TW200416490A - Improved semiconductor stress buffer coating edge bead removal compositions and method for their use - Google Patents

Abstract

An edge bead remover composition that includes at least one ketone selected from the group consisting of: wherein R1 and R2 are independently selected from the group consisting of: methyl, ethyl, n-propyl, n-butyl, sec-butyl, and isobutyl, and wherein n equals 1 or 2; at least one ester other than lactones; and at least one lactone.

Description

200416490. · Description of the invention (The description of the invention should state: the technical field, the prior art, the content, the embodiments, and the drawings of the invention are briefly described.) [Technical field to which the invention belongs 1. Field of the invention The present invention relates to Manufacturing of 5 semiconductor elements on circles or other substrates, especially with regard to solvent compositions and methods, which are used to coat the top-side periphery of the wafer, the edge of the wafer, and the uncoated wafer The bottom side removes excess stress buffer coating material.

L Prior Art 2 Background of the Invention 10 Stress buffer coating materials such as polyimide and polybenzoxazole film evidence

It can improve the reliability of packaged semiconductor components (P.V. Robock and LT Nguyen, edited by R. Tummala and EJ Rymaszewski, Handbook of Microelectronic Packaging, (Van Nostrand Reinhold, New York, 540, (1989)). Stress The buffer coating is a 15-step continuous processing step using a spin-coating stress buffer coating composition, which is formed on a semiconductor element using standard semiconductor industry methods, with a layer thickness of 2-25 microns. Imine-based composition (edited by K. Horie and T. Yamashita, Photosensitive Polyimide: Basics and Applications, Technomic Publishing, Pennsylvania, Lancaster, and R. Hopla, P. Falcigno, S. Hagen, 20 J. Herbert, D. Huglin, HJ Kirner, T. Maw, A. Schaffner, W. Weber and O. Rhode, Proceedings of the 10th International Photopolymer SPE Conference, China and Kazakhstan Desen SPE, 1994, pp. 463-469, or polybenzoxazole-based precursor polymer ("A novel working photosensitive polymer vinegar for semiconductor surface coating", H. Makabe, T. Banba and T. Hirano, Photopolymer Science 6 玖, Invention Ming and Technical Journal, Vol. 10, No. 2, (1997), 307-3, p. 12), removing the lip 'soft baking dry and wet coating to obtain a hard film, this hard film will not flow at room temperature, use The lithography method forms a relief structure on the film, and then finally hardens in an oven or an oven at a temperature and time sufficient to convert the precursor into a polyimide or polybenzo sigma stress buffer film. It is buffered in the photosensitive stress In the case of the composition, the relief structure can be made by direct lithography exposure. In the case of non-photosensitive stress buffering composition, the indirect lithography method can be used to 'transfer the image through the sacrificial photoresist film, which sacrificial photoresist film It is applied in a separate and subsequent coating step to the stress buffer coating precursor film. For the direct or indirect lithography method, an image is formed on the photosensitive film by exposing the photosensitive film to actinic radiation that first passes through a patterned photomask. Actinic radiation in the range of 240 to 500 nanometers can be used, and 365, 405, and 436 nanometers of mercury lamps are particularly suitable for this project. When spin coating, stress buffer coating formulations remain A strip of material or "rim lip" surrounds the wafer. The lip is obviously thicker than the coating on the rest of the wafer area. This area has a significantly larger coating thickness. The width of the area is 丨 to 3 mm, which surrounds the entire wafer. Peripheral. The thickness of this lip can be twice the thickness of the rest of the coating area. In addition, the coating material is deposited on the edge of the wafer, often flows through the edge of the wafer, and is deposited on the uncoated bottom side of the wafer. As a result, the bottom and edges of the wafer are contaminated. The existence of a lip makes it difficult to maintain the optimal light focus when using a stepwise re-exposure tool such as a stepper to image the photosensitive coating, resulting in a loss of pattern resolution. ㈣The image focused on the inner region of the wafer that does not have a marginal lip becomes out of focus in the marginal lip area. As a result, the pattern resolution is poor, and the manufacturing yield is lost due to the 玖 and invention description. Since the thick lip has a light absorption ratio more south than the rest of the film, a larger exposure dose is required to form a latent image on the lip. Attempting to image the marginal lip resulted in overexposure of the rest of the film, which resulted in poor pattern resolution. Excess material on the edge of the wafer is easy to chip and produce particulate contamination, which adversely affects the yield of the process. Excess material on the underside of the wafer causes contamination of semiconductor device manufacturing equipment. The step-and-repeat exposure tool is particularly sensitive 'because the bottom side contamination prevents the wafer from being positioned orthogonal to the mask image. If the contamination is transferred to the stepper wafer platform, the focus of the wafer is then damaged. This transfer of contamination caused the wafer to be out of focus during subsequent processing of the exposure equipment in some areas of the wafer. In addition, the predetermined function of the wafer processing apparatus on the coating equipment and on the hot plate of the baking-coated substrate is adversely affected by the contamination of the bottom side of the wafer edge. Therefore, it is very important to reduce the thickness of the edge lip and remove the edge and bottom side pollution by using the edge lip remover (EBR) solvent before the exposure step, so as to reduce the adverse effects of the edge buffer of the stress buffer coating material and the edge side and Adverse effects of bottom side pollution. A lip-removing solvent has been developed for removing lip and bottom pollution from spin-coated photoresist compositions. Spin-coated photoresist compositions are mainly derived from novolac resin binders and photoactive compounds (o-quinonediazide).物) 组合。 Composition). US Patent 4,518,678 $ Tiger No. 2 provides a cross-sectional view (reproduced here as Figure 1) 'shown on the wafer substrate based on the composition of novolac resin and o-quinone diazide on the wafer substrate before removing the solvent Photoresist coating. The main features of Figure 丨 are substrate 1 and coating 2 ', where 2b is a coating extending around the edge of the substrate' and 2c is a coating extending to the bottom edge of the substrate. Figure 3 of US Patent No. 4,886,728 (herein reproduced as Figure 2) shows the result of removing the lip of the photoresist coating of 200416490 (1) and the description of the invention. The main feature of FIG. 2 is to expose the "peripheral band of the substrate" on the upper surface of the substrate 1, to expose the edge lb of the substrate, and the bottom edge 1c of the substrate, from which the bottom side photoresist pollution has been removed. Several solvents have been explained and used And solvent mixture as the photoresist edge 5 lip remover. For example, US Patent No. 4,886,728 teaches the application of a mixture of ethyl lactate and isobutyl ketone as the edge lip removal solvent for removing photoresist from the edge and bottom of the wafer. US Patent No. 5,426,017 No. Description Use a mixture containing ^ to alkyl alkyl acetate, C4 to C8 alkanol and water as a lip remover for novolak resin adhesive and o-quinonediazide photoactive compound as the main light of 10 U.S. Patent No. 5,814,433 teaches the use of a mixture of ethyl lactate and methylpyrrolidone (NMP) as a lip removal composition for photoresist removal. As NMP has been known to chemically amplify 248 nm and 193 nm Rice photoresist performance is harmful (U.S. Patent No. 6,277,546277 "Influence of Polymer Properties on Chemical Pollution Carried by Chemically Amplified Photoresist in Air 15" W. D, Hinsberg S · A. MacDonald, N · J. Clecak, C · D.

Snyder and H.Ito, SPIE 1925, pp. 43-52, 1993), so NMP-containing compositions are banned in many semiconductor manufacturing plants, which use such chemically amplified photoresists. U.S. Patent No. 5,362,608 describes the use of tetrahydrofurfuryl alcohol as the active ingredient of the marginal lip removal composition without 1 <] ^] ?, which is said to be compatible with 248 nm photoresist. U.S. Patent No. 5,866,305 describes the application of a marginal lip remover and a bottom cleaner composition that includes at least ethyl lactate and ethyl ethoxypropionate, and preferably includes less than 10% γ-butyrolactone. U.S. Patent No. 6,015,467 describes a method for removing lip using a solvent composition including dipropylene 9 200416490 玖, a description of the invention glycol monoalkyl ether, such ether and a volatile organic solvent A mixture, and one of the ether, a volatile organic solvent, and a basic aqueous solution mixture. U.S. Patent No. 6,117,623 describes a marginal lip remover composition containing a lactone compound together with a second solvent selected from the group consisting of an alkoxybenzene or an aromatic alcohol. A preferred embodiment is described as: A mixture of γ-butyrolactone and anisole. US Patent No. 6,159,646 teaches the use of ethyl lactate, ethyl 3-ethoxypropionate and γ-butyrolactone, or a mixture of ethyl lactate and ethyl 3-ethoxypropionate, or ethyl lactate The composition of the mixture with γ-butyrolactone is the preferred composition for the method of reprocessing the wafer through photoresist coating. The method of reprocessing 10 is to dissolve the photoresist coating from the entire area of the wafer. JP 10-097079 teaches the use of a photoresist edge lip remover containing 60_90% ethyl lactate and 10_40% butyrolactone. JP 06-212193 claims a solvent composition, which contains an alkyl lactate which may be methyl, ethyl, isopropyl or butyl lactate, and additionally contains NMP, DMF, DMAc, methyl acetate, acetic acid At least one of ethyl acetate, 15 GBL, DMSO, or tetramethylene chloride, the composition is directed to the residue remaining after removal of photoresist. GB 2357343 claims a photoresist remover composition containing acetone, GBL and an ester solvent mixture and its use. JP 2936897 requests a lip removal solvent 20 for polyimide precursors, which contains 70-85% N, N-diamidinofluorene and 15-30% methanol. JP 2000-31969 claims a solvent composition containing 60-100% γ-butyrin S and preferably 1-40% solvent. The boiling point range of the solvent is lower than that of the factory. 'This composition is aimed at Removal of the lip of the heat-resistant t-composite with a fluorene imine ring or other ring structure. The cited wealth-heating polymers include, for example, polyfluorene 10 200416490 fluorene, invention description amines, polyfluorene polyfluorene, polybenzoxazole, polybenzothiophene, and polybenzimidazole; and the polymer may be Copolymer or adduct. Importantly, the requirements for the removal of the edge lip of the stress buffer coating are different from the requirements for the removal of the edge lip of the photoresist of the previous technical standard described above, and there are several major differences in 5 points. First, the components / valley resolution of the stress buffer coating composition are different from the solubility of the photoresist component. This solubility difference is truer for the polymer component of the stress buffer coating composition than the photoresist polymer component. The polymer used in the photoresist composition includes cresol-formaldehyde novolac resin, sham polyhydroxystyrene and derived polypropionate copolymer; the stress buffer coating composition is based on polyarylamide derivatives and polyarylate Methylamidate. The solvents used in the photoresist composition are typically esters, including ethyl lactate, propylene glycol monomethyl ether acetate, and other boiling points of 120-170. A range of solvents or solvent mixtures. Photoresist solvents alone are generally not good solvents for stress buffer coating compositions. Solvents used in stress buffer coating compositions are typically polar aprotic solvents having a boiling point in the range of 190-230 ° C, such as N-methylpyrrolidone (NMP, boiling point 202 C) and γ-butyrolactone. (GBL, boiling point 204-205 ° C). Because the edge lip removal solvent used for the photoresist lip removal method is mainly photoresist solvents, so when the stress buffer coating edge lip removal method tries to use the photoresist lip to remove the composition, it is not difficult to remove the composition. Surprisingly. The second 'stress buffer coating process involves the formation of a coating with a thickness in the range of 4-50 micrometers after baking; and the common film thickness of photoresist after baking is in the range of 0.5 to 3 micrometers. As a result, the material weight mass of the stress buffer coating lip is greater than that of the photoresist lip material. 11 200416490 发明, description of invention Third, the rheology of spin-coated films is very different. During the spin coating process, the photoresist formed a strong non-flowing film; the stress buffer coating composition produced a wet and soft gel-like coating, and was flowable after spin coating. This rheological difference between the photoresist and the stress buffer coating is due to both the difference in film thickness 5 and the difference in volatility of the casting solvent. Because the lip removal processing is after the spin coating method, the wet stress buffer coating continues to move during the substrate rotation operation, and continues to move during the substrate rotation operation in the lip removal processing. This movement complicates the lip removal processing. It is true that the solvent is removed at the margin and lips. After the application is completed, a shorter and lower speed spin processing cycle is often required to reduce the tendency of the dissolved stress buffer coating material to move beyond the edge of the wafer and to the bottom side of the wafer. The edge lip removal treatment of the stress buffer coating causes a unique problem compared to the photoresist lip removal treatment. In the case of photoresist, the leading edge lip can be removed, leaving the clean outer edge of the exposed wafer, about 1 to 3 mm wide, as shown in Figure 2. Since the 15 wet stress buffer coating flows during wafer rotation, during the edge lip removal process, the side lip before the stress buffer coating cannot be completely removed. Figure 3 is a cross-sectional side view of a wafer that has been spin-coated with a stress buffer coating composition and soft-dried. The main features of Figure 3 are wafer 1 and stress buffer coating 3, where 3a represents the thick lip characteristics of the stress buffer coating, 3b represents the coating that extends around the edge of the substrate 20 and 3c represents the edge that extends on the bottom edge of the substrate coating. The purpose of the edge lip removal treatment on the stress buffer coating film is to reduce the negative effect of the edge lip on wafer processing and yield. The edge lip removal treatment is performed by reducing the thickness of the edge lip area (3a) to as close to the thickness of the rest of the film as possible. At the same time, the contamination is removed from the bottom surface of the substrate. 12 200416490 发明 、 Explanation of the invention The solvent on the edge of the right edge containing the dissolved stress buffer coating material is left on the wafer: for a long time, it can flow or reflow to the bottom side of the wafer, resulting in contamination of the bottom surface, as shown in Figure 3c Show. The use of a volatile lip-lip removal composition provides a solvent mixture that dries faster, thereby preventing recirculation of dissolved materials, and reduces contamination of the clean area during the lip-lip removal process. But quick drying is not the only requirement. The cereal or solvent mixture needs to be strong enough to reduce the thickness of the lip and lips, and remove the small spots of the coating material that has been dried on the back side of the wafer. Such small dots of the coating material on the Yen test side are formed due to the reduced emission of the coating material during spin coating. Due to the convective drying of such material dots during wafer rotation, the dot material 10 is less soluble than the top side wet film. Another reason for good solubility is that spin-coating and lip removal are performed in the same-coating cup. Solvents or solvent mixtures using poor solvents can cause residues to build up in the spin cup of the coating equipment. These residues add additional sources of contamination, which may be shot onto the wall of the coating cup and deposited on the 15 wafer. In addition, the residue of the coating cup can be used to prevent or prevent the waste material from rotating away from the wafer into the coating cup without flowing into the waste container. Importantly, the stress buffer coating edge lip removal composition and method meet the following combination requirements: (1) reducing the thickness of the coating edge lip, (2) having drying characteristics so that the solvent material will not be deposited on the bottom of the wafer, (3) Remove 20% of the dry coating material from the bottom side of the wafer, and (4) Do not have the tendency to promote the accumulation of coating waste in the coating cup. Therefore, the present invention can solve the following requirements by providing a novel edge-lip removal composition that meets the aforementioned requirements. Due to the insufficient performance of the photoresist edge-lip removal solvent, it is necessary to improve the edge-lip removal treatment of the stress buffer coating.

13 200416490 2. Description of the invention [Summary of the invention 2 Summary of the invention Therefore, one object of the present invention is to provide a marginal lip remover (ebr) composition for buffering coating materials with performance superior to that of components known in the industry. The composition for removing the lip from the substrate includes at least one ketone selected from the group consisting of:

-r2

(CH2) n wherein R! And R2 are each selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, second butyl, and isobutyl, and wherein η is equal to 10 2 ; At least one ester other than lactones; and at least one lactone.

In a broad aspect of the invention, the at least one is present in an amount of about 25 wt.% To about 55 wt.%; The at least one ester is present in an amount of about 20 to 15 about 55 wt.%; And the at least one The lactone is present in an amount of about 10 wt.% To about 35 wt.%. The present invention also provides a composition for removing a lip from a substrate, comprising about 25 wt ·% to about 55 wt ·% 2-pentanone; about 20 wt ·% to about 55 wt. ° / 〇ethyl lactate; and about 10 wt.% To about 35 wt.% Γ-butyrolactone. 20 The present invention also provides a composition for removing a lip from a substrate, comprising about 30 wt ·% to about 50 wt ·% 2-pentanone; about 30 wt ·% to about 50 wt ·% lactic acid 14 200416490 发明, description of the invention Ethyl ester; and about 15 wt.% To about 35 wt% y_T lactone. The present invention provides an additional

The invention provides a method for removing residues from a substrate. This method includes the following steps: and about 20 wt.% To about 30 wt.% Γ-butene. Including applying a coating composition to a substrate to form a coated substrate with a lip formed thereon; the lip formed on the coated substrate contacting a lip remover composition comprising: at least one selected Ketones from the group consisting of:

Its center and 2 are respectively selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, second butyl, and isobutyl, and other than 1 or at least one lactone Ester; and at least one lactone, thereby dissolving the marginal lip; and removing the dissolved marginal lip from the coated substrate. The invention also provides a method for removing a lip from a substrate. The method includes contacting the edge lip coating with a composition comprising: 20 at least one ketone selected from the group consisting of: 15 200416490 玖, description of the invention

Rl R2 ^ _yCH2) n Formula 1 Formula 2 where Ri and R2 are selected from the group consisting of methyl, ethyl n-propyl, n-butyl, second butyl and isobutyl, and where η is equal to } Or 2;

5 at least one ester other than lactones; and at least one lactone to thereby dissolve the marginal lip; and removing the dissolved marginal lip from the coated substrate. The substrate is typically coated with a stress buffer coating or a positive photoresist coating. Brief description of the drawings 10 Figure 1 is a cross-sectional view of a substrate with photoresist coating just before applying the solvent according to the prior art. The photoresist coating is based on a phenolic varnish resin and o-quinone II. The main composition of azide;

Fig. 2 is a prior art substrate according to Fig. 1 which has been subjected to a lip removal treatment according to the prior art; 15 Fig. 3 is a sectional side view of the substrate according to the prior art, which has been spin-coated with stress buffer coating The composition is soft-dried; and FIG. 4 is a cross-sectional side view of the substrate shown in FIG. 3 after the edge lip is removed according to the present invention.

Embodiment C; J 20 Detailed description of the preferred embodiment The present invention provides a supply with slower performance than known compositions in the industry. 16 200416490 发明, description of the invention edge lip remover (EBR) composition for punch coating materials , Verify its performance as described here. The present invention also provides a method for removing an undesired coating composition from a peripheral region of a substrate coated with a stress buffer coating composition using the aforementioned composition. 5 The method includes the following steps: (a) spin coating a substrate with a stress buffer coating composition; contacting the peripheral region of the coated substrate with a sufficient amount of the marginal lip remover composition of the present invention; and ((:) The coated substrate separates and dissolves the coating composition. Suitable substrates for use in the present invention include (but are not limited to) silicon, aluminum, 10 copper, chromium, nickel, gold, buttons, titanium, tungsten, ferrous metals, aluminum / copper Alloy, polymer resin, silicon dioxide, doped silicon dioxide, polysiloxane, silicon carbide, silicon nitride, titanium nitride, nitride button, silicon arsenide, gallium arsenide, indium sulfide, indium selenide, Indium tin oxide, buttons, polycrystalline silicon, inorganic glass and ceramics have been spin-coated with a stress buffer coating composition. The preferred substrate is a thermally grown silicon oxide / silicon wafer, such as a microprocessor, memory And other substrates used in the fabrication of micro integrated circuit components. The optimal substrate is a silicon wafer on which all the processing necessary for the manufacture of functional semiconductor elements has been completed. It is applied to silicon wafers or other wafers by spin coating. Stress buffer coating composition as a coating The material may be a polyimide or polybenzoxazole-based precursor polymer, but is not limited to these components. The preferred stress buffer coating is mainly a positive phase-modulating photosensitive material. The material includes The water-soluble polyamine resin is mixed with o-diazide photosensitizer, and it is dissolved in polar aprotic solvents such as N-methyl sulfide steel or γ-butyrolactone (U.S. Patent No. I Iron ⑻, The reference method is incorporated herein. In addition, the 'positive phase-modulating photosensitive composition may be 17 200416490. The invention description contains a polyamine bearing an o-quinone diazide substituent. The o-quinone diazide photosensitizer is selectively mixed, and Dissolved in polar aprotic solvents such as N-fluorenylpyrrolidone or γ-butyrolactone (U.S. Patent No. 6,127,086 and U.S. Patent No. 6,617,225 'are incorporated herein by reference). Can also be used Negative phase modulation 5 Photochemical composition containing polyamine ester with a radiation-crosslinkable ester group, a radical-generating photoinitiator compound, and a suitable solvent such as N-methylpyrrolidone or γ -Butyrolactone (US Patent No. 4,548,891; US Patent No. 5,011, No. 755; and U.S. Patent No. 5,019,482, incorporated herein by reference.) 10 Spin coating is a preferred method of applying a stress buffer coating composition. During a spin coating operation, a silicon wafer or other substrate is placed. Rotate on the vacuum chuck and rotate at a high speed (such as 5000-3,000 rpm) after being dispersed in the top surface of the wafer or in the center of the stress buffer coating composition. The parameters of the spin coating method such as rotation speed and rotation time can be According to the intended use. As shown in Figure 3 above, during spin coating, the stress buffer 15 coating formulation leaves a band or "edge lip" coating material on the edge of the wafer, which is obviously larger than the rest of the wafer. The coating is thicker. The width of the edge lip is about 丨 to about 3 mm. It appears on the entire periphery of the wafer. The thickness of the edge lip can be up to twice the thickness of the rest of the coating area after drying. A good method is to use a spin coater equipped with a front side 20 and a bottom edge lip to remove the solvent dispensing nozzle. The bottom nozzle is a fixed nozzle 'which applies a solvent to the bottom side of the wafer. During the lip removal solvent application, the circle rotates, the solvent moves to the outer edge of the wafer, and the dissolved coating material is thrown out. The top nozzle can be fixed or can be equipped with a programmable mobile mechanism. The solid nozzles apply a lip to remove the solvent flow to a single position. The single position is typically set at about 3 to about 3 mm inward from the wafer edge. The nozzle with a programmable movement mechanism can apply the solvent in a sweeping manner, sweeping from the edge of the wafer to a point about 2 mm inside the wafer. The lip removal treatment and the bottom cleaning treatment can be performed simultaneously or successively. The best method is to use the top side and the bottom side at the same time to apply the lip to remove the solvent. The lip removal process is completed using a centrifugal drying cycle that includes rotating the wafer through an & shake off the rim lip removal solvent and the lip removal solvent containing the stress buffer coating composition dissolved in the towel. Time, and drying the wafer. Figure 4 shows the results of spin-coating a wafer with a stress buffer coating composition, performing a 10-lip removal process, and then soft-baking the coated wafer. Figure 4 is a cross-sectional side view of the wafer in Figure 3 after the wafer and the lip are removed, showing the reduction in the thickness of the lip in accordance with the present invention, and the removal of material on the wafer edge and bottom side. The main structure of Figure 4 is the wafer! , Stress buffer coating 3, where% represents the edge of the stress buffer coating with a thickness substantially smaller than 3a, and ratios representing the wafer edges 15 and 10 represent the clean bottom side of the wafer. The solvent composition of the edge lip removal solvent of the present invention can be formulated and processed to solve four engineering problems: 丨) reduce the thickness of the edge lip of the stress buffer coating; 2) have drying characteristics so that the solvent material will not be deposited on the bottom of the wafer; 3 ) Removing part of the dried coating material from the bottom side of the wafer; and 4) there is no tendency to cause the coating waste 20 to accumulate in the coating cup. The strength of a good solvent using one or more stress buffer coating compositions Polar inert solvents can address the need for excellent solubility. Powerful polar aprotic solvents suitable for use in the present invention include, for example, dibutyrolactone, divalerolactone, y-caprolactone, delta-valerolactone, or any combination thereof. It is preferred that the one or more 19 玖, the invention shows that a kind of powerful polar aprotic solvent is γ-butyrolactone, high bud point of butyric vinegar 4-20 rc) and low vapor pressure (1.5 mm Hg), delay Drying of the coating cup and reducing accumulation of coating waste in the coating cup. However, purely strong polar inert solvents such as γ-butyrolactone dry very slowly during the edge-lip removal process, resulting in material movement beyond the wafer edge to the wafer bottom side contamination. Regarding the issue of slow drying, a low polar solvent can be added to one of the present invention. A strong polar protic solvent is inert to obtain a solvent mixture with improved drying protons. However, the meltdown composition must not contain excessive volatility. 10 15 Solvents 'Because the solubility of the mixture in the coating composition may be reduced to a certain point, the thickness of the lip cannot be effectively reduced.' Unacceptable. The formation of coating cup residues can be reduced by slowing the drying of the coating cup with solvents having intermediate volatility. In the context of the present invention, such intermediate volatile solvents are called "buffer solvents". The drying speed of the lip removal composition can be adjusted by changing the amount of the buffer solvent used. Therefore, the preferred lip-removing composition is composed of a solvent mixture selected from the respective solvents having three kinds of boiling point ranges of low, medium and high. The preferred boiling point range is

About 80 ° C to about 160t (low), about 135 ° C to about 185 ° C (medium) and about 190 ° C to about 235. 〔:(high). A solvent 20 having a boiling point in the range of about 8 (rc to about 160 t) can be used to promote the drying of the lip-removing composition, and can optionally be used to improve the solubility of the stress buffer coating material. It ranges from about 135 to about 185 t in boiling point The buffer solvent is particularly useful for adjusting the drying characteristics of the composition. Solvents with a boiling point in the range of about 90 ° C to about 235 ° C can be used to reduce the thickness of the lip and provide additional means to adjust the drying characteristics of the lip removal solvent composition 20 200416490 发明, invention description Boiling point is about 80. (: The solvent in the range of about 160 ° C is selected from the group consisting of ketones having 4 to 6 carbon atoms according to formula j and formula 2 below.

'R! And R2 in formula (I) are each selected from the group consisting of alkyl groups, and include methyl group, ethyl group, n-propyl group, n-butyl group, second butyl group, and isobutyl group. In Equation 2, the values of η are 1 and 2. These solvents can be used singly or in combination, wherein the mixture contains at least two ketones in an amount of about 0.05% to about 99.5 wt.% Of the ketone mixture. The preferred solvent is a group selected from the group consisting of 2-pentanone, 3-pentanone, 2-hexanone, and hexanone, and a mixture of these solvents, wherein the mixture is composed of two 10 solvents to make up about 0.5 wt.% Of the mixture Content to about 99.5 wt.%. The best solvents are 2-pentanone and 3-hexanone. The boiling point is about 135. (: The buffer solvent in the range of 185t is one or more esters. The esters suitable for use in the present invention such as ethyl lactate, propylene glycol monomethyl acetate, isobutyl isobutyrate, ethylene glycol ether acetate, 15% ethyl acetate, ethyl acetate ethyl acetate, and 3-ethoxypropionic acid ethyl alcohol. You can use it alone as the main mixture, where the mixture contains at least two esters, the respective contents of which are in the mixture. About 0.5 wt.% To about 99.5 esters. Wt.%. The best ester is a solvent of the Beverly Lactic Acid point in the range of about 190 ° C to about 235 ° C. It can be used to reduce the thickness of the lip by 20, and provide adjustment of the lip Removes the drying characteristics of the solvent composition

It can be selected from the group consisting of γ-butyrolactone, γ-valerolide 21 200416490 玖, description of the invention 酉 Y, caprolactone, δ-valerolactone. The lactone can be used singly or as a mixture, and the mixture contains two lactones, each content of which ranges from about 0.5 wt.% To about 99.5 wt.% Of the lactone mixture. The best lactone is γ_τ lactone. According to the novel photosensitive stress buffer coating edge lip remover composition 5 according to the present invention, the composition includes about 25 Wt.% To about 55 wt.% Of the ketone according to Formula 1 and Formula 2 or a mixture of two or two rhenium, wherein according to Formula 丨The ketone contains about 4 to 6 carbon atoms, and X and X are each selected from the group consisting of alkyl groups, including methyl, ethyl, n-propyl, n-butyl, second butyl, and isobutyl; and Wherein the ketone system according to formula 2 is selected from the group consisting of η equal to about 1 or 2; esters or ester mixtures within about 20% to about 55 π ·% within 10 S days; and about wt.% To about 35 wt. -% Lactones or lactone mixtures. Preferred compositions include about 30 wt% to about 50 plus% panvalerone; about 30 wt.% To about 50 wt.% Ethyl lactate; and about 15 ".% To about 35 butyrolactone. Best The composition includes about% w [% to about 50 plus% 2-pentanone, about 35 wt.% To about 50 wt.% Ethyl lactate; and about 20 wt% to 15 about 30 wt.% Γ- The following examples of yoke are used to illustrate the present invention, but not to limit the scope of the present invention. Example 概略 The general preparation procedure for the removal of the solvent composition of the lip is an appropriate amount of each microelectronic grade solvent combined by weight in 4 Li plastic discarded plastic road bottles were ceremonially sealed, and the plastic bottles were rolled on a bottle grinder for 2 hours to mix > cereals. The obtained solution was tested for its use as a lip removal solvent composition. Formulation Examples and Comparative Examples The solvents used are shown in the following Table 22 玖, Description of the invention Table 1 Solvents used to prepare the solvent composition to remove the lip solvent Solvent name CAS number Boiling point ° C Solvent A Ethyl lactate 97-64-3 154 Solvent B γ-butane Ester 96-48-0 204-205 Solvent C 2-pentanone 107-87-9 100-101 Solvent D Butyl lactate 138-22-7 185-187 Solvent E γ-pentene 108-29-2 207-208 Solvent F 2_hexanone 591-78-6 127 Solvent G Pinacolone 75-97-8 106 Margin lip removal solvent drying test results fast and complete bottom side drying Important properties of the edge-lip-removing solvent composition for stress buffer coating invented. The drying performance characteristics of the edge-lip-removing solvent composition were determined using the edge-lip-removing solvent drying test. A series of 100 mm diameter silicon wafers were tested On a SVG 8600 spin coating tool chuck equipped with fixed top and bottom spraying and dispensing nozzles, rotate at a speed of 1200 rpm for 3 · 5 seconds, while removing the solvent composition from the lip and applying it to the bottom of the wafer. This procedure is repeated using marginal lip removal solvent application parameters but changing the rotation time and rotation speed used to dry the wafer. The variable combination of drying time and speed parameters used are 1500 rpm 15 seconds, 2000 rpm 20 seconds, and 2500 rpm 25 seconds. Check the wafer after spin-drying to see if there is residual solvent on the back side of the wafer. The test results are reported in Table 2 to achieve complete spin-drying parameters. The preferred result is after 25 seconds at 2500 rpm The bottom side is completely dry. The best result is to obtain complete dryness of the bottom side after 2000 s rotation for 20 seconds, because this condition is more economical in terms of the processing time of the drying cycle. Obtained from Comparative Example 1 shown in Table 2 -6 Composition drying test data shows that the mixture 200416490 玖, invention description contains 30% or less γ-butyrolactone, under the best conditions, ethyl lactate (Buddha point 154 ° C) and γ-butyrolactone ( Drying of a mixture with a boiling point of 204-205 ° C). This is the opposite of the teaching of JP 2000-3 19691. In this case, the claimed patent contained a composition of 60- 100% γ-butyrolactone and 10-40% of a solvent with a boiling point lower than γ-butyrolactone. When the composition is used as a marginal lip of the stress buffer coating, the valley is easy to dry when the solvent is removed. The drying data obtained from the composition of Comparative Example 7 shows that if 35% of the more volatile solvent pinacone (boiling point 106.0) is added to the composition, the ethyl lactate content can be reduced to 45%. Similarly, the implementation The drying results of the compositions of Examples 1-6 show that the formulation contains 25-45% 2-pentanone (boiling point i0 (Morc) 10 or 2-hexanone (boiling point 127.0), which allows reducing ethyl lactate required to dry the composition. Ester buffer solvent content. The dried composition uses a preferred drying cycle of about 2500 rpm for 25 seconds and contains up to 30% γ-butyrolactone. Adjusting the ketone to 35-45% results in a better use of 200 rpm for 20 seconds Complete drying can be achieved in the drying cycle. The composition information of Example 4 shows that yvalvalactone can replace γ_τlactone; 15 Example 6 shows that a lactone mixture can be used. Thus, the ternary formulation according to the present invention is provided to achieve the required Means to remove the drying characteristics of the edge-lip removal solvent while maintaining the composition with a significant amount of lactones or lactone mixtures. Results of the edge-lip removal solvent removal test to remove stress buffer coating contamination deposited on the bottom side of the wafer during spin-coating. One of the lip removal solvent compositions Important function. The bottom side pollution removal method is commonly known in the industry as "backside cleaning". It should be understood that this method belongs to a part of the present invention. The bottom side pollution often occurs as deposits of individual coating materials. Convection and substantial drying. Removal of the individual deposits of such substantially dry materials requires a stronger solvent than removal of wet coating materials. Thus 24 200416490 发明, description of the invention, the lip removal solvent composition of the invention is tested for its removal The effect of coating materials after drying. In the test, a series of 100 mm diameter silicon wafers were spin-coated using a SVG Model 8600 coating tool equipped with a top and bottom lip solvent distribution nozzle. The composition of the stress buffering coating material is Durimide 9005, which is a commercially available positive phase photosensitizing agent available from Arch Chemical Co., Ltd. The spin coating conditions are distributed at 12,000 rpm and unfolded1 The milliliter composition was subjected to 4 seconds, and then rotated at 2500 rpm for 15 seconds. Then the wafer was soft-baked on a hot plate at 115 ° c for 3 minutes. The resulting coating thickness was 10KLA-Tanco (Tencor ) P_ll profile measurement. Then the edge lip removal solvent to be tested is applied to the center of the wafer using the top side lip removal delivery nozzle, and the delivery time is 60 seconds. The solvent flow rate is 675 g / min at 1000. , Followed by a spin-drying cycle at 2000 rpm for 20 seconds. Then repeat the thickness measurement to find the difference between the thickness of the soft baked coating without the lip removal treatment and the thickness of the coating with 15 lip removal. The difference in thickness is used as a measure of the effect of the composition in removing the soft-drying coating. Table 2 shows the experimental results of the examples and comparative examples of the present invention. Although Comparative Examples 1-3 meet the better drying characteristics, their solubility in the dried material Poor, only moderate amounts of film can be removed. As in the composition of Comparative Examples 4-6, increasing the amount of known content by 20 will not improve the results. The inventors believe that the main reason for this performance is the swelling of the film at higher concentrations of the lactone solvent. On the contrary, the composition of Example 丨 _6 also shows good solubility in dry materials, which meets the requirements for better drying. Examples 1-3 verify that the dried film is completely removed and provides optimal drying characteristics. Examples 1-6 also show that the solubility of ketone (boiling point 127 ° C) in the composition can be greatly improved by including 2.pentanone (boiling point 10rc) or 2-hexanone 25 200416490 玖. The use of any one of the ketones in the composition allows the inclusion of up to 30% of a high boiling lactone solvent in the composition. Table 2 Solvent drying test and solvent removal test results of Examples 1 to 6 and Comparative Examples 1-8 of the present invention

The top and bottom side application tests show that the optical stress buffer coating lip removal treatment poses unique problems. Using the front edge lip can be removed for a clear and clean outer edge of tl_3 mm. Using photosensitive stress buffer coating, the front edge edge can be minimized but not completely removed during the edge lip solvent application. The purpose is to reduce the marginal lip area of the film; as close as possible to the thickness of the remaining part of the thin film, the negative influence of the transitional lip on 26 10 200416490 发明, the description of the invention, and the yield is minimized. In order to test this requirement, a series of 100 mm diameter silicon wafers were spin-coated with Duramag 905 using SVG 8600 spin-coating tools, equipped with fixed top- and bottom-side solvent delivery nozzles. As is common in the industry, the coating tool operation program combines the spin coating process and the lip removal process into a single continuous machine process. The program used is: (1) 1200 rpm for 4 seconds, applying stress buffer coating composition; (2) 2500 rpm for 15 seconds, spin coating stress buffer coating composition;

(3) 750 rpm for 1.5 seconds, apply EBR solvent to the top side of the wafer; (4) 1200 rpm for 3 seconds, apply EBR solvent to the bottom side of the wafer; and 10 (5) 2000 rpm for 20 seconds, centrifuge and dry the wafer.

Then the wafer was dried on a hot plate at Π5 ° for 3 minutes, and optically inspected the presence of the bottom-side residue. The degree of removal of the top-side lip was evaluated using a KLA-Tanco P-11 profile meter. The outer profile needle is set at a point about 6 mm from the wafer edge on the film. Then the needle is scanned toward the wafer edge to a point offset from the 15 wafer edge. The lip height above the surface of the film is scanned by the outer corridor gauge Data determination. The removal quality of the bottom edge lip and the cleanliness of the edge are determined by optical inspection and rated as pass when the bottom side is clean, and rated as failed when the coating material can still be observed on the bottom side of the wafer 27 200416490 发明, Description of the invention Table 3 Examples 7 and 8 of the present invention and Comparative Examples 9-12 Top and bottom side application test results A% B% C% Test results Edge lip height (micron) Example 7 45 20 35 P 3.0 Example 8 35 20 45 P 7.8 Comparative Example 9 80 20 0 F -1.0 Comparative Example 10 70 30 0 F -4.0 Comparative Example 11 55 0 45 P 16.0 Comparative Example 12 (Rimless Lip Removal) 0 0 0 F 13.0 The data of Examples 7 and 8 in Table 3 shows that when the marginal lip removal treatment is not used (more than 5 12), the thickness of the edge lip is reduced relative to the thickness of the 13 micron edge lip. In the experiments of Examples 7 and 8, the bottom side of the wafer did not contain coating contamination; the wafers of Comparative Examples 9 and 10 had reduced thickness. It ’s a lip, but because of the slow-drying characteristics and poor solubility of the comparison composition, there is still contamination on the bottom side. Contrary to Example 3, 'Comparative Example 丨 丨 The results show that only 10% of the group containing pentanone and ethyl lactate Although the object can remove backside pollution, it cannot effectively reduce the thickness of the edge lip. In fact, the thickness of the edge lip must be increased. Therefore, in the preparation, lactone or lactone mixture must be included to reduce the thickness of the edge lip. Example 13 is working The photoresist edge lip removal treatment is also δ flat. The best edge lip removal solvent composition is used to remove the photoresist-coated 15 edge lips and the bottom side pollution. In this way, a stone wafer with a diameter of 1000 mm Spin-coated with OrRTM 620, which is a working photoresist composition from YAK. The coating was applied using a SVG 8600 spin-coater at a speed of 3000 rpm and a spin-coating time of 30 seconds. The top side lip was subsequently contacted to implement EBR solvent formulation of Example 3. Marginal lip removal treatment Includes EBR solvent 6 28 配送 distributed on the top side of the 100 玖, the description of the invention seconds, and then the cycle of the bottom side coffee solvent used at 3000 rpm for 8 seconds delivery time. The lip removal treatment is a magical 7 seconds The centrifugation and drying cycle is completed._Crystal® is baked on a hot plate for 3 () seconds to obtain a solid film with a thickness of 0 microns. The wafer after baking does not contain contamination on the edges and the bottom side, and has 5 lips on the coating edge. It is removed to obtain a clean substrate as shown in Figure 2. Therefore, the edge-lip-removing coating composition of the present invention can be used to process a photoresist film.

It should be understood that the foregoing description is only illustrative of the present invention. The skilled artist may make many changes and modifications without departing from the invention. As such, the invention is intended to cover all such alternatives, modifications, and variations. 10 [Schematic description] Figure 1 is a cross-sectional view of a substrate with photoresist coating just before the solvent is removed according to the prior art. The photoresist coating is based on a novolac resin and o-quinone. The composition of diazide is mainly; Fig. 2 is a substrate of the prior art according to Fig. 1, which has been subjected to a lip removal treatment according to the prior art of 15;

FIG. 3 is a cross-sectional side view of a substrate according to the prior art, the substrate has been spin-coated with a stress buffer coating composition and soft-dried; and FIG. 4 is a substrate shown in FIG. Later section side view. Symbols of the main components of the drawing] 20 [1 ... substrate, wafer la ... exposed substrate peripheral band lb ... exposed substrate edge lc ... substrate peripheral bottom edge 2, 2b, 2c, 3b, 3c ... coating 3 ... ·· stress buffer coating 3 a ... thick edge 胥 3d ... stress buffer coating edge lip 29

Claims (1)

200416490 Scope of patent application 1. A lip remover composition comprising: at least one ketone selected from the group consisting of: Formula 1 and Formula 2 are each selected from the group consisting of methyl, 10 15 ethyl, n-propyl, n-butyl, second butyl and isobutyl, and ^ equals 1 or 2 At least one ester other than lactones; and at least one lactone. 2. The composition of the scope of application for item i, wherein the at least one class contains 4 to 6 carbon atoms. 3. The composition of item i in the scope of patent application, wherein the at least one copper-clad 35 or 6 carbon atoms; and wherein ~ and ~ are each selected from the group consisting of methyl, ethyl, N-propyl, n-tau and isobutyl. 4. The composition in item 1 of the patent application scope 2-pent. 5. The composition according to item 丨 of the patent application, ethyl lactate. 6. The composition according to item 1 of the scope of patent application is selected from the group consisting of butyrolactone, γ-valerolactone, y-caprolactone, δ-valerolactone and any combination thereof. Wherein the at least one_ wherein the at least one ester is a composition in which the at least one lactone is as described in item 7 of the patent application, wherein the lactone is butyrolactone 30 20 200416490 The composition of range 1, wherein the at least one ketone is present in an amount of about 25 wt.% To about 55 wt.%; The at least one ester is present in an amount of about 20 wt.% To about 55 wt.%; And The at least one internal vinegar is present in an amount of about 10 wt.% To about 35 wt.%. 9 · The composition according to item 8 of the patent application range, wherein the at least one _ is present in an amount of about 30 wt.% To about 50 wt.%; The at least one ester is present in an amount of about 30 wt.% To about 50 wt.%; and the at least one inner cooler is present in an amount of about 15 wt.% to about 35 wt.%. 10. The composition according to item 8 of the patent application range, wherein the at least one ketone is present in an amount of about 35 wt.% To about 50 wt.%; The presence of the at least one ester is about 35 wt.% To about 50 wt.%; and the at least one internal vinegar is present in an amount of about 20 wt.% to about 30 wt.%. 11. The composition according to item 1 of the patent application range, wherein the at least one is about 25 wt.% To about 55 wt.% 2-pentanone; the at least one ester is about 20 wt.% To about 55 wt. % Ethyl lactate; and the at least one lactone is about 10 wt.% To about 35 wt.% Γ-butyrolactone. 12. The composition as claimed in claim 1, wherein the at least one _ is about 30 wt. ° / 0 to about 50 wt.% 2-pentamidine; the at least one S is about 30 wt. ° / °. To about 50 wt.% Ethyl lactate; and the at least one lactone is about 15 wt.% To about 35 wt.% Y-butyrolactone. 13. The composition according to item 1 of the patent application range, wherein the at least one ketone is about 35 wt.% To about 50 wt.% 2-pentanone; the at least one ester is about 35 wt.% To about 50 wt. ·% Ethyl lactate; and the at least one lactone is from about 20 wt.% To about 30 wt.% Γ-butyrolactone. 31 200416490 10 15 Pick up and apply for patent scope 14 · A method for removing residue from a substrate, including: · applying a coating composition to the substrate to form a coated substrate with a lip formed thereon; The lip on the coated substrate is in contact with a lip remover composition containing at least one ketone selected from the group consisting of: Formula 2 whose center and ruler 2 are respectively selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, second butyl, and isobutyl, and wherein η is equal to 1 or 2; at least one Esters other than lactones; and at least one lactone, thereby dissolving the marginal lip; and removing the dissolved marginal lip from the coated substrate. 15. The method of claim 14 further comprising dissolving any undesired coating composition from the bottom side of the coated substrate after the coated substrate contacts the lip removal composition. 16. The method of claim 14 in which the coating composition is selected from the group consisting of a stress buffer coating and a positive working photoresist coating. 17. The method of claim 14 in which the coating composition is a stress buffer coating. 32 200416490 Patent application scope 18 · For example, the method of patent application scope No. 17 顼 士, method, wherein the stress buffer coating composition is selected from the group consisting of polyimide polymer, Polyimide precursor polymer, and any combination thereof. 19. The method according to claim 17, wherein the stress buffer coating composition is selected from the group consisting of a polyurethane polymer with a radiation-sensitive moiety based on acetic acid, and Polyvinylamine S polymer containing a radiation-sensitive moiety in an acetic acid group. ίο The method of claim 17 in the scope of patent application, wherein the stress buffer coating composition is selected from the group consisting of polybenzodeca polymers, polybenzode precursor polymers, and any of the following: combination. , Shen. The method of item 14 of the monthly patent domain, wherein the coating composition is applied to the substrate by a semiconductor wafer spin coater. 15 22 · As in the method 1 of the scope of application for patent No. 14, the substrate comprises a material selected from the group consisting of: Xi, Ming, copper 'chrome, nickel, gold, group, copper, tungsten, iron metal, aluminum' steel Alloys, polymer resins, silicon dioxide, doped stone dioxide, polylithium oxide resins, carbides, nitrides, titanium nitrides: nitride groups, stone fossils, gallium sulfide, indium sulfide , Coded Indium, Indium Tin Oxide, Group, Setase Interview ^ ^ Daylight Silicon, Inorganic Glass, Ceramic and any combination of i. 8 20 S If you apply for the full-time _22 method, the substrate cutting wafer. A method for removing a marginal lip from a substrate, the method comprising: contacting a delta lip coating with a composition comprising: to > a group selected from the group consisting of: 33 200416490 Patent application scope Its center and heart are selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, second butyl, and isobutyl, and wherein η is equal to 1 or 2; 5 at least one lactone Esters other than; and at least one lactone, thereby dissolving the marginal lip; and removing the dissolved marginal lip from the coated substrate. The method of claim 24, wherein the substrate is coated with a stress buffer coating. 102. The method according to item 24 of the patent, wherein the substrate is coated with a positive working photoresist. 27. The method of claim 24, wherein the at least one net contains 4 to 6 carbon atoms. 28. The method according to item 24 of the patent application, wherein the at least one kind of package includes 15 3 5 or 6 * antiatoms, and wherein R, and r2 are each selected from the group consisting of methyl, ethyl , N-propyl, n-butyl and isobutyl. 29. The method of claim 24, wherein the at least one ketone is 2-pentanone. 30. The method of claim 24, wherein the at least one vinegar is 20 ethyl lactate. 34 200416490 Patent application scope 3 I The method according to item 24 of the patent application scope, wherein the at least one lactone is selected from the group consisting of γ-butyrolactone, valerolactone, y-caprolactone, Delta-valerolactone and any combination thereof. 32. The method of claim 31, wherein the lactone is γ-butyrolactone. 3 3 · The method of claim 24 in the scope of patent application, wherein the at least one ketone is present in an amount of about 25 wt.% To about 55 wt.%; The at least one ester is present in an amount of about 20 wt.% To about 55 wt.%; And the at least one lactone is present in an amount of about 10 wt.% To about 35 wt.%. 34. The method of claim 33, wherein the at least one ketone is present in an amount of about 30 wt.% To about 50 wt.%; The presence of the at least one ester is about 30 wt.% To about 50%. wt. 0/0; and the at least one lactone is present in an amount of about 15 wt.% to about 35 wt. 0 / 〇. 35. The method of claim 33, wherein the at least one ketone is present in an amount of about 35 wt.% To about 50 wt.%. The at least one ester is present in an amount of about 35 wt.% To about 50. wt.%; and the at least one lactone is present in an amount of about 20 wt.% to about 30 wt.o / o. 36. The method of claim 24, wherein the at least one ketone is about 25 wt ·% to about 55 wt ·% 2-pentanone; the at least one ester is about 20 wt ·% to about 55 wt · % Ethyl lactate; and the at least one lactone is about 10 Wt.% To about 35 Wt ·% γ-butyrolactone. 37. The method of claim 24, wherein the at least one sea bream is about 30 wt.% To about 50 wt.% 2-pentanone; the at least one ester is about% wt.% To about 50 wt.% Ethyl lactate; and the at least one lactone is about 15 wt.% To about 35 wt.% Y-butyrolactone. 35 200416490 The scope of patent application 38. The method according to the scope of patent application No. 24, wherein the at least one ketone is about 35 wt.% To about 50 wt% 2 Λ m ./〇2-pentan is the same; the at least one The ester is about 35 wt.% To about 50 wt.Q / o ethyl lactate; and the at least one lactone is about 20 wt.% To about 30 wt.% Γ-butyrolactone. 39. The method of claim 24, further comprising dissolving the coating composition from the bottom side of the substrate after the edge-lip contact composition. 36