Substrate processing apparatus and substrate processing method

Abstract

This invention provides a substrate processing apparatus and a substrate processing method, capable of performing appropriate processing using a processing solution containing OH free radicals. The substrate processing apparatus of one embodiment includes: a mounting section for rotating the mounted substrate; a nozzle extending along the surface of the substrate; and a light source for irradiating a raw material liquid flowing inside the nozzle with ultraviolet light.

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a substrate processing apparatus and a substrate processing method. [Previous Technology]

[0002] In the manufacture of semiconductor devices, photomasks, flat panel displays, etc., a process is performed to remove particles or organic matter that are attached to the surface of a substrate.

[0003] For example, a technique is proposed in which ozone water is supplied to the surface of a substrate with attached particles or organic matter to decompose and remove the particles or organic matter. However, if ozone water is used alone for removal, sufficient removal effect cannot be obtained.

[0004] Therefore, a technique is proposed in which ozone water supplied to the surface of a substrate is irradiated with ultraviolet light (for example, see Patent Document 1). When ozone water is irradiated with ultraviolet light, a treatment liquid containing OH radicals can be generated. If a treatment liquid containing OH radicals is used, OH radicals can be used to decompose and remove particles or organic matter attached to the surface of the substrate.

[0005] However, when ozone water is supplied to the surface of a substrate and ultraviolet light is irradiated, oxidation may occur on the substrate surface, leading to changes in the surface properties. Furthermore, the ozone water supplied to the substrate surface is discharged within a relatively short period. Therefore, the cumulative amount of ultraviolet light irradiating the ozone water is low, resulting in low OH radical generation efficiency. Moreover, it is difficult to achieve uniform irradiation of the ozone water on the substrate surface. Therefore, the amount of generated OH radicals may exhibit an in-plane distribution. If the OH radical generation efficiency is low, or if the amount of generated OH radicals exhibits an in-plane distribution, proper substrate processing may not be possible. Therefore, it is desirable to develop a substrate processing apparatus and a substrate processing method capable of performing appropriate processing using a processing liquid containing OH radicals. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2008-311256 [Summary of the Invention]

[0007] [Problem to be solved by the invention] The problem to be solved by the present invention is to provide a substrate processing apparatus and a substrate processing method, which can perform appropriate processing using a processing liquid containing OH free radicals.

[0008] [Technical means to solve the problem] The substrate processing apparatus and substrate processing method of the embodiment include: a mounting section for rotating the mounted substrate; a nozzle extending along the surface of the substrate; and a light source for irradiating raw material liquid flowing inside the nozzle with ultraviolet light.

[0009] [Effects of the Invention] According to an embodiment of the present invention, a substrate processing apparatus and a substrate processing method are provided, which can perform appropriate processing using a processing solution containing OH free radicals.

Implementation Method

[0011] Hereinafter, embodiments will be illustrated with reference to the accompanying drawings. In addition, the same reference numerals will be used for the same constituent elements in each drawing, and detailed descriptions will be omitted where appropriate. Furthermore, the substrate 100 illustrated below may be, for example, a semiconductor wafer, a printing template, a photolithography mask, or a plate-like body used in microelectromechanical systems (MEMS). However, the substrate 100 is not limited to those illustrated. For example, the substrate 100 may be a substrate with patterns (e.g., fine irregularities) formed on its surface, or it may be a so-called bulk substrate.

[0012] FIG1 is a schematic diagram illustrating the substrate processing apparatus 1 of this embodiment. FIG2 is a schematic plan view of the substrate processing apparatus 1 in FIG1 viewed from the direction of line AA. In addition, in FIG2, a substrate 100 with a planar shape of quadrilateral is shown, but the planar shape of the substrate 100 is not limited to this. For example, the planar shape of the substrate 100 may also be a circle or the like. Moreover, in FIG2, the processing liquid 5a supplied to the surface 100a of the substrate 100 in FIG1 is omitted from the illustration.

[0013] As shown in Figures 1 and 2, the substrate processing apparatus 1 includes, for example, a chamber 2, a mounting section 3, a liquid supply section 4, a processing liquid supply section 5, and a controller 6.

[0014] The controller 6 includes an arithmetic unit such as a central processing unit (CPU) and a memory unit such as memory. The controller 6 may be, for example, a computer. The controller 6 controls the operation of each component provided in the board processing apparatus 1 based on the control program stored in the memory unit.

[0015] The chamber 2 is box-shaped. The chamber 2 has an airtight structure, for example, to the extent that particles in the external environment cannot intrude. Inside the chamber 2, a cover 21 may be provided to surround the mounting part 3 (mounting stage 31). The cover 21 blocks the liquid 4a or processing liquid 5a, which will be described later, that is supplied to the substrate 100 and discharged to the outside of the substrate 100 due to the rotation of the mounting stage 31 on which the substrate 100 is mounted. The used liquid 4a or processing liquid 5a blocked by the cover 21 is discharged to the factory piping, for example, through the discharge port 2a provided on the bottom side of the chamber 2.

[0016] The mounting section 3 rotates the mounted substrate 100. The mounting section 3 includes, for example, a mounting stage 31, a rotation shaft 32, and a drive section 33. The mounting stage 31 is plate-shaped and rotatably disposed inside the chamber 2. On one of the main surfaces (mounting surfaces) of the mounting stage 31, a plurality of support portions 31a for supporting the substrate 100 are provided. When the substrate 100 is supported on the plurality of support portions 31a, the surface 100a (processed surface) of the substrate 100 faces a direction opposite to that of the mounting stage 31. Furthermore, a hole 31b penetrating the thickness direction of the mounting stage 31 is provided in the central portion of the mounting stage 31.

[0017] The rotating shaft 32 is cylindrical. The end of the rotating shaft 32 on the mounting platform 31 side is provided on the mounting platform 31. The opening of the hole through which the rotating shaft 32 passes in the axial direction faces the back surface 100b of the substrate 100 placed on the mounting platform 31. The end of the rotating shaft 32 on the opposite side to the mounting platform 31 side may be provided outside the chamber 2.

[0018] The drive unit 33 is located outside the chamber 2. The drive unit 33 is connected to the rotation shaft 32. The rotational force of the drive unit 33 is transmitted to the mounting stage 31 via the rotation shaft 32. Therefore, the mounting stage 31, and even the substrate 100 placed on the mounting stage 31, can be rotated by the drive unit 33.

[0019] Furthermore, the drive unit 33 can not only start and stop the rotation, but also change the rotational speed. The drive unit 33 may be, for example, a drive unit that includes a control motor such as a servo motor.

[0020] The liquid supply unit 4 supplies liquid 4a to the back surface 100b of the substrate 100 placed on the mounting stage 31. The liquid supply unit 4 is provided, for example, to supply liquid 4a to protect the back surface 100b of the substrate 100. For example, the liquid supply unit 4 prevents the processing liquid 5a supplied to the surface 100a of the substrate 100 from flowing back to the back surface 100b of the substrate 100 and adhering to the back surface 100b of the substrate 100. In this case, there is no particular limitation as long as the liquid 4a is unlikely to react with the material of the substrate 100. The liquid 4a can be, for example, pure water.

[0021] Furthermore, the liquid supply unit 4 may also be provided for cleaning or processing the back surface 100b of the substrate 100. In this case, the liquid 4a may be a cleaning solution or a processing solution. The liquid 4a may be hydrogen peroxide, ozone water, pure water, inorganic acid, inorganic alkali, organic acid, organic alkali and electrolyzed water, or a mixture of two or more of these. Moreover, the liquid 4a may also be a liquid containing OH free radicals, similar to the processing solution 5a described later.

[0022] The liquid supply unit 4 may be provided, for example, according to the needs of protection, cleaning, and processing of the back side 100b of the substrate 100. Therefore, the liquid supply unit 4 may not be necessary and may be omitted.

[0023] The liquid supply unit 4 includes, for example, a liquid collection unit 41, a supply unit 42, a flow control unit 43, and a nozzle 44. The liquid collection unit 41, the supply unit 42, and the flow control unit 43 are located outside the chamber 2.

[0024] The liquid receiving section 41 receives liquid 4a. The supply section 42 is connected to the liquid receiving section 41 via piping. The supply section 42 supplies the liquid 4a received in the liquid receiving section 41 to the nozzle 44. The supply section 42 may be, for example, a pump or the like that has resistance to liquid 4a.

[0025] The flow control unit 43 is connected to the supply unit 42 via piping. The flow control unit 43 controls the flow rate of the liquid 4a supplied by the supply unit 42. The flow control unit 43 may be configured as a flow control valve, for example. Furthermore, the flow control unit 43 can also start and stop the supply of liquid 4a.

[0026] The nozzle 44 is disposed inside the hole of the rotating shaft 32. The nozzle 44 may be disposed, for example, near the end of the rotating shaft 32 on the side of the mounting platform 31. One end of the nozzle 44 is connected to the flow control unit 43 via a pipe. An outlet is provided at the other end of the nozzle 44. The outlet of the nozzle 44 faces the back surface 100b of the substrate 100 placed on the mounting platform 31. The spray pattern of the nozzle 44 may be, for example, a flat type, a full cone type, a curtain type, etc. In addition, the spray pattern of the nozzle 44 illustrated in FIG1 is a flat type or a full cone type.

[0027] The processing liquid supply unit 5 generates processing liquid 5a and supplies the generated processing liquid 5a to the surface 100a of the substrate 100 placed on the mounting stage 31. The processing liquid 5a may be a liquid containing OH free radicals as active substances.

[0028] The processing fluid supply unit 5 includes, for example, a raw material liquid receiving unit 51, a supply unit 52, a flow control unit 53, a moving unit 54, and a processing fluid generation and supply unit 55. The raw material liquid receiving unit 51, the supply unit 52, and the flow control unit 53 may be located outside the chamber 2. The moving unit 54 and the processing fluid generation and supply unit 55 may be located inside the chamber 2.

[0029] The raw material liquid receiving section 51 receives the raw material liquid used to generate the treatment liquid 5a. That is, the raw material liquid is used to generate a liquid containing OH free radicals. The raw material liquid can be, for example, ozone water, hydrogen peroxide, pure water, or other liquids containing hydrogen and oxygen atoms. As described later, the treatment liquid 5a is generated by irradiating the raw material liquid with ultraviolet light. Therefore, considering the generation efficiency of the treatment liquid 5a, the raw material liquid is preferably ozone water or hydrogen peroxide, and more preferably ozone water.

[0030] The supply unit 52 is connected to the raw material liquid receiving unit 51 via piping. The supply unit 52 supplies the raw material liquid stored in the raw material liquid receiving unit 51 to the processing liquid generation supply unit 55. The supply unit 52 may be, for example, a pump or the like that has tolerance to raw material liquid.

[0031] The inflow side of the flow control unit 53 is connected to the supply unit 52 via a pipe. The outflow side of the flow control unit 53 is connected to the processing liquid generation supply unit 55 (nozzle 55d) via a pipe 53a. The pipe 53a may be a deformable pipe made of a fluoropolymer such as polytetrafluoroethylene (PFA). The flow control unit 53 controls the flow rate of the raw material liquid supplied to the processing liquid generation supply unit 55 via the supply unit 52, and even the flow rate of the processing liquid 5a supplied from the processing liquid generation supply unit 55 to the surface 100a of the substrate 100. The flow control unit 53 may be, for example, a flow control valve. Furthermore, the flow control unit 53 can also start and stop the supply of the raw material liquid and the processing liquid 5a.

[0032] The moving part 54 causes the processing liquid generation and supply part 55 to move, for example, in a direction substantially parallel to the surface 100a of the substrate 100. As described above, the stage 31 on which the substrate 100 is placed rotates, therefore the moving speed (circumferential speed) of the surface 100a of the substrate 100 is different in the central region and the peripheral region of the substrate 100. Therefore, the amount of processing liquid 5a supplied per unit area is greater in the central region of the substrate 100 than in the peripheral region. Therefore, uneven processing is easily generated on the surface 100a of the substrate 100.

[0033] At this time, as long as the processing liquid generation and supply unit 55 is moved in a direction that is approximately parallel to the surface 100a of the substrate 100, the deviation in the amount of processing liquid 5a supplied per unit area can be reduced, and even the uneven processing on the surface 100a of the substrate 100 can be suppressed.

[0034] At this time, in a plane that is substantially parallel to the surface 100a of the substrate 100, the processing liquid generation supply section 55 can move in either an arc-shaped trajectory or a straight trajectory. The moving section 54 illustrated in Figures 1 and 2 causes the processing liquid generation supply section 55 to oscillate in an arc-shaped trajectory in a plane that is substantially parallel to the surface 100a of the substrate 100.

[0035] The moving part 54 includes, for example, an arm 54a, a support column 54b, and a driving part 54c. The arm 54a extends in one direction above the substrate 100, for example, along the surface 100a. One end of the arm 54a is located near the support column 54b. The other end of the arm 54a, when viewed from above, is located on the side opposite to the support column 54b, clamping the rotation center 100c of the substrate 100. Furthermore, a cover 54a1 may be provided at the end of the arm 54a on the side opposite to the substrate 100.

[0036] The support column 54b extends in a direction substantially perpendicular to the surface 100a (the mounting surface of the mounting portion 3) of the substrate 100. One end of the support column 54b may be located above the substrate 100. The other end of the support column 54b may be located near the bottom surface of the chamber 2.

[0037] The drive unit 54c can be located either inside or outside the chamber 2. The drive unit 54c illustrated in FIG1 is located on the bottom surface of the chamber 2. The drive unit 54c may be, for example, a motor or cylinder, a driving mechanism.

[0038] In addition, when the processing fluid generation supply unit 55 moves along a linear trajectory, a guide mechanism such as a linear motion bearing can be provided, for example, instead of the support column 54b.

[0039] The processing fluid generation and supply unit 55 may be provided at the end of the mounting portion 3 side of the arm 54a. FIG3 is a schematic perspective view illustrating the processing fluid generation and supply unit 55. FIG4 is a schematic perspective view of the processing fluid generation and supply unit 55 in FIG3 viewed from direction B. FIG5 is a schematic perspective view of the processing fluid generation and supply unit 55 in FIG4, omitting the cover 54a1 and the light shield 55c.

[0040] As shown in Figures 3 to 5, the processing liquid generation and supply unit 55 includes, for example, a support 55a, a light source 55b, a light shield 55c, a nozzle 55d, and a cover 55e.

[0041] The bracket 55a holds the light source 55b, for example. The bracket 55a can be mounted to the end of the arm 54a on the substrate 100 side using fastening components such as screws. The bracket 55a extends, for example, in the direction in which the arm 54a extends. Alternatively, multiple brackets 55a may be provided spaced apart, for example, in the direction in which the arm 54a extends.

[0042] The light source 55b is located on the opposite side of the nozzle 55d from the side where the plurality of nozzle outlets 55da1 open. The light source 55b extends along the direction in which the nozzle 55d extends. The light source 55b irradiates the feed liquid flowing inside the nozzle 55d with ultraviolet light. The light source 55b irradiates ultraviolet light with a wavelength of approximately 200 nm to 350 nm, for example. The light source 55b is, for example, rod-shaped, cylindrical with a circular cross-section orthogonal to the long side direction. The light source 55b can be, for example, a discharge lamp such as an excimer lamp. Furthermore, the light source 55b can also be, for example, a light-emitting element such as a light-emitting diode. When the light source 55b is a light-emitting element, a plurality of light-emitting elements can be arranged along the direction in which the arm 54a extends.

[0043] The light shield 55c is, for example, box-shaped and extends along the direction in which the arm 54a extends. Inside the light shield 55c, a light source 55b, a cover 55e, and a nozzle 55d are housed. As mentioned above, the light source 55b irradiates ultraviolet light. Moreover, as described later, the cover 55e and the nozzle 55d are formed of a material that allows ultraviolet light to pass through. Therefore, the light shield 55c is provided to suppress the ultraviolet light irradiated from the light source 55b and the ultraviolet light irradiated from the light source 55b and transmitted through the cover 55e and the nozzle 55d from irradiating through to the outside of the processing liquid generation supply unit 55. The light shield 55c may be formed of a material that does not allow ultraviolet light to pass through. For example, the light shield 55c may be formed of a metal such as stainless steel or aluminum alloy.

[0044] On the surface of the light shield 55c facing the nozzle 55d, there is a hole 55c1 through which the treatment liquid 5a ejected from the plurality of nozzle outlets 55da1 of the nozzle 55d (described later) passes. The hole 55c1 is, for example, a slit extending in the direction in which the plurality of nozzle outlets 55da1 are arranged.

[0045] The light shield 55c can be mounted to the arm 54a or the bracket 55a, for example, using fastening components such as screws. In addition, in Figures 3 and 4, the light source 55b at the other end of the arm 54a is not covered by the light shield 55c, but the end of the light source 55b can be covered by further providing a surface that is a surface that is intersecting with the direction of extension of the arm 54a and is connected to the surface extending in the direction of extension of the arm 54a.

[0046] The nozzle 55d is, for example, provided on the opposite side of the arm 54a side of the light source 55b. The nozzle 55d is plate-shaped and extends along the surface 100a (the mounting surface of the mounting portion 3) of the substrate 100. The nozzle 55d is, for example, plate-shaped and has an outlet portion 55da extending in the direction of the arm 54a, and an inlet portion 55db with an opening on the side of the outlet portion 55da. In the direction of the outlet portion 55da, the inlet portion 55db is provided near the end of the outlet portion 55da. The inlet portion 55db is connected to the raw material liquid receiving portion 51 via a pipe 53a and a flow control portion 53. The inlet portion 55db is provided for supplying raw material liquid to the flow path 55d1 of the nozzle 55d described later. The nozzle 55d (outlet portion 55da) is, for example, formed of a material that transmits ultraviolet light, such as synthetic quartz glass.

[0047] Figure 6 is a schematic perspective view of the nozzle 55d as viewed from the light source 55b side. Figure 7 is a cross-sectional view of the nozzle 55d along line CC in Figure 6. As shown in Figures 6 and 7, a flow path 55d1 for the flow of raw material liquid is provided inside the nozzle 55d. The flow path 55d1 opens on one side of the nozzle 55d. The flow path 55d1 is, for example, trough-shaped, with a coiled shape. For example, the flow path 55d1 has a portion 55d1a extending in the direction of the outflow portion 55da, and a portion 55d1b extending in a direction intersecting the direction of the outflow portion 55da. For example, multiple portions 55d1a may be provided. The portion 55d1b connects the end of one portion 55d1a to the end of another portion 55d1a. The portion 55d1c connects the end of one portion 55d1a to the inflow portion 55db.

[0048] One end of a flow path 55d1 is located at an outlet 55da. In a direction intersecting the direction extending from the outlet 55da, for example, at a portion 55d1a located approximately at the center of the outlet 55da, one end of the flow path 55d1 becomes one end 55d1d (end) of the flow path 55d1. The other end of the flow path 55d1 is connected to an inlet 55db. For example, one end of a portion 55d1b connected to the inlet 55db becomes another end 55d1e (end) of the flow path 55d1.

[0049] Furthermore, as shown in Figures 5 and 7, a plurality of nozzles 55da1 are connected to the flow path 55d1 (part 55d1a) located approximately at the center of the outflow portion 55da. That is, the plurality of nozzles 55da1 are connected to the flow path 55d1 located approximately at the center of the nozzle 55d (outflow portion 55da) in a direction intersecting the direction in which the nozzle 55d extends. The plurality of nozzles 55da1 open on the side of the nozzle 55d (outflow portion 55da) opposite to the side where the flow path 55d1 opens (the side facing the surface 100a of the substrate 100). The plurality of nozzles 55da1 are arranged in a manner that extends along the direction in which the nozzle 55d (outflow portion 55da) extends.

[0050] The processing liquid 5a generated inside the flow path 55d1 of the nozzle 55d is supplied to the surface 100a of the substrate 100 via a plurality of nozzle outlets 55da1. The number, arrangement, diameter, etc. of the plurality of nozzle outlets 55da1 can be appropriately changed according to the size of the substrate 100 or the required flow rate of the processing liquid 5a. In addition, details related to the generation of the processing liquid 5a will be described later.

[0051] FIG8 is a schematic perspective view illustrating the cover 55e. As shown in FIG8, the cover 55e is plate-shaped and covers the side of the opening of the flow path 55d1 of the nozzle 55d.

[0052] The planar shape of the cover 55e can be the same as the planar shape of the nozzle 55d. The cover 55e can be installed on the nozzle 55d using fasteners such as screws, or it can be glued to the nozzle 55d. The cover 55e is made of, for example, a material that transmits ultraviolet light, such as synthetic quartz glass.

[0053] Next, the generation of the processing liquid 5a and the processing of the substrate 100 using the processing liquid 5a will be described. First, the raw material liquid, such as ozone water, stored in the raw material liquid storage unit 51 is supplied to the flow path 55d1 of the processing liquid 5a by the supply unit 52 and the flow control unit 53. Moreover, ultraviolet light is irradiated from the light source 55b toward the nozzle 55d. The ultraviolet light irradiated from the light source 55b passes through the cover 55e and irradiates the raw material liquid flowing inside the flow path 55d1. Furthermore, the nozzle 55d (outlet 55da) is also formed of a material that allows ultraviolet light to pass through, so the ultraviolet light incident on the nozzle 55d (outlet 55da) irradiates the raw material liquid flowing inside the flow path 55d1, for example, from the side wall of the flow path 55d1. Therefore, as long as the nozzle 55d (outlet 55da) is formed of a material that allows ultraviolet light to pass through, the utilization efficiency of the ultraviolet light irradiated from the light source 55b can be improved.

[0054] As described above, OH radicals are generated by irradiating the raw material liquid with ultraviolet light through the nozzle 55d (cover 55e) using the light source 55b. It is also considered to irradiate the raw material liquid directly with the light source 55b, but irradiating the raw material liquid with ultraviolet light through the nozzle 55d will prevent particles generated from dust from the light source 55b from being mixed into the raw material liquid and generating a treatment liquid 5a containing OH radicals.

[0055] By irradiating the raw material liquid flowing inside a flow path 55d1 with ultraviolet light, a processing liquid 5a containing OH radicals is generated. For example, by irradiating the raw material liquid with ultraviolet light, the raw material liquid decomposes to generate OH radicals. Therefore, a processing liquid 5a containing OH radicals is generated from the raw material liquid. The generated processing liquid 5a is supplied to the surface 100a of the substrate 100 through a plurality of nozzles 55da1 provided in the nozzle 55d. By supplying the processing liquid 5a containing OH radicals to the surface 100a of the substrate 100, particles or organic matter adhering to the surface 100a of the substrate 100 are decomposed and removed.

[0056] Here, as described above, the nozzle 55d extends along the surface 100a of the substrate 100 (in a direction parallel to the surface 100a of the substrate 100). The raw material liquid flowing inside the nozzle 55d is irradiated with ultraviolet light by a light source 55b that irradiates ultraviolet light. Therefore, compared to the case where the nozzle 55d extends in a direction perpendicular to the surface 100a of the substrate 100, the influence of gravity on the flow rate of the raw material liquid flowing inside the nozzle 55d can be reduced. If the influence of gravity on the flow rate of the raw material liquid is reduced, it is easier to control the flow rate of the raw material liquid by controlling the supply pressure of the raw material liquid. In this case, if the flow rate of the raw material liquid is slowed down by controlling the supply pressure of the raw material liquid, the residence time of the raw material liquid in the flow path 55d1 along the light source 55b can be increased, and even more importantly, the cumulative amount of ultraviolet light irradiating the raw material liquid can be increased. Therefore, a processing liquid 5a containing OH radicals can be generated efficiently.

[0057] Furthermore, as described above, one flow path 55d1 provided at the nozzle 55d has a curved shape. Therefore, the overall length of the flow path 55d1 can be increased, thereby increasing the time the feed liquid passes through the flow path 55d1, and even increasing the cumulative amount of ultraviolet light irradiating the feed liquid. Therefore, the processing liquid 5a containing OH free radicals can be generated efficiently. The overall length or cross-sectional dimensions of the flow path 55d1 can be appropriately changed according to the size of the substrate 100 or the required flow rate of the processing liquid 5a, etc.

[0058] Furthermore, as described above, the generated processing liquid 5a containing OH radicals is supplied to the surface 100a of the substrate 100 via a plurality of nozzles 55da1. Moreover, the plurality of nozzles 55da1 are arranged along the direction in which the nozzles 55d extend. Therefore, as shown in FIG1, the processing liquid 5a can be supplied to a large area of ​​the surface 100a of the substrate 100 simultaneously.

[0059] Here, OH radicals are easily deactivated. Therefore, for example, when a processing solution 5a containing OH radicals is supplied to the surface 100a of the substrate 100 from a nozzle 55da1, the concentration of OH radicals at positions directly below and away from the nozzle 55da1 becomes different. More specifically, on the surface 100a of the substrate 100, OH radicals at positions away from the nozzle 55da1 are more easily deactivated than OH radicals at positions directly below the nozzle 55da1, resulting in a lower concentration of OH radicals in the processing solution 5a and a weakened removal effect on organic matter. Therefore, the removal effect on organic matter is prone to in-plane distribution.

[0060] At this time, as shown in FIG1, as long as a treatment liquid 5a containing OH free radicals is supplied to the surface 100a of the substrate 100 from multiple nozzles 55da1, the in-plane distribution of the concentration of OH free radicals in the surface 100a of the substrate 100 can be suppressed. Therefore, the in-plane distribution of the removal effect of organic matter, etc. can be suppressed.

[0061] Furthermore, as mentioned above, OH radicals are easily deactivated. Therefore, as shown in FIG1, the distance L between the nozzle 55d and the surface 100a of the substrate 100 is preferably set to 12 mm or less. In this way, the deactivation of OH radicals can be suppressed, thereby improving the removal efficiency of organic matter, etc.

[0062] Furthermore, the processing liquid 5a supplied to the surface 100a of the substrate 100 is discharged to the outside of the substrate 100 due to the rotation of the substrate 100. Therefore, the residence time of the processing liquid 5a supplied to the peripheral region of the substrate 100 is shorter than the residence time of the processing liquid 5a supplied to the central region of the substrate 100. Therefore, the flow rate of the processing liquid 5a supplied to the peripheral region of the substrate 100 can be greater than the flow rate of the processing liquid 5a supplied to the central region of the substrate 100. For example, the spacing dimension of the nozzles 55da1 facing the peripheral region of the substrate 100 can be shorter than the spacing dimension of the nozzles 55da1 facing the central region of the substrate 100. Moreover, for example, the opening area of ​​the nozzles 55da1 facing the peripheral region of the substrate 100 can be larger than the opening area of ​​the nozzles 55da1 facing the central region of the substrate 100.

[0063] Figures 9(a) and 9(b) are schematic diagrams illustrating flow paths 155d1 and 255d1 in another embodiment. As shown in Figure 9(a), a flow path 155d1 has a serpentine shape in the direction extending from the outlet 55da. As shown in Figure 9(b), a flow path 255d1 has a serpentine shape in a direction intersecting the direction extending from the outlet 55da.

[0064] In these ways, the total length of flow path 155d1 and flow path 255d1 can also be increased, thus increasing the time for the feed liquid to pass through flow path 155d1 and flow path 255d1, and even increasing the cumulative amount of ultraviolet light irradiating the feed liquid. Therefore, a treatment liquid 5a containing OH free radicals can be generated efficiently.

[0065] However, as shown in FIG6, as long as one flow path 55d1 has a shape that is curved in a coiled manner, multiple nozzles 55da1 can be provided in the flow path 55d1 (part 55d1a) located approximately at the center of the outlet portion 55da. In this case, as shown in FIG5, the light source 55b faces the flow path 55d1 (part 55d1a) located approximately at the center of the outlet portion 55da. The light source 55b is cylindrical and extends in the direction of the nozzle 55d (outlet portion 55da), and is configured such that the axial center of the light source 55b is located in the region facing approximately the center of the outlet portion 55da. Therefore, the distance between the flow path 55d1 (part d1a) located approximately at the center of the outlet portion 55da and the surface (irradiation surface) of the light source 55b can be reduced. This increases the irradiance of the ultraviolet light irradiating the flow path 55d1 (partially 55d1a) which has multiple nozzles 55da1, thereby increasing the generation efficiency of OH free radicals and thus increasing the concentration of OH free radicals contained in the treatment liquid 5a before it is supplied to the surface 100a of the substrate 100. By increasing the concentration of OH free radicals contained in the treatment liquid 5a before it is supplied to the surface 100a of the substrate 100, the removal efficiency of organic matter and the like can be improved.

[0066] FIG10 is a schematic diagram illustrating a flow path 355d1 according to another embodiment. The dimension of the flow path 355d1 shown in FIG10, which is orthogonal to the direction in which the outflow portion 55da extends, can be, for example, larger than the width dimension of the light source 55a. As shown in FIG10, the volume of the portion of the flow path 355d1 extending in the direction in which the outflow portion 55da extends can be increased. In this way, the residence time of the raw material liquid in the flow path 355d1 can be increased, and even more so, the cumulative amount of ultraviolet light irradiating the raw material liquid can be increased. Therefore, the processing liquid 5a containing OH free radicals can be generated efficiently.

[0067] FIG11 is a schematic perspective view illustrating a nozzle 455d according to another embodiment. As shown in FIG11, the nozzle 455d is straw-shaped (tubular). The interior of the straw-shaped nozzle 455d forms a flow path 455d1 for the flow of the raw material liquid. The nozzle 455d has a portion facing the light source 55b, which extends along the light source 55b. The portion of the nozzle 455d facing the light source 55b is formed of a material that transmits ultraviolet light, such as synthetic quartz glass. Therefore, ultraviolet light irradiated from the light source 55b is incident on the raw material liquid flowing in the flow path 455d1 inside the nozzle 455d. By irradiating the raw material liquid flowing in the flow path 455d1 with ultraviolet light, a treatment liquid 5a containing OH free radicals is generated.

[0068] One end of the nozzle 455d is connected to the piping 53a. The piping 53a may be a deformable piping made of fluoropolymer such as PFA. The other end of the nozzle 455d is open. The processing liquid 5a generated by irradiating the raw material liquid flowing inside the nozzle 455d (flow path 455d1) with ultraviolet light is supplied from the opening 455da of the nozzle 455d to the surface 100a of the substrate 100. By supplying the processing liquid 5a containing OH free radicals to the surface 100a of the substrate 100, particles or organic matter adhering to the surface 100a of the substrate 100 are decomposed and removed.

[0069] As described above, in this embodiment, the deformable piping 53a is connected to one end of the tubular nozzle 455d. Therefore, compared with the aforementioned plate-shaped nozzle 55d that has a flow path inside, the location where the nozzle 455d (flow path 455d1) is configured can be freely selected.

[0070] Furthermore, the straight-line distance of the flow path 455d1 through which ultraviolet light from the light source 55b is incident can be increased. If the flow path 455d1 extends in a straight line, the generated OH radicals can be prevented from colliding with the curved flow path and causing OH radical deactivation. Therefore, it is easy to supply the processing liquid 5a containing OH radicals to the surface 100a of the substrate 100. Moreover, if the straight-line distance of the flow path 455d1 is increased, the amount of OH radicals generated can be increased.

[0071] Alternatively, it is also considered to directly irradiate the raw material liquid with ultraviolet light by contacting it directly with the light source 55b, but there is a risk that particles generated by the dust from the light source 55b may mix into the raw material liquid. If the raw material liquid is irradiated with ultraviolet light through the nozzle 455d, the mixing of particles generated by the dust from the light source 55b into the raw material liquid can be suppressed. Therefore, the processing liquid 5a without foreign matter can be supplied to the surface 100a of the substrate 100.

[0072] Furthermore, the nozzle 455d extends along the surface 100a of the substrate 100 (in a direction parallel to the surface 100a of the substrate 100). Therefore, compared to the case where the nozzle 455d extends in a direction perpendicular to the surface 100a of the substrate 100, the influence of gravity on the flow rate of the raw material liquid flowing in the flow path 455d1 inside the nozzle 455d can be reduced. If the influence of gravity on the flow rate of the raw material liquid is reduced, it is easier to control the flow rate of the raw material liquid by means of supply pressure.

[0073] At this time, if the flow rate of the raw material liquid is slowed down by controlling the supply pressure of the raw material liquid, the residence time of the raw material liquid in the flow path 455d1 along the light source 55b can be increased, and even the cumulative amount of ultraviolet light irradiating the raw material liquid can be increased. Therefore, the treatment liquid 5a containing OH free radicals can be generated efficiently.

[0074] In addition, in FIG11, the nozzle 455d is configured such that the raw material liquid flows from the other end side of the arm 54a toward the support 54b side of the arm 54a, but the nozzle 455d may also be configured such that the raw material liquid flows from the support 54b side of the arm 54a toward the other end side of the arm 54a. The configuration of the nozzle 455d is not particularly limited as long as the opening 455da of the nozzle 455d is located above the center of the substrate 100.

[0075] FIG12 is a schematic perspective view illustrating the case where a light shield 55c is provided around the nozzle 455d shown in FIG11. As shown in FIG12, the light shield 55c can be provided in a manner that surrounds the light source 55b. If the light shield 55c is provided, ultraviolet rays irradiated from the light source 55b and ultraviolet rays irradiated from the light source 55b and transmitted through the nozzle 455d can be suppressed from irradiating the outside of the processing liquid generation supply unit 55.

[0076] Furthermore, on the surface of the light shield 55c facing the nozzle 455d and the surface 100a of the substrate 100, a hole 55c2 may be provided for the processing liquid 5a ejected from the opening 455da of the nozzle 455d to pass through. The size of the hole 55c2 may be larger than, for example, the size of the opening 455da of the nozzle 455d. In addition, in the light shield 55c of FIG. 12, the surface facing the nozzle 455d and the surface 100a of the substrate 100 may be omitted. In this case, the light shield 55c includes a sidewall that surrounds the light source 55b, which is arranged intersecting with the direction extending along the arm 54a, and a portion of the opening facing the surface 100a of the substrate 100. The opening of the light source 55b and the opening 455da of the nozzle 455d are exposed through this opening.

[0077] Figure 13 is a graph illustrating the generation of OH radicals by ultraviolet irradiation. C1 in Figure 13 represents the case where ozone water is not irradiated with ultraviolet light. In this case, the decomposition of ozone (generation of OH radicals) by ultraviolet irradiation does not occur, so the ozone concentration remains unchanged.

[0078] In Figure 13, C2 represents the case where ozone water is irradiated with ultraviolet light in the wavelength range of 200 nm to 350 nm. Under this irradiation, ozone decomposes to generate OH radicals. Therefore, as irradiation time increases, the ozone concentration decreases, and correspondingly, the concentration of OH radicals increases. That is, there is a positive correlation between the concentration of OH radicals and the cumulative amount of ultraviolet light. Therefore, by determining the relationship between the concentration of OH radicals and the cumulative amount of ultraviolet light through experiments or simulations, the total length or cross-sectional area of, for example, a flow path 55d1 as described above can be set.

[0079] Figure 14 is a graph illustrating the removal effect of the treatment solution 5a containing OH radicals on the corrosion inhibitor. That is, Figure 14 is an example of the removal effect of the treatment solution 5a containing OH radicals on organic matter.

[0080] C1a in Figure 14 represents the case where ozone water was not irradiated with ultraviolet light. That is, the case where the resist was removed by the oxidation of ozone water.

[0081] C2a in Figure 14 represents the case of irradiating ozone water with ultraviolet light in the wavelength range of 200 nm to 350 nm. That is, it represents the case of removing the resist using treatment solution 5a containing OH free radicals. As can be seen from C1a in Figure 14, the resist can be removed even when using ozone water. However, as can be seen from C2a in Figure 14, the removal efficiency of the resist can be significantly improved when using treatment solution 5a containing OH free radicals.

[0082] Figure 15 is a graph illustrating the effect of the treatment solution 5a containing OH free radicals on the surface 100a of the substrate 100.

[0083] C1b in Figure 15 represents the case where ozone water was not irradiated with ultraviolet light. That is, it represents the amount of oxidation (silicon oxidation) on the surface 100a of the substrate 100 caused by the oxidation of ozone water.

[0084] C2a in Figure 15 represents the case of irradiating ozone water with ultraviolet light in the wavelength range of 200 nm to 350 nm. That is, it represents the amount of oxidation (silicon oxidation) on the surface 100a of the substrate 100 caused by OH free radicals. As can be seen from Figure 15, if a treatment solution 5a containing OH free radicals is used, the amount of oxidation on the surface 100a of the substrate 100 can be suppressed compared to the case of using ozone water.

[0085] That is, as can be seen from Figures 14 and 15, if a treatment solution 5a containing OH free radicals is used, the removal efficiency of organic matter can be improved compared with the use of ozone water, and damage to the surface 100a of the substrate 100 can be suppressed.

[0086] Figure 16 is a graph illustrating the removal effect of the treatment solution 5a containing OH free radicals on foreign matter. If foreign matter such as particles is attached to the surface 100a of the substrate 100, the contact angle of the surface 100a of the substrate 100 will increase. Moreover, the higher the cleanliness of the surface 100a of the substrate 100, the smaller the contact angle of the surface 100a of the substrate 100.

[0087] As can be seen from Figure 16, if a treatment liquid 5a containing OH radicals is supplied to the surface 100a of the substrate 100, the contact angle of the surface 100a of the substrate 100 can be reduced. That is, if a treatment liquid 5a containing OH radicals is supplied to the surface 100a of the substrate 100, foreign matter such as particles attached to the surface 100a of the substrate 100 can be removed (cleaned).

[0088] Next, a substrate processing method according to this embodiment will be illustrated. The substrate processing method of this embodiment processes the substrate 100 as follows. First, a raw material liquid flowing inside a flow path 55d1 provided inside a nozzle 55d is irradiated with ultraviolet light to generate a processing liquid 5a containing OH free radicals. Next, the generated processing liquid 5a is supplied to the surface 100a of the substrate 100 through a plurality of nozzles 55da1 connected to the flow path 55d1.

[0089] At this time, the plurality of nozzles 55da1 are arranged substantially parallel to the surface 100a of the substrate 100. Furthermore, the specific details of the substrate processing method can be the same as described above, therefore a detailed description is omitted.

[0090] The embodiments have been illustrated above. However, the present invention is not limited to these descriptions. Any additions, deletions, or design changes to constituent elements, or additions, omissions, or condition changes to engineering processes made by those skilled in the art in relation to the foregoing embodiments, as long as they possess the features of the present invention, are also included within the scope of the present invention.

[0091] For example, the shape, size, material, and arrangement of each component included in the substrate processing apparatus 1 are not limited to those illustrated and can be appropriately modified. Moreover, the components included in the foregoing embodiments can be combined as much as possible, and any combination thereof that contains the features of the present invention is also included within the scope of the present invention. [Simplified Explanation of the Diagram]

[0010] FIG1 is a schematic diagram illustrating the substrate processing apparatus of this embodiment. FIG2 is a schematic plan view of the substrate processing apparatus in FIG1 viewed from the AA direction. FIG3 is a schematic perspective view illustrating the processing liquid generation supply section. FIG4 is a schematic perspective view of the processing liquid generation supply section in FIG3 viewed from the B direction. FIG5 is a schematic perspective view of the processing liquid generation supply section in FIG4, omitting the cover and light shield. FIG6 is a schematic perspective view of the nozzle viewed from the light source side. FIG7 is a cross-sectional view of the nozzle in FIG6 along the CC line. FIG8 is a schematic perspective view illustrating the cover. FIG9(a) and FIG9(b) are schematic diagrams illustrating the flow path of another embodiment. FIG10 is a schematic diagram illustrating the flow path of another embodiment. FIG11 is a schematic perspective view illustrating the nozzle of another embodiment. FIG12 is a schematic perspective view illustrating the case where a light shield is provided around the nozzle shown in FIG11. FIG13 is a graph illustrating the generation of OH free radicals achieved by ultraviolet irradiation. Figure 14 is a graph illustrating the effect of the treatment solution containing OH radicals on the removal of photoresist. Figure 15 is a graph illustrating the effect of the treatment solution containing OH radicals on the substrate surface. Figure 16 is a graph illustrating the effect of the treatment solution containing OH radicals on the removal of foreign matter.

Claims

1. A substrate processing apparatus, comprising: The mounting section rotates the mounted substrate. A nozzle is disposed above the substrate placed on the mounting portion and extends along the surface of the substrate. The nozzle has: a flow path for the raw material liquid to flow through, and at least one nozzle outlet, one end of which is connected to the flow path and the other end of which opens on the surface of the nozzle facing the surface of the substrate; and a light source disposed on the opposite side of the nozzle outlet opening to irradiate the raw material liquid flowing inside the flow path with ultraviolet light.

2. The substrate processing apparatus of claim 1, wherein the nozzle is plate-shaped and has: the flow path has a curved shape; and a plurality of nozzle outlets are arranged in the direction in which the nozzle extends.

3. The substrate processing apparatus of claim 2, wherein a processing liquid containing OH radicals is generated by irradiating the raw material liquid flowing inside the flow path with the ultraviolet light, and the generated processing liquid is supplied to the surface of the substrate through the plurality of nozzles.

4. The substrate processing apparatus as claimed in claim 2 or 3, wherein the light source extends in the direction in which the nozzle extends.

5. The substrate processing apparatus as claimed in claim 2 or 3, wherein the plurality of nozzles are connected in a direction intersecting the direction in which the nozzle extends to a flow path disposed approximately at the center of the nozzle.

6. A method for processing a substrate, wherein a raw material liquid flowing inside a flow path inside a nozzle disposed above the substrate is irradiated with ultraviolet light from a light source disposed on the opposite side of one side of a plurality of nozzle openings connected to the flow path to generate a processing liquid containing OH free radicals, and the generated processing liquid is supplied to the surface of the substrate through the plurality of nozzles.

7. The substrate processing method as described in claim 6, wherein the plurality of nozzles are arranged substantially parallel to the surface of the substrate.

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