JP2008277748A - Method for forming resist pattern, and semiconductor device manufactured by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a resist pattern having a sufficiently-high water-shedding property required in a liquid immesion exposure and a suppressive effect for an exfoliation of a film, and to provide a semiconductor device manufactured by the method. <P>SOLUTION: The embodiment of this invention comprises the steps of arranging an objective lens on a substrate of the semiconductor device with a film to be processed; and forming the resist pattern by the liquid immersion exposure for forming the liquid film between the objective lens and the substrate to exposure. The substrate processed by a water-shedding chemical comprising at least the water shedding agent and the solvent is exposed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for forming a resist pattern, which is required in immersion exposure, has a high water repellency and has a large effect of suppressing film peeling, and a semiconductor device manufactured by the method.

  When the resist pattern is formed by immersion exposure, an apparatus having a structure as shown in FIG. 2 is used (see Non-Patent Document 1). In this immersion type exposure apparatus, a wafer 22 is disposed below a lens 21, and pure water flows through a nozzle 24 so that pure water 23 is filled between the lens 21 and the irradiated surface of the wafer 22. It enters from the inlet 24a and is discharged from the inlet 24b. A fine processing resist film is formed on the irradiated surface as a single layer resist film or a multilayer resist film. In the case of the latter multilayer resist film, the structure of the fine processing resist film is complicated, and is composed of at least three layers of a lower organic film layer, a silicon-containing intermediate layer, and a photosensitive resist layer. Also, in immersion type exposure (immersion lithography), the immersion of the immersion liquid by direct contact between the immersion liquid and the photosensitive resist layer on the uppermost photosensitive resist layer of the microfabrication resist film. In order to avoid organic contamination of the liquid, a top coat layer may be formed.

  In immersion type exposure, there is a method to increase the refractive index between the lens and the wafer to be irradiated by forming a water film (meniscus) using the surface tension of water in the minute gap between the lens and the wafer. Has been taken. When the peripheral edge of the wafer is exposed using this type of liquid immersion apparatus for forming a meniscus, there are chipped shots in which a part of the meniscus protrudes from the wafer. FIG. 8A shows a plan view of the immersion type exposure apparatus. A liquid immersion shower head 82 scans the wafer 81 placed on the stage 80 in the direction of the arrow. The shower head 82 is loaded with a lens 85, and pure water enters from the water inlet 84 and is discharged from the water inlet 83. FIG. 8B is an enlarged view of the portion of the immersion shower head 82 when the peripheral portion of the wafer 81 is exposed, and the two chips marked with a circle can be used as operating chips, but the meniscus is shown. Is protruding out of the wafer, the four chips marked with x are discarded. In this way, when exposing the peripheral edge portion of the wafer, a chip shot is generated in which a part of the meniscus protrudes from the wafer.

  In the case of the chip shot as shown in FIG. 8B, a part of the water filling the space between the wafer 81 and the lens 85 may spill out from the gap 86 between the wafer 81 and the outer peripheral frame of the stage 80. If a large amount of immersion liquid is spilled, the meniscus will collapse and immersion exposure itself will be impossible. Further, even if the amount of spilling is small, the exposure apparatus and the back surface of the substrate are contaminated, and secondary damage that causes defocus due to foreign matters on the back surface of the substrate occurs in a wafer that is exposed later. In addition, when the chip shot is subjected to immersion exposure, if the adhesion of the coating film on the wafer edge to the substrate is weak, film peeling occurs, and foreign matter that has peeled off from the edge is mixed into the immersion liquid with a flow rate. There is a problem that the wafer immersion liquid is contaminated and a pattern defect occurs in the central portion of the wafer.

  FIG. 3 shows the behavior of water in the capillary tube. FIG. 3A shows a case where the inner surface of the capillary is hydrophilic, and water advances in the direction of the arrow in the capillary by the capillary force. On the other hand, FIG. 3B shows a case where the inner surface of the capillary is water-repellent, and water is retracted by the capillary force. For this reason, conventionally, the apparatus is designed to have a structure in which the distance between the wafer and the outer peripheral frame of the stage is as narrow as possible, a water-repellent member is used for the outer peripheral frame of the stage, and the water-repellent coating film is also formed on the entire surface of the wafer. By coating with, spillage of the immersion liquid was suppressed using capillary force.

Thus, in order to lift the liquid upward by the capillary force, it is necessary to make the water contact surface of the capillary water-repellent and increase the contact angle. FIG. 6 illustrates a conventional multilayer resist film subjected to a water repellent treatment. As shown in FIG. 6, the film 62 itself formed on the substrate 61 is vapor-phase silylated with hexamethyldisilazane (hereinafter also referred to as “HMDS”) to form the HMDS treatment region 63. Thus, the substrate is water repellent, and the side surface portion (bevel portion) of the wafer and the peripheral edge portion of the top surface are water repellent by HMDS. Thereafter, a lower organic film layer 64, a silicon-containing intermediate layer 65, and a photosensitive resist layer 66 are formed. Subsequently, a water-repellent and developer-soluble topcoat layer 67 serving as an immersion protection film is formed. Further, a top coat layer 67 that is water-repellent and soluble in the developer is also exposed on the outermost surface in the vicinity of the outer periphery of the wafer, thereby increasing the capillary force. FIG. 7 illustrates a conventional single-layer resist film that has been subjected to water repellency treatment. As shown in FIG. 7, the substrate is made water repellent by forming a HMDS treatment region 73 on the film 72 to be processed formed on the substrate 71. Thereafter, a coating-type organic antireflection film 74 and a photosensitive resist layer 76 are formed, and a water-repellent and developer-soluble topcoat layer 77 serving as an immersion protection film is formed.
Tomoharu Fujiwara et al., "Wafer Management between Coat / Developer Track and Immersion Lithography Tool," Optical Microlithography XIX edited by Donis G. Flagello, Proc. Of SPIE, vol. 6154, 2006

  However, in such a conventional method, the water repellency of the bevel portion remains at the HMDS treatment level, and the water contact angle is about 60 °, so that the water repellency may be insufficient. In addition, HMDS can process only the film to be processed before forming various coating films, and the process is premised on the entire surface of the wafer. There was a problem that it could not be granted. In addition, in order to maintain the water repellency of the outer peripheral portion of the wafer, there is a problem that the removal of the edge of the resist on the outer periphery of the wafer is restricted and the countermeasure against dust generation is restricted. Furthermore, in order to suppress peeling, only the film to be processed and the coating film immediately above the film can be improved.This is not sufficient as a pattern defect suppression effect due to film peeling, and the immersion liquid is not effective during immersion exposure. There has been a problem that foreign matter floats due to peeling from the wafer edge due to convection and induces pattern defects. Further, in the conventional water repellency treatment, there is a concern that the water repellency treatment on the entire surface of the wafer has an adverse effect in the exposure process, and a method for imparting preferable water repellency to the entire surface has not been studied. An object of the present invention is to provide a method for forming a resist pattern having a sufficiently high water repellency required in immersion exposure and having a large effect of suppressing film peeling, and a semiconductor device manufactured by the method.

  According to an embodiment of the present invention, a resist pattern by immersion exposure in which an objective lens is disposed on a substrate of a semiconductor device on which a film to be processed is formed, and a liquid film is formed between the objective lens and the substrate for exposure. The method of forming a resist pattern is characterized in that a substrate treated with a water repellent chemical solution comprising at least a water repellent and a solvent is exposed. Moreover, according to another embodiment of the present invention, a semiconductor device manufactured by such a resist pattern forming method is provided.

  According to the embodiment of the present invention, since the substrate is strongly water-repellent, it is possible to enhance the effect of suppressing immersion liquid spillage by a strong capillary force.

  The resist pattern forming method of the present invention is characterized by exposing a substrate treated with a water repellent chemical solution comprising at least a water repellent agent and a solvent in a resist pattern forming method by immersion exposure. By treating the wafer with the liquid water repellent chemical, the water can be made strongly water repellent, so that the effect of suppressing spillage of the immersion liquid can be enhanced by a strong capillary force. In the conventional HMDS treatment, the water contact angle is only about 60 °, and only water repellency that does not affect pattern formation can be obtained, but according to the present invention, the water contact angle is about 80 ° or More powerful water repellent treatment is possible. Therefore, the resist pattern forming method of the present invention prevents the meniscus from collapsing and the contamination of the backside of the substrate, so that it is possible to provide a high-quality semiconductor device free from pattern defects caused by defocusing due to foreign matter on the backside of the wafer. it can. In immersion lithography, a top coat layer that is soluble in a developer may be formed on the photosensitive resist layer in order to prevent organic contamination from the immersion liquid. Since the top coat layer soluble in the developer is generally water-repellent, when the top coat layer is structured to cover the outermost surface, it is relatively free from liquid spills during immersion exposure at the wafer periphery. Is advantageous, but the water repellent treatment method of the present invention is particularly effective when a topcoat layer soluble in a developer is not used from the viewpoint of cost and the like.

  In addition, when the water repellency treatment affects the resist coating performance, etc., and adversely affects pattern formation, the water repellency treatment is selectively performed only on the outer periphery of the wafer where a chip shot is generated where a semiconductor chip cannot be obtained. There is a need to. In the method of the present invention, since the chemical used for the water repellent treatment is liquid, only the outer peripheral portion of the wafer is selectively water repellent treated by spraying a water repellent treatment agent only on the outer peripheral portion of the wafer. It is possible. Further, since the process is performed on the outer peripheral portion of the wafer that does not affect the patterning, a strong water repellent process with a water contact angle of about 80 ° or more is possible. Edge removal is often performed on the outer peripheral portion of the wafer as a measure against dust generation, and various edge removal shapes may be required for the convenience of the multi-layer resist process. In the conventional method, since the hydrophilic surface may be exposed on the outermost surface when the edge is arbitrarily removed, the degree of freedom of edge removal is low. However, in the present invention, the outermost surface can be made water-repellent with respect to all edge removal shapes by selectively spraying and contacting the water-repellent treatment agent only to the outer peripheral portion of the wafer where the semiconductor product cannot be manufactured. .

  When forming a lower organic film layer, a silicon-containing intermediate layer, and a photosensitive resist layer on the substrate, it may be formed by a multilayer resist method including a step of spin-coating these layers on the substrate. Preferably, a mode in which the treatment with the water repellent chemical is performed at least between each spin coat, before the first spin coat, and after the last spin coat is preferable. According to such an aspect, unlike the conventional aspect in which the adhesion between the film to be processed and the lower organic film layer immediately above it is increased, the adhesion between each film of the multilayer resist structure can be improved. it can. In addition, it does not affect the pattern formation area, is easily peeled off during immersion exposure, and is selectively treated only with a water repellent chemical such as a silane coupling agent only on the wafer outer periphery where adhesion is required. It is possible to suppress peeling. When a silane coupling agent is used as the water repellent agent, an effect of enhancing adhesion can be obtained. Similarly, increasing the adhesion between the substrate and the photosensitive resist layer formed on the substrate, increasing the adhesion between the photosensitive resist layer and the topcoat layer formed on the photosensitive resist layer, It is preferable to use a photolithography process including a step of spin-coating a photosensitive resist layer on a substrate in terms of suppressing peeling at the time of exposure. In this photolithography step, at least during each of the spin coatings, before the first spin coating, And after either the last spin coating, an embodiment in which treatment with a water repellent chemical containing a silane coupling agent or the like is preferred.

  The film to be formed under the fine processing resist film for forming the resist pattern is not particularly limited and is usually inorganic such as polysilicon, silicon oxide film, silicon nitride film, CVD-formed amorphous carbon film, etc. It is a film or a film on which a lower layer inorganic antireflection film is formed. Water repellent treatment is a film composed of a laminate of a processed film surface, which is an underlayer of the above-described fine processing resist film, a lower organic film layer formed on the substrate, a silicon-containing intermediate layer, and a photosensitive resist layer. Of these, it is performed on the outermost surface that comes into contact with water during immersion exposure. Further, the water repellent treatment is not a vapor phase treatment, but is performed by spraying or immersing a liquid with a water repellent chemical, thereby imparting water repellency to the treated surface. Moreover, the process (adhesion reinforcement | strengthening process) by the chemical | medical solution containing a silane coupling agent as a water repellent chemical | medical solution can be performed similarly to a water repellent process, and can provide adhesiveness.

  The water repellent treatment may be performed on the entire surface of the wafer by padding a treatment chemical solution including a water repellent chemical solution containing one or more water repellent agents and forming a liquid film, for example, using the apparatus shown in FIG. Is possible. In this case, the rotation speed of the wafer is basically static (0 rpm), and the liquid can be agitated by giving a swing of 50 rpm at intervals of several seconds. However, when processing the entire surface of the wafer, the patterning portion of the resist film for microfabrication to be applied in a later step will be water repellent, so that the coating performance, development performance, and multilayer process dry development performance will be improved. The water repellent treatment method is restricted due to concerns about adverse effects. For this reason, it may be considered that the desired water repellency is insufficiently provided. In such a case, it is preferable to use a non-fluorine-based water repellent as the water repellent described later, and a water repellent containing at least one of an alkyl group and an epoxy group in the structure, Further, water repellency can be sufficiently imparted by adding at least one of water, acid and alkali to the water repellent chemical. When the water repellent treatment is performed on the entire wafer surface, the effect of suppressing the resist pattern collapse can be further improved. FIG. 17 shows a schematic diagram of a resist pattern. FIG. 17A shows an example of a pattern having a film thickness (resist pattern height) H and a line width d, FIG. 17B is a schematic diagram showing pattern collapse, and FIG. It is the schematic which shows a normal pattern. Regardless of immersion exposure, as the resist pattern is miniaturized, the aspect ratio and the film thickness H / line width d increase, and the contact area between the substrate and the resist pattern decreases, so that the resist pattern collapse easily occurs. There is a problem. In the present invention, when the entire surface of the wafer is treated with a water repellent chemical solution containing a water repellent as described above, it becomes possible to improve the adhesion between the substrate and the resist, resulting in a pattern. It was found that the collapse can be suppressed. Therefore, when the water repellency treatment on the entire surface of the wafer is restricted, the outer periphery of the wafer can be locally processed as described later. However, in order to suppress problems such as pattern collapse, the entire surface of the wafer is It is desirable to perform a water repellent treatment.

  In addition, when the water repellency treatment on the entire wafer surface is restricted, the side surface of the wafer excluding the portion to be patterned, the peripheral edge portion of the top surface, and the peripheral edge portion of the bottom surface (collectively, hereinafter referred to as “peripheral portion”) There is also a method of locally performing a water repellent treatment. As shown in FIG. 5, this method is a method in which a water repellent chemical or the like is locally processed on the wafer outer peripheral portion using an edge rinse mechanism. Specifically, only the peripheral edge of the top surface of the wafer is selectively treated with a water repellent chemical solution while rotating the wafer at about 100 rpm to 2000 rpm to increase the contact angle of the immersion liquid. At this time, the area width of the water repellent treatment or the like at the peripheral edge can be adjusted to about 0.3 mm to 3.0 mm from the wafer edge by controlling the position of the nozzle with high accuracy by a step motor. As this nozzle, an edge rinse nozzle that removes the coating film on the wafer edge by an existing technique may be used as it is. When the nozzle is used separately from the edge rinse, it can be easily performed by adding an edge rinse nozzle. The coating film is a film temporarily formed on a substrate to obtain a desired pattern, such as a lower organic film, a silicon-containing intermediate layer, a resist and an antireflection film, and a top coat. A film that does not remain as a film. In addition, the film to be processed includes the above-described coating film, and finally the semiconductor among the films including the substrate portion (silicon substrate, oxide film, nitride film, Low-K film, etc.) that is the base of the lower organic film. It includes members that remain as device forming films.

  With respect to the peripheral portion of the bottom surface of the wafer, water repellent treatment or the like can be performed on the peripheral portion of the bottom surface by spraying a water repellent chemical or the like from the back surface side. By making the bottom surface water-repellent, the immersion liquid can reach the bottom surface during immersion exposure and the influence of foreign matter on the exposure machine stage can be eliminated. As the nozzle for water repellency on the back surface, the back rinse nozzle for removing the coating film of the existing technology may be used as it is, and when using separately from the back rinse, it can be easily performed by adding a back rinse nozzle. . The area where water repellent treatment or the like is necessary is a portion that generates a force to lift water by capillary force, and is the outermost surface of the portion where the surface of the wafer edge is not horizontal. The influence on the capillary force is the greatest in the bevel portion of the wafer substrate itself, which is close to the outer peripheral frame of the stage, but it is desirable that the non-horizontal portion of the coating film on the inside is also water repellent. Therefore, it is not necessary to make the wafer central portion water repellent, and it is only necessary to make a predetermined region of the wafer outer peripheral portion water repellent.

  Since the water repellent treatment is performed using the edge rinse mechanism of the coating machine, the minimum value of the water repellent area is determined by the edge rinse positioning accuracy (about 0.2 mm to 0.3 mm). Further, as shown in the enlarged view of the wafer edge in FIG. 8B, the maximum value is set to such a value that the effective chips (◯ marks) in the edge exposure shot are not reduced. Normally, due to various processes described below, the edge rinse removal width of the resist may reach up to about 3.0 mm. In that case, even if water repellent treatment is performed up to 3.0 mm, the product Since the yield is not affected, the value that does not reduce the number of effective chips is the maximum edge rinse removal width. At this time, the water repellent treatment is performed on the substrate surface before or after the formation of the fine processing resist film. When the resist film for microfabrication has a multilayer structure, it can be processed on an arbitrary surface before and after application of each layer of the multilayer film stack. For the reaction between the water repellent used in the water repellent treatment and the substrate, it is preferable to select one that reacts at room temperature, but in the case of a water repellant with poor reactivity, a water repellent chemical solution is applied to the surface. After the contact, heat treatment can be performed at a temperature of 60 ° C. to 120 ° C. for about 1 minute using a hot plate (hot plate) or the like, and it is preferable to perform a heat treatment of about 110 ° C. to 150 ° C. If the temperature of the heat treatment is too low, the reactivity between the water repellent and the substrate may not be assisted. In addition, if the temperature of the heat treatment is too high, the properties of the laminated film existing on the substrate may be changed, which is not preferable.

  As the water repellent, a fluorine water repellent, a silicone water repellent, a fluorine / silicone water repellent, a silane coupling agent, a silylating agent, an alkylating agent or an acylating agent may be used. it can. You may use these 1 type or in mixture of 2 or more types. In either case, a solvent suitable for each water repellent agent is diluted to 0.5% by mass to 5.0% by mass. Examples of the water repellent agent include those represented by the following formulas (1) and (2). In order to avoid hydrolysis of the water repellent, the solvent to be used is dehydrated by distillation treatment, use of an absorbent, or use of a water removal filter, and the water content is preferably 50 ppm or less, more preferably 30 ppm or less. The water content can be confirmed by the Karl Fischer method.

  Examples of the fluorine water repellent, the silicone water repellent, and the fluorine / silicone water repellent include the following.

(In the formula (1), R ₁ , R ₂ and R ₃ are H, CH ₃ , C ₂ H ₅ or C ₃ H _7.
n is an integer R of 0~5, C _m F _{2m + 1} or a C _m H _{2m + 1, m} is an integer from 1 to 10. )

(In the formula _{(2), R 1, R} 2, R 3 is _{(CH 2) n -C m F} 2m + 1, n is an integer from 0 to 5, m is from 1 to 10 The integer R ₀ is H, C _k H _{2k + 1} , Si (OCH ₃ ) ₃ , Si (OC ₂ H ₅ ) ₃ , Si (OC ₃ H ₇ ) ₃ , or the structure on the right side of the NH bond (SiR ₁ R ₂ R ₃ ) and k is an integer of 1 to 3)
When water repellent treatment is performed on the entire surface of the wafer, the fluorine-based water repellent does not have sufficient interaction with the wafer and may not be sufficient to suppress pattern collapse, but contains alkyl groups or epoxy groups. When the compound represented by the above formula (2) is used as a water repellent, the adhesion is improved and the adhesion can be improved as compared with the conventional treatment using HMDS. As a result, the pattern The effect of suppressing the collapse is remarkably improved. Among the above formulas (2), the terminal is preferably an amino group.

  A silylating agent can also be used as the water repellent. Examples of the silylating agent include BSA (N, O-bis (trimethylsilyl) acetamide), BSTFA (N, O-bis (trimethylsilyl) trifluoroacetamide), HMDS (hexamethyldisilazane), MSTFA (N-methyl-N-trimethylsilyl-trifluoroacetamide). ), TMCS (trimethylchlorosilane), TMSI (N-trimethylsilylimidazole), DMSDMA (dimethylsilyldimethylamine), and the like.

  A silane coupling agent can be mainly used as a water repellent agent having an adhesion strengthening effect. Some silane coupling agents exhibit water repellency treatment performance. As a high water repellency treatment performance, a propoxysilane derivative is effective because of its slow hydrolysis in water. Silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid. Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. Among them, methoxysilane and ethoxysilane were replaced with propoxyoxysilane thing Is effective as a water repellent. In the adhesion strengthening treatment, a highly reactive methoxysilane derivative is preferable. In order to avoid hydrolysis of the water repellent chemical solution containing the silane coupling agent, the solvent used is dehydrated by distillation treatment, use of an absorbent or use of a water removal filter, and moisture is preferably 50 ppm or less. Preferably it is 30 ppm or less.

  As the alkylating agent, pentafluorobenzyl bromide, 1,4,7,10,13,16-hexaoxacyclooctadecane or the like is used. As the acylating agent, PFPA (pentafluoropropionic anhydride), HFBA (anhydrous heptafluorobutyric acid), acetic anhydride, or the like is used. When the water-repellent treatment surface is an organic film such as a lower organic film layer or a photosensitive resist layer used for a multilayer resist, a compound having a structure as shown in the following formula (3) or formula (4) is used: It is desirable to use a water repellent chemical solution dissolved in a ratio of 0.5 mass% to 5.0 mass% in a solvent that does not dissolve.

(In the formula (3), R ₁ , R ₂ and R ₃ are a methoxy group, an ethoxy group, a propoxy group or an acetoxy group n, an integer functional group Y of 0 to 5, a vinyl group, an epoxy group, a methacryl group, (Amino group, mercapto group, styryl group, acryloxy group, ureido group, chloropropyl group, sulfide group, isocyanate group or alkoxy group)

(In the formula (4), R is C _m F _{2m + 1} or C _m H _{2m + 1, m} is an integer n of 1 to 10, an integer functional group Y of 0 to 5, a vinyl group, (Epoxy group, methacryl group, amino group, mercapto group, styryl group, acryloxy group, ureido group, chloropropyl group, sulfide group, isocyanate group or alkoxy group)
Based on the above contents, a preferable combination of water repellent agents is illustrated in Table 1 by dividing into an inorganic film and an organic film which are materials to be processed. On the other hand, a solvent that dissolves the multilayer resist layer, a solvent that does not dissolve the multilayer resist layer, and a solvent that does not dissolve the top coat layer that is soluble in the developer, and examples of solvents that are preferably used are shown in Table 2. . Moreover, when processing with edge rinse and processing with respect to an exposed substrate, it is preferable to select the solvent which melt | dissolves the coating film before thermosetting. Furthermore, when the coating film is a film to be processed and edge rinsing is not performed, a mode in which a solvent that does not dissolve the coating film is selected is preferable. On the other hand, when a heat treatment after coating is performed immediately after the treatment, the silane coupling agent is preferably an ethoxysilanol derivative or a propoxysilanol derivative in terms of reducing hydrolyzability and improving hydrophobicity. However, a methoxysilanol derivative that reacts at room temperature is preferred when a coating treatment is performed immediately after the treatment, rather than a heat treatment. When both water repellency and adhesion strengthening effects of a water repellent are obtained with a single chemical, the water repellent with the structure shown in formula (1) and a moderately reactive ethoxysilanol-based silane coupling It is preferred to use a mixture of agents. In addition, since the water repellent having the structure shown in Formula (2) and the silazane compound used as the silylating agent generate ammonia as a by-product, it is necessary to pay attention to patterning. Furthermore, the mode of using a mixture of two or more water repellents as described above is preferable in that a highly versatile water repellent / adhesion reinforcing material can be obtained by ensuring reactivity to various substrates.

  A typical example of the water repellent treatment of the present invention is shown in FIGS. 1 and 9 to 13. Basically, the treatment with a water repellent chemical solution that has an effect of strengthening the adhesion including the silane coupling agent is performed between the films having low adhesion between the upper layer and the lower layer, and does not contain the silane coupling agent. The water repellency treatment with the hydrating agent chemical is preferably performed after the formation of all layers. However, there is a possibility of dust generation due to peeling in subsequent exposure processes, etching, diffusion or implantation, dust generation due to physical contact by clamping, etc., peeling due to film characteristics itself, and the like. The circumstances of these various processes determine the necessity of removing the lower organic film layer, the silicon-containing intermediate layer, the photosensitive resist layer, and the top coat layer soluble in the developer at the edge portion of the resist. Therefore, variations are necessary for the process flow, and the following embodiment is an example of the processing flow, and many variations are conceivable depending on circumstances.

  FIG. 1 shows an example in which a top coat layer covers the outermost surface. FIG. 1 (a) shows a process flow, and FIG. 1 (b) shows a cross-sectional structure of a wafer outer peripheral portion after processing. As shown in FIG.1 (b), after forming the to-be-processed film | membrane 2 on the board | substrate 1, the water-repellent treatment layer 3 which consists of a water-repellent agent chemical | medical solution in this invention is formed, and coating type organic reflection is carried out after that. The prevention film 4, the photosensitive resist layer 6, and the top coat layer 7 are formed. The water-repellent treatment surface is generally an inorganic film, and it is desirable to use the formula (1), formula (2), a silylating agent, or a silane coupling agent as the water-repellent treatment agent. Moreover, although any compound is used by diluting to 0.5% by mass to 5.0% by mass in the solvent, the solvent to be used is not particularly limited such as alcohol, acetate, ketone, water, and aromatic, A compound having high dissolution stability can be used. When the water repellent treated surface is an organic film, it is desirable to use a silane coupling agent containing formula (3) or propoxysilanol or ethoxysilanol. When the water repellent chemical solution is supplied onto the substrate, the water repellent is adsorbed on the substrate surface, and a monomolecular layer of the water repellent is formed by a chemical reaction. Spilling of immersion liquid can be avoided. After the immersion exposure is completed, after the photosensitive resist developing process and the etching process, ashing with oxygen plasma and wet processing using a mixed solution of sulfuric acid and hydrogen peroxide solution are performed to remove the resist. When this wet treatment is performed, the water repellent treatment layer 3 formed on the front surface and the back surface is peeled off.

  FIG. 9 shows an example in which the top coat layer is not formed. FIG. 9A shows a process flow, and FIGS. 9B and 9C show a cross-sectional structure of the wafer outer peripheral portion after processing. . First, the film 2 to be processed, the coating type organic antireflection film 4 and the photosensitive resist layer 6 are formed on the substrate 1, and then the water repellent treatment layer 3 is formed. Since the water repellent treated surface is a mixture of an inorganic film and an organic film, the water repellent agent is a mixed solution of formula (1), formula (2) and formula (3), propoxysilanol or ethoxysilanol. It is desirable to use a silane coupling agent containing Each compound is diluted to 0.5% by mass to 5.0% by mass in the solvent, and the solvent used is sensitive from higher alcohols higher than butyl alcohol, higher alkyl ethers higher than butyl ether, aqueous systems, and the like. A solvent that does not dissolve the resist is selected. The water repellent treatment layer 3 is peeled off in the resist removal step. In the example of FIG. 9B, the water repellent treatment layer 3 is formed on the side surface of the substrate, the peripheral edge of the top surface of the substrate, and the peripheral edge of the bottom surface of the substrate. In the example shown in FIG. 9C, the water repellent treatment layer 3 is formed on the side surface of the substrate, the top surface of the substrate, and the peripheral edge of the bottom surface of the substrate.

  FIG. 10 shows an example in which a top coat layer is formed and edge rinse and water repellency treatment are simultaneously performed. FIG. 10A shows a process flow, and FIG. The cross-sectional structure of is shown. As shown in FIG. 10 (b), after forming the film 2 to be processed, the coating type organic antireflection film 4, the photosensitive resist layer 6 and the topcoat layer 7 on the substrate 1, a topcoat edge rinse is performed. The water repellent treatment layer 3 is formed. Since the water repellent treated surface is a mixture of an inorganic film and an organic film, the water repellent agent is a mixed solution of formula (1), formula (2) and formula (3), propoxysilanol or ethoxysilanol. It is desirable to use a silane coupling agent containing Moreover, any compound is used by diluting to 0.5 mass%-5.0 mass% in a solvent. The solvent to be used is selected from higher alcohols higher than butyl alcohol, higher alkyl ethers higher than butyl ether, etc. used for the topcoat solvent soluble in the developer, and dissolves the topcoat layer soluble in the developer. A solvent that does not dissolve the photosensitive resist is selected. The water repellent treatment layer 3 is peeled off in the resist removing step.

  FIG. 11 shows an example in which edge rinse and water repellent treatment are simultaneously performed without forming a top coat layer. FIG. 11 (a) shows a process flow, and FIG. 11 (b) shows a wafer after treatment. The cross-sectional structure of the outer periphery is shown. As shown in FIG. 11 (b), after forming the film 2 to be processed, the coating type organic antireflection film 4, and the photosensitive resist layer 6 on the substrate 1, edge rinsing is performed to form the water repellent treatment layer 3. Form. Since the water repellent treated surface is a mixture of an inorganic film and an organic film, the water repellent agent is a mixed solution of formula (1), formula (2) and formula (3), propoxysilanol or ethoxysilanol. It is desirable to use a silane coupling agent containing In addition, each compound is used by diluting 0.5% to 5.0% by weight in a solvent. The solvent used is an acetate solvent such as PGMEA (propyleneglycolmonomethylether acetate) or a glycol ether such as PGME (propyleneglycolmonomethylether). A solvent that dissolves the photosensitive resist, such as a system solvent, a ketone solvent such as cyclohexanone and γ-butyllactone, is selected. The water repellent treatment layer 3 is peeled off in the resist removing step.

  Next, a method for improving the adhesion between the multilayer films will be described in order to suppress pattern defects induced by peeling during immersion exposure of the multilayer film in the multilayer resist method. FIG. 12 shows an embodiment in which edge rinsing of the photosensitive resist layer is performed without forming a topcoat layer, and is an example in the case of improving the adhesion between the silicon-containing intermediate layer and the photosensitive resist layer. FIG. 12A shows a process flow, and FIG. 12B shows a cross-sectional structure of the wafer outer periphery after processing. As shown in FIG. 12 (b), after the film to be processed 2, the lower organic film layer 8, and the silicon-containing intermediate layer 5 are formed on the substrate 1, an adhesion strengthening process is performed on the surface of the silicon-containing intermediate layer 5. Next, immediately after the photosensitive resist layer 6 is formed, the film below the photosensitive resist layer 6 is made water-repellent by edge rinsing, and the water-repellent adhesion strengthening treatment is performed by a treatment chemical solution containing a silane coupling agent in the water-repellent chemical solution. Layer 3a is formed. Since the adhesion strengthening treatment of the silicon-containing intermediate layer 5 is performed immediately before the spin coating of the photosensitive resist, it is not heat-treated immediately after the treatment, and the unreacted water repellent is washed away by the solvent that dissolves the photosensitive resist. It is preferable to use a methoxysilanol derivative having high reactivity at room temperature.

  The water repellent treatment is carried out continuously without carrying out heat treatment from the coating cup. The silicon-containing intermediate layer is thermoset at this point and is not dissolved by the solvent. In the next water repellency treatment, the photosensitive resist layer must be edge-rinsed and at the same time, all exposed surfaces below the photosensitive resist must be water repellant. Since this water repellent treated surface is a mixture of an inorganic film and an organic film, the water repellent agent is a mixed solution of formula (1), formula (2) and formula (3), propoxysilanol or ethoxysilanol. It is desirable to use a silane coupling agent containing In addition, any compound is used by diluting it in a solvent to 0.5 mass% to 5.0 mass%, and the solvent used has a good edge rinse characteristic among alcoholic, acetate and ketone types. May be used. The water repellent agent is adsorbed on the water repellent treated surface and chemically reacted to form a monomolecular layer of the water repellent agent, so that spillage of the immersion liquid can be avoided. After immersion exposure is completed, after the photosensitive resist development process and etching process, ashing with oxygen plasma and wet treatment using a mixed solution of sulfuric acid and hydrogen peroxide are performed for resist removal. The hydration treatment layer (water repellent adhesion strengthening treatment layer 3a) is peeled off.

  FIG. 13 shows an example in which the adhesion between the photosensitive resist and the topcoat layer is increased. FIG. 13A shows a process flow, and FIGS. 13B and 13C are cross-sectional views of a wafer outer peripheral portion after processing. First, the processed film 2, the lower organic film layer 8, and the silicon-containing intermediate layer 5 are formed on the substrate 1, and after resist application, the photosensitive resist layer 6 is formed by baking at about 100 ° C. for 1 minute. Next, the surface of the photosensitive resist layer 6 is treated with a water repellent chemical solution containing a silane coupling agent, and the treated surface in which an inorganic film and an organic film below the photosensitive resist layer are mixed is made water repellent. After the treatment, a top coat layer 7 is formed. Before the top coat layer 7 is formed, it is treated with a water repellent chemical solution containing a silane coupling agent, so that the interface between the photosensitive resist layer 6 and the top coat layer 7 that is soluble in the immersion developer is used. Adhesion can be improved. As the solvent used for the adhesion strengthening treatment and the water repellency treatment, a solvent that does not dissolve the photosensitive resist layer is selected from among higher alcohols higher than butyl alcohol, higher alkyl ethers higher than butyl ether, and water. The adhesion strengthening treatment and the water repellency treatment can be performed with separate solutions, but a one-liquid treatment is also possible by selecting a treatment agent. A water repellent chemical solution containing a silane coupling agent is a silane cup containing a reactive neutral ethoxysilanol in consideration of the fact that heat treatment does not occur immediately after treatment and that the hydrolyzability of alkoxysilanol is suppressed as much as possible. It is preferable to use a ring agent. As the water repellent, it is desirable to use a silane coupling agent containing formula (1), a mixed solution of formula (2) and formula (3), propoxysilanol or ethoxysilanol. The water repellent treatment layer is peeled off in the resist removal step.

  FIG. 13B illustrates a mode in which the side surface of the substrate is processed with a water repellent chemical solution, and the peripheral portion of the top surface of the substrate and the peripheral portion of the bottom surface of the substrate are processed. The side surface of the substrate, the peripheral portion of the top surface of the substrate, and the peripheral portion of the bottom surface of the substrate are regions that do not affect the pattern formation region and have an unstable adhesive force that is liable to peel off during immersion exposure. This is an area where immersion liquid is likely to leak. Therefore, an embodiment in which the outer peripheral portion of such a substrate is made water-repellent to enhance adhesion is preferable. In addition to the side surface of the substrate, it is also effective to make the peripheral edge portion of the top surface of the substrate or the peripheral edge portion of the bottom surface of the substrate water-repellent and strengthen the adhesion depending on the variety of wafer processes. Similarly, as shown in FIG. 13C, the side surface of the substrate, the top surface of the substrate, and the peripheral portion of the bottom surface of the substrate are made water repellent by treating with a water repellent chemical solution to enhance adhesion. This aspect is also effective. In addition, after forming the coating film on the substrate, the coating film is removed with a solvent that dissolves the coating film on the side surface of the substrate, the peripheral portion of the top surface of the substrate, and the peripheral portion of the bottom surface of the substrate. The method in which the area where the water is dissolved and removed is treated with a water repellent chemical solution, etc., without affecting the patterning. By strengthening, it is preferable in terms of enhancing the dust generation prevention effect and the water repellency effect.

  In any of the above embodiments, other additives and the like may be added to the water repellent chemical solution and the like as long as the effects of the present invention are not impaired. In order to control the water repellent performance and adhesion performance of the water repellent, it is preferable to contain at least one of water, acid and alkali in each chemical solution to be used. The acid is not particularly limited, and examples thereof include alkyl carboxylic acids such as acetic acid and aromatic carboxylic acids. The alkali is not particularly limited, and organic amines such as tetramethylammonium hydroxide (TMAH) can be used. As the acid and alkali, from the viewpoint of the chemical stability of the prepared drug, it is preferable that the acid and alkali be appropriately volatile. For example, it is preferable to use one having a boiling point of 100 ° C. or higher. If the desired water repellency and adhesion cannot be obtained due to the progress of the hydrolysis reaction and accompanying oligomerization of the water repellent, etc., undiluted stock solutions (raw materials) or pure of these acids and alkalis A water repellent is dissolved and stored in an ether solvent whose water content is preferably controlled to 50 ppm or less, and a chemical solution dissolved and stored immediately before use and an alcohol solvent containing the desired water content or a resist such as PGMEA are dissolved. The solvent to be mixed is prepared and used. The content of water or the like to be added may be determined in consideration of the type and concentration of the water repellent or adhesion agent, but should be in the range of 0.01 to 5% by mass with respect to the entire treatment chemical. Is preferred. When it is necessary to maintain the desired water repellency and adhesiveness during long-term storage such as 1 to 2 months or more, the content of at least one of water, alkali and acid in the treatment chemical solution is more accurately determined. Need to control. In this case, the content is preferably 00.4 to 2.7% by mass with respect to the whole chemical solution, and in order to suppress the fluctuation range in a range of ± 0.2% by mass of each value of the range during storage. In addition, it is preferable to perform contact blocking with outside air and purging the container with nitrogen. When adding an acid or an alkali, it is preferable to adjust these addition amounts to be in the range of pH 4 to 10, and it is more preferable to adjust the addition amounts to be in the range of pH 6 to 8.

  In the case where at least one of water, alkali and acid is contained in the water repellent chemical solution, even when these are mixed immediately before use, or when stored and used after mixing as described above, including water or the like If the amount is too small, the required water repellency may not be obtained, and if the amount is too large, hydrolysis proceeds too much and the chemical solution becomes cloudy, and the desired water repellency and adhesion performance are achieved. It may not be obtained. Therefore, especially when it is necessary to maintain these qualities during long-term storage, it is preferable to control the content and fluctuation range of water and the like as described above.

  In the case of a water repellent chemical solution that does not dissolve the resist, an ether solvent such as diisoamyl ether or n-butyl ether, an alcohol solvent such as isoamyl alcohol or isopropanol, or a mixed solution thereof can be used. In the case of a mixed solution, these mixing ratios may be adjusted in consideration of compatibility with at least one of water, acid and alkali to be contained. For example, ether solvent: alcohol solvent = 5: 5 to 7: It is desirable to set it to about 3. In addition, when long-term storage as described above is required, it is desirable to suppress the content of water and the fluctuation range within the above range. In the case of using a water-repellent agent solution that dissolves the resist in a mixed solvent, replace the “alcohol solvent” with the “solvent that dissolves the photosensitive resist” and adjust the treatment solution within the same range as above. do it.

  In addition, if the quality of the water repellent chemical solution due to the addition of water or the like does not change, before use, at least one of water, acid, and alkali is used without controlling the content and fluctuation range as described above. It can be contained in a water repellent chemical. It is preferable that content at this time is 0.01-5 mass% with respect to the whole process chemical | medical solution, for example.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
A water repellent chemical solution A using a solvent that does not dissolve the resist was prepared mainly for the purpose of improving the water repellency of the Si wafer. In addition, a water repellent chemical solution D using a solvent for dissolving a resist was prepared mainly for the purpose of improving the water repellency of the Si wafer. As the water repellent chemical solution A, 3,3,3-trifluoropropyltrimethoxysilane (KBM7103 manufactured by Shin-Etsu Chemical Co., Ltd.), tridecafluorohexyltrimethoxysilane (SIT8176-0 manufactured by GELEST Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.), a mixture of KBM7103 and KBM303 (mixing ratio 3: 1), or a mixture of SIT8176-0 and KBM303 (mixing ratio 3: 1) Prepared. Each water repellent was dissolved in diisoamyl ether or n-butyl ether to prepare a diluted solution of about 3.0% by mass. On the other hand, as a water repellent chemical solution D, KBM7103, KBM303, a mixture of KBM7103 and KBM303 (mixing ratio 3: 1), or a mixture of SIT8176-0 and KBM303 (mixing ratio 3: 1) was prepared. Each water repellent was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a diluted solution of about 3.0% by mass. In order to avoid hydrolysis of the water repellent agent, the solvent used was dehydrated by distillation treatment, use of an absorbent, or use of a water removal filter to make the water content 50 ppm or less.

  In this example, the water repellent chemical liquid A was used alone and the water repellent chemical liquid D alone was used as the water repellent chemical liquid A. Also, a wafer having the structure shown in FIG. 1B was manufactured according to the process flow of FIG. First, the film 2 to be processed was formed on the surface to be irradiated on the Si substrate 1, and then the water repellent treatment layer 3 was formed by spraying the water repellent chemical using the application cup shown in FIG. . The water-repellent treatment layer 3 is formed by rotating the wafer at 1000 rpm, with the nozzle stationary at a position 0.5 mm from the wafer edge, and using the edge rinse nozzle for the top surface direction of the wafer and the back rinse nozzle for the bottom surface direction. The chemical solution was sprayed to advance the water repellency / adhesion strengthening reaction. By optimizing the spray time of the water repellent chemical solution from the nozzle and the number of rotations of the wafer, the amount of water repellent adsorbed was controlled and the water repellency could be adjusted.

  Then, the coating type organic antireflection film 4 was formed with a film thickness of about 40 nm to 80 nm, and heat-cured at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. Next, a methacrylate-based ArF chemically amplified positive resist (thickness: 100 nm to 200 nm) was spin-coated and baked at 120 ° C. for 60 seconds to form a photosensitive resist layer 6. Subsequently, a top coat layer 7 soluble in a developer was applied on the resist with a film thickness of about 35 nm to 90 nm, and baked at 110 ° C. for 60 seconds to form a resist film. As described above, the water repellency / adhesion strengthening process can be performed only on the peripheral edge of the wafer excluding the central portion of the wafer that affects the patterning.

The substrate coated with this resist is exposed with an immersion exposure machine, and then developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation, using the resist film as a mask. The film to be processed was plasma dry etched. The film to be processed was performed on polysilicon in the transistor formation process. After the etching was completed, the photosensitive resist layer and the coating type organic antireflection film were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide. At that time, it was also confirmed that the previously formed water repellent layer was peeled off. Next, a silicon oxide film in a contact hole forming process (contact process) was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the wiring formation process (metal process) and the via process were repeatedly carried out to cool the semiconductor device. In the case of the water repellent chemical liquid A alone, the water repellent chemical liquid D alone, or the case where the water repellent chemical liquids A and D are mixed as the water repellent chemical liquid A, liquid immersion is performed during immersion exposure. No liquid spillage was observed.

In addition, the concentration of tridecafluorohexyltrimethoxysilane (SIT8176-0) with respect to diisoamyl ether was fixed at 3.0% by mass, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, which is an epoxysilane coupling agent. Table 3 and FIG. 14 show the adhesion strength and the contact angle when the concentration of silane (KBM303) is shifted from 0% by mass to 2.0% by mass. As is apparent from the results of FIG. 14, by increasing the amount of the epoxysilane coupling agent, the adhesion strength could be increased to 13.5 N / cm ² or more while maintaining the contact angle at a high level of about 70 °.

(Example 2)
In this example, the water repellent chemical liquid A or the water repellent chemical liquid B was used as the water repellent chemical liquid, respectively. As the water repellent chemical solution A, the one used in Example 1 was used. The water repellent chemical solution B was prepared using a solvent that does not dissolve the resist, mainly for the purpose of improving the water repellency of the organic film. As a water repellent, decyltrimethoxysilane (KBM3103C manufactured by Shin-Etsu Chemical Co., Ltd.), KBM7103, or a mixture of KBM3103C and KBM7103 (mixing ratio 1: 1) is used as a water repellent with an effect of enhancing adhesion. KBM303 was used by adjusting the mixing ratio to 3: 1 with respect to the total mass of the water repellent agent. Each water repellent was dissolved in diisoamyl ether or n-butyl ether to prepare a 3.0% by weight diluted solution. In order to avoid hydrolysis of the water repellent agent, the solvent used was dehydrated by distillation treatment, use of an absorbent, or use of a water removal filter to make the water content 50 ppm or less.

  In this example, a wafer having the structure shown in FIGS. 9B and 9C was manufactured according to the process flow of FIG. 9A. First, the film 2 to be processed is formed on the surface to be irradiated on the Si substrate 1, and then the coating type organic antireflection film 4 is formed with a film thickness of about 40 nm to 80 nm, and about 200 to 250 ° C. for about 1 minute to 1 The solvent was sufficiently volatilized by the heat curing treatment for 5 minutes, and the polymer was cross-linked by the reaction at the thermal reaction active site. Thereafter, a methacrylate-based ArF chemically amplified positive resist (film thickness: 100 nm to 200 nm) was spin-coated, and baked at 120 ° C. for 60 seconds to form a photosensitive resist layer 6. Next, using the application cup shown in FIG. 4 or 5, in the case of FIG. 4, the water repellent chemical solution is applied with a straight nozzle while rotating at 1000 rpm, and as shown in FIG. A water repellent treatment layer 3 was formed on the top surface of the wafer, the side surface of the wafer, and the peripheral edge of the bottom surface of the wafer. In the case of FIG. 5, the nozzle is stopped at a position 0.5 mm from the wafer edge while the water repellent chemical solution is rotated at 1000 rpm, the top surface of the wafer is repelled by the edge rinse nozzle, and the bottom surface is repelled by the back rinse nozzle. A hydrating chemical was sprayed and applied. As a result, it was possible to perform the water repellent treatment on the peripheral portion of the top surface of the wafer, the side surface of the wafer, and the peripheral portion of the bottom surface of the wafer, except for the central region of the top surface of the wafer that affects patterning. . Further, by optimizing the spraying time of the water repellent agent liquid from the nozzle and the number of rotations of the wafer, it was possible to control the amount of water repellent adsorbed and adjust the water repellency.

After forming the water repellent treatment layer 3, an exposure process was performed with an immersion exposure machine, but no spillage of the immersion liquid was observed during the immersion exposure. Next, development processing was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation, and the film to be processed was plasma dry etched using the resist film as a mask. The film to be processed was performed on polysilicon in the transistor formation process. In any case, after the etching was completed, the resist and the organic antireflection film were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide. At this time, it was also confirmed that the previously formed water-repellent layer was peeled off. Subsequently, a silicon oxide film in the contact process was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the metal process and via process were repeated to complete the semiconductor device.

(Example 3)
In this example, a wafer having the structure shown in FIG. 10B was manufactured according to the process flow of FIG. The water repellent chemical liquid is the water repellent chemical liquid A alone, the water repellent chemical liquid B alone, or a mixture of the water repellent chemical liquid A and the water repellent chemical liquid B (mixing ratio 5: 5). ). The water repellent chemical solution A used was the one used in Example 1, and the water repellent chemical solution B was the same as that used in Example 2. First, after forming the film 2 to be processed on the substrate 1, the coating type organic antireflection film 4 is formed with a film thickness of about 40 nm to 80 nm, and is heated and cured at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. The solvent was sufficiently volatilized by the treatment, and the polymer was cross-linked by the reaction at the thermal reaction active site. Thereafter, a methacrylate-based ArF chemically amplified positive resist (film thickness: 100 nm to 200 nm) was spin-coated, and a baking process was performed at 120 ° C. for 60 seconds to form a photosensitive resist layer 6. Next, immediately after the top coat layer 7 soluble in the developer is applied in a film thickness of about 35 nm to 90 nm, the water repellent treatment layer 3 is applied only to the outer peripheral portion of the wafer using the application cup shown in FIG. Formed. The water repellent layer 3 is formed by stopping the nozzle at a position 0.5 mm from the wafer edge during rotation at 1000 rpm, the top surface of the wafer by the edge rinse nozzle, and the bottom surface by the water repellent chemical solution from the back rinse nozzle. Spraying was performed by simultaneously proceeding with edge cutting of the top coat layer and water repellent reaction. Thereafter, a baking process was performed at 110 ° C. for 60 seconds to form a resist film.

After forming the water repellent treatment layer, the substrate was exposed with an immersion exposure machine. During immersion exposure, no spillage of immersion liquid was observed. Next, development processing was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation, and the film to be processed was plasma dry etched using this resist film as a mask. The film to be processed was performed on polysilicon in the transistor formation process. In either case, after the etching was completed, the resist and the organic antireflection film were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide. At this time, it was also confirmed that the previously formed water-repellent layer was peeled off. Next, a silicon oxide film in the contact process was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the metal process and via process were repeated to complete the semiconductor device.

  In addition, the concentration of tridecafluorohexyltrimethoxysilane (SIT8176-0) is fixed to 3.0% by mass, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303) which is an epoxysilane coupling agent As a result, the adhesion strength could be increased while maintaining the contact angle at a high level by increasing the amount of the epoxysilane coupling agent.

Example 4
In this example, the water repellent chemical liquid D or the water repellent chemical liquid E was used as the water repellent chemical liquid, respectively. As the water repellent chemical solution D, the one used in Example 1 was used. The water repellent chemical solution E was prepared by using a solvent for dissolving a resist mainly for the purpose of improving the water repellency of an organic film. As the water repellent, decyltrimethoxysilane (KBM3103C manufactured by Shin-Etsu Chemical Co., Ltd.), KBM7103, or a mixture of KBM3103C and KBM7103 (mixing ratio 1: 1) is used, and a water repellent having an effect of enhancing adhesion. KBM303 was prepared by adjusting the mixing ratio to 3: 1 with respect to the total mass of the water repellent agent. Each water repellent was dissolved in PGMEA to prepare a 3.0% by weight diluted solution. In order to avoid hydrolysis of the water repellent agent, the solvent used was dehydrated by distillation treatment, use of an absorbent, or use of a water removal filter to make the water content 50 ppm or less.

  In this example, a wafer having a structure shown in FIG. 11B was manufactured according to the process flow of FIG. First, after forming the film 2 to be processed on the substrate 1, the coating type organic antireflection film 4 is formed with a film thickness of 40 nm to 80 nm, and heat-cured at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. As a result, the solvent was sufficiently volatilized and the polymer was cross-linked by reaction at the thermal reaction active site. Thereafter, a methacrylate-based ArF chemically amplified positive resist (film thickness: 100 nm to 200 nm) was spin-coated to form a photosensitive resist layer 6. The photosensitive resist layer is formed using the coating cup shown in FIG. 5 while the water repellent chemical solution is rotated at 1000 rpm, the nozzle is stopped at a position 0.5 mm from the wafer edge, and the top surface of the wafer is edge rinsed. The nozzle and the bottom surface were applied by spraying a water repellent chemical from a back rinse nozzle. Further, the edge coat of the top coat and the water repellency reaction were allowed to proceed at the same time, and then a baking process was performed at 120 ° C. for 60 seconds to form a resist film.

Next, exposure processing was performed with an immersion exposure machine, but no spillage of the immersion liquid was observed. Thereafter, development processing was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation. Next, the film to be processed was plasma dry etched using the resist film as a mask. The film to be processed was performed on polysilicon in the transistor formation process. In either case, after the etching was completed, the resist and the organic antireflection film were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide. At this time, it was also confirmed that the previously formed water repellent layer was also peeled off. Next, a silicon oxide film in the contact process was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the metal process and via process were repeated to complete the semiconductor device.

  In addition, the concentration of tridecafluorohexyltrimethoxysilane (SIT8176-0) is fixed to 3.0% by mass, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303) which is an epoxysilane coupling agent As a result, the adhesion strength could be increased while maintaining the contact angle at a high level by increasing the amount of the epoxysilane coupling agent.

(Example 5)
In this example, a wafer having a structure shown in FIG. 12B was manufactured according to the process flow of FIG. The water repellent chemical liquid is the water repellent chemical liquid D alone, the water repellent chemical liquid E alone, or a mixture of the water repellent chemical liquid D and the water repellent chemical liquid E (mixing ratio 5: 5). ). The water repellent chemical solution D used was that used in Example 1, and the water repellent chemical solution E used was that used in Example 4. On the other hand, in this example, the water repellent chemical solution C or the water repellent chemical solution F was used. The water repellent chemical solution C was prepared using a solvent that does not dissolve the resist for the purpose of improving the adhesion between the inorganic film and the organic film, and was prepared using 3-glycidoxypropylmethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.). KBE403) manufactured by diisoamyl ether or n-butyl ether was used to prepare a 3.0% by weight diluted solution. Further, the adhesion improver F is mainly prepared to improve the adhesion between the inorganic film and the organic film, and is prepared using a solvent that dissolves the resist, and 3-glycidoxypropylmethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.). KBE403) manufactured by dissolving in PGMEA to obtain a 3.0% by mass diluted solution was used. In addition, in order to avoid hydrolysis of the water repellent chemical solution containing the silane coupling agent, the solvent used was dehydrated by distillation treatment, use of an absorbent, or use of a water removal filter, and the water content was adjusted to 50 ppm or less.

  First, after forming the film 2 to be processed on the substrate 1, the lower organic film layer 8 is applied with a film thickness of about 150 nm to 300 nm, and is heat-cured at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. The solvent was sufficiently volatilized, and the polymer was crosslinked by reaction at the thermal reaction active site. Thereafter, as the silicon-containing intermediate layer 5, a silsesquioxane-based polymer derivative such as inorganic SOG or organic SOG is spin-coated at a film thickness of about 80 nm, and is heated at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. It was crosslinked by reacting a reactive site such as a dehydration condensation reaction or an epoxy functional group by heat treatment.

  Next, using the coating cup shown in FIG. 5, the nozzle is stopped at a position 0.5 mm from the wafer edge during rotation at 1000 rpm, the top surface of the wafer is repelled by the edge rinse nozzle, and the bottom surface is repelled from the back rinse nozzle. The hydrating agent chemical solution C or the water repellent agent chemical solution F was sprayed to form an adhesion strengthening treatment layer. When it was difficult to complete the reaction at room temperature, the wafer was transferred from the spinner cup and heated on a hot plate at 120 ° C. for 60 seconds. In addition, by optimizing the spraying time of the water repellent chemical solution from the nozzle and the number of rotations of the wafer, the adsorption amount of the water repellent chemical solution containing the silane coupling agent can be controlled and the adhesion strength can be adjusted. did it.

  Thereafter, a methacrylate-based ArF chemically amplified positive resist (thickness: 100 nm to 200 nm) is spin-coated as the photosensitive resist layer 6 and then is rotated from the wafer edge while rotating at 1000 rpm using the coating cup shown in FIG. The nozzle was stopped at a position of 0.5 mm, the top surface of the wafer was sprayed with an edge rinse nozzle, and the bottom surface was sprayed with a water repellent chemical solution from the back rinse nozzle to advance the resist edge cut and water repellent reaction. Thereafter, baking treatment was performed at 120 ° C. for 60 seconds to form a water-repellent adhesion strengthening treatment layer 3a.

As a result of exposing the substrate after this water repellent adhesion strengthening treatment using an immersion exposure machine, there was no spillage of the immersion liquid, and either the water repellent chemical solution C alone or the water repellent chemical solution F alone was used. Even in this case, peeling from the wafer edge due to convection of the immersion liquid was not recognized. Thereafter, development processing was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation. Using this resist film as a mask, the film to be processed was plasma dry etched. The film to be processed was performed on polysilicon in the transistor formation process. In any case, after the etching was completed, the resist and the lower organic film layer were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide solution. At this time, it was also confirmed that the previously formed water-repellent adhesion reinforcing treatment layer was peeled off.

  In this example, the top surface of the wafer is not covered with the top coat layer, and the patterning process after the formation of the photosensitive resist layer is shown in FIG. First, as shown in FIG. 15A, a wafer provided with a film to be processed 2, a lower organic film layer 8, a silicon-containing intermediate layer 5 and a photosensitive resist layer 6 on a substrate 1 is exposed and developed, and FIG. As shown in b), a resist pattern 6a was formed. Next, as shown in FIG. 15C, the silicone-containing intermediate layer 5 was etched using the resist pattern 6a as a mask. Thereafter, as shown in FIG. 15D, the lower organic film layer 8 was etched using the intermediate layer pattern 5a as a mask to form an organic film layer pattern 8a. Subsequently, as shown in FIG. 15E, the film 2 to be processed was etched using the organic film layer pattern 8a as a mask to form the film pattern 2a to be processed. Finally, as shown in FIG. 15F, the organic film layer pattern 8a was removed to complete the pattern formation. Thereafter, a silicon oxide film was formed in the contact process, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the metal process and the via process were repeated to complete the semiconductor device.

(Example 6)
In this example, a wafer having a structure shown in FIGS. 13B and 13C was manufactured according to the process flow of FIG. The following water repellent chemicals were used.
Water repellent chemical A
Water repellent chemical liquid G; mixture of water repellent chemical liquid A and water repellent chemical liquid C (mixing ratio 5: 1)
Water repellent chemical B
Water repellent chemical liquid H; mixture of water repellent chemical liquid B and water repellent chemical liquid C (mixing ratio 5: 1)
Water repellent chemical liquid I; mixture of water repellent chemical liquid A and water repellent chemical liquid B (mixing ratio 5: 5)
Water repellent chemical solution J; mixture of water repellent chemical solution G and water repellent chemical solution H (mixing ratio 5: 5)
Further, the water repellent chemical solution A was used in Example 1, the water repellent chemical solution B was used in Example 2, and the water repellent chemical solution C was used in Example 5. .

  First, after forming the film 2 to be processed on the substrate 1, the lower organic film layer 8 is applied with a film thickness of about 150 nm to 300 nm, and is heat-cured at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. As a result, the solvent was sufficiently volatilized and the polymer was cross-linked by the reaction at the thermal reaction active site. Thereafter, as the silicon-containing intermediate layer 5, a silsesquioxane-based polymer derivative such as inorganic SOG or organic SOG is spin-coated at a film thickness of about 80 nm, and is heated at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes. It was crosslinked by reacting a reactive site such as a dehydration condensation reaction or an epoxy functional group by heat treatment.

  Thereafter, a methacrylate-based ArF chemically amplified positive resist (film thickness: 100 nm to 200 nm) is spin-coated as the photosensitive resist layer 6, and the water-repellent adhesion strengthening treatment layer is used using the coating cup shown in FIG. 4 or FIG. 3a was formed. In the case of FIG. 4, each of the above water repellent chemicals is applied with a straight nozzle during rotation at 1000 rpm, and as shown in FIG. 13C, the water repellent adhesion enhancing treatment layer 3a is applied to the top surface of the wafer. And formed on the side surface of the wafer and the peripheral edge of the bottom surface of the wafer. On the other hand, in the case of FIG. 5, while rotating at 1000 rpm, the nozzle is stopped at a position of 0.5 mm from the wafer edge, and each water repellent chemical solution is applied to the top surface of the wafer by the edge rinse nozzle and the bottom surface by the back rinse nozzle. Jetted. As a result, as shown in FIG. 13B, the water-repellent adhesion enhancing treatment layer 3a was formed on the peripheral edge of the top surface of the wafer, the side surface of the wafer, and the peripheral edge of the bottom surface of the wafer. Thereafter, baking was performed at 120 ° C. for 60 seconds, a top coat film 7 soluble in a developer was applied on the resist with a film thickness of about 35 nm to 90 nm, and baking was performed at 110 ° C. for 60 seconds.

Thereafter, as a result of exposure processing with an immersion exposure machine, no immersion liquid spilled off and no peeling from the wafer edge due to convection of the immersion liquid was observed for any of the water repellent chemicals. Thereafter, development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation, and the film to be processed was plasma dry etched using the resist film as a mask. The film to be processed was performed on polysilicon in the transistor formation process. In any case, after the etching was completed, the resist and the lower organic film layer were removed by O ₂ plasma ashing and wet treatment using sulfuric acid and hydrogen peroxide solution. At that time, it was also confirmed that the previously formed water-repellent adhesion reinforcing treatment layer was peeled off.

  In this embodiment, patterning after formation of the photosensitive resist layer in an embodiment in which the outermost surface of the wafer is covered with a developer-soluble topcoat layer and the water-repellent adhesion enhancing treatment layer is formed only on the outer periphery of the wafer. The process is shown in FIG. First, as shown in FIG. 16A, for a wafer provided with a film to be processed 2, a lower organic film layer 8, a silicon-containing intermediate layer 5 and a photosensitive resist layer 6 on a substrate 1, FIG. ), A top coat layer 7 soluble in a developer was formed. Next, exposure is performed as shown in FIG. 16C, development is performed as shown in FIG. 16D, the top coat layer 7 soluble in the developer and the exposed portion 6b of the resist are removed, and a resist pattern 6a is obtained. Formed. Next, as shown in FIG. 16E, the silicon-containing intermediate layer 5 was etched using the resist pattern 6a as a mask. Thereafter, as shown in FIG. 16F, the lower organic film layer 8 was etched using the intermediate layer pattern 5a as a mask to form an organic film layer pattern 8a. Subsequently, as shown in FIG. 16G, the film 2 to be processed was etched using the organic film layer pattern 8a as a mask to form the film pattern 2a to be processed. Finally, as shown in FIG. 16H, the organic film layer pattern 8a was removed to complete the pattern formation. Thereafter, a silicon oxide film was formed in the contact process, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process. Similarly, the metal process and via process were repeated to complete the semiconductor device.

(Example 7)
A water repellency treatment was performed in the same manner as in Example 1 except that the water repellency chemical was changed and the entire surface of the wafer was subjected to a water repellency treatment, and then a semiconductor device was manufactured. In this example, 3% by mass of tridecafluorohexyltrimethoxysilane (SEL 8176-0 manufactured by GELEST Co., Ltd.) as a water repellent, and 2- (3,4-) as a water repellent having an adhesion enhancing effect. A treatment chemical solution A was prepared by adding 0.005 ml of ultrapure water to 3 g of a chemical solution in which 1% by mass of epoxycyclohexyl) ethyltrimethoxysilane (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in isoamyl ether. Layer separation of isoamyl ether as a solvent did not occur depending on the content of the ultrapure water. Moreover, the processing chemical | medical solution B which does not add ultrapure water as a control was prepared.

  In order to evaluate the water repellency of the substrate surface subjected to the water repellency treatment, the contact angle on the substrate surface was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle when the treatment chemical solution B was used was 41.4 °, and the contact angle when the treatment chemical solution A to which ultrapure water was added was 54.1 °.

(Example 8)
Instead of ultrapure water added to treatment chemical A, 0.001 ml of 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution as alkali and 0.04 ml of isopropyl alcohol (IPA) to improve the solubility of TMAH Except for using the treatment chemical solution C to which was added, the entire surface of the wafer was subjected to a water repellency treatment by the same procedure as in Example 7, and then a semiconductor device was manufactured. In addition, the said processing chemical | medical solution B was used as a control.

  The contact angle when the treatment chemical solution B was used was 41.4 °, but the contact angle when the treatment chemical solution A to which ultrapure water was added was 58.1 °.

Example 9
As a water repellent, 3% by mass of tridecafluorohexyltrimethoxysilane (SIT8176-0 manufactured by GELEST Co., Ltd.) and 2- (3,4-epoxycyclohexyl) ethyltri as a water repellent with an effect of enhancing adhesion Treatment chemical solution D in which 0.002 ml of 2.38% TMAH aqueous solution is added to 3 g of chemical solution in which 1% by mass of methoxysilane (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in isopropyl alcohol (IPA), 0.01 ml is added. Three types of treatment chemical E and 0.13 ml of treatment chemical F added were prepared. Except that the processing chemical solution A was changed to each of these processing chemical solutions D to F, a water repellent treatment was performed on the entire wafer surface by the same procedure as in Example 7, and then a semiconductor device was manufactured. As a result of measuring the pH of each processing chemical solution with a pH meter, the processing chemical solution D was pH 7-8, the processing chemical solution E was pH 7-8, and the processing chemical solution F was pH 9-10.

  The contact angles when using each of the treatment chemicals D to F are 105.1 ° (treatment chemical D), 103.7 ° (treatment chemical E), and 104.5 ° (treatment chemical F). There was no big difference between them. Further, when the state of the wafer surface after the water repellent treatment was observed, there was no processing unevenness in the case of the processing chemical solution D, a slight processing unevenness was observed in the case of the processing chemical solution E, and in the case of the processing chemical solution F. Uneven treatment was observed. The presence or absence of processing unevenness was confirmed by visual observation, and it was determined that there was processing unevenness when color unevenness was observed on the processed wafer.

(Example 10)
In this embodiment, in order to confirm that the enhanced water repellency is maintained in the above-described processing when a film to be processed or heat treatment is applied to the wafer after the water repellency treatment or the adhesion strengthening treatment. To do.

  As a water repellent, Rf (fluorine structure-containing) trimethoxysilane (Rf (fluorine structure-containing) trimethoxysilane (70409: manufactured by Asahi Glass Co., Ltd.)) 1.94% by mass, and a water-repellent effect having an adhesion strengthening effect 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.97% by mass as a hydrating agent, and amyl alcohol and isoamyl ether mixed at a volume ratio of 3: 7 A treatment chemical solution G was prepared by dissolving in a solvent and adding ultrapure water to 1.9% by mass. On the wafer, 1 ml of the processing chemical solution G was dropped from an edge rinse nozzle set so as to drop the processing chemical solution at the center of the wafer, and water repellent treatment was performed on the entire wafer surface in the same manner as in Example 7. Three wafers subjected to the water repellency treatment as described above were manufactured, and an initial baking treatment was performed for 1 minute at different temperatures. Thereafter, the contact angle showing water repellency was measured for each wafer surface. The temperatures of the initial baking treatment were 110 ° C., 130 ° C., and 150 ° C., respectively. Subsequently, all wafers were baked at 205 ° C. for 1 minute, and the contact angles were measured again. When the initial baking temperature was 110 ° C., the contact angle was decreased by 9.7 °. However, when the initial baking temperature was 130 ° C., the reduction range was 8.4 °, and when the initial baking temperature was 150 ° C., the contact angle decreased by 2. The decrease was only 6 ° C. Further, it was found that when the initial baking temperature is set high, the contact angle on the wafer surface after the decrease is increased as compared with the processing at a lower temperature.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  A high-quality semiconductor device free from pattern defects can be provided.

It is a figure which is a typical example of the water-repellent treatment of this invention, Comprising: It is a figure which shows the example in case a topcoat layer covers the outermost surface, Fig.1 (a) shows a process flow, FIG.1 (b) shows after a process. It is a schematic diagram which shows the cross-section of the wafer outer peripheral part. It is a figure which shows the structure of the apparatus which forms a resist pattern by immersion type exposure. FIG. 3 (a) is a schematic diagram showing the behavior of water when the inner surface of the capillary is hydrophilic, and FIG. 3 (b) is a diagram showing the behavior of water in the capillary. It is the schematic which shows the behavior of the water in the case of aqueous | water-based. It is a figure which shows an example of the apparatus which performs water-repellent treatment by forming liquid films, such as a water repellent chemical | medical solution. It is a figure which shows the other example of the apparatus which performs water-repellent treatment by forming liquid films, such as a water repellent chemical | medical solution. It is a figure which shows the structure of the conventional multilayer resist film which performed the water-repellent process. It is a figure which shows the structure of the conventional single layer resist film which performed the water-repellent process. FIG. 8A is a plan view showing an immersion type exposure apparatus, and FIG. 8B is a plan view showing the immersion type exposure apparatus. FIG. It is the schematic diagram which expanded the part of the shower head 82. FIG. FIG. 9A is a typical example of the water repellency treatment of the present invention, and shows an example in which a topcoat layer is not formed. FIG. 9A shows a process flow, and FIG. 9B and FIG. ) Is a schematic view showing an example of a cross-sectional structure of the outer peripheral portion of the wafer after the water repellent treatment. FIG. 10A is a typical example of the water repellency treatment of the present invention, and shows a case where a top coat layer is formed and edge rinse and water repellency treatment are simultaneously performed. FIG. 10A shows a process flow. FIG. 10B is a schematic view showing an example of a cross-sectional structure of the outer peripheral portion of the wafer after the water repellent treatment. FIG. 11A is a typical example of the water repellency treatment of the present invention, and shows an example in which edge rinse and water repellency treatment are simultaneously performed without forming a topcoat layer. FIG. FIG. 11B is a schematic diagram showing an example of a cross-sectional structure of the outer peripheral portion of the wafer after the water repellent treatment. This is a typical example of the water repellency treatment of the present invention, in which an edge rinse of the photosensitive resist layer is performed without forming a topcoat layer, and the adhesion between the silicon-containing intermediate layer and the photosensitive resist layer is improved. FIG. 12A shows a process flow, and FIG. 12B is a schematic view showing an example of a cross-sectional structure of a wafer outer peripheral portion after water repellency treatment. It is a figure which is a typical example of the water-repellent treatment of the present invention and shows an example in the case of improving the adhesion between the photosensitive resist and the top coat layer, FIG. 13 (a) shows a process flow, and FIG. FIG. 13B and FIG. 13C are schematic views each showing an example of a cross-sectional structure of the outer peripheral portion of the wafer after the water repellent treatment. It is a figure which shows the change of the contact angle and adhesion strength by increasing the amount of epoxysilane coupling agents. FIGS. 15A to 15F are schematic views showing each patterning step when the top surface of the wafer is not covered with the top coat layer, and FIG. 15A to FIG. is there. It is a figure which shows the patterning process after the photosensitive resist layer formation in the case where the outermost surface of the wafer is covered with a developer-soluble top coat layer and a water-repellent adhesion strengthening treatment layer is formed only on the outer periphery of the wafer. FIGS. 16A to 16H are schematic views showing each patterning step. FIG. 17A is a schematic diagram showing an example of a pattern, FIG. 17B is a schematic diagram showing pattern collapse, and FIG. 17C shows a normal pattern. FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Substrate, 2 Processed film, 3 Water-repellent treatment layer, 3a Water-repellent adhesion strengthening treatment layer, 4 Coating type organic antireflection film, 5 Silicon-containing intermediate layer, 6 Photosensitive resist layer, 7 Top coat layer, 8 Lower layer Organic film layer, 9 stage outer periphery.

Claims (13)

A method for forming a resist pattern by immersion exposure, in which an objective lens is disposed on a substrate of a semiconductor device on which a film to be processed is formed, and a liquid film is formed between the objective lens and the substrate for exposure.
A resist pattern forming method of exposing a substrate treated with a water repellent chemical solution comprising at least a water repellent agent and a solvent.   The method for forming a resist pattern according to claim 1, wherein the water repellent chemical is supplied to the substrate, and the water repellent is adsorbed on the substrate.   The water repellent is at least one of a fluorine water repellent, a silicone water repellent, a fluorine / silicone water repellent, a silane coupling agent, a silylating agent, an alkylating agent, and an acylating agent. The method for forming a resist pattern according to claim 1, comprising at least one of the above. The film to be processed includes a lower organic film layer formed on the substrate, a silicon-containing intermediate layer, and a photosensitive resist layer,
The film to be processed is formed by a multilayer resist method including a step of spin coating on the substrate,
The treatment according to any one of claims 1 to 3, further comprising a step of treating with the water repellent chemical solution at least between each spin coat, before the first spin coat, and after the last spin coat. A method for forming a resist pattern. The substrate comprises a photosensitive resist layer on the substrate,
The photosensitive resist layer is formed by a photolithography process including a process of spin coating on the substrate,
The process according to any one of claims 1 to 3, further comprising a step of treating with the water repellent chemical solution at least between each of the spin coats, before the first spin coat, and after the last spin coat. A method for forming a resist pattern. The substrate comprises a topcoat layer,
The method for forming a resist pattern according to claim 4, comprising a step of treating with the water repellent chemical solution before forming the top coat layer.   The method for forming a resist pattern according to claim 4, wherein the water repellent chemical solution contains a silane coupling agent.   The method for forming a resist pattern according to claim 1, wherein the water repellent chemical solution contains at least one of water, acid, and alkali. The step of treating with the water repellent chemical is as follows:
A step of processing a side surface of the substrate and a peripheral portion of the top surface of the substrate, a peripheral portion of the bottom surface of the substrate, or a peripheral portion of the top surface of the substrate and a peripheral portion of the bottom surface of the substrate; Item 9. A method for forming a resist pattern according to any one of Items 4 to 8. The step of treating with the water repellent chemical is as follows:
The method for forming a resist pattern according to any one of claims 4 to 9, which is a step of processing a side surface of the substrate, a top surface of the substrate, and a peripheral edge portion of a bottom surface of the substrate.   The method for forming a resist pattern according to any one of claims 4 to 10, wherein two or more types of the water repellent agent are mixed and used. The step of treating with the water repellent chemical is as follows:
Forming a coating film on the substrate;
After the step of removing the coating film with a solvent that dissolves the coating film at the side surface of the substrate, the peripheral edge portion of the top surface of the substrate, and the peripheral edge portion of the bottom surface of the substrate,
The method for forming a resist pattern according to any one of claims 4 to 11, wherein a region where the coating film is dissolved and removed is treated with the water repellent chemical solution.   The semiconductor device manufactured by the formation method of the resist pattern in any one of Claims 1-12.

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