JP2006059918A - Development processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a development processing method by which the occurrence of particle-like precipitation-based defects caused by a developing process etc., a CD fluctuation and the deterioration of LER can be suppressed, and the tilting of a pattern can be prevented. <P>SOLUTION: In the development processing method, a resist film is exposed to light in a prescribed pattern, and a wafer W developed with a prescribed developing solution thereafter is rinsed by supplying a first rinsing solution containing a prescribed surface active agent to the wafer W. Then the resist film is hardened by the synergetic effect of a crosslinking agent used for hardening the resist pattern and the irradiation of a prescribed high-energy ray, by supplying a liquid chemical containing the crosslinking agent and irradiating the surface of the wafer W with the high-energy ray. Thereafter, an inert liquid having specific gravity larger than that of the liquid chemical is supplied to the wafer W and the inert liquid is settled by leaving the liquid for a prescribed period of time so that the resist film may be affected by the inert liquid. After the inert liquid is settled, spin drying is performed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for developing a resist film provided on a substrate such as a semiconductor wafer.

  For example, in a semiconductor device manufacturing process, a resist solution is applied to the surface of a semiconductor wafer (hereinafter referred to as “wafer”) to form a resist film, and this resist film is exposed in a predetermined pattern, thus forming a resist film. A so-called photolithography technique for developing the exposed exposure pattern is used, and a resist pattern corresponding to the exposure pattern is formed by development processing.

  In the development process in each step of such a photolithography technique, a developer is supplied to the wafer to form a developer paddle, and after a predetermined time of natural convection, the developer is shaken off. Next, pure water is supplied as a cleaning solution to wash away the developer remaining on the wafer, and then the wafer is rotated at a high speed to shake off the developer and cleaning solution remaining on the wafer to dry the wafer.

  By the way, in recent years, semiconductor devices have been further miniaturized due to advances in exposure technology and the like, leading to the appearance of fine and high aspect ratio resist patterns, in the final shake-off drying in the development process as described above, When the rinsing liquid comes out between the patterns, there is a problem that a so-called “pattern collapse” occurs in which the resist pattern is pulled and falls due to the surface tension of the rinsing liquid.

  As a technique for solving such a problem, Patent Document 1 proposes a technique for reducing the surface tension of a rinsing liquid by mixing a surfactant solution in the rinsing liquid, for example. Patent Document 2 discloses a process for supplying a surfactant when the substrate is rinsed after the development process. Further, Patent Document 3 discloses a method of developing and rinsing a resist film, solidifying the rinsing liquid in a state where the rinsing liquid is attached to the resist film, and sublimating the rinse liquid solidified product. Yes.

2. Description of the Related Art Conventionally, in the resist development process, there has been a problem that reaction products and residues of the resist and the developer become particles and contaminate the wafer. In addition, LER (Line Edge Roughness) deterioration due to resist or exposure contrast and CD (Critical Dimension) fluctuation have occurred, but these can be further improved by treating with chemical substances such as surfactants. There is a problem of getting worse. For this reason, in the rinsing treatment using a surfactant or the like, an optimum process that takes these problems into consideration has not yet been found. Furthermore, with such a conventional technique, it is difficult to sufficiently prevent the pattern collapse of the recently thinned resist pattern.
JP-A-7-142349 JP 2001-5191 A JP-A-7-20737

  The present invention has been made in view of such circumstances, and provides a development processing method that suppresses generation of precipitation defects such as particles in development processing, CD fluctuation, and deterioration of LER, and prevents pattern collapse. The purpose is to do. Another object of the present invention is to provide a development processing method capable of preventing pattern collapse of a thinned resist pattern.

In order to solve the above problems, in the first aspect of the present invention, a resist film provided on the surface of the substrate is exposed in a predetermined pattern, and then developed in a predetermined developer. Supplying a first rinsing liquid containing a predetermined surfactant at a critical micelle concentration or less, and rinsing;
Supplying a chemical solution containing a crosslinking agent for curing the resist film on the substrate onto the substrate;
Irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate, and curing the resist film by a synergistic effect of the irradiation of the crosslinking agent and the high energy ray;
A development processing method characterized by comprising:

  In this development processing method, the occurrence of precipitation defects is suppressed by the previous processing, that is, the processing with the first rinsing liquid, the deterioration of LER is prevented, and the CD fluctuation is further suppressed. The pattern collapse of the resist film can be prevented by subsequent processing, that is, processing for curing the resist film.

  In the development processing method according to the first aspect, the step of rotating the substrate after the resist film curing process is rotated to shake off the chemical solution from the substrate, and the surface tension of the substrate to be 50 dyne / cm or less. Supplying a second rinse liquid to which a predetermined surfactant or fluorine-based chemical agent is added, and rinsing, and rotating the substrate at a predetermined rotation number to remove the second rinse liquid from the substrate It is preferable to further add a step of shaking and drying the substrate. Thereby, the pattern collapse of the resist film can be further prevented from occurring.

  In the development processing method according to the first aspect, as another method for making the pattern collapse of the resist film more unlikely to occur, in the state where the chemical solution is accumulated on the substrate after the resist film is cured, A specific inert liquid that has a specific gravity greater than that of the chemical solution and does not mix with the chemical solution is supplied, and the resist film is left to stand for a predetermined time so that the resist film is immersed in the inert liquid. And a step of rotating the substrate at a predetermined number of revolutions, shaking off the chemical solution and the inert liquid from the substrate, and drying the substrate. Here, an alternative chlorofluorocarbon is preferably used as the inert liquid.

In a second aspect of the present invention, a resist film provided on a substrate is exposed to a predetermined pattern, and then the resist film on the substrate is cured on a substrate that has been developed with a predetermined developer. Supplying a chemical solution containing a crosslinking agent for
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
Supplying a first rinsing liquid containing a predetermined surfactant at a critical micelle concentration or less to the substrate, and rinsing;
A development processing method characterized by comprising:

  The development processing method according to the second aspect is obtained by switching the order of the preceding process and the subsequent process in the development processing method according to the first aspect. Similarly to the development processing method, the generation of precipitation defects is suppressed, the deterioration of LER is prevented, the CD fluctuation is further suppressed, and the pattern collapse of the resist film can be prevented. Further, the treatment using an inert liquid added to the development processing method according to the first aspect can be additionally applied to the development processing method according to the second aspect, thereby reducing the pattern collapse of the resist film. Furthermore, it can be made difficult to occur.

In a third aspect of the present invention, a critical surfactant is applied to a substrate on which a resist film provided on the surface is exposed with a predetermined pattern and then developed with a predetermined developer. Supplying a first rinsing liquid containing at a concentration or less and rinsing;
Supplying a second rinsing liquid to which a predetermined surfactant or fluorine-based chemical is added so that the surface tension of the substrate is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of revolutions, shaking off the second rinse liquid from the substrate, and drying the substrate;
A development processing method characterized by comprising:

In a fourth aspect of the present invention, a critical surfactant is applied to a substrate on which a resist film provided on the surface is exposed in a predetermined pattern and subsequently developed with a predetermined developer. Supplying a first rinsing liquid containing at a concentration or less and rinsing;
In a state where the first rinse liquid is piled on the substrate, a predetermined inert liquid having a specific gravity greater than that of the first rinse liquid and not mixed with the first rinse liquid is supplied. Leaving the inert liquid by allowing it to stand for a predetermined time so that the resist film is immersed in the inert liquid;
Rotating the substrate at a predetermined number of revolutions, shaking off the first rinse liquid and the inert liquid from the substrate, and drying the substrate;
A development processing method characterized by comprising:

  In the development processing method according to the fourth aspect, alternative chlorofluorocarbon is preferably used as the inert liquid.

  In such development processing methods according to the first to fourth aspects, the surfactant contained in the first rinsing liquid is preferably an ethylene glycol-based, ether-based or acetylene glycol-based surfactant. Furthermore, the surfactant contained in the first rinsing liquid preferably has a molecular weight of 1280 or more, and the hydrophobic group preferably has 14 or more carbon atoms, and the hydrophobic group contains double bonds and triple bonds. It is preferable that there is no bond. Thereby, the various effects of suppressing the occurrence of precipitation defects, preventing the deterioration of LER, and suppressing the CD fluctuation can be further enhanced.

In a fifth aspect of the present invention, a resist film provided on a substrate is exposed to a predetermined pattern, and then the substrate is developed with a predetermined developer, and the surface of the substrate is wetted with the developer. Supplying a chemical solution containing a cross-linking agent for curing the resist film on the substrate,
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
Rotating the substrate after the resist film curing process, and shaking off the chemical solution from the substrate;
Supplying the substrate with a rinsing liquid to which a predetermined surfactant or fluorine-based agent is added so that the surface tension thereof is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of rotations to shake off the rinse liquid from the substrate and drying the substrate;
A development processing method characterized by further comprising:

In a sixth aspect of the present invention, a resist film provided on a substrate is exposed in a predetermined pattern, and then the substrate is developed with a predetermined developer, and the surface of the substrate is wetted with the developer. Supplying a chemical solution containing a cross-linking agent for curing the resist film on the substrate,
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
In a state where the chemical liquid is piled on the substrate, a predetermined inert liquid having a specific gravity greater than that of the chemical liquid and not mixed with the chemical liquid is supplied, and the resist film is immersed in the inert liquid. Leaving the inert liquid to stand for a predetermined period of time, and
Rotating the substrate at a predetermined number of rotations to shake off the chemical solution and the inert liquid from the substrate, and drying the substrate;
A development processing method characterized by further comprising:

  In the development processing method according to the sixth aspect, alternative chlorofluorocarbon is preferably used as the inert liquid. The development processing methods according to the fifth and sixth aspects are used when precipitation defects are not a quality problem and it is important to prevent pattern collapse.

  According to the present invention, occurrence of precipitation defects such as particles is suppressed, deterioration of LER is suppressed, CD fluctuation is suppressed, and occurrence of pattern collapse is further suppressed. Thereby, a precise resist pattern can be obtained. In addition, the effect of preventing the occurrence of pattern collapse can be further enhanced.

  FIG. 1 is a plan view showing an example of a development processing apparatus in which the development processing method of the present invention is carried out, and FIG. 2 is a cross-sectional view thereof. In these figures, two directions perpendicular to a horizontal plane are X directions. , The Y direction, and the vertical direction is the Z direction.

  As shown in FIGS. 1 and 2, this development processing apparatus (DEV) has a housing 1, and a fan / filter unit F for forming a downflow of clean air in the housing on the ceiling of the housing 1. Is provided. In addition, an annular cup CP is disposed at the center of the housing 1, and a spin chuck 2 is disposed inside the cup CP. The spin chuck 2 holds and holds the wafer W by vacuum suction. A drive motor 3 is disposed below the spin chuck 2, and the spin chuck 2 is rotationally driven by the drive motor 3. The drive motor 3 is attached to the floor board 4.

  In the cup CP, lift pins 5 for transferring the wafer W are provided so as to be lifted and lowered by a drive mechanism 6 such as an air cylinder. A drain port 7 for waste liquid is provided in the cup CP. A waste liquid pipe 8 (see FIG. 1) is connected to the drain port 7, and the waste liquid pipe 8 passes through a space N between the bottom plate 4 and the housing 1 as shown in FIG. Connected to the waste outlet.

  An opening 1 a through which the transfer arm T of the wafer transfer device enters is formed on the side wall of the housing 1, and the opening 1 a can be opened and closed by a shutter 9. When the wafer W is loaded / unloaded, the shutter 9 is opened and the transfer arm T enters the housing 1. The transfer of the wafer W between the transfer arm T and the spin chuck 2 is performed in a state where the lift pins 5 are raised.

  In the housing 1, a developer nozzle 11 for supplying a developer to the surface of the wafer W, and a chemical solution (hereinafter referred to as “curing”) for curing a resist film on the surface of the wafer W after development. A chemical liquid nozzle 12a for supplying a chemical liquid for use), a first rinse liquid nozzle 13 for supplying a first rinse liquid containing a predetermined surfactant to the wafer W after development, and a wafer W after development. A second rinse liquid nozzle 14 for supplying a second rinse liquid containing a predetermined surfactant is provided. As will be described in detail later, pure water (DIW) can be discharged from the first rinse liquid nozzle 13, and an inert liquid having a higher density than pure water is discharged from the second rinse liquid nozzle 14. It can be made to.

  The developer nozzle 11 has a long shape and is horizontally arranged so that the longitudinal direction thereof is the X direction. A plurality of discharge ports (not shown) are provided on the lower surface of the developer nozzle 11 so that the developer discharged from each discharge port has a belt shape as a whole. The developer nozzle 11 is detachably attached to the distal end portion of the first nozzle scan arm 16 by a holding member 41a. The first nozzle scan arm 16 is laid on the bottom plate 4 along the Y direction. The first guide rail 26 is attached to the upper end portion of the first vertical support member 36 extending in the vertical direction (Z direction). The developer nozzle 11 is horizontally movable along the Y direction by the Y-axis drive mechanism 46 together with the first vertical support member 36, and moves between a supply position on the wafer W and a standby position outside the wafer W. It is provided as possible. Further, the first vertical support member 36 can be moved up and down by the Z-axis drive mechanism 56, so that the developer nozzle 11 can be moved up and down in the vicinity of the wafer W by raising and lowering the first vertical support member 36. It is movable between non-ejection positions.

  When the developing solution is applied to the wafer W, the developing solution nozzle 11 is positioned above the wafer W, and the developing solution nozzle 11 is ejected from the developing solution nozzle 11 in a strip shape, and the wafer W is rotated 1/2 turn or more. By making one rotation, the developer is applied to the entire surface of the wafer W, and a developer paddle is formed. When the developer is discharged, the developer nozzle 11 may be scanned along the first guide rail 26 without rotating the wafer W. As the developer nozzle 11, a developer nozzle having a slit discharge port may be used.

  The chemical nozzle 12 a has the same structure as the developer nozzle 11. An ultraviolet irradiation unit 12b provided with an ultraviolet lamp 42 is attached to the side surface of the chemical nozzle 12a in the Y direction. The chemical nozzle 12a is detachably attached to the tip of the second nozzle scan arm 17 by a holding member 41b, and the second nozzle scan arm 17 is laid on the bottom plate 4 along the Y direction. It is attached to the upper end of a second vertical support member 37 extending in the vertical direction (Z direction) from above the second guide rail 27.

  The chemical nozzle 12a and the ultraviolet irradiation unit 12b can be moved horizontally along the Y direction by the Y-axis drive mechanism 47 together with the second vertical support member 37. The chemical supply position on the wafer W, the ultraviolet irradiation position, and the wafer W It is provided so as to be movable between the outside standby position. Further, the second vertical support member 37 can be moved up and down by a Z-axis drive mechanism 57, so that the chemical solution nozzle 12 a and the ultraviolet irradiation unit 12 b can discharge close to the wafer W by moving up and down the second vertical support member 37. It can move integrally between the position and the non-ejection position above it.

  When the curing chemical is applied to the wafer W, the chemical nozzle 12a is positioned above the wafer W, and the wafer W is ejected from the chemical nozzle 12a in a strip shape, and the wafer W is rotated 1/2 turn or more, for example, one rotation. By doing so, the curing chemical solution is applied to the entire surface of the wafer W, and a curing chemical solution paddle is formed. The ultraviolet irradiation unit 12b has a slit irradiation type structure, and the ultraviolet rays are irradiated in a band shape extending in the X direction downward from the ultraviolet irradiation unit 12b. For this reason, when the surface of the wafer W is irradiated with ultraviolet rays, the ultraviolet irradiation unit 12 b is scanned in the Y direction along the second guide rail 27 without rotating the wafer W. Note that the chemical nozzle 12 a may be scanned along the second guide rail 27 without rotating the wafer W when discharging the curing chemical.

  The first rinse liquid nozzle 13 is a straight nozzle, and discharges a first rinse liquid containing a predetermined surfactant in a columnar shape. The first rinse liquid nozzle 13 is moved onto the wafer W after development, and supplies the first rinse liquid to the resist film on which the development pattern is formed on the wafer W. The first rinsing liquid nozzle 13 is detachably attached to the tip of the third nozzle scan arm 18. A third guide rail 28 is laid on the bottom plate 4, and the third nozzle scan arm 18 has an X-axis at the upper end portion of a third vertical support member 38 extending vertically from the third guide rail 28. It is attached via a drive mechanism 44. The first rinsing liquid nozzle 13 can move horizontally along the Y direction by the Y-axis drive mechanism 48 together with the third vertical support member 38. The third vertical support member 38 can be moved up and down by the Z-axis drive mechanism 58, and the first rinse liquid nozzle 13 can move up and down in the vicinity of the wafer W as the third vertical support member 38 moves up and down and non-discharge. It can move between positions. The third nozzle scan arm 18 can be moved along the X direction by the X-axis drive mechanism 44.

  As a method of supplying the first rinse liquid from the first rinse liquid nozzle 13 to the surface of the wafer W, the first rinse liquid nozzle 13 is disposed on the center of the wafer W, and the rinse liquid is discharged while rotating the wafer W. And a method of scanning the first rinsing liquid nozzle 13 in the Y direction. In addition, the shape of the 1st rinse liquid nozzle 13 is not specifically limited, The thing of the same structure as the developing solution nozzle 11 and a discharge port may be a slit shape.

  The configuration of the second rinse liquid nozzle 14 is the same as that of the first rinse liquid nozzle 13. The second rinse liquid nozzle 14 is detachably attached to the distal end portion of the fourth nozzle scan arm 19. A fourth guide rail 29 is laid on the bottom plate 4, and the fourth nozzle scan arm 19 is arranged at the upper end of a fourth vertical support member 39 extending vertically from the fourth guide rail 29 on the X axis. It is attached via a drive mechanism 45. The second rinse liquid nozzle 14 can move horizontally along the Y direction by the Y-axis drive mechanism 49 together with the fourth vertical support member 39. The fourth vertical support member 39 can be moved up and down by the Z-axis drive mechanism 59, and the second rinse liquid nozzle 14 can move up and down in the vicinity of the wafer W by the up and down movement of the fourth vertical support member 39 and the non-discharge above it. It can move between positions. The fourth nozzle scan arm 19 can be moved along the X direction by the X-axis drive mechanism 45.

  The method of supplying the second rinse liquid from the second rinse liquid nozzle 14 to the surface of the wafer W is the same as that for the first rinse liquid nozzle 13. The shape of the second rinsing liquid nozzle 14 is not particularly limited, and the same structure as the developing liquid nozzle 11 may be used.

  The Y-axis drive mechanisms 46, 47, 48, and 49, the Z-axis drive mechanisms 56, 57, 58, and 59, the X-axis drive mechanisms 44 and 45, and the drive motor 3 are controlled by the drive control unit 40. .

  As shown in FIG. 2, a developer nozzle standby unit 31 on which the developer nozzle 11 stands by is provided on the right side of the cup CP. The developer nozzle standby unit 31 is a cleaning unit that cleans the developer nozzle 11. A mechanism (not shown) is provided. In addition, a chemical nozzle standby unit 32 for waiting for the chemical nozzle 12a is provided between the developer nozzle standby unit 31 and the cup CP, and the chemical nozzle standby unit 32 has a cleaning mechanism for cleaning the chemical nozzle 12a. (Not shown) is provided. Further, on the left side of the cup CP, there are provided a first rinse liquid nozzle standby part 33 and a second rinse liquid nozzle standby part 34 on which the first rinse liquid nozzle 13 and the second rinse liquid nozzle 14 wait, respectively. Are provided with a cleaning mechanism (not shown) for cleaning the first rinse liquid nozzle 13 and the second rinse liquid nozzle 14, respectively.

  FIG. 3 is a schematic view showing a liquid supply system of the development processing apparatus (DEV). As shown in FIG. 3, the developer nozzle 11 is connected to a developer supply pipe 72 that supplies the developer from a developer tank 71 that stores the developer. The developer supply pipe 72 is provided with a pump 73 and an on / off valve 74 for supplying the developer.

  A chemical solution supply pipe 76 for supplying a chemical solution for curing from a chemical solution tank 75 in which a chemical solution containing a crosslinking agent is stored is connected to the chemical solution nozzle 12a. The chemical solution supply pipe 76 is provided with a pump 77 and an on / off valve 78 for supplying a curing chemical solution.

  The first rinse liquid nozzle 13 is connected to a first rinse liquid supply pipe 82 that supplies the first rinse liquid from the first rinse liquid tank 81 in which the first rinse liquid is stored. A pump 83 and an on / off valve 84 for supplying the first rinse liquid are interposed in the first rinse liquid supply pipe 82. Further, a pure water supply pipe 86 for supplying pure water from a pure water tank 85 is connected to the first rinse liquid supply pipe 82, and a pump for supplying pure water is connected to the pure water supply pipe 86. 87 and an on / off valve 88 are interposed.

  With such a configuration, for example, only the first rinse liquid is discharged from the first rinse liquid nozzle 13 by opening the on / off valve 84 and operating the pump 83 and closing the on / off valve 88. Can do. On the other hand, only the pure water can be discharged from the first rinse liquid nozzle 13 by opening the on / off valve 88 and operating the pump 87 and closing the on / off valve 84. Further, by controlling the opening / closing amounts of the on / off valve 84 and the on / off valve 88 and simultaneously driving the pump 83 and the pump 87, the rinse liquid in which the concentration of the first rinse liquid is changed (diluted) is first rinsed. It can be discharged from the liquid nozzle 13.

  As the surfactant dissolved in the first rinse liquid, it is preferable to use an ethylene glycol, ether or acetylene glycol surfactant. Specific examples include polyethylene glycol sorbitan fatty acid ester, polyethylene glycol linear alkyl ether, polyethylene glycol fatty acid ester, linear alkyl addition type polyethylene glycol phenyl ether, and branched chain alkyl addition type polyethylene glycol phenyl ether. Examples of the acetylene glycol surfactant include EO addition type acetylene glycol.

  The surfactant concentration of the first rinsing liquid is preferably set to a critical micelle concentration or less. This is to prevent micelles from forming in the first rinse liquid when the critical micelle concentration is exceeded, and particles remaining on the wafer W to form particles. However, if the surfactant concentration is too low, the surface tension of the first rinsing liquid does not decrease, and therefore, the resist pattern tends to collapse when the first rinsing liquid is removed from the wafer W. For this reason, the surfactant concentration of the first rinsing liquid is preferably equal to or less than the critical micelle concentration. In addition, the inventors use a surfactant having a large molecular weight and a large number of carbon atoms in the hydrophobic group, and further having a hydrophobic group consisting only of a single bond, which improves CD uniformity and improves LER. Confirm that it will be. Therefore, it is preferable to use a surfactant that further satisfies such conditions.

  A second rinse liquid supply pipe 92 that supplies the second rinse liquid from the second rinse liquid tank 91 in which the second rinse liquid is stored is connected to the second rinse liquid nozzle 14. A pump 93 and an on / off valve 94 for supplying the second rinse liquid are interposed in the second rinse liquid supply pipe 92. Further, the second rinsing liquid supply pipe 92 has an inert liquid from an inert liquid tank 95 in which an inert liquid (specifically, an alternative chlorofluorocarbon) having a specific gravity greater than that of pure water and a small surface tension is stored. An inert liquid supply pipe 96 is connected to the inert liquid supply pipe 96. A pump 97 and an on / off valve 98 for supplying the inert liquid are interposed in the inert liquid supply pipe 96.

  With such a configuration, for example, only the second rinse liquid is discharged from the second rinse liquid nozzle 14 by opening the on / off valve 94 to operate the pump 93 and closing the on / off valve 98. Can do. On the other hand, only the inert liquid can be discharged from the second rinse liquid nozzle 14 by opening the on / off valve 98 and operating the pump 97 and closing the on / off valve 94.

  The second rinse liquid is supplied before the wafer W is dried. That is, after the second rinse liquid is supplied onto the wafer W, the wafer W is dried by rotating the wafer W and shaking off the second rinse liquid. Therefore, the second rinse liquid is a resist pattern. Those whose surface tension is lowered are preferably used so that the pattern collapse is difficult to occur. Specifically, those having a surface tension reduced to 50 dyne / cm or less are preferably used.

  An inert liquid is used in place of the second rinse liquid. In other words, an inert liquid such as alternative chlorofluorocarbon does not dissolve the resist pattern and has a surface tension of 10 to 20 dyne / cm, which is extremely small compared to an aqueous rinsing liquid. By making the pattern immersed in an inert liquid and then performing spin drying, the occurrence of pattern collapse can be more effectively prevented. Whether to use the second rinse liquid or the inert liquid can be determined in consideration of the line width of the resist pattern, for example.

  The pumps 73, 77, 83, 87, 93, 97 and the on / off valves 74, 78, 84, 88, 94, 98 are controlled by the control unit 60.

  Next, a development processing step using a development processing apparatus (DEV) will be described. FIG. 4 is a diagram simply showing the first to tenth development processing methods. The first development processing method is performed in the order of development processing with a developing solution, rinsing processing with a first rinsing solution, application of a curing chemical solution and curing of a resist pattern by ultraviolet irradiation processing, and spin drying. The second development processing method is performed in the order of development processing with a developing solution, application of a curing chemical solution and curing of a resist pattern by ultraviolet irradiation processing, rinsing processing with a first rinsing liquid, and spin drying. In the first development processing method, the development reaction is stopped by supplying the first rinsing liquid, and in the second development processing method, the developing reaction is stopped by supplying the curing chemical.

  In the first development processing method, it is possible to remove resist residues (development defects) while suppressing generation of precipitation defects, deterioration of LER, and CD fluctuations by rinsing with the first rinsing liquid, and for clean curing. By using the chemical solution, it is possible to avoid the occurrence of precipitation defects in the resist pattern curing process. In the second development processing method, even when a deposition defect occurs on the wafer W due to the resist pattern curing process, such a defect can be removed by a subsequent rinsing process using the first rinsing liquid. It is common to the first and second development processing methods that the occurrence of pattern collapse can be suppressed by curing the resist pattern.

  In the first development processing method, rinsing treatment with pure water may be performed after the resist pattern curing treatment, and then spin drying may be performed. In the second development processing method, pure treatment is performed after rinsing treatment with the first rinsing liquid. A rinse treatment with water may be performed, followed by spin drying. This is because, since the resist pattern is cured, even if spin drying is performed after the rinse treatment with pure water, the pattern collapse hardly occurs.

  The third development processing method includes: a development process using a developer, a rinse process using a first rinse liquid, a resist pattern curing process using a curing chemical solution application and an ultraviolet irradiation process, a rinse process using a second rinse liquid, and a spin drying. Done. This third development processing method is used only when the surface tension of the second rinse liquid is smaller than that of the curing chemical liquid and the cleanliness is high. The fourth development processing method includes: a development process with a developer, a rinse process with a first rinse liquid, a resist pattern curing process by applying a curing chemical solution and an ultraviolet irradiation process, a resist pattern coating with an inert liquid, and a spin drying sequence. Done in

  The fifth development processing method is the order of development processing with a developer, application of a curing chemical solution and curing of a resist pattern by ultraviolet irradiation processing, rinsing processing with a first rinsing liquid, rinsing processing with a second rinsing liquid, and spin drying. Done. This fifth development processing method is used only when the surface tension of the second rinse liquid is smaller than the surface tension of the first rinse liquid and the cleanliness is high. The sixth development processing method is the order of development processing with a developing solution, curing of a resist pattern by applying a curing chemical solution and ultraviolet irradiation processing, rinsing processing with a first rinsing liquid, coating of a resist pattern with an inert liquid, and spin drying. Done in

  In these third to sixth development processing methods, compared with the first and second development processing methods, a liquid having a low surface tension is supplied onto the wafer W before spin drying. The effect of preventing the occurrence is further enhanced as compared with the first and second development processing methods.

  The seventh development processing method is performed in the order of development processing with a developing solution, application of a curing chemical solution and curing of a resist pattern by ultraviolet irradiation processing, rinsing processing with a second rinsing liquid, and spin drying. The eighth development processing method is performed in the order of development processing with a developer, curing of a resist pattern by applying a curing chemical solution and ultraviolet irradiation processing, coating of the resist pattern with an inert liquid, and spin drying. These seventh and eighth development processing methods are used for the purpose of preventing pattern collapse when development defects are not a problem.

  The ninth development processing method is performed in the order of development processing using a developer, rinsing processing using a first rinsing solution, rinsing processing using a second rinsing solution, and spin drying. The ninth development processing method is used only when the surface tension of the second rinse liquid is smaller than the surface tension of the first rinse liquid and the cleanliness is high. The tenth development processing method is performed in the order of development processing with a developing solution, rinsing processing with a first rinsing solution, coating of a resist pattern with an inert liquid, and spin drying. In these ninth and tenth development processing methods, development defects can be removed while suppressing CD fluctuation and the like, and a liquid with a small surface tension is spun off from the wafer W and spin-dried, so that pattern collapse is prevented. be able to. The effect of preventing pattern collapse is higher in the third to eighth development processing methods than in the ninth and tenth development processing methods.

  In the present invention, among the above first to tenth development processing methods, an appropriate one is considered in consideration of the resist pattern line width and target characteristics (the number of precipitation defects, CD value, LER value, etc.). Is selected. From the viewpoint of improving the quality of the wafer W in total, it is preferable to use the third to sixth development processing methods. Other methods have an advantage that processing can be performed with a short tact time while maintaining a specific quality. In the development processing method including the treatment with the first rinse solution, 99% or more of the resist residue can be removed. Also, a resist pattern is cured or a liquid having a low surface tension is supplied to the wafer W, and then spin drying is performed to form a resist pattern with an aspect ratio of 3.6 or more (or the aspect ratio is equal to the resist pattern). The pitch (unit: μm) is 20 / μm or more. That is, it is possible to prevent the pattern collapse of the resist pattern having a narrow line width.

  Next, taking the third and sixth development processing methods as examples, the process will be described in more detail. FIG. 5 shows a flowchart of the third development processing method, and FIG. 6 shows a flowchart of the sixth development processing method.

  In the third development processing method, first, the wafer W that has been exposed in a predetermined pattern, post-exposure bake processing and cooling processing is transferred to the position just above the cup CP by the transfer arm T of the wafer transfer device, and the lift pins 5 is placed on the spin chuck 2 and vacuum-sucked (STEP 1).

  Next, the developing solution nozzle 11 is moved above the center of the wafer W, and the developing solution is discharged by discharging the developing solution from the developing solution nozzle 11 in a strip shape, for example, by rotating the wafer W 1/2 turn or more, for example, 1 turn. Coating is performed on the entire surface of the wafer W to form a developer paddle (STEP 2). The developer may be discharged while the developer nozzle 11 is scanned in the Y direction.

  In this way, the developing solution is allowed to stand for an appropriate time, for example, 60 seconds with the developer applied on the wafer W (STEP 3). At this time, the developing solution nozzle 11 is retracted outside the cup CP, and the first rinsing solution nozzle 13 is positioned above the center of the wafer W (STEP 4).

  When the development reaction is completed, the wafer W is rotated by the spin chuck 2 and the developer is shaken off (STEP 5). At the same time that the developer is shaken off, the first rinsing liquid is discharged from the first rinsing liquid nozzle 13 to perform rinsing with the first rinsing liquid (STEP 6). The rotation speed of the wafer W in STEP 6 can be set to 500 to 2000 rpm, for example.

  Before supplying the first rinsing liquid, dummy dispensing of the first rinsing liquid nozzle 13 is performed at the retreat position so that the residue of the surfactant adhering to the first rinsing liquid nozzle 13 is not supplied to the wafer W. It is desirable to make it. Thereby, generation | occurrence | production of the particle resulting from a rinse liquid can be suppressed more reliably. Further, the rinsing process with the first rinsing liquid may be performed by scanning the first rinsing liquid nozzle 13 in the Y direction while rotating the wafer W.

  After supplying the first rinsing liquid for a predetermined time, the surface of the wafer W is kept wet with the first rinsing liquid, the first rinsing liquid nozzle 13 is retracted outside the cup CP, and the chemical liquid nozzle 12a is placed on the wafer W. It is moved above the center (STEP 7). Next, the wafer W is rotated 1/2 turn or more, for example, 1 turn while discharging the hardening chemical liquid from the chemical nozzle 12a. As a result, the curing chemical solution is applied to the entire surface of the wafer W, and a curing chemical solution paddle is formed (STEP 8).

  Subsequently, after the second nozzle scan arm 17 is slid in the Y direction so that the ultraviolet irradiation unit 12b is located outside the wafer W, the ultraviolet lamp 42 is turned on to move the ultraviolet irradiation unit 12b in the Y direction of the wafer W. Scanning is performed a predetermined number of times between the ends (STEP 9). Thereby, a crosslinking agent couple | bonds with a resist film on the surface of a resist film, and hardens a resist film.

  When the resist pattern curing process is completed, the chemical solution nozzle 12a and the ultraviolet irradiation unit 12b are retracted outside the cup CP, and the second rinse solution nozzle 14 is positioned at the center of the wafer W (STEP 10). The wafer W is rotated at a predetermined number of revolutions, the curing chemical solution is spun off from the wafer W, and at the same time, the second rinse liquid is supplied to the wafer W, and the wafer W is rinsed with the second rinse liquid ( (Step 11). At this time, the second rinse liquid nozzle 14 may be scanned in the Y direction.

  After rinsing with the second rinsing liquid for a predetermined time, the wafer W is rotated to spread the rinsing liquid, and the rinsing liquid is shaken off to dry the wafer W (STEP 12). This spin drying step is performed first at a rotation speed of the wafer W of more than 300 rpm and less than 1000 rpm, for example, 500 rpm, for 5 to 15 seconds, for example, 10 seconds. Subsequently, the rotation speed of the wafer W is set to 1000 to 4000 rpm, for example, 2000 rpm. It is preferable to perform for 20 seconds, for example, 15 seconds. In this way, the rinse of the rinse liquid from the wafer W and spin drying of the wafer W can effectively suppress the occurrence of pattern collapse.

  The wafer W thus dried is lifted onto the spin chuck 2 by the elevating pins 5 and is unloaded from the development processing device (DEV) by the transfer arm T of the wafer transfer device (STEP 13) and subjected to post-bake processing. .

  Next, a sixth development processing method will be described. In the sixth development processing method, first, the wafer W that has been exposed in a predetermined pattern, post-exposure bake processing and cooling processing is transferred to the position just above the cup CP by the transfer arm T of the wafer transfer device, and the lift pins 5 is placed on the spin chuck 2 and is vacuum-sucked (STEP 101).

  Next, the developing solution nozzle 11 is moved above the center of the wafer W, and the developing solution is discharged by discharging the developing solution from the developing solution nozzle 11 in a strip shape, for example, by rotating the wafer W 1/2 turn or more, for example, 1 turn. Coating is performed on the entire surface of the wafer W to form a developer paddle (STEP 102). The developer may be discharged while the developer nozzle 11 is scanned in the Y direction.

  In this way, development is advanced by allowing the developer to be applied on the wafer W for a suitable time, for example, 60 seconds (STEP 103). At this time, the developing solution nozzle 11 is retracted outside the cup CP, and the chemical solution nozzle 12a is moved above the center of the wafer W (STEP 104).

  When the development reaction is completed, the wafer W is rotated by the spin chuck 2 and the developer is shaken off (STEP 105). The developer is shaken off so that a thin film of the developer remains on the surface of the wafer W. Then, the wafer W is rotated 1/2 turn or more, for example, 1 turn, while the curing solution is discharged from the chemical nozzle 12a in a strip shape. As a result, the curing chemical solution is applied to the entire surface of the wafer W, and a curing chemical solution paddle is formed (STEP 106).

  Subsequently, after the second nozzle scan arm 17 is slid in the Y direction so that the ultraviolet irradiation unit 12b is located outside the wafer W, the ultraviolet lamp 42 is turned on to move the ultraviolet irradiation unit 12b in the Y direction of the wafer W. Scanning is performed a predetermined number of times between the ends (STEP 107). Thereby, a crosslinking agent couple | bonds with a resist film on the surface of a resist film, and hardens a resist film.

  When the resist pattern curing process is completed, the chemical solution nozzle 12a and the ultraviolet irradiation unit 12b are retracted outside the cup CP, and the first rinse solution nozzle 13 is positioned above the center of the wafer W (STEP 108). The wafer W is rotated at a predetermined number of revolutions, the curing chemical is spun off from the wafer W, and substantially simultaneously with this, the first rinse liquid is discharged from the first rinse liquid nozzle 13 to perform the rinsing process with the first rinse liquid. Perform (STEP 109).

  After the treatment with the first rinsing liquid is performed for a predetermined time, the surface of the wafer W is wetted with the first rinsing liquid (a state where a paddle of the first rinsing liquid is formed, or a thin film of the first rinsing liquid). The first rinse liquid nozzle 13 is retracted outside the cup CP, and the second rinse liquid nozzle 14 is positioned at the center of the wafer W (STEP 110). Then, an inert liquid is supplied to the wafer W (STEP 111). Since the specific gravity of the inert liquid is larger than that of the first rinse liquid, the inert liquid settles below the first rinse liquid and is replaced with the first rinse liquid, and the resist pattern is immersed in the inert liquid. At this time, the first rinse liquid chemical is pushed out of the wafer W.

  After the supply of the inert liquid is stopped and the resist pattern is immersed in the inert liquid, the wafer W is rotated at a predetermined number of rotations, and the inert liquid is spread and shaken to dry the wafer W. (STEP 112). The wafer W thus dried is lifted onto the spin chuck 2 by the elevating pins 5 and is unloaded from the development processing device (DEV) by the transfer arm T of the wafer transfer device (STEP 113) and subjected to post-bake processing. .

  As mentioned above, although embodiment of this invention was described, this invention is not limited to such embodiment, A various deformation | transformation is possible. In the above description, the case where a surfactant is added to the rinsing liquid has been described. However, a fluorochemical may be used instead of the surfactant.

  In the sixth development processing method, the curing chemical solution is supplied to the wafer W while shaking off the developer solution from the wafer W. However, the chemical solution is not formed in the state where the developer paddle is formed without rotating the wafer W. The chemical liquid paddle may be formed by replacing the developer with the chemical liquid for curing by scanning the chemical liquid nozzle 12a between the Y direction ends of the wafer W while discharging the chemical liquid for curing from the nozzle 12a.

  Further, if pure water (DIW) is not supplied to the wafer W before spin drying, a rinsing process with pure water may be added in the previous process. For example, the wafer W may be processed in the order of forming a developer paddle, rinsing with pure water, curing with a chemical for curing, rinsing with pure water, rinsing with a first rinsing liquid, and spin drying.

  In the above embodiment, the case where the present invention is applied to the development processing of a semiconductor wafer has been described. However, the present invention is not limited to this, and a substrate for a liquid crystal display device (LCD) can be used as long as it is a substrate on which a fine resist pattern is formed. The present invention can also be applied to other substrate development processes. Further, a combination of the constituent elements of the above-described embodiment as appropriate or a part of the constituent elements of the above-described embodiment removed is also within the scope of the present invention without departing from the scope of the present invention.

The top view which shows the image development processing apparatus with which the method concerning one Embodiment of this invention is implemented. 1 is a cross-sectional view showing a development processing apparatus in which a method according to an embodiment of the present invention is performed. FIG. 3 is a diagram showing a schematic configuration of a liquid supply system of the development processing apparatus of FIGS. 1 and 2. The figure which shows the 1st-10th image development processing method simply. 9 is a flowchart showing a third development processing method. 10 is a flowchart showing a sixth development processing method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Housing | casing 2; Spin chuck 11; Developer nozzle 12a; (Curing) Chemical nozzle 12b; Ultraviolet irradiation unit 13; First rinse nozzle 14; Second rinse nozzle 42; Ultraviolet lamp W; Semiconductor wafer

Claims (15)

A first rinse containing a predetermined surfactant at a critical micelle concentration or less on a substrate that has been exposed to light in a predetermined pattern on a resist film provided on the surface and subsequently developed with a predetermined developer. Supplying liquid and rinsing,
Supplying a chemical solution containing a crosslinking agent for curing the resist film on the substrate onto the substrate;
Irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate, and curing the resist film by a synergistic effect of the irradiation of the crosslinking agent and the high energy ray;
A development processing method characterized by comprising: Rotating the substrate after the resist film curing process, and shaking off the chemical solution from the substrate;
Supplying a second rinsing liquid to which a predetermined surfactant or fluorine-based chemical is added so that the surface tension of the substrate is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of revolutions, shaking off the second rinse liquid from the substrate, and drying the substrate;
The development processing method according to claim 1, further comprising: Supplying a predetermined inert liquid having a specific gravity larger than that of the chemical liquid and not mixed with the chemical liquid in a state where the chemical liquid is piled on the substrate after the resist film is cured. Leaving the inert liquid by allowing it to stand for a predetermined time so that the liquid is immersed in the inert liquid;
Rotating the substrate at a predetermined number of rotations to shake off the chemical solution and the inert liquid from the substrate, and drying the substrate;
The development processing method according to claim 1, further comprising: A chemical solution containing a cross-linking agent for curing the resist film on the substrate is supplied to the substrate on which the resist film provided on the substrate is exposed with a predetermined pattern and then developed with a predetermined developer. And a process of
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
Supplying a first rinsing liquid containing a predetermined surfactant at a critical micelle concentration or less to the substrate, and rinsing;
A development processing method characterized by comprising: Rotating the substrate supplied with the first rinsing liquid and shaking off the first rinsing liquid from the substrate;
Supplying a second rinsing liquid to which a predetermined surfactant or fluorine-based chemical is added so that the surface tension of the substrate is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of revolutions, shaking off the second rinse liquid from the substrate, and drying the substrate;
The development processing method according to claim 4, further comprising: In a state where the first rinse liquid is piled on the substrate, a predetermined inert liquid having a specific gravity greater than that of the first rinse liquid and not mixed with the first rinse liquid is supplied. Leaving the inert liquid by allowing it to stand for a predetermined time so that the resist film is immersed in the inert liquid;
Rotating the substrate at a predetermined number of revolutions, shaking off the first rinse liquid and the inert liquid from the substrate, and drying the substrate;
The development processing method according to claim 4, further comprising: A first rinse containing a predetermined surfactant at a critical micelle concentration or less on a substrate that has been exposed to light in a predetermined pattern on a resist film provided on the surface and subsequently developed with a predetermined developer. Supplying liquid and rinsing,
Supplying a second rinsing liquid to which a predetermined surfactant or fluorine-based chemical is added so that the surface tension of the substrate is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of revolutions, shaking off the second rinse liquid from the substrate, and drying the substrate;
A development processing method characterized by comprising: A first rinse containing a predetermined surfactant at a critical micelle concentration or less on a substrate that has been exposed to light in a predetermined pattern on a resist film provided on the surface and subsequently developed with a predetermined developer. Supplying liquid and rinsing,
In a state where the first rinse liquid is piled on the substrate, a predetermined inert liquid having a specific gravity greater than that of the first rinse liquid and not mixed with the first rinse liquid is supplied. Leaving the inert liquid by allowing it to stand for a predetermined time so that the resist film is immersed in the inert liquid;
Rotating the substrate at a predetermined number of revolutions, shaking off the first rinse liquid and the inert liquid from the substrate, and drying the substrate;
A development processing method characterized by comprising:   The development processing method according to claim 3, wherein the inert liquid is alternative chlorofluorocarbon.   10. The surfactant according to claim 1, wherein the surfactant contained in the first rinsing liquid is an ethylene glycol-based, ether-based, or acetylene glycol-based surfactant. 11. Development processing method.   The surfactant contained in the first rinsing liquid has a molecular weight of 1280 or more, and the hydrophobic group has 14 or more carbon atoms. 11. 2. The development processing method according to item 1.   The development according to any one of claims 1 to 11, wherein the surfactant contained in the first rinsing liquid has a hydrophobic group that does not have a double bond or a triple bond. Processing method. A resist film provided on a substrate is exposed in a predetermined pattern and then developed with a predetermined developer, and the resist on the substrate is wet with the developer surface. Supplying a chemical solution containing a cross-linking agent for curing the film;
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
Rotating the substrate after the resist film curing process, and shaking off the chemical solution from the substrate;
Supplying the substrate with a rinsing liquid to which a predetermined surfactant or fluorine-based agent is added so that the surface tension thereof is 50 dyne / cm or less, and a rinsing process;
Rotating the substrate at a predetermined number of rotations to shake off the rinse liquid from the substrate and drying the substrate;
A development processing method characterized by further comprising: A resist film provided on a substrate is exposed in a predetermined pattern and then developed with a predetermined developer, and the resist on the substrate is wet with the developer surface. Supplying a chemical solution containing a cross-linking agent for curing the film;
A step of irradiating the surface of the substrate with a predetermined high energy ray in a state where the chemical liquid is deposited on the substrate and curing the resist film by a synergistic action of the irradiation of the crosslinking agent and the high energy ray. When,
In a state where the chemical liquid is piled on the substrate, a predetermined inert liquid having a specific gravity greater than that of the chemical liquid and not mixed with the chemical liquid is supplied, and the resist film is immersed in the inert liquid. Leaving the inert liquid to stand for a predetermined period of time, and
Rotating the substrate at a predetermined number of rotations to shake off the chemical solution and the inert liquid from the substrate, and drying the substrate;
A development processing method characterized by further comprising:   The development processing method according to claim 14, wherein the inert liquid is alternative chlorofluorocarbon.

Images