cleaning agents D1 to D4 are compared and compared with the dissolution and cleaning effects of the pigment-dispersed negative-type photoresist. The following is a series of test results to illustrate the photoresist of the embodiment 200923597 for various negative plastics. The ability of the photoresist to be cleaned. Test 1: 2 drops of red photoresist (in this case, Acrylic type red negative photoresist, PGMEA main solvent) was dropped on 5×1〇 (cm2) SUS304 stainless steel sheet, coated with No. 6 After the bar was applied, the red photoresist film layer was dried at room temperature (2 Torr., left to stand for 60 seconds, and the drying conditions of the actual operation were simulated. After drying, the stainless steel with the red photoresist film layer was respectively attached. The film was taken out in the conventional photoresist cleaning S1 to S6 and the photoresist cleaning agents D1 to D4 of the preferred embodiment for 60 seconds, and then dried at room temperature for 60 seconds to observe the residual condition of the red photoresist on the stainless steel sheet. Please refer to Table 1, Table 1 for transmission Comparison of the photoresist cleaning agent and the photoresist cleaning agent of the preferred embodiment of the present invention for the cleaning ability of the negative red photoresist. Table 1. Conventional photoresist cleaning agent and photoresist cleaning agent of the preferred embodiment Comparison of the cleaning ability of _ negative red photoresist _ composition of photoresist cleaning agent against red photoresist PGMEP (%) Anone (%) PGME (%) PGMEA (%) NBAc (%) cleaning ability

D1 20 20 60 - - Δ D2 35 55 10 - - 〇D3 60 30 10 - - 〇D4 80 10 10 - - Δ S1 - 75 25 - - XX S2 - 25 75 - - XX S3 - 20 60 - 20 XX S4 - 20 60 20 - XX S5 - 10 10 80 - X S6 - - 70 30 - XX Note 1: Description of the cleaning ability level. 〇: no residue; △: micro residue; X: obvious residue; χχ · · severe residue. 200923597

- Rb, 21 PA As can be seen from the above table, the photoresists D1 to D4 of the preferred embodiment of the present invention are significantly superior to the conventional photoresists in terms of negative red light cleaning ability. detergent. Even with the currently widely used photoresist cleaner S6 (explained in U.S. Patent No. 4,983,490), the red photoresist resisting ability of the negative type is still not as good as the photoresist cleaner of the preferred embodiment of the present invention. The conventional photoresist cleaners si and S2 contain different ratios of cyclohexanone (Anone) and monodecyl ether propylene glycol (pGME), and the composition of the photoresist of the preferred embodiment is only a single one. The ether ether propylene glycol vinegar [PGMEP], but the ability to clean the negative red photoresist is significantly reduced. Furthermore, if the monoterpene ether propylene glycol propionate (PGMEP) is replaced by an ester compound or a structural analog, for example, the conventional photoresist cleaning agent S3 is replaced by n-Butyl acetate (NBAc). Example of photo-resistance/monthly lotion D1 mono-mercapto ether propylene glycol propionate (PGMEP), conventional photoresist cleaner S4 is similarly structured with monomethyl ether propylene glycol acetate (Pr〇pylene glycol mono methyl ether acetate, PGM) £A) Substituting the monomethyl ether propylene glycol propionate (pGMEP) of the photoresist cleaner D1 of the conventional example, the photoresist is S5 with a similar structure of monodecyl ether propanol B@@曰> (PGMEA) replaces the monomethyl ether propionate (PGMEP) of the photoresist cleaner D4 of the example, but the cleaning power of the negative red photoresist is poor. It can be proved that the photoresist cleaning agent has a good ability to dissolve negatively, and monodecyl ether propylene glycol propionate (PGMEP) is an integral component of t. Even adding a compound belonging to the same ester (i_e•Acetylhydrazine 酉曰> (NBAc)) or even adding a structural analog Ο.e. I-mercaptopropane-, acetate (PG Μ EA)) Similar effects are not produced in photoresist cleaners. 200923597 > 1 pa Further, all include monodecyl ether propylene glycol propionate (PGMEP), cyclohexanone (Anone), and monodecyl ether propylene glycol (PGME). The three-component photoresist cleaner has good cleaning ability for negative red photoresist regardless of the mixing ratio. Preferably, the weight of monomethyl ether propylene glycol propionate (PGMEP) is from about 20% to 80% by weight of the photoresist cleaner, and the weight of cyclohexanone (Anone) is about the weight of the photoresist cleaner. From 10% to 55% by weight, the weight of monodecyl ether propylene glycol (PGME) is from about 1% to about 60% by weight of the photoresist. More preferably, the monomethyl ether propylene di C propionate (PGMEP) weighs from about 20% to about 60% by weight of the photoresist. Most preferably, the weight of monomethyl ether propylene glycol propionate (PGMEP) is from about 35% to 60% by weight of the photoresist cleaner because of the weight of monomethyl ether propylene glycol propionate (PGMEP). When it accounts for 35% to 60% of the weight of the photoresist cleaner, the photoresist cleaner has a strong cleaning ability for the negative red photoresist (refer to the photoresist cleaners D2 and D3 of the examples). I' test to drop 2 drops of green photoresist (in this case, Acrylic type green negative photoresist, PGMEA as the main solvent) onto the above stainless steel sheet, and test various photoresist cleaners for the negative green under the same operating conditions. The ability to clean the photoresist. Referring to Table 2, Table 2 is a comparison of the cleaning ability of the conventional photoresist cleaner and the photoresist cleaner of the preferred embodiment of the present invention for the negative green photoresist. 9

200923597 —_____21PA Table 2 Comparison of the cleaning ability of the conventional photoresist cleaner and the photoresist cleaner of the preferred embodiment for the negative green photoresist _ The composition of the photoresist cleaner against the green photoresist PGMEP (%) Anone (%) PGME (%) PGMEA (%) NBAc (%) washing ability "D1 20 20 60 - - 〇D2 35 55 10 - - 〇D3 60 30 10 - - 〇D4 80 10 10 - - 〇S1 - 75 25 - - XX S2 - 25 75 - - XX S3 - 20 60 - 20 X S4 - 20 60 20 - X S5 - 10 10 80 - X S6 - - 70 30 - X Note 1: Description of the cleaning ability level. : no residue; Δ: microresidue; X: significant residue; XX: severe residue. As can be seen from Table 2, the photoresist cleaning agents D1 to D4 of the preferred embodiment of the present invention are negative for the mixing ratio. The green photoresist washability is also very good, and is significantly better than the traditional photoresist cleaner. When the weight of monomethyl ether propylene glycol propionic acid vinegar (PGMEP) accounts for 20% to 80% of the weight of the photoresist cleaner In the meantime, the negative green resist is equally good. The second test will be 2 drops of blue photoresist (in this case, the Acrylic type blue negative photoresist is used, The main solvent is PGMEA), which is dropped on the above stainless steel sheet, and the cleaning ability of various photoresist cleaners for the negative blue photoresist is tested under the same operating conditions. Please refer to Table 3, Table 3 for the traditional photoresist cleaning agent and Compared with the present invention 10 200923597

MPA -»Α3^/|/Γτα j</u ,, - - - - i · Comparison of the cleaning ability of the photoresist of the preferred embodiment for the negative blue photoresist. Table 3: Comparison of the cleaning ability of the conventional photoresist cleaner and the photoresist cleaner of the preferred embodiment for the negative blue photoresist _ ~ The composition of the photoresist cleaner to the blue photoresist PGMEP (%) Anone ( %) PGME (%) PGMEA (%) NBAc (%) Washing capacity to 1 D1 20 20 60 - - Δ D2 35 55 10 - - 〇D3 60 30 10 - - 〇D4 80 10 10 - - Δ S1 - 75 25 - - XX S2 - 25 75 - - XX S3 - 20 60 - 20 XX S4 - 20 60 20 - X S5 - 10 10 80 - X S6 - - 70 30 - Δ Note 1: Description of the cleaning ability level. 〇: no residue; Δ: microresidue; X: significant residue; X; X: severe residue. As can be seen from Table 3, the photoresist cleaners D1 to D4 of the preferred embodiment of the present invention have a negative blue resist. The cleaning ability is significantly better than the traditional photoresist cleaner. When the weight of monomethyl ether propylene glycol propionate (PGM EP) is between about 20% and 80% by weight of the photoresist cleaner, the photoresist cleaner confirms that it has a good dissolution or wash negative The ability of blue photoresist. Preferably, the weight of monodecyl ether propylene glycol propionic acid vinegar (PGM EP) is from about 35% to 60% by weight of the photoresist cleaner because of the weight of monodecyl ether propylene glycol propionic acid vinegar (PGMEP). When it is about 35% to 60% by weight of the photoresist cleaner, the photoresist cleaner has a negative blue photoresist of 11 200923597

— Violent muscle · 1 w-f /21PA Strong cleaning ability (please refer to the photoresist cleaners D2 and D3 of the examples). Test 4 will drop 2 drops of black photoresist (in this case, Acrylic type black negative photoresist, main solvent is PGMEA) on the above stainless steel sheet, and test various photoresist cleaners for negative black light under the same operating conditions. Resistance to washing. Referring to Table 4, Table 4 compares the cleaning ability of a conventional photoresist with a photoresist of a preferred embodiment of the present invention for a negative black photoresist. Table 4. Comparison of the conventional photoresist cleaning agent and the photoresist cleaner of the preferred embodiment _ for the cleaning ability of the negative black photoresist _ the composition of the photoresist cleaner against the black photoresist PGMEP (%) Anone ( %) PGME (%) PGMEA (%) NBAc (%) Washability Note 1

D1 20 20 60 - - Δ D2 35 55 10 - - 〇D3 60 30 10 - - Δ D4 80 10 10 - - Δ S1 - 75 25 - - X S2 - 25 75 - - X S3 - 20 60 - 20 X S4 - 20 60 20 - XX S5 - 10 10 80 - Δ S6 _ _ 70 30 One X Note 1: Description of the cleaning ability level. 〇: no residue; △: micro residue; X: obvious residue; XX: severe residue. As can be seen from Table 4, the photoresist cleaning agents D1 to D4 of the preferred embodiment of the present invention are significantly superior to the conventional light 12 200923597 1 Ρ Δ I for the negative black photoresist cleaning ability. η -, ί I /fnj -JO U » I. L i\ Resistant cleaning agent. When the weight of monodecyl ether propylene glycol propionic acid vinegar (PG Μ EP) is between about 20% and 80% by weight of the photoresist cleaner, the photoresist cleaner confirms that it has a good dissolution or cleaning negative The ability of black photoresist. Preferably, the weight of monomethyl ether propylene glycol propionic acid vinegar (PGM EP) is about 35% by weight of the photoresist cleaner because the weight of monomethyl ether propylene glycol propionic acid vinegar (PGMEP) is about When the photoresist is 35% by weight, the photoresist cleaner has a strong cleaning ability for the negative black photoresist (refer to the photoresist cleaner D2 of the embodiment). In summary of the above tests, it has been found that the photoresist cleaner of the preferred embodiment of the present invention has superior solubility compared to conventional photoresist cleaners, regardless of which pigment-dispersed photoresist is processed. The weight of monodecyl ether propylene glycol propionate (PGMEP) is preferably from 20% to 80% by weight of the photoresist cleaning agent, more preferably from 20% to 60% by weight of the photoresist cleaning agent, most Preferably, it is from 35% to 60% by weight of the photoresist. Further, the weight of the cyclohexanone is preferably from 10% to 55% by weight based on the weight of the photoresist. Further, the weight of monodecyl ether propylene glycol (PGME) is preferably from 1% to 60% by weight based on the weight of the photoresist. It is clear to those skilled in the art that the above test results are only presented by the most original cleaning method (ie short-time soaking, dissolution), if it is combined with such as brush cleaning, ultrasonic cleaning, two-fluid flushing or high pressure. The physical cleaning method such as steam washing enhances the cleaning ability, and the cleaning ability of the photoresist cleaner of the preferred embodiment is far superior to the cleaning ability of the conventional photoresist cleaning agent, and the difference in the cleaning effect is even more It is obvious. The invention further provides a method for cleaning a photoresist comprising: (a) providing a device with a photoresist of 13 200923597 -* i vv-^/λΙΡΑ; and (b) a photoresist cleaning device with the above-mentioned photoresist cleaning agent, a photoresist cleaning agent Including propylene glycol monomethyl ether propionate (PMMEP), cyclohexanone (cyclohexanone) and propylene glycol monomethyl ether (PGME). Since the photoresist cleaning agent of the invention can be applied in a wide range, including direct related mechanisms of the photoresist coating machine (such as internal pipelines, slit nozzles) and indirect related mechanisms (such as pre-discharge rollers and nozzle wiping pads) , substrate edge, rotating machine hall, inkjet, etc., all of the mechanisms that may be exposed to photoresist, so there are many ways to clean these devices with photoresist cleaner. The following are based on the existing photoresist coating technology. A method of cleaning the above various devices by applying the photoresist cleaning agent of the present invention will be described. Referring to Figures 1A to 1B, a flow chart of a method of spin coating photoresist is shown. The spin coating method applies the photoresist 10 to the substrate 12. Then the rotating machine 14 rotates with the substrate 12, and the photoresist 10 is dispersed by centrifugal force to the substrate 12, as shown in FIG. 1A. Show. The photoresist of the part will be pulled onto the substrate edge 12a or even the rotary table 14. The photoresist 10a at the edge of the substrate can be removed by the substrate edge cleaning machine 16 by means of the photoresist cleaning agent 100, as shown in Fig. 1B. The photoresist on the rotating table 14 is, for example, wiped, soaked, washed or otherwise removed by a photoresist. Referring to Figures 2A to 2C, there is shown a flow chart showing a method of non-rotating coated photoresist. The non-rotating coating (spjn|ess coating) method directly applies the photoresist 20 to the substrate 22, and there is no other step of homogenizing the photoresist, 14 200923597 ) 1 ρΔ

-Χ3^/|7ΓΤ11 JU U *· r, —, — " 1 L Therefore, the photoresist applied to the substrate must be very uniform. In operation, as shown in FIG. 2A, a non-uniform photoresist of the slit nozzle 24 is first applied to the priming roller 26, and a part of the pre-discharge roller 26 is immersed in the photoresist. In the cleaning agent 100, the pre-discharging roller 26 carries away the uneven photoresist while rolling, and is then dissolved and washed by the photoresist cleaning agent. Thereafter, as shown in Fig. 2B, the slit type nozzle 24 is moved onto the substrate 22 to apply a uniform photoresist 20 to the substrate 22. It is worth mentioning that, as shown in Fig. 2C, the slit type nozzle 24 can physically scrape or erase the photoresist by means of a nozzle wipe C' wiper 28. In the above process, the inner tube of the coating machine (not shown) for supplying the photoresist, the slit type nozzle 24, the pre-discharging drum 26, and the nozzle wiping pad 28 are all in contact with the photoresist, and can also be utilized in the same manner. The photoresist cleaner 100 is wiped, soaked, washed or otherwise removed and washed with photoresist. Other photoresist coating methods, for example, a slit type nozzle in combination with a spin coating method or an ink jet method, the apparatus also has a similar structure, and can also be cleaned by the above method, and no longer Narration. The photoresist cleaning agent disclosed in the above embodiments of the present invention and the method for cleaning the photoresist thereof can clean all kinds of photoresists, particularly negative photoresists which are difficult to handle with conventional photoresist cleaners. In the above test, the photoresist of the preferred embodiment of the present invention has a significantly better cleaning ability for negative photoresist than conventional photoresist cleaners. In the above, the present invention has been disclosed in the above preferred embodiments, but it is not intended to limit the present invention. Those having ordinary skill in the art to which the present invention pertains can be made into various types without departing from the spirit and scope of the present invention.

One by one 21PA change and retouch. Therefore, the scope of the invention is defined by the scope of the appended claims.

16 200923597

- Move; /! Fine 3 / Child - A 2 1PA [Simple Description of the Drawings] Figures 1A to 1B show a flow chart of a method of spin coating photoresist. 2A to 2C are flow charts showing a method of non-rotating coated photoresist. [Main component symbol description] 10: Photoresist 10a: Photoresist at the edge of the substrate 12: Substrate (12a: Substrate edge 14: Rotary table 16: Substrate edge cleaning machine 20: Photoresist 22: Substrate 24: Slit nozzle 26: pre-discharge roller 28: nozzle wiping pad ◎ 100: photoresist cleaning agent 17

Claims (1)

200923597 X. Patent Application Range 1. A photoresist cleaning agent consists of propylene glycol mono methyl ether propionate (PGMEP), cyclohexanone and monomethyl ether propylene glycol ( Propylene glycol mono methyl ether, PGME). 2. The photoresist cleaner according to claim 1, wherein the monomethyl ether propylene glycol propionate (PGMEP) has a weight of about 20% to 80% by weight of the photoresist cleaner. (3) The photoresist cleaning agent of claim 1, wherein the monomethyl ether propylene glycol propionate (PGM EP) has a weight of about 20% to 60% by weight of the photoresist cleaning agent. %. 4. The photoresist cleaner according to claim 1, wherein the monomethyl ether propylene glycol propionate (PGMEP) has a weight of about 35% to 60% by weight of the photoresist cleaner. 5. The photoresist cleaning agent of claim 1, wherein the cyclohexanone comprises from about 10% to about 55 % by weight of the photoresist. 6. The photoresist cleaner according to claim 1, wherein the monomethyl ether propylene glycol (P G Μ E) has a weight of about 10% to 60% by weight of the photoresist cleaner. 7. A method of cleaning photoresist, comprising: providing a device with a photoresist; and cleaning the device with a photoresist cleaning agent comprising a monomethyl propylene glycol propionate (propylene g)丨ycol mono methyl 18 200923597 -.21PA ether-PGMEp), one ring of the net (_. heart_(four) and one morning methyl-propanediol (P "_ene glycol m_ methyl ether, PGME). y 8. As claimed in claim 7 The method according to the item, wherein a slit type nozzle, a pre-discharging roller, a nozzle wiping soft palate, a two-resistance coating machine table, or a substrate edge. The method of the present invention, wherein the device is immersed in the photoresist cleaning agent. ^ The method of claim 7, wherein the device is washed with the photoresist cleaning agent. The method of the present invention, the method of claim 7, wherein the weight of the monomethyl propylene glycol propionic acid vinegar (PGMEP) accounts for approximately the light barrier. 20% to 80% of the weight. 13. If you apply for a patent The method according to item 7, wherein the weight of the monomethylpropanediol propylene (PGMEP) is about 20% to 60% by weight of the photoresist cleaning agent. β 14 · as claimed in claim 7 The method wherein the monomethyl ether propylene glycol propionate (PGMEp) has a weight of about 35% to 60% by weight of the photoresist clearing agent. θ 15. As described in claim 7 The method wherein the cyclohexanone is present in an amount of from about 10% to about 55% by weight of the photoresist. 16. The method of claim 7, wherein the single one is 19 200923597 71 Ρ Δ u. .. LLA\. The weight of the phenyl propylene glycol (PGME) is 10% to 60%. About the weight of the photoresist cleaner. 17. The aryl ether propylene glycol (PGME) according to claim 7 The weight is about 5% to 30% of the light, and the weight of the β lotion is 18. A negative type resist as described in claim 7 of the patent application. · According to item 7 of the patent application, a pigment-dispersed photoresist is used. The method, wherein the photoresist 20