WO2013132881A1 - 液処理方法、液処理装置及び記憶媒体 - Google Patents
液処理方法、液処理装置及び記憶媒体 Download PDFInfo
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- WO2013132881A1 WO2013132881A1 PCT/JP2013/050409 JP2013050409W WO2013132881A1 WO 2013132881 A1 WO2013132881 A1 WO 2013132881A1 JP 2013050409 W JP2013050409 W JP 2013050409W WO 2013132881 A1 WO2013132881 A1 WO 2013132881A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S134/00—Cleaning and liquid contact with solids
- Y10S134/902—Semiconductor wafer
Definitions
- the present invention relates to a technique for hydrophobizing a substrate subjected to liquid treatment.
- a single wafer spin cleaning apparatus liquid processing apparatus
- liquid processing apparatus liquid processing apparatus
- a wafer that performs liquid processing on a semiconductor wafer (hereinafter referred to as a wafer) that is a substrate
- alkaline or acidic chemical liquid is supplied to the surface of the rotating wafer. Is spread on the surface of the wafer to remove dust and natural oxides on the wafer surface.
- the chemical solution remaining on the wafer surface is removed by a rinse solution or the like, and when the supply of the rinse solution is stopped while the wafer is rotated, the remaining rinse solution is shaken off to obtain a dried wafer.
- Pattern collapse is a surface that pulls this convex part to the left and right as the liquid remaining on the right and left of the convex part and the convex part forming the pattern dries unevenly when the rinse liquid that has entered the pattern is shaken off. This is a phenomenon in which the balance of tension is lost and the convex part falls in the direction in which a large amount of liquid remains.
- Patent Document 1 Technology to reduce the surface tension acting on the pattern by hydrophobizing the wafer surface and increasing the contact angle between the wafer and the rinse liquid as a technique to remove the rinse liquid remaining on the wafer surface while suppressing the occurrence of pattern collapse.
- Patent Document 2 the wafer surface is hydrophobized by bringing the wafer to be processed into contact with a hydrophobizing liquid.
- some hydrophobizing agents are expensive, and in order to reduce the amount used, the wafer surface using vaporized hydrophobizing agents or gas containing hydrophobizing agent mist (hereinafter referred to as hydrophobizing gas) Attempts have also been made to hydrophobize (Patent Document 2).
- the present inventor has been developing a technique for hydrophobizing the wafer surface using a hydrophobizing gas. After finishing the process using the hydrophobizing gas and rinsing, the surface of the wafer is contaminated with a large number of particles. It was newly found out that it might be done.
- Japanese Patent Laid-Open No. 7-273083 paragraphs 0027, 0053 to 0055, FIG. JP 2010-258068 A: Paragraph 0035, FIG. 4 (a)
- the present invention has been made in view of such circumstances, and its purpose is to make the surface hydrophobic using a hydrophobizing gas while suppressing the generation of a watermark on the surface of the substrate.
- An object of the present invention is to provide a liquid processing method, a liquid processing apparatus, and a storage medium storing the method.
- the liquid processing method comprises: A substrate holding part for holding the substrate horizontally and rotating it around a vertical axis; A chemical nozzle for supplying a chemical to the surface of the substrate; A hydrophobizing gas nozzle for supplying a hydrophobizing gas to the surface of the substrate; A rinsing liquid nozzle for supplying a rinsing liquid to the surface of the substrate, and a liquid processing method using a liquid processing apparatus comprising: Supplying a chemical solution from the chemical solution nozzle to the surface of the substrate held and rotated by the substrate holding unit to perform a liquid treatment; Next, supplying the rinse liquid from the rinse liquid nozzle to the surface of the substrate while rotating the substrate, replacing the chemical liquid with the rinse liquid; Next, a hydrophobic gas for hydrophobizing the surface of the substrate is supplied from the hydrophobic gas nozzle to the surface of the substrate while rotating the substrate, and the substrate after the hydrophobic gas is supplied Supplying the rinsing liquid to the surface of the substrate while rotating the substrate alternately to
- the supply of the next rinse solution may be started before the rinse solution on the surface of the substrate supplying the hydrophobizing gas is dried.
- the substrate has a pattern formed on a surface of the substrate; While performing the hydrophobization of the substrate, the hydrophobized gas enters the pattern while gradually reducing the position of the surface of the rinse liquid present in the pattern formed on the surface of the substrate, The area of the hydrophobized region in the depth direction of the pattern may be increased.
- the number of rotations of the substrate while the substrate is being dried may be lower than the number of rotations of the substrate while the substrate is being hydrophobized.
- the liquid processing method according to the present invention comprises: The method may further include supplying a solvent to the surface of the substrate to remove the by-product of the hydrophobizing gas between the hydrophobicization of the substrate and the drying of the substrate.
- the substrate has a pattern formed on a surface of the substrate;
- the number of times of alternately supplying the rinsing liquid to the surface of the substrate and supplying the hydrophobizing gas to the surface of the substrate is equal to the rinsing liquid for the surface portion of the substrate where the pattern is not formed.
- the contact angle may be equal to or greater than a preset angle.
- a storage medium comprises: A storage medium storing a computer program used in a liquid processing apparatus that performs liquid processing on the surface of the substrate, The program causes the liquid processing apparatus to execute the liquid processing method described above.
- the liquid processing apparatus comprises: A substrate holding part for holding the substrate horizontally and rotating it around a vertical axis; A chemical nozzle for supplying a chemical to the surface of the substrate; A hydrophobizing gas nozzle for supplying a hydrophobizing gas to the surface of the substrate; A rinse liquid nozzle for supplying a rinse liquid to the surface of the substrate; Supplying the chemical solution from the chemical solution nozzle to the surface of the substrate held and rotated by the substrate holder, and then supplying the rinse solution from the rinse solution nozzle to the surface of the substrate while rotating the substrate.
- a hydrophobic gas for hydrophobizing the surface of the substrate is supplied to the surface of the substrate, and the substrate after the hydrophobic gas is supplied is supplied to the substrate.
- Supplying the rinsing liquid to the surface of the substrate while rotating the substrate alternately to make the substrate hydrophobic, and then rotating the substrate holding portion to rotate the substrate while rotating the substrate.
- a controller for removing and drying; Is provided.
- the controller is While the substrate is being hydrophobized, the next rinsing liquid supply may be started before the rinsing liquid on the surface of the substrate supplying the hydrophobizing gas is dried.
- the controller is Finishing hydrophobizing the substrate by supplying a rinsing liquid to the surface of the substrate,
- the number of revolutions of the substrate while the substrate is being dried may be lower than the number of revolutions of the substrate while the substrate is being hydrophobized.
- the liquid processing apparatus comprises: A solvent nozzle for supplying a solvent to the surface of the substrate;
- the control unit may cause the solvent to be supplied from the solvent nozzle to the surface of the substrate between the hydrophobicity of the surface of the substrate and the drying of the substrate.
- the hydrophobized gas supply to the surface of the substrate and the supply of the rinsing liquid are alternately repeated in a state where the droplets remaining on the substrate are not dried, thereby stepping the hydrophobized region on the surface of the substrate. And the generation of watermarks can be suppressed.
- the liquid processing apparatus is connected to a disk-like support plate 21 provided with a plurality of, for example, three support pins 23 that horizontally support a wafer W, and a lower surface of the support plate 21. And a rotating shaft 22 extending in the vertical direction.
- the support plate 21, the support pins 23, and the rotation shaft 22 correspond to the substrate holding unit of the present liquid processing apparatus.
- a pulley 33 is provided on the lower end side of the rotary shaft 22, and a rotary motor 31 is disposed on the side of the pulley 33.
- the drive belt 32 is wound around the pulley 33 and the rotary shaft of the rotary motor 31 to constitute the rotary drive unit 30 that rotates the wafer W on the support plate 21 around the vertical axis.
- the rotation motor 31 can change the rotation speed of the support plate 21, that is, the rotation speed of the wafer W supported on the support plate 21.
- the rotary shaft 22 is fixed to the floor plate 12 of the housing in which the liquid treatment device is disposed via a bearing 34.
- the center portion of the support plate 21 is cut into a circular shape, and a disk-shaped lifting plate 24 is disposed in the cutout.
- a plurality of, for example, three lift pins 26 are provided on the upper surface of the elevating plate 24 for supporting the wafer W from the back surface (lower surface) side when delivered to an external wafer transfer mechanism.
- a lift shaft 25 penetrating the rotary shaft 22 in the vertical direction is connected to the lower surface of the lift plate 24, and a lift mechanism 35 for raising and lowering the lift shaft 25 is provided at the lower end of the lift shaft 25. It has been. Further, a cup 11 is provided outside the support plate 21 to cover the wafer W supported by the support pins 23 from the periphery and obliquely upward.
- the liquid processing apparatus of the present embodiment switches the chemical solution to the surface of the wafer W and supplies it to perform liquid processing on the surface.
- SC-1 mixed aqueous solution of ammonia and hydrogen peroxide
- SC-1 mixed aqueous solution of ammonia and hydrogen peroxide
- the liquid processing apparatus includes a liquid nozzle 411 as a means for supplying a chemical solution.
- the liquid nozzle 411 plays a role of supplying the chemical liquid (SC-1) and DIW which is a rinse liquid to the central portion of the surface (upper surface) of the rotating wafer W.
- the liquid nozzle 411 corresponds to a chemical liquid nozzle in terms of supplying a chemical liquid, and corresponds to a rinse liquid nozzle in terms of supplying a rinsing liquid.
- the liquid processing apparatus includes a gas nozzle 412 for supplying a gas of a silylating agent (hydrophobizing gas), which is a kind of a hydrophobizing agent, and N 2 gas used when the wafer W is dried, to the surface of the wafer W, and hydrophobization.
- a gas nozzle 412 for supplying a gas of a silylating agent (hydrophobizing gas), which is a kind of a hydrophobizing agent, and N 2 gas used when the wafer W is dried, to the surface of the wafer W, and hydrophobization.
- An IPA nozzle 413 that is used after the gas supply and supplies IPA (IsoPropyl Alcohol), which is a kind of processing liquid, is provided.
- the silylating agent gas, N 2 gas, and IPA are supplied to the gas nozzle 412 and the IPA nozzle 413 through a flow path different from the chemical solution and DIW, respectively.
- nozzles 411 to 413 are provided on the lower surface side of the nozzle block 42, and the nozzle block 42 is attached to the tip of the nozzle arm 43.
- the base end portion of the nozzle arm 43 is supported by a slider 44 that can run on the guide rail 45. Then, by moving the slider 44 between one end and the other end of the guide rail 45, a position above the central portion of the wafer W (rotation center of the wafer W) (shown by a solid line in FIG. 2).
- the nozzle block 42 that is, the liquid nozzle 411, the gas nozzle 412, and the IPA nozzle 413 are moved between the position retracted from the upper side of the wafer W to the side (shown by a one-dot chain line in the figure).
- the illustration of the cup 11 is omitted in FIG. 1, but the position where the nozzle block 42 is retracted is set to the outside of the cup 11.
- the liquid nozzle 411, the gas nozzle 412, and the IPA nozzle 413 are not limited to being provided in the common nozzle block 42, and a nozzle block or a moving mechanism dedicated to each nozzle 411 to 413 may be used. .
- the nozzle arm 43 and the nozzle block 42 are provided with liquid passages and gas passages (not shown) connected to the liquid nozzle 411, the gas nozzle 412, and the IPA nozzle 413, respectively.
- a DIW supply unit 64 and a chemical solution supply unit 65 each having a tank for each processing solution (chemical solution and DIW) and a flow rate adjusting mechanism are connected to the flow path connected to the liquid nozzle 411.
- each processing liquid is switched from the liquid nozzle 411 to the wafer W by opening and closing on-off valves V4 and V5 provided on connection pipes connecting the liquid flow paths and the processing liquid supply sections 64 and 65. Can be supplied.
- TMSDMA TriMethyl Silyl DiMethyl Amine
- a TMSDMA supply unit 62 having a mechanism and a flow rate adjusting mechanism, and an N2 gas cylinder and an N2 gas supply unit 63 having the flow rate adjusting mechanism are connected.
- TMSDMA gas and N2 gas are supplied from the gas nozzle 412 to the wafer W. It can be switched and supplied.
- the gas nozzle 412 corresponds to a hydrophobized gas nozzle.
- TMSDMA plays a role of increasing the contact angle between the wafer W and DIW when the surface of the wafer W is silylated to make the surface hydrophobic and remove DIW used in the rinsing process.
- the silylation in this example means that a hydrophilic functional group bonded to Si atoms on the surface of the wafer W, such as an OH group, is replaced with a hydrophobic functional group containing Si atoms. This is a treatment for hydrophobizing the surface.
- substitution with a trimethylsilyl group is performed.
- the TMSDMA is stored in a tank in the TMSDMA supply unit 62 in a liquid state, for example, heated and gasified by a heater mechanism or the like, and a carrier gas (N 2 gas or the like) supplied from the carrier gas supply unit 621 is used. ) And is supplied to the gas nozzle 412.
- the flow path connected to the IPA nozzle 413 is connected to an IPA supply unit 61 having an IPA tank as a solvent and a flow rate adjusting mechanism.
- IPA can be supplied from the IPA nozzle 413 to the wafer W by opening and closing an open / close valve V1 provided on a connection pipe line connecting the liquid flow path and the IPA supply unit 61.
- V1 an open / close valve
- the liquid processing apparatus having the above-described configuration is connected to the control unit 7 as shown in FIGS.
- the control unit 7 includes a computer having a CPU and a storage unit (not shown).
- the storage unit operates the liquid processing apparatus, that is, rotates the wafer W supported on the support plate 21 to have a preset schedule.
- the processing liquid is switched and supplied, and after the liquid processing, hydrophobization processing and drying of the wafer W, a program in which a group of steps (commands) for controlling the wafer W is carried out is recorded. ing.
- This program is stored in a storage medium such as a hard disk, a compact disk, a magnetic optical disk, or a memory card, and installed in the computer therefrom.
- control unit 7 adjusts the supply timing, supply time and supply amount of TMSDMA gas, DIW, IPA, and the like, the rotation speed of the wafer W, and the like using the hydrophobized gas described in the background art. Particle contamination that occurs when the surface of W is hydrophobized can be reduced.
- the main cause of generation of particles is the generation of watermarks due to drying of droplets on the surface of the wafer W when the hydrophobized gas is supplied.
- DIW is supplied to the surface of the rotating wafer W to replace it with chemicals and rinse, and then continuously supply a hydrophobizing gas to hydrophobize the entire surface of the wafer W.
- the wafer W is rotated at a rotation speed of 1000 rpm or more. Is preferred.
- the hydrophobized gas spreads over the surface of the wafer W evenly on the swirl flow formed on the surface of the wafer W.
- the hydrophobizing gas is supplied at a low rotation speed of less than 500 rpm, there is a portion where the pattern surface is not exposed because the rinsing liquid is not shaken off, so the hydrophobizing gas cannot enter the pattern, making it hydrophobic The area which is not done remains.
- the liquid processing apparatus of this example repeats supply of DIW and supply of TMSDMA gas (hydrophobization gas) alternately in order to suppress formation of a watermark while spreading the hydrophobic gas over the entire surface of the wafer W. Then, a process of expanding the region in which the surface of the wafer W is hydrophobized stepwise in the radial direction of the wafer W and the depth direction in the pattern is performed. In addition, when the wafer W is dried, a function of reducing the rotation speed of the wafer W and suppressing the remaining of minute droplets on the surface of the wafer W is also provided. The detailed contents of these processes will be described later in the explanation of the operation.
- FIG. 3 showing supply timings of various processing liquids and gases
- FIGS. 4 to 8 schematically showing the state of the surface of the wafer W during processing.
- the description will be given with reference.
- 3A to 3E schematically show the supply / stop timings of the processing liquids and gases from the nozzles 411 to 413 over time. These processing liquids and gases It does not accurately represent the supply time.
- the liquid processing apparatus stands by with the nozzle head 42 retracted to the outside of the cup 11 and the support plate 21 stopped. Then, when the external wafer transfer mechanism advances the fork holding the wafer W to the upper side of the support plate 21, the lift plate 24 is lifted to intersect the fork, and the wafer W is received on the lift pins 26 of the lift plate 24. hand over.
- the elevating plate 24 is lowered and the wafer W is placed on the support pins 23 of the support plate 21.
- the rotation motor 31 is operated to rotate the wafer W on the support plate 21, and when the wafer W reaches a predetermined rotation speed, the nozzle block 42 is moved to a position above the central portion of the wafer W.
- SC-1 is supplied from the liquid nozzle 411 for a preset time, and organic dirt and particles are removed.
- the rotational speed of the wafer W is increased and the processing liquid supplied from the liquid nozzle 411 is switched to DIW to perform a rinsing process to wash away SC-1 on the surface of the wafer W (FIG. 4).
- the rotation speed of the wafer W at this time is a rotation speed at which the TMSDMA gas can spread over the surface of the wafer W, for example, 1000 rpm or more.
- the TMSDMA gas is supplied at a supply rate of 5 l / min in the range of 5 to 20 l / min (standard condition at 0 ° C. and 1 atm). For example, 1 second is supplied in the range of 0.5 to 2 seconds.
- DIW is supplied at a supply rate of 2 l / min in the range of 1 to 3 l / min, for example 0.5 seconds in the range of 0.5 to 5 seconds.
- the fluid supplied to the surface of the wafer W is switched to DIW in a relatively short time before the fine droplet 81 is dried and a watermark is formed (FIG. 6).
- DIW the minute droplets 81 are washed away, so that the formation of watermarks is suppressed.
- TMSDMA gas is supplied for a short time of about 0.5 to 2 seconds, it is not sufficient to provide sufficient hydrophobicity to the inside of the pattern over the entire surface of the wafer W. Therefore, when the fine droplet 81 is washed away, the fluid supplied to the surface of the wafer W is switched to the TMSDMA gas. Thus, DIW and TMSDMA gas are alternately supplied.
- DIW is supplied (FIG. 9A).
- TMSDMA gas comes into contact with the upper end of the pattern from which the rinsing liquid has been shaken off.
- FIG. 9B the TMSDMA gas comes into contact with the upper end of the pattern from which the rinsing liquid has been shaken off.
- DIW remains between the patterns.
- DIW is supplied again. While the wafer is covered with DIW, the DIW flushes out the fine droplets 81 remaining at the upper end of the hydrophobic pattern (FIG. 9C).
- the liquid level of the DIW in the pattern is gradually lowered and the pattern is made hydrophobic in the depth direction.
- the area of the formed region can be increased.
- the hydrophobic area 83 that has been hydrophobized to the inside of the pattern has a DIW liquid level that gradually decreases from the center of the wafer toward the outside in the radial direction.
- the side portions of the are gradually hydrophobized. Therefore, the hydrophobized gas gradually spreads in the radial direction of the wafer W.
- the alternate supply of TMSDMA gas and DIW is repeated several times to several hundred times, for example, and when the entire surface of the wafer W uniformly becomes the hydrophobic region 83, the alternate supply of TMSDMA gas and DIW is finished.
- the number of repetitions of the alternate supply is as many as the hydrophobicity capable of drying the wafer W without causing pattern collapse is obtained. Whether or not the pattern collapse occurs can be evaluated using, for example, the contact angle of DIW with respect to the surface of the wafer W on which the pattern is not formed as a guide, and the number of repetitions is such that a contact angle of 80 to 90 ° or more is obtained. Is preferably selected.
- the hydrophobized region on the surface of the substrate is gradually expanded and the generation of watermarks can be suppressed.
- the rotational speed of the wafer W is reduced to about 30 to 100 rpm, and the liquid nozzle 411 (nozzle block 42) for supplying the DIW is moved from the central portion of the wafer W toward the peripheral portion. (FIG. 8).
- the DIW spreads in the circumferential direction of the wafer W while the liquid film is formed, and the region where the liquid pool is formed by the movement of the liquid nozzle 411 It can be moved to extrude toward the peripheral edge. As a result, it is possible to widen a dry region that is not in contact with DIW from the central portion toward the peripheral portion while suppressing generation of droplets due to tearing of the liquid pool.
- the extruded DIW is dropped from the wafer W at the outer peripheral edge of the wafer W and removed.
- N 2 gas may be supplied from a gas nozzle 412 positioned closer to the center of the wafer W than the liquid nozzle 411 that supplies DIW (see “rinse cleaning and cleaning” in FIG. 3D). “Drying process” period, FIG. 8).
- the N2 gas plays a role of flowing the DIW, and is supplied to the surface of the wafer W rotating at a low speed, so that it is possible to prevent DIW that acts only with a relatively small centrifugal force from remaining on the surface of the wafer W.
- the nozzle block 42 is retracted from above the wafer W and the rotation of the wafer W is stopped. Thereafter, the elevating plate 24 is raised to lift the wafer W, the processed wafer W is delivered to the external wafer transfer mechanism, and then the elevating plate 24 is lowered to wait for the next wafer W to be loaded.
- the reaction by-product 82 generated when the hydrophobized gas comes into contact with DIW may remain on the surface of the wafer W ( It was found that this reaction by-product 82 is difficult to remove by DIW, but can be removed by using IPA as a solvent, as indicated by black circles in FIGS.
- IPA which is a solvent for removing the reaction by-product 82
- IPA is supplied to the surface of the wafer W before the drying process and in a state where the liquid film of DIW after the hydrophobization process is formed (FIG. 3 (e) ) “Solvent treatment” period, FIG. 7).
- the reaction by-product 82 is removed from the surface of the wafer W, and adhesion and remaining of two types of particles generated by using the hydrophobized gas can be suppressed.
- Examples of the rotation speed of the wafer W at the time of supplying IPA include a range of 300 to 2000 rpm at which an IPA liquid film is formed on the entire surface of the wafer W.
- reaction by-product 82 and microdroplets 81 remain on the surface of the wafer W, but the microdroplets 81 are soluble in IPA.
- the solvent treatment shown in FIGS. 3 (e) and 7 may be performed.
- the liquid processing apparatus has the following effects.
- the hydrophobized region on the surface of the wafer W is stepped in the depth direction inside the pattern and in the diameter direction of the wafer W. Expand.
- the fine droplets 81 generated when the TMSDMA gas is supplied can be washed away by supplying the DIW.
- the by-product generated by supplying TMSDMA gas to the surface of the wafer W after the chemical solution is replaced with DIW is removed by IPA, contamination of the wafer W by the by-product can be reduced.
- the processing liquid on the surface of the hydrophobized wafer W is replaced with DIW, and when removing the DIW, the rotation speed of the wafer W is reduced, and the liquid nozzle 411 for supplying DIW is set to the central portion side of the wafer W.
- the DIW is pushed into the peripheral edge side of the wafer W while being taken into the liquid film while suppressing the tearing of the DIW, and the wafer W can be dried.
- N 2 gas from the central portion side of the wafer W it is possible to suppress the DIW from spreading to the central portion side of the wafer W rotating at a low speed.
- the silylating agent used as the hydrophobizing agent is not limited to TMSDMA.
- TMSDMA hexamethyldisilazane
- TMSDEA trimethylsilyldiethylamine
- Reaction by-products generated from these silylating agents can also suppress particle contamination of the wafer W by supplying IPA as a solvent after the hydrophobization treatment.
- the present invention can be applied not only to the silylating agent but also to other types of hydrophobizing gas as long as the hydrophobizing agent generates a reaction by-product that can be removed by a solvent. .
- the method of removing reaction by-products using a solvent alone has the effect of reducing the contamination of the wafer W by particles, and therefore, a process of continuously supplying a hydrophobized gas and drying the wafer It can also be applied to.
- the solvent capable of removing the reaction by-product is not limited to IPA, and for example, acetone may be used.
- a liquid hydrophobizing agent for example, a liquid silylating agent
- DIW and hydrophobizing agent are replaced through replacement with IPA as in the following processing sequence.
- Example of treatment sequence (1) Chemical treatment ⁇ (2) Rinse washing with DIW ⁇ (3) Replacing DIW with IPA ⁇ (4) Replacing IPA with liquid hydrophobizing agent ⁇ (5) Liquid hydrophobization Replacing the agent with IPA ⁇ (6) Replacing IPA with DIW and rinse washing ⁇ (7) Removal of DIW (drying process).
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Abstract
Description
基板を水平に保持し、鉛直軸周りに回転させる基板保持部と、
前記基板の表面に薬液を供給する薬液ノズルと、
前記基板の表面に疎水化ガスを供給する疎水化ガスノズルと、
前記基板の表面にリンス液を供給するリンス液ノズルと、を備えた液処理装置を用いた液処理方法であって、
前記基板保持部に保持され、回転する前記基板の表面に前記薬液ノズルから薬液を供給して液処理を行うことと、
次いで、前記基板を回転させながら前記基板の表面に前記リンス液ノズルからリンス液を供給し、前記薬液を前記リンス液に置換することと、
次いで、前記基板を回転させながら前記基板の表面に、この基板の表面を疎水化するための疎水化ガスを前記疎水化ガスノズルから供給することと、前記疎水化ガスが供給された後の前記基板を回転させながら前記基板の表面に前記リンス液を供給することとを交互に繰り返して、前記基板を疎水化することと、
次いで、前記基板を回転させることにより前記リンス液を除去して、前記基板を乾燥することと、
を備える。
前記基板を疎水化することを行っている間、前記疎水化ガスを供給している前記基板の表面上にあるリンス液が乾燥する前に、次のリンス液の供給を開始してもよい。
前記基板は当該基板の表面に形成されたパターンを有し、
前記基板を疎水化することを行っている間、前記基板の表面に形成された前記パターン内に存在するリンス液の液面の位置を次第に低下させながら前記パターン内に疎水化ガスを進入させ、前記パターンの深さ方向に疎水化された領域の面積を広げていってもよい。
前記基板を疎水化することを前記基板の表面に前記リンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数は、前記基板を疎水化することを行っている間の前記基板の回転数よりも低くなっていてもよい。
前記基板を疎水化することを前記基板の表面に前記リンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数は、前記基板を疎水化することを行っている間の前記基板の回転数よりも低く、
前記基板を乾燥することを行っている間、回転する前記基板の表面に前記リンス液を供給しながら前記リンス液の供給位置を前記基板の中央部から周縁部へ向けて移動させることにより、前記基板の表面上にあるリンス液を前記基板の外へ押し出して除去してもよい。
前記基板を疎水化することと前記基板を乾燥することとの間に、前記基板の表面に溶剤を供給して、前記疎水化ガスの副生成物を除去することをさらに備えてもよい。
前記基板は当該基板の表面に形成されたパターンを有し、
前記基板の表面に前記リンス液を供給することと前記基板の表面に前記疎水化ガスを供給することとを交互に繰り返す回数は、前記パターンが形成されていない前記基板の表面部分に対する前記リンス液の接触角が予め設定された角度以上となるような回数となっていてもよい。
前記基板の表面に対して液処理を行う液処理装置に用いられるコンピュータプログラムを格納した記憶媒体であって、
前記プログラムは前記液処理装置に上述された液処理方法を実行させる。
基板を水平に保持し、鉛直軸周りに回転させる基板保持部と、
前記基板の表面に薬液を供給する薬液ノズルと、
前記基板の表面に疎水化ガスを供給する疎水化ガスノズルと、
前記基板の表面にリンス液を供給するリンス液ノズルと、
前記基板保持部に保持され、回転する前記基板の表面に前記薬液ノズルから薬液を供給することと、次いで、前記基板を回転させながら当該基板の表面に前記リンス液ノズルからリンス液を供給することと、次いで、前記基板を回転させながら当該基板の表面に、この基板の表面を疎水化するための疎水化ガスを前記疎水化ガスノズル供給することと、疎水化ガスが供給された後の基板を回転させながら当該基板の表面にリンス液を供給することとを交互に繰り返して、前記基板を疎水化することと、次いで、前記基板保持部を回転させることにより前記基板を回転しながらリンス液を除去し乾燥することと、をさせる制御部と、
を備える。
前記制御部は、
前記基板を疎水化することを行っている間、前記疎水化ガスを供給している前記基板の表面上にあるリンス液が乾燥する前に、次のリンス液の供給を開始させてもよい。
前記制御部は、
前記基板を疎水化することを前記基板の表面にリンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数を、前記基板を疎水化することを行っている間の前記基板の回転数よりも低くしてもよい。
前記基板の表面に溶剤を供給する溶剤ノズルをさらに備え、
前記制御部は、前記基板の表面を疎水化することと前記基板を乾燥することとの間に、前記基板の表面に前記溶剤ノズルから前記溶剤を供給させてもよい。
また、支持プレート21の外方には、支持ピン23によって支持されたウエハWをその周縁及び斜め上方側から覆うカップ11が設けられている。
液ノズル411に接続された流路には各処理液(薬液及びDIW)のタンクと、流量調節機構とを備えたDIW供給部64、薬液供給部65が接続されている。
主要なパーティクルの発生原因は、疎水化ガス供給時にウエハWの表面の液滴が乾燥することによるウォーターマークの発生である。例えば、薬液処理を終えた後、回転するウエハWの表面にDIWを供給して薬液との置換、リンス洗浄を行い、次いで連続的に疎水化ガスを供給してウエハWの表面全体を疎水化しつつリンス液を除去する処理シーケンスについて考える。
まずDIWを供給する(図9(a))。次にDIWの供給を止めDIWで覆われたウエハWを回転させながら、その表面にTMSDMAガスを供給すると、リンス液が振り切られたパターンの上端部にTMSDMAガスが接触し、このパターンの上端部が疎水化される(図9(b))。この際、パターン間にはDIWが残っている。次にDIWを再び供給する。ウエハはDIWで覆われた状態になるとともに、DIWは疎水化されたパターンの上端部に残っている微小液滴81を洗い流す(図9(c))。
深さ方向に疎水化された領域の面積を広げることができる。パターンの内部まで疎水化がされた疎水化領域83は、図10に模式的に示すように、ウエハ中心から径方向外方に向けてDIWの液面が徐々に下がっていくため、露出したパターンの側面部分が徐々に疎水化される。そのため疎水化ガスがウエハWの径方向に向けて徐々に広がっていく。そして、TMSDMAガス、DIWの交互供給を例えば数回~数百回繰り返し、ウエハWの表面全体が一様に疎水化領域83となったら、TMSDMAガスとDIWとの交互供給を終える。
反応副生成物82及び微小液滴81が残存しているが、微小液滴81はIPAに可溶なの
で、TMSDMAガスの停止後、図3(e)、図7の溶剤処理を行ってもよい。
この他、反応副生成物を除去可能な溶剤は、IPAに限定されるものではなく例えばアセトンなどを利用してもよい。
処理シーケンス例:(1)薬液処理→(2)DIWによるリンス洗浄→(3)DIWをIPAと置換→(4)IPAを液体疎水化剤と置換して疎水化処理→(5)液体疎水化剤をIPAと置換→(6)IPAをDIWと置換してリンス洗浄→(7)DIWの除去(乾燥処理)。
なお、例えばTMSDMAは、IPAとの接触によっても反応副生成物を生成するが、この反応副生成物は上述の処理シーケンスの例ではIPA自身の溶剤作用により除去されるので問題とはなっていない。
21 支持プレート
22 回転軸
23 支持ピン
411 液ノズル
412 ガスノズル
413 IPAノズル
81 微小液滴
82 反応副生成物
83 疎水化領域
Claims (12)
- 基板を水平に保持し、鉛直軸周りに回転させる基板保持部と、
前記基板の表面に薬液を供給する薬液ノズルと、
前記基板の表面に疎水化ガスを供給する疎水化ガスノズルと、
前記基板の表面にリンス液を供給するリンス液ノズルと、を備えた液処理装置を用いた液処理方法であって、
前記基板保持部に保持され、回転する前記基板の表面に前記薬液ノズルから薬液を供給して液処理を行うことと、
次いで、前記基板を回転させながら前記基板の表面に前記リンス液ノズルからリンス液を供給し、前記薬液を前記リンス液に置換することと、
次いで、前記基板を回転させながら前記基板の表面に、この基板の表面を疎水化するための疎水化ガスを前記疎水化ガスノズルから供給することと、前記疎水化ガスが供給された後の前記基板を回転させながら前記基板の表面に前記リンス液を供給することとを交互に繰り返して、前記基板を疎水化することと、
次いで、前記基板を回転させることにより前記リンス液を除去して、前記基板を乾燥することと、
を備えたことを特徴とする液処理方法。 - 前記基板を疎水化することを行っている間、前記疎水化ガスを供給している前記基板の表面上にあるリンス液が乾燥する前に、次のリンス液の供給を開始することを特徴とする請求項1に記載の液処理方法。
- 前記基板は当該基板の表面に形成されたパターンを有し、
前記基板を疎水化することを行っている間、前記基板の表面に形成された前記パターン内に存在するリンス液の液面の位置を次第に低下させながら前記パターン内に疎水化ガスを進入させ、前記パターンの深さ方向に疎水化された領域の面積を広げていくことを特徴とする請求項1または2に記載の液処理方法。 - 前記基板を疎水化することを前記基板の表面に前記リンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数は、前記基板を疎水化することを行っている間の前記基板の回転数よりも低いことを特徴とする請求項1または2に記載の液処理方法。 - 前記基板を疎水化することを前記基板の表面に前記リンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数は、前記基板を疎水化することを行っている間の前記基板の回転数よりも低く、
前記基板を乾燥することを行っている間、回転する前記基板の表面に前記リンス液を供給しながら前記リンス液の供給位置を前記基板の中央部から周縁部へ向けて移動させることにより、前記基板の表面上にあるリンス液を前記基板の外へ押し出して除去することを特徴とする請求項1または2に記載の液処理方法。 - 前記基板を疎水化することと前記基板を乾燥することとの間に、前記基板の表面に溶剤を供給して、前記疎水化ガスの副生成物を除去することをさらに備えたことを特徴とする請求項1または2に記載の液処理方法。
- 前記基板は当該基板の表面に形成されたパターンを有し、
前記基板の表面に前記リンス液を供給することと前記基板の表面に前記疎水化ガスを供給することとを交互に繰り返す回数は、前記パターンが形成されていない前記基板の表面部分に対する前記リンス液の接触角が予め設定された角度以上となるような回数となっていることを特徴とする請求項1または2に記載の液処理方法。 - 前記基板の表面に対して液処理を行う液処理装置に用いられるコンピュータプログラムを格納した記憶媒体であって、
前記プログラムは前記液処理装置に請求項1または2に記載された液処理方法を実行させることを特徴とする記憶媒体。 - 基板を水平に保持し、鉛直軸周りに回転させる基板保持部と、
前記基板の表面に薬液を供給する薬液ノズルと、
前記基板の表面に疎水化ガスを供給する疎水化ガスノズルと、
前記基板の表面にリンス液を供給するリンス液ノズルと、
前記基板保持部に保持され、回転する前記基板の表面に前記薬液ノズルから薬液を供給することと、次いで、前記基板を回転させながら当該基板の表面に前記リンス液ノズルからリンス液を供給することと、次いで、前記基板を回転させながら当該基板の表面に、この基板の表面を疎水化するための疎水化ガスを前記疎水化ガスノズル供給することと、疎水化ガスが供給された後の基板を回転させながら当該基板の表面にリンス液を供給することとを交互に繰り返して、前記基板を疎水化することと、次いで、前記基板保持部を回転させることにより前記基板を回転しながらリンス液を除去し乾燥することと、をさせる制御部と、
を備えたことを特徴とする液処理装置。 - 前記制御部は、
前記基板を疎水化することを行っている間、前記疎水化ガスを供給している前記基板の表面上にあるリンス液が乾燥する前に、次のリンス液の供給を開始させることを特徴とする請求項9に記載の液処理装置。 - 前記制御部は、
前記基板を疎水化することを前記基板の表面にリンス液を供給することで終え、
前記基板を乾燥することを行っている間の前記基板の回転数を、前記基板を疎水化することを行っている間の前記基板の回転数よりも低くすることを特徴とする請求項9または10に記載の液処理装置。 - 前記基板の表面に溶剤を供給する溶剤ノズルをさらに備え、
前記制御部は、前記基板の表面を疎水化することと前記基板を乾燥することとの間に、前記基板の表面に前記溶剤ノズルから前記溶剤を供給させることを特徴とする請求項9または10の液処理装置。
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US11923212B2 (en) | 2019-10-17 | 2024-03-05 | Semes Co., Ltd. | Apparatus and method for treating substrate |
WO2021235479A1 (ja) * | 2020-05-21 | 2021-11-25 | セントラル硝子株式会社 | 半導体基板の表面処理方法、及び表面処理剤組成物 |
WO2021235476A1 (ja) * | 2020-05-21 | 2021-11-25 | セントラル硝子株式会社 | 半導体基板の表面処理方法、及び表面処理剤組成物 |
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KR101497288B1 (ko) | 2015-02-27 |
TW201351493A (zh) | 2013-12-16 |
JP6044371B2 (ja) | 2016-12-14 |
US20140338706A1 (en) | 2014-11-20 |
JP2013214724A (ja) | 2013-10-17 |
KR20140037977A (ko) | 2014-03-27 |
TWI544535B (zh) | 2016-08-01 |
US8956465B2 (en) | 2015-02-17 |
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