Substrate Processing Method, Semiconductor Manufacturing Method, and Substrate Processing Apparatus

Abstract

In a substrate processing method, a substrate (W) having a pattern PT including a plurality of structures (63) is processed. The substrate processing method includes the following steps: a step (S1) of performing a prescribed treatment using a non-liquid on the plurality of structures (63) to increase the hydrophilicity of the surface (62) of each of the plurality of structures (63) as compared with before the prescribed treatment; and a step (S3) of supplying a treatment liquid to the plurality of structures (63) after the step (S1) of increasing the hydrophilicity.

Description

Technical Field

[0001] The present invention relates to a substrate processing method, a semiconductor manufacturing method, and a substrate processing apparatus. Background Art

[0002] The substrate processing apparatus described in Patent Document 1 performs a treatment for removing an organic substance from a substrate. A plurality of fine structures are formed on the surface of the substrate. The fine structures are formed in a process before the substrate is carried into the substrate processing apparatus. For example, by supplying a chemical solution to a substrate having a resist pattern formed thereon and performing an etching treatment, a plurality of fine structures are formed on the surface of the substrate. And, after the etching treatment, a rinsing treatment, a hydrophobic treatment, and a drying treatment are performed. The rinsing treatment is a treatment for supplying pure water to the substrate to wash away the chemical solution. The drying treatment is a treatment for drying the substrate by rotating the substrate in a horizontal plane. During the drying process, the fine structures may collapse due to the surface tension of pure water.

[0003] In order to suppress the collapse of the fine structures, a hydrophobic treatment is performed before the drying treatment. The hydrophobic treatment is a treatment for supplying a treatment liquid containing a hydrophobic agent to the surface of the substrate to form a hydrophobic film (organic substance) on the surface of the fine structures. By the hydrophobic treatment, the surface tension of pure water acting on the fine structures can be reduced, and the collapse of the fine structures during the drying treatment can be suppressed. On the other hand, the hydrophobic film (organic substance) is not required for semiconductor products. Therefore, it is desired to remove the hydrophobic film (organic substance) after the drying treatment.

[0004] Thus, the substrate processing apparatus irradiates ultraviolet rays on the substrate to perform a treatment for removing the hydrophobic film (organic substance). Specifically, the ultraviolet rays act on the hydrophobic film (organic substance) present on the substrate and decompose and remove the hydrophobic film (organic substance).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018-166183 Summary of the Invention

[0008] However, in the substrate processing apparatus described in Patent Document 1, only ultraviolet rays are irradiated on the substrate after etching to remove the organic substance.

[0009] In other words, since ultraviolet rays are irradiated on the substrate after etching, the effect of the ultraviolet rays does not affect the etching. Further in other words, since ultraviolet rays are irradiated on the substrate after the treatment with the treatment liquid, the effect of the ultraviolet rays does not affect the treatment with the treatment liquid.

[0010] On the other hand, in recent years, the patterns formed on the substrate have been further miniaturized. That is, on the surface of the substrate, the space between multiple microstructures has been further narrowed. Therefore, there is a possibility that the surface tension (surface free energy) of the substrate inhibits the treatment liquid from infiltrating into the space between the multiple microstructures. As a result, in the substrate, there may be a part where the treatment liquid penetrates sufficiently and a part where the penetration of the treatment liquid is insufficient. Thus, there is a possibility that the treatment results of the multiple microstructures using the treatment liquid are uneven.

[0011] The present invention is proposed in view of the above problems, and aims to provide a substrate treatment method, a semiconductor manufacturing method, and a substrate treatment apparatus that can promote the infiltration of a treatment liquid into the space between multiple structures in a substrate.

[0012] According to one aspect of the present invention, in a substrate treatment method, a substrate having a pattern including multiple structures is treated. The substrate treatment method includes the following steps: a step of performing a specified treatment using a non-liquid on the multiple structures to increase the hydrophilicity of the surface of each of the multiple structures compared to before performing the specified treatment; and a step of supplying a treatment liquid to the multiple structures after the step of increasing the hydrophilicity.

[0013] Preferably, the substrate treatment method of the present invention further includes a step of supplying a removal liquid for removing oxides from the substrate to the multiple structures before the step of increasing the hydrophilicity.

[0014] In the substrate treatment method of the present invention, preferably, the specified treatment is a treatment of irradiating ultraviolet rays on the multiple structures.

[0015] In the substrate treatment method of the present invention, preferably, the specified treatment is a treatment of irradiating plasma on the multiple structures.

[0016] In the substrate treatment method of the present invention, preferably, the specified treatment is a treatment of supplying oxygen or an isotope of oxygen to the multiple structures.

[0017] In the substrate treatment method of the present invention, preferably, the treatment liquid dissolves the gas present in the space between adjacent structures among the multiple structures.

[0018] Preferably, the substrate treatment method of the present invention further includes the following steps: after the step of supplying the treatment liquid, a step of supplying a water repellent to the multiple structures to increase the hydrophobicity of the surface of each of the multiple structures compared to before supplying the water repellent; and a step of drying the substrate after the step of increasing the hydrophobicity.

[0019] In the substrate processing method of the present invention, it is preferable that the distance between adjacent structures among the plurality of structures satisfies a specified condition. It is preferable that the specified condition means that before the step of increasing hydrophilicity, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures.

[0020] In the substrate processing method of the present invention, it is preferable that the specified condition includes a first condition and a second condition. It is preferable that the first condition means that before the step of increasing hydrophilicity, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures by capillary action. It is preferable that the second condition means that after the step of increasing hydrophilicity, the processing liquid can penetrate into the space between the adjacent structures by capillary action.

[0021] In the substrate processing method of the present invention, it is preferable that in the step of increasing hydrophilicity, the specified treatment is performed on the plurality of structures, and the hydrophilicity of the surface of the recesses each of the plurality of structures has is increased compared with before the specified treatment is performed. It is preferable that the recesses are recessed along a direction crossing the direction in which the structures extend with respect to the side wall surfaces of the structures.

[0022] According to another aspect of the present invention, in a semiconductor manufacturing method, a semiconductor substrate having a pattern including a plurality of structures is processed to manufacture a semiconductor as the processed semiconductor substrate. The semiconductor manufacturing method includes the following steps: a step of performing a specified treatment using a non-liquid on the plurality of structures to increase the hydrophilicity of the surface of each of the plurality of structures compared with before the specified treatment is performed; and a step of supplying a processing liquid to the plurality of structures after the step of increasing hydrophilicity.

[0023] According to still another aspect of the present invention, a substrate processing apparatus processes a substrate having a pattern including a plurality of structures. The substrate processing apparatus includes a hydrophilic treatment unit and a processing liquid supply unit. The hydrophilic treatment unit performs a specified treatment using a non-liquid on the plurality of structures to increase the hydrophilicity of the surface of each of the plurality of structures compared with before the specified treatment is performed. The processing liquid supply unit supplies a processing liquid to the plurality of structures after the hydrophilicity of the surface of each of the plurality of structures is increased.

[0024] It is preferable that the substrate processing apparatus of the present invention further includes a removal liquid supply unit. It is preferable that the removal liquid supply unit supplies a removal liquid for removing oxides from the substrate to the plurality of structures before the hydrophilicity of the surface of each of the plurality of structures is increased.

[0025] In the substrate processing apparatus of the present invention, it is preferable that the specified treatment is a treatment of irradiating ultraviolet rays on the plurality of structures.

[0026] In the substrate processing apparatus of the present invention, it is preferable that the specified processing is a process of irradiating plasma to the plurality of structures.

[0027] In the substrate processing apparatus of the present invention, it is preferable that the specified processing is a process of supplying oxygen or an isotope of oxygen to the plurality of structures.

[0028] In the substrate processing apparatus of the present invention, it is preferable that the processing liquid dissolves the gas present in the space between the structures adjacent to each other among the plurality of structures.

[0029] Preferably, the substrate processing apparatus of the present invention further includes a hydrophobic treatment unit and a drying treatment unit. Preferably, the hydrophobic treatment unit supplies a hydrophobic agent to the plurality of structures after supplying the processing liquid to the plurality of structures, and increases the hydrophobicity of the surface of each of the plurality of structures as compared with before supplying the hydrophobic agent. Preferably, the drying treatment unit dries the substrate after the hydrophobicity of the surface of each of the plurality of structures is increased.

[0030] In the substrate processing apparatus of the present invention, it is preferable that the distance between the structures adjacent to each other among the plurality of structures satisfies a specified condition. Preferably, the specified condition indicates that before the hydrophilicity of the surfaces of the plurality of structures is increased, a processing liquid identical to the processing liquid cannot penetrate into the space between the adjacent structures.

[0031] In the substrate processing apparatus of the present invention, it is preferable that the specified condition includes a first condition and a second condition. Preferably, the first condition indicates that before the hydrophilicity of the surfaces of the plurality of structures is increased, a processing liquid identical to the processing liquid cannot penetrate into the space between the adjacent structures by capillary action. Preferably, the second condition indicates that after the hydrophilicity of the surfaces of the plurality of structures is increased, the processing liquid can penetrate into the space between the adjacent structures by capillary action.

[0032] In the substrate processing apparatus of the present invention, it is preferable that the hydrophilic treatment unit performs the specified processing on the plurality of structures, and increases the hydrophilicity of the surface of the recess provided in each of the plurality of structures as compared with before performing the specified processing. Preferably, the recess is recessed along a direction crossing the direction in which the structure extends with respect to the side wall surface of the structure.

[0033] Advantages of the Invention

[0034] According to the present invention, it is possible to provide a substrate processing method, a semiconductor manufacturing method, and a substrate processing apparatus capable of promoting the immersion of a processing liquid into the space between a plurality of structures in a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a schematic top view showing the substrate processing apparatus of Embodiment 1 of the present invention.

[0036] Figure 2 (a) is a schematic cross-sectional view showing an example of the substrate of Embodiment 1. (b) is a schematic cross-sectional view showing another example of the substrate of Embodiment 1.

[0037] Figure 3 is a schematic cross-sectional view showing the hydrophilic treatment apparatus of Embodiment 1.

[0038] Figure 4 is a schematic cross-sectional view showing the processing apparatus of Embodiment 1.

[0039] Figure 5 is a graph showing the relationship between the penetration time of the processing liquid and the contact angle of Embodiment 1.

[0040] Figure 6 is a flowchart showing the substrate processing method of Embodiment 1.

[0041] Figure 7 shows Figure 6 the flowchart of step S1 of

[0042] Figure 8 is a schematic top view showing the processing apparatus of the modification example of Embodiment 1.

[0043] Figure 9 is a schematic cross-sectional view showing the processing apparatus of Embodiment 2 of the present invention.

[0044] Figure 10 is a schematic cross-sectional view showing the hydrophilic treatment nozzle of Embodiment 2.

[0045] Figure 11 is a schematic cross-sectional view showing the processing apparatus of Embodiment 3 of the present invention.

[0046] Figure 12 is a schematic cross-sectional view showing the processing apparatus of Embodiment 4 of the present invention.

[0047] Figure 13 is a flowchart showing the substrate processing method of Embodiment 4. Detailed Embodiments

[0048] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals and will not be described repeatedly. In the embodiments of the present invention, the X-axis, Y-axis, and Z-axis are orthogonal to each other, the X-axis and Y-axis are parallel to the horizontal direction, and the Z-axis is parallel to the vertical direction. In addition, to simplify the drawings, the hatching indicating the cross section is appropriately omitted.

[0049] (Embodiment 1)

[0050] Refer to Figures 1 to 7 , and describe the substrate processing apparatus 100 of Embodiment 1 of the present invention. The substrate processing apparatus 100 processes a substrate W using a processing liquid. Hereinafter, the processing liquid will be referred to as "processing liquid LQ". The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a plasma display device, a substrate for a field emission display (FED), a substrate for an optical disc, a substrate for a magnetic disk, a substrate for an optical magnetic disk, a substrate for a photomask, a ceramic substrate, or a substrate for a solar cell. The substrate W is, for example, substantially circular plate-shaped. In the following description of Embodiment 1, the substrate W is a semiconductor substrate.

[0051] First, refer to Figure 1 and describe the substrate processing apparatus 100. Figure 1 is a schematic top view showing the substrate processing apparatus 100. As Figure 1 shown, the substrate processing apparatus 100 includes an indexer unit U1, a processing unit U2, and a control device U3. The indexer unit U1 includes a plurality of substrate containers C and an indexer robot IR. The processing unit U2 includes a plurality of processing devices 200, a transfer robot CR, and a transfer portion PS.

[0052] The substrate containers C respectively stack and accommodate a plurality of substrates W. The indexer robot IR takes out an unprocessed substrate W from one of the plurality of substrate containers C and transfers the substrate W to the transfer portion PS. Then, the substrate W taken out from the substrate container C is placed on the transfer portion PS. The transfer robot CR receives the unprocessed substrate W from the transfer portion PS and transfers the substrate W into one of the plurality of processing devices 200.

[0053] Then, the processing device 200 processes the unprocessed substrate W. The processing device 200 is a single wafer type that processes the substrate W one by one. The processing device 200 processes the substrate W using the processing liquid LQ.

[0054] After the processing device 200 finishes processing, the transfer robot CR takes out the processed substrate W from the processing device 200 and hands over the substrate W to the transfer part PS. Then, the substrate W processed by the processing device 200 is placed on the transfer part PS. The indexing robot IR receives the processed substrate W from the transfer part PS and accommodates the substrate W in one of the plurality of substrate containers C.

[0055] The control device U3 controls the indexing unit U1 and the processing unit U2. The control device U3 includes a computer. Specifically, the control device U3 includes a processor such as a CPU (Central Processing Unit) and a storage device. The storage device stores data and computer programs. The storage device includes a main storage device such as a semiconductor memory, a semiconductor memory, and / or an auxiliary storage device such as a hard disk drive. The storage device may also include a removable medium. The processor of the control device U3 executes the computer programs stored in the storage device of the control device U3 to control the indexing unit U1 and the processing unit U2.

[0056] Next, refer to Figure 2 of (a) and Figure 2 of (b) to describe the substrate W. Figure 2 (a) of is a schematic cross-sectional view showing an example of the substrate W. In Figure 2 (a) of, a part of the surface of the substrate W is enlarged and shown. As shown in Figure 2 (a) of, the substrate W has a substrate body 61 and a pattern PT. The substrate body 61 is formed of silicon. The pattern PT is, for example, a fine pattern. The pattern PT includes a plurality of structures 63. The structures 63 are, for example, fine structures.

[0057] The plurality of structures 63 each extend along the first direction D1. The first direction D1 represents a direction intersecting the surface 61a of the substrate body 61. In Embodiment 1, the first direction D1 represents a direction substantially orthogonal to the surface 61a of the substrate body 61. The surface 62 of the structure 63 includes a side wall surface 63a and a top wall surface 63b.

[0058] The plurality of structures 63 are each composed of a single layer or multiple layers. When the structure 63 is composed of a single layer, the structure 63 is an insulating layer, a semiconductor layer, or a conductor layer. When the structure 63 is composed of multiple layers, the structure 63 may include an insulating layer, may include a semiconductor layer, or may include a conductor layer, or may include two or more of an insulating layer, a semiconductor layer, and a conductor layer.

[0059] The insulating layer is, for example, a silicon oxide film or a silicon nitride film. The semiconductor layer is, for example, a polysilicon film or an amorphous silicon film. The conductor layer is, for example, a metal film. The metal film is, for example, a film containing at least one of titanium, tungsten, copper, and aluminum.

[0060] Figure 2 FIG. (b) is a schematic cross-sectional view showing another example of the substrate W. In Figure 2 FIG. (b), a part of the surface of the substrate W is shown enlarged. As Figure 2 shown in FIG. (b), the plurality of structures 63 each have at least one recess 65. In Figure 2 the example of FIG. (b), the plurality of structures 63 each have a plurality of recesses 65. The plurality of recesses 65 are respectively recessed in a direction intersecting the direction in which the structure 63 extends with respect to the side wall surface 63a of the structure 63. In Embodiment 1, the direction in which the structure 63 extends is substantially parallel to the first direction D1. Specifically, the plurality of recesses 65 are respectively recessed along the second direction D2. The second direction D2 represents a direction along the surface 61a of the substrate main body 61. Specifically, the second direction D2 represents a direction intersecting the first direction D1. In Embodiment 1, the second direction D2 represents a direction substantially orthogonal to the first direction D1.

[0061] Next, referring to Figure 3 FIG., the hydrophilic treatment device 1 included in the substrate processing device 100 will be described. Figure 3 FIG. is a schematic cross-sectional view showing the hydrophilic treatment device 1. The hydrophilic treatment device 1 corresponds to an example of the "hydrophilic treatment unit". The hydrophilic treatment device 1 is provided, for example, at Figure 1 the transfer portion PS shown in FIG. In addition, the installation position of the hydrophilic treatment device 1 is not particularly limited. For example, the hydrophilic treatment device 1 may also replace Figure 1 one of the plurality of processing devices 200 shown in FIG. and be included in the substrate processing device 100.

[0062] The hydrophilic treatment device 1 performs a prescribed treatment using a non-liquid on the plurality of structures 63 of the substrate W, and increases the hydrophilicity of the surface 62 of each of the plurality of structures 63 as compared with before the prescribed treatment. Hydrophilicity indicates the ease of attachment of a liquid to a solid surface. The greater the hydrophilicity, the easier the liquid adheres to the solid surface. That is, the greater the hydrophilicity, the easier the solid surface is wetted. Hydrophilicity can be represented by the contact angle CA. The contact angle CA is the angle formed by the liquid surface and the solid surface at the three-phase contact boundary when the solid surface is in contact with the liquid and the gas. The smaller the contact angle CA, the greater the hydrophilicity. The smaller the contact angle CA, the greater the surface tension of the solid. The greater the hydrophilicity, the greater the surface tension of the solid. "Non-liquid" means an electromagnetic wave or a non-liquid substance. "Electromagnetic wave" is, for example, light. "Non-liquid substance" is, for example, plasma or gas. In this specification, "prescribed treatment" means "prescribed treatment using a non-liquid". "Prescribed treatment using a non-liquid" means "treatment using a non-liquid".

[0063] In particular, in Embodiment 1, before supplying the processing liquid LQ to the substrate W, the hydrophilic treatment device 1 performs a prescribed treatment on the plurality of structures 63 of the substrate W, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 as compared with before the prescribed treatment. Therefore, it is possible to increase the surface tension of the surface 62 of the structure 63 before performing the prescribed treatment. As a result, when the substrate W is treated with the processing liquid LQ, it is possible to promote the immersion of the processing liquid LQ into the space SP between the plurality of structures 63 in the substrate W.

[0064] If it is possible to promote the immersion of the processing liquid LQ into the space SP between the plurality of structures 63, it is possible to cause the processing liquid LQ to rapidly penetrate into the space SP between the plurality of structures 63 substantially uniformly within the entire range of the substrate W. Therefore, it is possible to suppress non-uniformity in the processing results of the plurality of structures 63 using the processing liquid LQ. For example, when the processing liquid LQ is an etching liquid, it is possible to suppress non-uniformity in the etching results of the plurality of structures 63. In addition, since it is possible to cause the processing liquid LQ to rapidly penetrate into the space SP between the plurality of structures 63, it is possible to effectively use the processing liquid LQ to process the plurality of structures 63. For example, when the processing liquid LQ is an etching liquid, it is possible to effectively etch the plurality of structures 63.

[0065] In addition, as long as Figure 2 the hydrophilicity of at least the side wall surface 63a in the surface 62 of the structure 63 shown in (a) is greater than that before the prescribed treatment. In Embodiment 1, for example, before the prescribed treatment, the substrate W is dried. "Drying" means removing the liquid from the substrate W.

[0066] In addition, regarding Figure 2 the substrate W shown in (b), before supplying the processing liquid LQ to the substrate W, the hydrophilic treatment device 1 performs a prescribed treatment on the plurality of structures 63, increasing the hydrophilicity of the respective side wall surfaces 63a and top wall surfaces 63b of the plurality of structures 63 and the hydrophilicity of the surfaces of the recesses 65 each provided in the plurality of structures 63 as compared with before the prescribed treatment. Therefore, when the substrate W is treated with the processing liquid LQ, it is possible not only to promote the immersion of the processing liquid LQ into the space SP between the plurality of structures 63 in the substrate W, but also to promote the immersion of the processing liquid LQ into the respective recesses 65. As a result, it is possible to cause the processing liquid LQ to rapidly penetrate into the recesses 65, and it is possible to effectively use the processing liquid LQ to process the recesses 65.

[0067] In addition, Figure 2 the surface 62 of the structure 63 shown in (b) includes the surfaces of the recesses 65. And as long as the hydrophilicity of the side wall surface 63a in the surface 62 of the structure 63 and the hydrophilicity of the surfaces of the recesses 65 are greater than those before the prescribed treatment.

[0068] In the following description, sometimes increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 compared to performing the specified treatment is referred to as "hydrophilic treatment". In addition, "penetration" means that the treatment liquid LQ infiltrates into the space SP between the structures 63 and reaches the surface 61a of the substrate main body 61 or the vicinity of the surface 61a.

[0069] In particular, in Embodiment 1, the specified treatment is a treatment of irradiating ultraviolet rays to the plurality of structures 63 of the substrate W. That is, the hydrophilic treatment device 1 irradiates ultraviolet rays to the plurality of structures 63 of the substrate W, and increases the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 compared to before the irradiation of ultraviolet rays. Since the energy of ultraviolet rays is greater than the energy of visible light, the surface 62 of the structure 63 can be effectively hydrophilized.

[0070] Specifically, as Figure 2 shown, the hydrophilic treatment device 1 includes an ultraviolet irradiation unit 3, a substrate holding unit 5, a housing unit 7, a plurality of gas supply units 10, an exhaust unit 11, a moving mechanism 13, and a rotating mechanism 15.

[0071] The substrate holding unit 5 holds the substrate W. Specifically, the substrate holding unit 5 horizontally holds the substrate W while rotating the substrate W around the rotation axis AX1 of the substrate holding unit 5. The rotation axis AX1 is substantially parallel to the vertical direction and passes through the center of the substrate W. More specifically, the substrate holding unit 5 includes a rotating base 51 and a plurality of chuck members 53. The plurality of chuck members 53 are provided on the rotating base 51 along the circumferential direction around the rotation axis AX1. The plurality of chuck members 53 hold the substrate W in a horizontal posture. The rotating base 51 is substantially disk-shaped or substantially cylindrical and supports the plurality of chuck members 53 in a horizontal posture. When the rotating base 51 rotates around the rotation axis AX1, the substrate W held by the plurality of chuck members 53 rotates around the rotation axis AX1.

[0072] The moving mechanism 13 moves the substrate holding unit 5 in the vertical direction. Specifically, the moving mechanism 13 reciprocates the substrate holding unit 5 between a first position and a second position. The first position represents the position where the substrate holding unit 5 is close to the ultraviolet irradiation unit 3. In Figure 2 it, the substrate holding unit 5 located at the first position is shown. The second position represents the position where the substrate holding unit 5 is far from the ultraviolet irradiation unit 3. The first position is the position of the substrate holding unit 5 when performing ultraviolet treatment on the substrate W. The second position is the position of the substrate holding unit 5 when delivering the substrate W. The moving mechanism 13 includes, for example, a ball screw mechanism.

[0073] The rotating mechanism 15 rotates the substrate holding unit 5 around the rotation axis AX1. As a result, the substrate W held by the substrate holding unit 5 rotates around the rotation axis AX1. The rotating mechanism 15 includes, for example, a motor.

[0074] The ultraviolet irradiation unit 3 and the substrate holding unit 5 are arranged along the rotation axis AX1 and face each other. The ultraviolet irradiation unit 3 faces the substrate W with a space SPA therebetween. The ultraviolet irradiation unit 3 generates ultraviolet rays. The space SPA is the space between the ultraviolet irradiation unit 3 and the substrate holding unit 5. The ultraviolet irradiation unit 3 irradiates the surfaces 62 of the plurality of structures 63 on the substrate W with ultraviolet rays, making the hydrophilicity of the surfaces 62 of the plurality of structures 63 greater than before the ultraviolet irradiation. As a reason for the increase in hydrophilicity, it is considered that the oxidation of the surfaces 62 of the structures 63 is promoted by the irradiation with ultraviolet rays.

[0075] In particular, in Embodiment 1, the ultraviolet irradiation unit 3 irradiates the surfaces 62 of the plurality of structures 63 on the substrate W with ultraviolet rays during the rotation of the substrate W. Therefore, compared with the case of irradiating the stationary substrate W with ultraviolet rays, the ultraviolet rays can be irradiated more uniformly onto the surfaces 62 of the plurality of structures 63 on the substrate W. As a result, the hydrophilicity of the surfaces 62 of the plurality of structures 63 on the substrate W can be effectively increased compared with before the ultraviolet irradiation.

[0076] Specifically, the ultraviolet irradiation unit 3 includes an electrode 33, an electrode 35, and a quartz glass plate 31. The electrode 33 has a substantially flat plate shape. The electrode 35 has a substantially flat plate shape. In addition, the electrode 35 has a plurality of openings 351. Each of the openings 351 penetrates the electrode 35 in the vertical direction. The electrode 35 faces the electrode 33 with a space therebetween. The electrode 35 is located on the side of the quartz glass plate 31 with respect to the electrode 33. The quartz glass plate 31 is provided on the side of the substrate W. The quartz glass plate 31 is transparent to ultraviolet rays and has heat resistance and corrosion resistance. The quartz glass plate 31 is an insulator.

[0077] There is a discharge gas in the space between the electrode 33 and the electrode 35. And a high-frequency high voltage is applied between the electrode 33 and the electrode 35. As a result, the discharge gas is excited to become an excimer state. The discharge gas generates ultraviolet rays when returning from the excimer state to the ground state. The ultraviolet rays pass through the openings 351 of the electrode 35 and further transmit through the quartz glass plate 31 to irradiate the substrate W. In addition, the hydrophilic treatment device 1 includes a high-voltage power supply that applies a high-frequency high voltage between the electrode 33 and the electrode 35. In addition, as long as the ultraviolet irradiation unit 3 can irradiate ultraviolet rays, the configuration and shape of the ultraviolet irradiation unit 3 are not particularly limited.

[0078] The housing unit 7 houses the substrate holding unit 5, the moving mechanism 13, and the rotating mechanism 15. And the ultraviolet irradiation unit 3 closes the upper opening of the housing unit 7. Therefore, the ultraviolet irradiation unit 3 and the housing unit 7 function as a chamber.

[0079] Specifically, the housing portion 7 includes a cylindrical portion 71, a side wall portion 73, and a bottom portion 75. The lower part of the cylindrical portion 71 is connected to the upper part of the side wall portion 73. The lower part of the side wall portion 73 is connected to the bottom portion 75. The cylindrical portion 71 has a plurality of through holes 71a. The through holes 71a penetrate the cylindrical portion 71 respectively and communicate with the space SPA. The side wall portion 73 has a through hole 73a. The through hole 73a penetrates the side wall portion 73.

[0080] The gas supply portion 10 supplies an inert gas to the space SPA from the through holes 71a respectively. The inert gas is, for example, nitrogen or argon. Specifically, the gas supply portion 10 includes a pipe 91, an on-off valve 93, and a gas container 95 respectively. The gas container 95 houses the inert gas supplied to the space SPA. The gas container 95 is connected to one end of the pipe 91. The on-off valve 93 is provided in the pipe 91 to switch the opening and closing of the pipe 91. The other end of the pipe 91 is connected to the through hole 91a. The exhaust portion 11 exhausts the gas inside the housing portion 7 from the through hole 73a.

[0081] The control device U3 controls the hydrophilic treatment device 1. Specifically, the processor of the control device U3 executes the computer program stored in the storage device of the control device U3 to control the hydrophilic treatment device 1.

[0082] Next, refer to Figure 4 to describe the processing device 200. Figure 4 is a schematic cross-sectional view showing the processing device 200. As Figure 4 shown, after the hydrophilic treatment device 1 increases the hydrophilicity of the surfaces 62 of the respective structures 63 of the substrate W, the processing device 200 supplies the processing liquid LQ to the substrate W while rotating the substrate W to process the substrate W. Specifically, the processing device 200 includes a chamber 21, a rotating chuck 23, a rotating shaft 24, a rotating motor 25, a nozzle 27, a nozzle moving portion 29, a nozzle 30, a plurality of protective portions 49, a valve V1, a valve V2, a pipe P1, and a pipe P2.

[0083] The chamber 21 has a substantially box shape. The chamber 21 houses the substrate W, the rotating chuck 23, the rotating shaft 24, the rotating motor 25, the nozzle 27, the nozzle moving portion 29, the nozzle 30, a part of the pipe P1, and a part of the pipe P2.

[0084] The rotating chuck 23 holds the substrate W and rotates. Specifically, the rotating chuck 23 horizontally holds the substrate W in the chamber 21 while rotating the substrate W about the rotation axis AX2 of the rotating chuck 23.

[0085] The rotary chuck 23 includes a plurality of chuck members 231 and a rotary base 233. The plurality of chuck members 231 are provided on the rotary base 233. The plurality of chuck members 231 hold the substrate W in a horizontal posture. The rotary base 233 is substantially disc-shaped and supports the plurality of chuck members 231 in a horizontal posture.

[0086] The rotary shaft 24 is fixed to the rotary base 233. In addition, the rotary shaft 24 is fixed to the drive shaft of the rotary motor 25. And, the rotary motor 25 rotates the rotary shaft 24, thereby rotating the rotary base 233 about the rotation axis AX2. As a result, the substrate W held by the plurality of chuck members 231 provided on the rotary base 233 rotates about the rotation axis AX2.

[0087] After the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 of the substrate W is increased by the hydrophilic treatment device 1, the nozzle 27 supplies the treatment liquid LQ to the plurality of structures 63 of the rotating substrate W. Therefore, the treatment liquid LQ can be effectively permeated into the space SP between the plurality of structures 63 of the substrate W. As a result, the treatment liquid LQ can be effectively used to treat the structures 63. The nozzle 27 is an example of a "treatment liquid supply unit".

[0088] In particular, in the first embodiment, the treatment liquid LQ dissolves the gas present in the space SP between the adjacent structures 63 among the plurality of structures 63. As a result, the treatment liquid LQ can penetrate more quickly into the space SP between the plurality of structures 63 of the substrate W.

[0089] The treatment liquid LQ is, for example, a chemical solution (for example, an etching solution). The chemical solution is, for example, hydrofluoric acid (HF), hydrofluoric acid nitric acid (a mixed solution of hydrofluoric acid and nitric acid (HNO3)), diluted hydrofluoric acid (BHF), ammonium fluoride, HFEG (a mixed solution of hydrofluoric acid and ethylene glycol), phosphoric acid (H3PO4), sulfuric acid, acetic acid, nitric acid, hydrochloric acid, diluted hydrofluoric acid (DHF), ammonia water, hydrogen peroxide, organic acids (for example, citric acid, oxalic acid), organic bases (for example, TMAH: tetramethylammonium hydroxide), sulfuric acid hydrogen peroxide mixed solution (SPM), ammonia water hydrogen peroxide mixed solution (SC1), hydrochloric acid hydrogen peroxide mixed solution (SC2), surfactant or preservative. In addition, the type of the treatment liquid LQ is not particularly limited as long as it can treat the substrate W.

[0090] The nozzle moving unit 29 moves the nozzle 27 between the treatment position and the retracted position. The treatment position represents a position above the substrate W. When the nozzle 27 is located at the treatment position, the treatment liquid LQ is supplied to the surface 62 of the plurality of structures 63 of the substrate W. The retracted position represents a position radially outside the substrate W.

[0091] Specifically, the nozzle moving unit 29 includes an arm 291, a rotating shaft 293, and a nozzle moving mechanism 295. The arm 291 extends in a substantially horizontal direction. A nozzle 27 is mounted at the front end of the arm 291. The arm 291 is coupled to the rotating shaft 293. The rotating shaft 293 extends in a substantially vertical direction. The nozzle moving mechanism 295 rotates the rotating shaft 293 about a rotation axis along the substantially vertical direction, so that the arm 291 rotates along the substantially horizontal plane. As a result, the nozzle 27 moves along the substantially horizontal plane. For example, the nozzle moving mechanism 295 includes an arm swing motor that rotates the rotating shaft 293 about the rotation axis. The arm swing motor is, for example, a servo motor. In addition, the nozzle moving mechanism 295 raises and lowers the rotating shaft 293 along the substantially vertical direction, so that the arm 291 is raised and lowered. As a result, the nozzle 27 moves along the substantially vertical direction. For example, the nozzle moving mechanism 295 includes a ball screw mechanism and an arm lifting motor that applies a driving force to the ball screw mechanism. The arm lifting motor is, for example, a servo motor.

[0092] The pipe P1 supplies the processing liquid LQ to the nozzle 27. The valve V1 switches the start and stop of the supply of the processing liquid LQ to the nozzle 27.

[0093] After the substrate W is processed using the processing liquid LQ, the nozzle 30 supplies a rinsing liquid to the rotating substrate W. The rinsing liquid is, for example, deionized water, carbonated water, electrolyzed ion water, hydrogen water, ozone water, or hydrochloric acid water with a dilution concentration (for example, about 10 ppm to 100 ppm). The type of the rinsing liquid is not particularly limited as long as it can rinse the substrate W.

[0094] The pipe P2 supplies the rinsing liquid to the nozzle 30. The valve V2 switches the start and stop of the supply of the rinsing liquid to the nozzle 30.

[0095] Preferably, the processing apparatus 200 further includes a fluid supply unit 41, a unit operation unit 43, a valve V3, a valve V4, a pipe P, a pipe P3, and a pipe P4. The chamber 21 houses a part of the fluid supply unit 41, the unit operation unit 43, and the pipe P.

[0096] The fluid supply unit 41 is located above the rotary chuck 23. The fluid supply unit 41 includes a shielding plate 411, a support shaft 413, and a nozzle 415.

[0097] The shielding plate 411 is, for example, in the shape of a substantially circular plate. The diameter of the shielding plate 411 is, for example, substantially the same as the diameter of the substrate W. In addition, the diameter of the shielding plate 411 may be slightly smaller or slightly larger than the diameter of the substrate W. The shielding plate 411 is arranged such that the lower surface of the shielding plate 411 is substantially horizontal. In addition, the shielding plate 411 is arranged such that the central axis of the shielding plate 411 lies on the rotation axis AX2 of the rotary chuck 23. The lower surface of the shielding plate 411 faces the substrate W held by the rotary chuck 23. The shielding plate 411 is connected to the lower end of the support shaft 413 in a horizontal posture.

[0098] The unit operation unit 43 raises or lowers the fluid supply unit 41 between the approaching position and the retracted position. The approaching position means the position where the shielding plate 411 descends and approaches the upper surface of the substrate W with a predetermined interval therebetween. At the approaching position, the shielding plate 411 covers the surface of the substrate W to shield the upper part of the surface of the substrate W. That is, at the approaching position, the shielding plate 411 faces the surface of the substrate W to cover the upper part of the surface of the substrate W. The retracted position means the position that is above the approaching position and where the shielding plate 411 ascends and separates from the substrate W. In Figure 4 this case, the shielding plate 411 is in the retracted position. In addition, the unit operation unit 43 rotates the fluid supply unit 41 at the approaching position. For example, the unit operation unit 43 includes a ball screw mechanism and a lifting motor that applies a driving force to the ball screw mechanism. The lifting motor is, for example, a servo motor. For example, the unit operation unit 43 includes a motor and a transmission mechanism that transmits the rotation of the motor to the fluid supply unit 41.

[0099] The nozzle 415 of the fluid supply unit 41 is arranged inside the shielding plate 411 and the support shaft 413. The front end of the nozzle 415 protrudes from the lower surface of the shielding plate 411. A pipe P is connected to the nozzle 415. The pipe P is connected to the pipe P3 via the valve V3. When the valve V3 is opened, a water repellent is supplied to the nozzle 415. In addition, the pipe P is connected to the pipe P4 via the valve V4. When the valve V4 is opened, an organic solvent is supplied to the nozzle 415.

[0100] When the fluid supply unit 41 is in the approaching position and the valve V3 is opened, the nozzle 415 supplies a water repellent to the plurality of structures 63 of the rotating substrate W. The nozzle 415 is an example of a "hydrophobic treatment unit".

[0101] Specifically, the nozzle 415 supplies a water repellent to the plurality of structures 63, increasing the hydrophobicity of the respective surfaces 62 of the plurality of structures 63 as compared with before the water repellent is supplied.

[0102] Hydrophobicity represents the difficulty of a liquid adhering to a solid surface. The greater the hydrophobicity, the more difficult it is for the liquid to adhere to the solid surface. That is to say, the greater the hydrophobicity, the less likely the solid surface is to be wetted. Hydrophobicity can be represented by the contact angle CA. The greater the contact angle CA, the greater the hydrophobicity. The greater the contact angle CA, the smaller the surface tension of the solid. The greater the hydrophobicity, the smaller the surface tension of the solid.

[0103] The hydrophobic agent is, for example, a liquid. The hydrophobic agent is a silicon-based hydrophobic agent or a metal-based hydrophobic agent. The silicon-based hydrophobic agent hydrophobizes silicon itself and compounds containing silicon. The silicon-based hydrophobic agent is, for example, a silane coupling agent. The silane coupling agent includes, for example, at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluoroalkylchlorosilane, alkyldisilazane, and non-chlorinated hydrophobic agents. The non-chlorinated hydrophobic agent includes, for example, at least one of dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethylaminotrimethylsilane, N-(trimethylsilyl)dimethylamine, and organosilane compounds. The metal-based hydrophobic agent hydrophobizes metal itself and compounds containing metal. The metal-based hydrophobic agent includes, for example, at least one of an amine having a hydrophobic group and an organosilicon compound.

[0104] In particular, in Embodiment 1, after the processing liquid LQ is supplied to the plurality of structures 63 of the substrate W by the nozzle 27, the nozzle 415 supplies a hydrophobic agent to the plurality of structures 63, increasing the hydrophobicity of the respective surfaces 62 of the plurality of structures 63 compared to before the supply of the hydrophobic agent. Therefore, according to Embodiment 1, the surface tension of the respective surfaces 62 of the plurality of structures 63 can be reduced. As a result, it is possible to suppress the collapse of the plurality of structures 63 due to the surface tension of the structures 63.

[0105] In addition, after the hydrophobicity of the respective surfaces 62 of the plurality of structures 63 is increased by the nozzle 415, the rotating chuck 23 rotates at a high rotational speed by the rotation motor 25 to dry the substrate W. The rotating chuck 23 is an example of a "drying processing unit".

[0106] In the following description, sometimes increasing the hydrophobicity of the respective surfaces 62 of the plurality of structures 63 compared to before the supply of the hydrophobic agent is referred to as "hydrophobization".

[0107] On the other hand, when the fluid supply unit 41 is in the proximity position, if the valve V4 is opened, the nozzle 415 supplies an organic solvent to the plurality of structures 63 of the rotating substrate W. The organic solvent is, for example, a liquid. The surface tension of the organic solvent is smaller than that of the rinsing liquid. The organic solvent is, for example, IPA (isopropyl alcohol) or HFE (hydrofluoroether). Specifically, after supplying the rinsing liquid to the substrate W or after supplying the hydrophobic agent to the substrate W, the nozzle 415 supplies the organic solvent to the substrate W.

[0108] The plurality of protective parts 49 each have a substantially cylindrical shape. The plurality of protective parts 49 each catch the liquid (processing liquid LQ, rinsing liquid, water repellent, or organic solvent) discharged from the substrate W. In addition, the protective part 49 is provided corresponding to the type of the liquid discharged from the substrate W.

[0109] The processor of the control device U3 executes a computer program stored in the storage device of the control device U3 to control the processing device 200.

[0110] Next, with reference to Figure 2 (a) of Figure 2 (b) of Figure 5 , the preferred hydrophilicity of the pattern PT of the substrate W will be described. Figure 5 is a graph showing the relationship between the penetration time of the processing liquid LQ and the contact angle CA. In Figure 5 , the vertical axis represents the penetration time (μs) of the processing liquid LQ into the space SP between the structures 63 of the substrate W shown in Figure 2 (a) of Figure 2 (b) of. Specifically, the penetration time represents the time from when the processing liquid LQ adheres to the plurality of structures 63 until the processing liquid LQ immerses into the space SP and reaches the surface 61a of the substrate main body 61 or the vicinity of the surface 61a. The horizontal axis represents the contact angle CA (degrees) in descending order. The contact angle CA represents the angle formed between the surface of the processing liquid LQ and the surface 62 of the structure 63.

[0111] As Figure 5 shows, when the contact angle CA is θ1 degrees or more, the processing liquid LQ does not penetrate into the space SP between the structures 63. That is, θ2 degrees represents the contact angle CA when the penetration time is infinite. θ1 degrees is, for example, 90 degrees. That is, when the contact angle CA is 90 degrees or more, the processing liquid LQ does not penetrate into the space SP between the structures 63.

[0112] On the other hand, when the contact angle CA is θ2 degrees or less, the penetration time is substantially constant and the shortest. Therefore, it is preferable that the hydrophilization treatment device 1 performs a predetermined treatment on the plurality of structures 63 of the substrate W so that the plurality of structures 63 have a hydrophilicity equivalent to the contact angle CA when the penetration time of the processing liquid LQ is substantially constant.

[0113] In the first embodiment, the ultraviolet irradiation unit 3 of the hydrophilization treatment device 1 irradiates ultraviolet rays to the plurality of structures 63 of the substrate W so that the plurality of structures 63 have a hydrophilicity equivalent to the contact angle CA when the penetration time of the processing liquid LQ is substantially constant.

[0114] The θ2 degrees represent the maximum contact angle CA among the contact angles CA when the penetration time is approximately constant. Therefore, it is preferable that the hydrophilic treatment device 1 performs a specified treatment on the plurality of structures 63 of the substrate W so that the contact angle CA becomes θ2 degrees or less. In the first embodiment, it is preferable that the ultraviolet irradiation unit 3 irradiates ultraviolet rays on the plurality of structures 63 of the substrate W so that the contact angle CA is θ2 degrees or less. For example, when θ2 degrees is 70 degrees, the penetration time is 1.1 μs.

[0115] For example, the contact angle CA is less than 90 degrees, preferably less than 70 degrees, and more preferably less than 50 degrees. In addition, it is further preferable that the contact angle CA is less than 30 degrees, further preferably less than 10 degrees, and further preferably less than 5 degrees. This is because the smaller the contact angle CA, the greater the hydrophilicity.

[0116] Next, referring to Figure 2 (a) of Figure 2 and (b) of

[0117] the structure 63 of the substrate W will be further described. It is preferable that the distance L between the adjacent structures 63 among the plurality of structures 63 satisfies a specified condition (hereinafter referred to as "specified condition PC"). The specified condition PC means that before the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 is increased by the hydrophilic treatment device 1 (that is, before the step of increasing the hydrophilicity), the treatment liquid LQ identical to the treatment liquid cannot penetrate into the space SP between the adjacent structures 63. According to the first embodiment, even when the plurality of structures 63 are a plurality of ultra-fine structures having a narrow distance L that satisfies the specified condition PC, the treatment liquid LQ can penetrate into the space SP between the structures 63 by hydrophilizing the plurality of structures 63.

[0118] According to Embodiment 1, even when the plurality of structures 63 are a plurality of ultra-fine structures having a narrow distance L that satisfies the first condition, the treatment liquid LQ can penetrate into the space SP between the structures 63 by hydrophilizing the plurality of structures 63.

[0119] The distance L between adjacent ones of the plurality of structures 63 is, for example, 3 nm or less. For example, if the distance L is 3 nm or less, the distance L satisfies the specified conditions PC (the first condition and the second condition). The length H of each of the plurality of structures 63 is, for example, 0.02 μm or more and 0.1 μm or less. The length H represents the length along the first direction D1. The aspect ratio of the pattern PT is, for example, 6 or more and 100 or less. The aspect ratio represents the ratio of the length H to the distance L. In addition, the viscosity of the treatment liquid LQ is, for example, 1 cP (centipoise) or more and 70 cP or less.

[0120] Next, with reference to Figure 3 、 Figure 4 、 Figure 6 and Figure 7 the substrate processing method of Embodiment 1 will be described. The substrate processing apparatus 100 executes the substrate processing method. In the substrate processing method, the substrate W having the pattern PT including the plurality of structures 63 is processed. Figure 6 is a flowchart showing the substrate processing method. As Figure 6 shown, the substrate processing method includes steps S1 to S9. Steps S1 to S9 are executed according to the control by the control device U3.

[0121] As Figure 3 and Figure 6 shown, in step S1, the hydrophilization treatment apparatus 1 performs a specified treatment using a non-liquid on the plurality of structures 63 of the substrate W for a specified time, increasing the hydrophilicity of the surface 62 of each of the plurality of structures 63 as compared with before the specified treatment is performed. Specifically, the details of step S1 are shown in Figure 7 .

[0122] Figure 7 is a flowchart showing step S1. As Figure 7 shown, step S1 includes steps S21 to S23.

[0123] In step S21, the transfer robot CR transfers the substrate W into the hydrophilization treatment apparatus 1. Then, the substrate holding unit 5 holds the substrate W. Further, the rotation mechanism 15 drives the substrate holding unit 5, and the substrate holding unit 5 starts the rotation of the substrate W.

[0124] In step S22, the ultraviolet irradiation unit 3 irradiates ultraviolet rays on the plurality of structures 63 of the substrate W for a specified time, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 compared to before the irradiation of the ultraviolet rays. Then, the rotation mechanism 15 stops the substrate holding unit 5, and the substrate holding unit 5 stops the rotation of the substrate W.

[0125] In step S23, the transfer robot CR takes out the substrate W from the hydrophilic treatment device 1. Then, the hydrophilic treatment is completed, and the process returns Figure 6 to the routine shown, and proceeds to step S2.

[0126] As Figure 4 and Figure 6 shown, next, in step S2, the transfer robot CR takes the substrate W into the processing device 200. And the rotary chuck 23 holds the substrate W. Further, the rotary motor 25 drives the rotary chuck 23, and the rotary chuck 23 causes the substrate W to start rotating.

[0127] Next, in step S3, the nozzle 27 supplies the processing liquid LQ to the plurality of structures 63 of the substrate W. That is, after step S1 of increasing the hydrophilicity and after step S2, in step S3, the nozzle 27 supplies the processing liquid LQ to the plurality of structures 63. As a result, the substrate W is processed using the processing liquid LQ.

[0128] Next, in step S4, the nozzle 30 supplies the rinsing liquid to the substrate W. As a result, the processing liquid LQ on the substrate W is flushed away by the rinsing liquid, and the substrate W is cleaned.

[0129] Next, in step S5, the nozzle 415 supplies an organic solvent to the substrate W. As a result, the rinsing liquid attached to the substrate W is replaced with the organic solvent. In step S5, the valve V4 is opened and the valve V3 is closed.

[0130] Next, in step S6, the nozzle 415 supplies a water repellent to the substrate W. As a result, the substrate W is hydrophobized. That is, after step S3 of supplying the processing liquid LQ and after steps S4 and S5, in step S6, the nozzle 415 supplies the water repellent to the plurality of structures 63 of the substrate W, increasing the hydrophobicity of the respective surfaces 62 of the plurality of structures 63 compared to before the supply of the water repellent. In step S3, the valve V3 is opened and the valve V4 is closed.

[0131] Next, in step S7, the nozzle 415 supplies an organic solvent to the substrate W. As a result, the water repellent attached to the substrate W is replaced with the organic solvent. In step S7, the valve V4 is opened and the valve V3 is closed.

[0132] Next, in step S8, the rotation motor 25 drives the rotating chuck 23 to accelerate the rotating chuck 23 to a high rotation speed and maintain the rotation speed of the rotating chuck 23 at the high rotation speed. As a result, the substrate W rotates at a high rotation speed, and the organic solvent attached to the substrate W is thrown off and the substrate W is dried. That is, after the step S6 of increasing the hydrophobicity and after the step S7, the substrate W is dried in the step S8. If the step S8 is performed for a predetermined period, the rotation motor 25 stops and the rotation of the rotating chuck 23 stops. As a result, the substrate W stops. Further, the high rotation speed is higher than the rotation speed of the rotating chuck 23 in the steps S3 and S4.

[0133] Next, in step S9, the transfer robot CR takes out the substrate W from the processing apparatus 200. And the processing is completed.

[0134] As described above with reference to Figure 6 and Figure 7 According to the substrate processing method of the first embodiment, the plurality of structures 63 of the substrate W are hydrophilized before being processed with the processing liquid LQ. Therefore, it is possible to promote the immersion of the processing liquid LQ into the space SP between the plurality of structures 63. As a result, the processing liquid LQ can quickly penetrate into the space SP between the plurality of structures 63, and the processing liquid LQ can be effectively used to process the plurality of structures 63. For example, when the processing liquid LQ is an etching liquid, the etching liquid quickly penetrates into the space SP between the plurality of structures 63, and the plurality of structures 63 can be effectively etched.

[0135] Further, in the semiconductor manufacturing method of the first embodiment, the semiconductor substrate W having the pattern PT including the plurality of structures 63 is processed using the substrate processing method including the steps S1 to S9, and a semiconductor as the processed semiconductor substrate W is manufactured.

[0136] In addition, the substrate processing method and the semiconductor manufacturing method may not include the steps S5 to S7.

[0137] (Modification example)

[0138] Refer to Figure 8 A substrate processing apparatus 100 according to a modification example of the first embodiment of the present invention will be described. The main difference between the modification example and the first embodiment described with reference to Figures 1 to 7 is that in the modification example, the hydrophilic treatment apparatus 1A is mounted on the processing apparatus 200A. Hereinafter, the differences between the modification example and the first embodiment will be mainly described.

[0139] Figure 8 is a schematic top view showing the hydrophilic treatment apparatus 1A of the processing apparatus 200A according to the modification example. As Figure 7As shown, the processing device 200A includes a hydrophilic treatment device 1A on the basis of the configuration of the processing device 200 shown in Figure 4 . In addition, in a modified example, Figure 1 the substrate processing device 100 shown in Figure 3 does not include the hydrophilic treatment device 1 shown in

[0140] Before supplying the processing liquid LQ to the substrate W, the hydrophilic treatment device 1A performs a prescribed treatment using a non-liquid on a plurality of structures 63 of the substrate W, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 as compared with before performing the prescribed treatment. Therefore, in the modified example, similarly to the first embodiment, it is possible to promote the infiltration of the processing liquid LQ into the space SP between the plurality of structures 63, and it is possible to effectively cause the processing liquid LQ to penetrate into the space SP. As a result, it is possible to effectively process the plurality of structures 63.

[0141] Specifically, the hydrophilic treatment device 1A includes an ultraviolet irradiation unit 3A and a moving unit 9. The ultraviolet irradiation unit 3A emits ultraviolet rays. The ultraviolet irradiation unit 3A includes, for example, a lamp that emits ultraviolet rays or a light-emitting diode that emits ultraviolet rays. The ultraviolet irradiation unit 3A extends in a certain direction. The length in the length direction of the ultraviolet irradiation unit 3A is, for example, substantially the same as the diameter of the substrate W or substantially the same as the radius of the substrate W.

[0142] Before supplying the processing liquid LQ to the substrate W, the ultraviolet irradiation unit 3A irradiates the surfaces 62 of the plurality of structures 63 of the rotating substrate W with ultraviolet rays, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 as compared with before irradiating with ultraviolet rays. According to the modified example, it is possible to effectively hydrophilize the surface 62 of the structure 63 by irradiating ultraviolet rays having an energy greater than visible light.

[0143] The moving unit 9 moves the ultraviolet irradiation unit 3A between a processing position and a retracted position. The processing position indicates a position above the substrate W. The ultraviolet irradiation unit 3A irradiates the surfaces 62 of the plurality of structures 63 of the substrate W when located at the processing position. The retracted position indicates a position radially outside the substrate W as compared with the substrate W. Specifically, the moving unit 9 includes an arm 92, a rotating shaft 94, and a moving mechanism 96. The ultraviolet irradiation unit 3A is mounted on the arm 92. The arm 92 is driven by the rotating shaft 94 and the moving mechanism 96 to rotate along a substantially horizontal plane or move up and down along a substantially vertical direction. In addition, the configurations of the arm 92, the rotating shaft 94, and the moving mechanism 96 are respectively the same as those of Figure 4 the arm 291, the rotating shaft 293, and the nozzle moving mechanism 295 shown in

[0144] Next, with reference to Figures 6 to 8 the substrate processing method and the semiconductor manufacturing method of the modified example will be described. The substrate processing method and the semiconductor manufacturing method of the modified example are the same as those ofFigure 6 and Figure 7 The substrate processing method and semiconductor manufacturing method of Embodiment 1 shown below are the same. Among them, the differences between the modification example and Embodiment 1 are as follows.

[0145] That is, in Figure 7 in step S21, the transfer robot CR transfers the substrate W into the processing apparatus 200A. And, the rotation of the substrate W is started.

[0146] Next, in step S22, Figure 8 the ultraviolet irradiation unit 3A shown below irradiates ultraviolet rays to a plurality of structures 63 of the rotating substrate W for a predetermined time, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 compared to before the ultraviolet irradiation. Then, the rotation of the substrate W is stopped.

[0147] In the modification example, step S23 is not executed. Therefore, if step S22 ends, the process returns to Figure 6 the routine shown below. In this case, in the modification example, step S2 is not executed, and the process proceeds to step S4.

[0148] As described above with reference to Figures 6 to 8 In the modification example, steps S3 to S8 are executed by the processing apparatus 200A. Therefore, it is not necessary to carry the substrate W out of the processing apparatus 200A in order to hydrophilize the substrate W. As a result, the throughput when executing the substrate processing method and semiconductor manufacturing method can be improved.

[0149] In addition, the substrate processing method and semiconductor manufacturing method of the modification example may not include steps S5 to S7.

[0150] (Embodiment 2)

[0151] Refer to Figure 9 and Figure 10 to describe the substrate processing apparatus 100 of Embodiment 2 of the present invention. The main difference between Embodiment 2 and Embodiment 1 is that the processing apparatus 200B of Embodiment 2 irradiates plasma to the substrate W to hydrophilize the substrate W. Hereinafter, the differences between Embodiment 2 and Embodiment 1 will be mainly described.

[0152] Figure 9 is a schematic cross-sectional view showing the processing apparatus 200B of Embodiment 2. As Figure 9 shown, the processing apparatus 200B is based on the configuration of the processing apparatus 200 shown in Figure 4 and includes a hydrophilic treatment nozzle 45, a nozzle moving unit 47, a pipe P5, and a valve V5. In addition, in Embodiment 2, Figure 1 the substrate processing apparatus 100 shown below does not include Figure 2 the hydrophilic treatment apparatus 1 shown below.

[0153] Gas is supplied to the hydrophilic treatment nozzle 45 through the pipe P5. The valve V5 switches the start and stop of the gas supply to the hydrophilic treatment nozzle 45. The gas is, for example, air, an inert gas, or oxygen. The inert gas is, for example, nitrogen, argon, or helium. In addition, as long as plasma can be generated, the type of gas is not particularly limited.

[0154] Before supplying the treatment liquid LQ to the substrate W, the hydrophilic treatment nozzle 45 performs a prescribed treatment using a non-liquid on the plurality of structures 63 of the substrate W, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 as compared with before the prescribed treatment. Therefore, in the second embodiment, similarly to the first embodiment, it is possible to promote the immersion of the treatment liquid LQ into the space SP between the plurality of structures 63, and the treatment liquid LQ can effectively penetrate into the space SP. As a result, the treatment liquid LQ can be effectively used to treat the plurality of structures 63. In addition, the second embodiment has the same effect as the first embodiment. The hydrophilic treatment nozzle 45 is an example of the "hydrophilic treatment unit".

[0155] In the second embodiment, the prescribed treatment is a treatment of irradiating the plurality of structures 63 with plasma. In addition, in the second embodiment, for example, the substrate W is dried before performing the prescribed treatment.

[0156] Specifically, the hydrophilic treatment nozzle 45 emits plasma. That is, the hydrophilic treatment nozzle 45 ionizes the gas supplied from the pipe P5 to generate plasma, and emits the plasma together with the gas. In other words, the hydrophilic treatment nozzle 45 emits the plasma along with the gas flow. Further in other words, the hydrophilic treatment nozzle 45 generates and emits a plasma flow.

[0157] More specifically, before supplying the treatment liquid LQ to the substrate W, the hydrophilic treatment nozzle 45 irradiates the surfaces 62 of the plurality of structures 63 of the rotating substrate W with plasma, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 as compared with before the plasma irradiation. As a reason for the increase in hydrophilicity, it is considered that the oxidation of the surface 62 of the structure 63 is promoted by the plasma irradiation. According to the second embodiment, the surface 62 of the structure 63 can be effectively hydrophilized by irradiating the plasma.

[0158] The nozzle moving unit 47 moves the hydrophilic treatment nozzle 45 between the treatment position and the retracted position. The treatment position indicates a position above the substrate W. When the hydrophilic treatment nozzle 45 is located at the treatment position, plasma is irradiated onto the surfaces 62 of the plurality of structures 63 of the substrate W. The retracted position indicates a position radially outside the substrate W compared to the substrate W. Specifically, the nozzle moving unit 47 includes an arm 471, a rotating shaft 473, and a moving mechanism 475. The hydrophilic treatment nozzle 45 is attached to the tip of the arm 471. The arm 471 is driven by the rotating shaft 473 and the moving mechanism 475 to rotate along a substantially horizontal plane or move up and down along a substantially vertical direction. In addition, the configurations of the arm 471, the rotating shaft 473, and the moving mechanism 475 are respectively the same as those of Figure 4 the arm 291, the rotating shaft 293, and the nozzle moving mechanism 295 shown.

[0159] Next, with reference to Figure 10 the details of the hydrophilic treatment nozzle 45 will be described. Figure 10 FIG. is a cross-sectional view showing the hydrophilic treatment nozzle 45. As Figure 10 shown, the hydrophilic treatment nozzle 45 includes a first electrode 451 and a second electrode 453. The first electrode 451 is substantially columnar. The first electrode 451 is disposed on the flow path FW within the hydrophilic treatment nozzle 45. Gas is supplied from the pipe P5 to the flow path FW. The second electrode 453 is substantially cylindrical. The second electrode 453 is provided on the outer peripheral surface of the hydrophilic treatment nozzle 45.

[0160] The processing apparatus 200B further includes an AC power supply 46. The AC power supply 46 applies an AC voltage between the first electrode 451 and the second electrode 453. As a result, the gas supplied from the pipe P5 is ionized to generate plasma PM. The plasma PM is ejected from the hydrophilic treatment nozzle 45 together with the gas. The plasma PM is, for example, atmospheric pressure plasma. Atmospheric pressure plasma refers to plasma generated at atmospheric pressure. The first electrode 451, the second electrode 453, and the AC power supply 46 constitute a plasma generator 48. In addition, as long as plasma can be generated, the configuration of the plasma generator 48 is not particularly limited. Further, as long as plasma can be irradiated onto the substrate W, the arrangement of the plasma generator 48 is not particularly limited.

[0161] The first electrode 451 and the second electrode 453 are each formed of, for example, a resin containing carbon. The carbon is, for example, carbon nanotubes. The resin is, for example, a fluororesin. The fluororesin is, for example, polytetrafluoroethylene (tetrafluorinated) or polychlorotrifluoroethylene (trifluorinated). By configuring the first electrode 451 and the second electrode 453 in this way, conductivity can be ensured and chemical resistance can be improved.

[0162] Next, with reference to Figure 6 , Figure 7 and Figure 9Describe the substrate processing method and semiconductor manufacturing method of Embodiment 2. The substrate processing method and semiconductor manufacturing method of Embodiment 2 are the same as those of the substrate processing method and semiconductor manufacturing method of Embodiment 1 shown in Figure 6 and Figure 7 . Among them, the differences between Embodiment 2 and Embodiment 1 are as follows.

[0163] That is, in the process S21 of Figure 7 , the transfer robot arm CR transfers the substrate W into the processing device 200A. And, the rotation of the substrate W is started.

[0164] Next, in the process S22, Figure 9 the hydrophilic treatment nozzle 45 shown irradiates the plasma on the plurality of structures 63 of the substrate W for a specified time, increasing the hydrophilicity of the respective surfaces 62 of the plurality of structures 63 compared with before the plasma irradiation. Then, the rotation of the substrate W is stopped.

[0165] In addition, it is preferable that the hydrophilic treatment nozzle 45 irradiates the plasma on the plurality of structures 63 of the substrate W so that the plurality of structures 63 have hydrophilicity equivalent to the contact angle CA when the penetration time of the processing liquid LQ is substantially constant ( Figure 5 ). That is, it is preferable that the hydrophilic treatment nozzle 45 irradiates the plasma on the plurality of structures 63 of the substrate W so that the contact angle CA is θ2 degrees or less ( Figure 5 ).

[0166] In Embodiment 2, the process S23 is not executed. Therefore, at the end of the process S22, the process returns to the Figure 6 shown routine. In this case, in Embodiment 2, the process S2 is not executed, and the process proceeds to the process S4.

[0167] As described above with reference to Figure 6 , Figure 7 and Figure 9 , in Embodiment 2, the processes S3 to S8 are executed by the processing device 200B. Therefore, it is not required to carry the substrate W out of the processing device 200B to hydrophilize the substrate W. As a result, the throughput when executing the substrate processing method and the semiconductor manufacturing method can be improved.

[0168] In addition, the substrate processing method and semiconductor manufacturing method of Embodiment 2 may not include the processes S5 to S7.

[0169] (Embodiment 3)

[0170] Refer to Figure 11Describe the substrate processing apparatus 100 of Embodiment 3 of the present invention. The main difference between Embodiment 3 and Embodiment 2 is that the processing apparatus 200C in Embodiment 3 irradiates oxygen or an oxygen isotope onto the substrate W to hydrophilize the substrate W. Hereinafter, the differences between Embodiment 3 and Embodiment 2 will be mainly described.

[0171] Figure 11 is a schematic cross-sectional view showing the processing apparatus 200C of Embodiment 3. As Figure 11 shown, the processing apparatus 200C replaces Figure 9 the hydrophilic treatment nozzle 45, nozzle moving part 47, pipe P5, and valve V5 of the processing apparatus 200B shown, and includes a hydrophilic treatment nozzle 85, a pipe P6, and a valve V6. Specifically, the fluid supply unit 41A includes the hydrophilic treatment nozzle 85. The hydrophilic treatment nozzle 85 is disposed inside the shielding plate 411 and the support shaft 413. The front end of the hydrophilic treatment nozzle 85 protrudes from the lower surface of the shielding plate 411.

[0172] A pipe P6 is connected to the hydrophilic treatment nozzle 85. The valve V6 switches the start and stop of the supply of oxygen to the hydrophilic treatment nozzle 85. When the valve V6 is opened, oxygen (O2) or an oxygen isotope is supplied to the hydrophilic treatment nozzle 85. In addition, the gas supplied from the pipe P6 to the hydrophilic treatment nozzle 85 is not limited to oxygen, and may also be an oxygen isotope. The oxygen isotope is, for example, ozone (O3). In addition, as long as the surface 62 of the structure 63 of the substrate W can be oxidized, the oxygen isotope is not particularly limited.

[0173] Before supplying the processing liquid LQ to the substrate W, the hydrophilic treatment nozzle 85 performs a specified treatment using a non-liquid on the plurality of structures 63 of the substrate W, increasing the hydrophilicity of the surface 62 of each of the plurality of structures 63 compared to before the specified treatment. Therefore, in Embodiment 3, similarly to Embodiment 2, it is possible to promote the immersion of the processing liquid LQ into the space SP between the plurality of structures 63, and it is possible to effectively permeate the processing liquid LQ into the space SP. As a result, it is possible to effectively use the processing liquid LQ to process the plurality of structures 63. In addition, Embodiment 3 has the same effect as Embodiment 2. The hydrophilic treatment nozzle 85 is an example of a "hydrophilic treatment unit".

[0174] In Embodiment 3, the specified treatment is a treatment of supplying oxygen or an oxygen isotope to the plurality of structures 63. In addition, in Embodiment 3, for example, before performing the specified treatment, the substrate W is dried.

[0175] Specifically, before supplying the processing liquid LQ to the substrate W, the hydrophilic treatment nozzle 85 supplies oxygen or an oxygen isotope to the surfaces 62 of the plurality of structures 63 of the rotating substrate W, increasing the hydrophilicity of the surfaces 62 of the plurality of structures 63 compared to before the supply of oxygen or the oxygen isotope. As a reason for the increase in hydrophilicity, it can be considered that by supplying oxygen or the oxygen isotope, the surface 62 of the structure 63 is exposed to oxygen or the oxygen isotope, promoting the oxidation of the surface 62 of the structure 63. According to Embodiment 3, by supplying oxygen or the oxygen isotope, the surface 62 of the structure 63 can be effectively hydrophilized.

[0176] When the fluid supply unit 41A descends and the hydrophilic treatment nozzle 85 is in the proximity position, if the valve V6 is opened, the hydrophilic treatment nozzle 85 supplies oxygen or an oxygen isotope to the plurality of structures 63 of the rotating substrate W. Since the upper part of the substrate W is covered by the shielding plate 411, the plurality of structures 63 can be sufficiently exposed to oxygen or the oxygen isotope. As a result, the surfaces 62 of the plurality of structures 63 can be effectively hydrophilized.

[0177] Next, refer to Figure 6 、 Figure 7 and Figure 11 to describe the substrate processing method and semiconductor manufacturing method of Embodiment 3. The substrate processing method and semiconductor manufacturing method of Embodiment 3 are the same as those of the substrate processing method and semiconductor manufacturing method of Embodiment 2 described with reference to Figure 6 and Figure 7 . Among them, the differences between Embodiment 3 and Embodiment 2 are as follows.

[0178] That is, in the process S22 of Figure 7 , the hydrophilic treatment nozzle 85 shown in Figure 11 supplies oxygen or an oxygen isotope to the plurality of structures 63 of the substrate W for a specified time, increasing the hydrophilicity of the surfaces 62 of the plurality of structures 63 compared to before the supply of oxygen or the oxygen isotope.

[0179] In addition, it is preferable that the hydrophilic treatment nozzle 85 supplies oxygen or an oxygen isotope to the plurality of structures 63 of the substrate W so that the plurality of structures 63 have a hydrophilicity equivalent to the contact angle CA when the penetration time of the processing liquid LQ is substantially constant ( Figure 5 ). That is, it is preferable that the hydrophilic treatment nozzle 85 supplies oxygen or an oxygen isotope to the plurality of structures 63 of the substrate W so that the contact angle CA is θ2 degrees or less ( Figure 5 ).

[0180] (Embodiment 4)

[0181] Refer to Figure 12 and Figure 13Describe the substrate processing apparatus 100 according to Embodiment 4 of the present invention. In Embodiment 4, the main difference between Embodiment 4 and Embodiment 1 is that the processing apparatus 200D removes oxides from the substrate W. Hereinafter, the differences between Embodiment 4 and Embodiment 1 will be mainly described.

[0182] Figure 12 is a schematic cross-sectional view showing the processing apparatus 200D of Embodiment 4. As Figure 12 shown, the processing apparatus 200D is based on the configuration of the processing apparatus 200 shown in Figure 4 and includes a nozzle 81, a nozzle moving unit 83, a pipe P7, and a valve V7. In addition, in Embodiment 4, Figure 1 the substrate processing apparatus 100 shown does not include Figure 2 the hydrophilic treatment apparatus 1 shown.

[0183] The pipe P7 supplies the removal liquid to the nozzle 81. The valve V7 switches the start and stop of the supply of the removal liquid to the nozzle 81.

[0184] The removal liquid removes oxides from the substrate W. For example, the removal liquid removes the oxides formed on the surface 62 of the plurality of structures 63 of the substrate W. The removal liquid removes, for example, a silicon oxide film from the substrate W. The silicon oxide film is, for example, a natural oxide film. The removal liquid is, for example, a chemical solution. The chemical solution is, for example, hydrofluoric acid (HF), dilute hydrofluoric acid (DHF), or buffered hydrofluoric acid (BHF). In addition, the type of the removal liquid is not particularly limited as long as it can remove oxides from the substrate W.

[0185] The removal liquid is different from the processing liquid LQ. In Embodiment 4, the processing liquid LQ is, for example, an etching liquid. The etching liquid is, for example, an organic base (e.g., TMAH: tetramethylammonium hydroxide) or an ammonia hydrogen peroxide mixture (SC1). In addition, the type of the etching liquid is not particularly limited as long as it can etch the substrate W.

[0186] Before the hydrophilicity of each surface 62 of the plurality of structures 63 of the substrate W is increased, the nozzle 81 supplies a removal liquid that removes oxides from the substrate W to the substrate W. The nozzle 81 is an example of a "removal liquid supply unit".

[0187] The nozzle moving unit 83 moves the nozzle 81 between the processing position and the retracted position. The processing position indicates a position above the substrate W. When the nozzle 81 is at the processing position, it supplies a removal liquid to the surface 62 of the plurality of structures 63 on the substrate W. The retracted position indicates a position radially outside the substrate W compared to the substrate W. Specifically, the nozzle moving unit 83 includes an arm 831, a rotating shaft 833, and a moving mechanism 835. The nozzle 81 is attached to the front end of the arm 831. The arm 831 is driven by the rotating shaft 833 and the moving mechanism 835 to rotate along a substantially horizontal plane or move up and down along a substantially vertical direction. In addition, the configurations of the arm 831, the rotating shaft 833, and the moving mechanism 835 are respectively the same as those of Figure 4 the arm 291, the rotating shaft 293, and the nozzle moving mechanism 295 shown.

[0188] Next, referring to Figure 12 and Figure 13 the substrate processing method of Embodiment 3 will be described. The substrate processing apparatus 100 executes the substrate processing method. Figure 13 is a flowchart showing the substrate processing method. As shown in Figure 13 , the substrate processing method includes steps S31 to S44. Steps S31 to S44 are executed according to the control based on the control device U3.

[0189] As shown in Figure 12 and Figure 13 , in step S31, the transfer robot arm CR transfers the substrate W into the processing apparatus 200D. And the rotation of the substrate W is started.

[0190] Next, in step S32, the nozzle 81 supplies a removal liquid to the substrate W. Specifically, before the step S36 of increasing the hydrophilicity and before steps S33 to S35, a removal liquid for removing the oxide formed on the surface 62 of the plurality of structures 63 is supplied to the substrate W. As a result, the oxide is removed from the substrate W.

[0191] Next, in step S33, the nozzle 30 supplies a rinsing liquid to the substrate W. As a result, the removal liquid on the substrate W is flushed away by the rinsing liquid, and the substrate W is cleaned.

[0192] Next, in step S34, the rotation motor 25 drives the rotating chuck 23 to accelerate the rotating chuck 23 to a high rotation speed and maintain the rotation speed of the rotating chuck 23 at the high rotation speed. As a result, the substrate W rotates at a high rotation speed, and the rinsing liquid attached to the substrate W is thrown off to clean the substrate W. When step S34 has been performed for a predetermined period, the rotation motor 25 stops and the rotation of the rotating chuck 23 stops. As a result, the substrate W stops. In addition, the high rotation speed is higher than the rotation speed of the rotating chuck 23 in steps S32 and S33.

[0193] Next, in process S35, the transfer robot arm CR unloads the substrate W from the processing apparatus 200D.

[0194] Next, processes S36 to S44 are executed. Processes S36 to S44 are the same as processes S1 to S9 of Figure 6 respectively, and the description thereof is omitted.

[0195] As described above with reference to Figure 12 and Figure 13 For the substrate processing apparatus 100 according to the fourth embodiment, before the treatment with the treatment liquid LQ, the plurality of structures 63 of the substrate W are hydrophilized. Therefore, it is possible to promote the infiltration of the treatment liquid LQ into the space SP between the plurality of structures 63. As a result, the treatment liquid LQ can quickly penetrate into the space SP between the plurality of structures 63, and the treatment liquid LQ can be effectively used to treat the plurality of structures 63.

[0196] In particular, since the oxide is removed from the substrate W in process S32, there is a possibility that the hydrophobicity of the substrate W increases after the completion of process S32. Therefore, by hydrophilizing the substrate W in process S36, it is possible to effectively cause the treatment liquid LQ to penetrate into the space SP between the structures 63. In addition, in the fourth embodiment, the same effects as those in the first embodiment are achieved.

[0197] Here, for example, there may be a case where a liquid (for example, a removal liquid or a rinse liquid) adheres to a part of the substrate W and another part of the substrate W is dry. Specifically, after the spin drying in process S34, there may be a case where a rinse liquid adheres to a part of the substrate W and another part of the substrate W is dry. More specifically, after the spin drying in process S34, the following situation may occur, that is, in the region of the substrate W near the center, the rinse liquid remains in the space SP between the structures 63, while in the region of the substrate W near the outer edge, the rinse liquid is completely removed from the space SP. In this case, the following situation may occur, that is, in the region of the substrate W near the center, the rinse liquid remaining in the space SP is replaced by the treatment liquid LQ, and the treatment liquid LQ penetrates into the space SP, while in the region of the substrate W near the outer edge, it is difficult for the treatment liquid LQ to penetrate into the space SP. Therefore, in the fourth embodiment, by hydrophilizing the surfaces 62 of the plurality of structures 63 of the substrate W in process S36, it is possible to cause the treatment liquid LQ to quickly penetrate into the space SP between the plurality of structures 63 substantially uniformly over the entire range of the substrate W. As a result, it is possible to suppress unevenness in the treatment results of the plurality of structures 63 using the treatment liquid LQ. For example, when the treatment liquid LQ is an etching liquid, it is possible to suppress unevenness in the etching results of the plurality of structures 63.

[0198] In addition, in the semiconductor manufacturing method of Embodiment 4, a semiconductor substrate W having a pattern PT including a plurality of structures 63 is processed by a substrate processing method including steps S31 to S44, and a semiconductor as the processed semiconductor substrate W is manufactured.

[0199] Furthermore, the substrate processing method and the semiconductor manufacturing method may not include steps S40 to S42.

[0200] As described above, the embodiments of the present invention have been described with reference to the drawings. In addition, the present invention is not limited to the above-described embodiments, and can be implemented in various ways without departing from the gist thereof. In addition, a plurality of constituent elements disclosed in the above-described embodiments can be appropriately changed. For example, a certain constituent element among all the constituent elements shown in a certain embodiment can be added to the constituent elements of other embodiments, or several constituent elements among all the constituent elements shown in a certain embodiment can be deleted from the embodiment.

[0201] In addition, for easy understanding of the invention, the drawings mainly schematically show each constituent element, and there are cases where the thickness, length, number, interval, etc. of each constituent element shown in the drawings are different from the actual ones for convenience of drawing. In addition, the configuration of each constituent element shown in the above-described embodiments is an example and is not particularly limited, and of course, various changes can be made without substantially departing from the effects of the present invention.

[0202] (1) In Embodiment 4 described with reference to Figure 12 and Figure 13 , the processing apparatus 200D may also include the hydrophilic treatment apparatus 1A according to the modified example of Embodiment 1 described with reference to Figure 8 .

[0203] (2) The processing apparatus 200D of Embodiment 4 may also include the hydrophilic treatment nozzle 45, the nozzle moving unit 47, the pipe P5, and the valve V5 according to Embodiment 2 described with reference to Figure 9 .

[0204] (3) The processing apparatus 200D of Embodiment 4 may also include the hydrophilic treatment nozzle 85, the pipe P6, and the valve V6 according to Embodiment 3 described with reference to Figure 11 .

[0205] Industrial Applicability

[0206] The present invention relates to a substrate processing method, a semiconductor manufacturing method, and a substrate processing apparatus, and has industrial applicability.

[0207] Description of Reference Numerals

[0208] 1, 1A hydrophilic treatment apparatus (hydrophilic treatment unit)

[0209] 23 Rotary chuck (drying treatment section)

[0210] 27 Nozzle (treatment liquid supply section)

[0211] 45, 85 Hydrophilic treatment nozzle (hydrophilic treatment section)

[0212] 81 Nozzle (removing liquid supply section)

[0213] 415 Nozzle (hydrophobic treatment section)

[0214] 100 Substrate processing apparatus

[0215] W Substrate.

Claims

1. A substrate processing method for processing a substrate having a pattern including a plurality of structures, wherein the substrate processing method is characterized in that, the plurality of structures are formed on the surface of the substrate, and the distance between adjacent ones of the structures is 3 nm or less, the substrate processing method includes the following steps: a step of performing a prescribed treatment using a non-liquid on the plurality of structures to increase the hydrophilicity of the surfaces of the respective ones of the plurality of structures as compared with before performing the prescribed treatment; and a step of, after the step of increasing the hydrophilicity, supplying a processing liquid to the space between the plurality of structures and performing a treatment on the plurality of structures, in the step of increasing the hydrophilicity, the prescribed treatment is performed on the plurality of structures so that the plurality of structures have a hydrophilicity equivalent to a contact angle when the penetration time of the processing liquid into the space between the structures is constant, the contact angle is the angle formed by the surface of the processing liquid and the surface of the structure.

2. The substrate processing method according to claim 1, wherein, it further includes a step of, before the step of increasing the hydrophilicity, supplying a removal liquid for removing oxides from the substrate to the plurality of structures.

3. The substrate processing method according to claim 1 or 2, wherein, the prescribed treatment is a treatment of irradiating ultraviolet rays on the plurality of structures.

4. The substrate processing method according to claim 1 or 2, wherein, the prescribed treatment is a treatment of irradiating plasma on the plurality of structures.

5. The substrate processing method according to claim 1, wherein, the prescribed treatment is a treatment of supplying oxygen or an isotope of oxygen to the plurality of structures.

6. The substrate processing method according to any one of claims 1, 2, and 5, wherein, the processing liquid dissolves the gas present in the space between adjacent ones of the plurality of structures.

7. The substrate processing method according to any one of claims 1, 2, and 5, characterized in that, It further includes the following steps: a step of, after the step of supplying the processing liquid, supplying a water repellent to the plurality of structures to increase the hydrophobicity of the surfaces of the respective ones of the plurality of structures as compared with before supplying the water repellent; and a step of drying the substrate after the step of increasing the hydrophobicity.

8. The substrate processing method according to any one of claims 1, 2, and 5, wherein, the distance between adjacent ones of the plurality of structures satisfies a prescribed condition, the prescribed condition means that, before the step of increasing the hydrophilicity, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures.

9. The substrate processing method according to claim 8, wherein, the prescribed condition includes a first condition and a second condition, the first condition means that, before the step of increasing the hydrophilicity, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures by capillary action, The second condition means that after the step of increasing the hydrophilicity, the treatment liquid can penetrate into the space between the adjacent structures by capillary action.

10. The substrate processing method according to any one of claims 1, 2, 5, and 9, characterized in that in the step of increasing the hydrophilicity, the specified treatment is performed on the plurality of structures, and the hydrophilicity of the surface of the recesses respectively provided in the plurality of structures is increased as compared with before the specified treatment is performed. The recess is recessed with respect to the side wall surface of the structure in a direction intersecting the direction in which the structure extends.

11. A semiconductor manufacturing method, which processes a semiconductor substrate having a pattern including a plurality of structures to manufacture a semiconductor as the processed semiconductor substrate, wherein the semiconductor manufacturing method is characterized in that the plurality of structures are formed on the surface of the substrate, and the distance between the adjacent structures is 3 nm or less. The substrate processing method includes the following steps: a step of performing a specified treatment using a non-liquid on the plurality of structures to increase the hydrophilicity of the surface of each of the plurality of structures as compared with before the specified treatment is performed; and a step of supplying a treatment liquid to the space between the plurality of structures after the step of increasing the hydrophilicity and performing a treatment on the plurality of structures. in the step of increasing the hydrophilicity, the specified treatment is performed on the plurality of structures so that the plurality of structures have a hydrophilicity equivalent to the contact angle when the penetration time of the treatment liquid into the space between the structures is constant. The contact angle is the angle formed by the surface of the treatment liquid and the surface of the structure.

12. A substrate processing apparatus, which processes a substrate having a pattern including a plurality of structures, wherein the substrate processing apparatus is characterized in that the plurality of structures are formed on the surface of the substrate, and the distance between the adjacent structures is 3 nm or less. The substrate processing apparatus includes: a hydrophilic treatment unit that performs a specified treatment using a non-liquid on the plurality of structures to increase the hydrophilicity of the surface of each of the plurality of structures as compared with before the specified treatment is performed; and a treatment liquid supply unit that supplies a treatment liquid to the space between the plurality of structures and performs a treatment on the plurality of structures after the hydrophilicity of the surface of each of the plurality of structures is increased. The hydrophilic treatment unit performs the specified treatment on the plurality of structures so that the plurality of structures have a hydrophilicity equivalent to the contact angle when the penetration time of the treatment liquid into the space between the structures is constant. The contact angle is the angle formed by the surface of the treatment liquid and the surface of the structure.

13. The substrate processing apparatus according to claim 12, characterized in that it further includes a removal liquid supply unit that supplies a removal liquid for removing oxides from the substrate to the plurality of structures before the hydrophilicity of the surface of each of the plurality of structures is increased.

14. The substrate processing apparatus according to claim 12 or 13, wherein: the specified processing is a process of irradiating ultraviolet rays to the plurality of structures.

15. The substrate processing apparatus according to claim 12 or 13, wherein: the specified processing is a process of irradiating plasma to the plurality of structures.

16. The substrate processing apparatus according to claim 12, wherein: the specified processing is a process of supplying oxygen or an oxygen isotope to the plurality of structures.

17. The substrate processing apparatus according to any one of claims 12, 13, and 16, wherein: the processing liquid dissolves the gas present in the space between the adjacent structures among the plurality of structures.

18. The substrate processing apparatus according to any one of claims 12, 13, and 16, characterized in that, Further comprising: a hydrophobic treatment unit that, after supplying the processing liquid to the plurality of structures, supplies a hydrophobic agent to the plurality of structures, increasing the hydrophobicity of the surface of each of the plurality of structures as compared to before the supply of the hydrophobic agent; and a drying treatment unit that dries the substrate after the hydrophobicity of the surface of each of the plurality of structures is increased.

19. The substrate processing apparatus according to any one of claims 12, 13, and 16, wherein: the distance between the adjacent structures among the plurality of structures satisfies a specified condition, the specified condition means that, before the hydrophilicity of the surface of each of the plurality of structures is increased, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures.

20. The substrate processing apparatus according to claim 19, wherein: the specified condition includes a first condition and a second condition, the first condition means that, before the hydrophilicity of the surface of each of the plurality of structures is increased, a processing liquid the same as the processing liquid cannot penetrate into the space between the adjacent structures by capillary action, the second condition means that, after the hydrophilicity of the surface of each of the plurality of structures is increased, the processing liquid can penetrate into the space between the adjacent structures by capillary action.

21. The substrate processing apparatus according to any one of claims 12, 13, 16, and 20, wherein: the hydrophilic treatment unit performs the specified processing on the plurality of structures, increasing the hydrophilicity of the surface of the recess provided in each of the plurality of structures as compared to before the performance of the specified processing, the recess is recessed along a direction crossing the direction in which the structure extends with respect to the side wall surface of the structure.

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