Substrate processing method and substrate processing apparatus

Abstract

This invention provides a substrate processing method that can reliably adsorb polymer ions onto the surface of a substrate. [Solution] The substrate processing method includes: forming a first adsorption film F1 on the substrate surface by supplying a first polymer solution containing first polymer ions p1 that are electrically charged with a polarity opposite to that of the substrate surface in contact with the rinse solution, while the rinse solution is in contact with the substrate surface; and, after removing the first polymer solution from the substrate surface while leaving the first adsorption film F1 on the substrate surface, supplying a second polymer solution containing second polymer ions p2 that are electrically charged with a polarity opposite to that of the first polymer ions to the substrate surface by forming a second adsorption film F2 on the substrate surface containing the second polymer adsorbed on the first adsorption film F1.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Examples of the substrate include semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal display devices and organic EL (electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like.

Background Art

[0002] Patent Document 1 discloses an insulating film forming method using an alternate adsorption method. Specifically, Patent Document 1 discloses forming a chromium layer on a glass substrate whose surface is cleaned with a surfactant, forming a gold layer as a lower metal electrode on the chromium layer, introducing a hydroxyl group (hydroxyl group of a carboxyl group) onto the electrode surface, and immersing the substrate in an aqueous solution of PAH (polyallylamine hydrochloride) for 300 seconds.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the insulating film forming method described in Patent Document 1, since the substrate is immersed in an aqueous solution of PAH, it is considered that the substrate comes into contact with the aqueous solution of PAH in a state where it is not in contact with a liquid other than the aqueous solution of PAH.

[0005] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus capable of reliably adsorbing polymer ions onto the surface of a substrate.

Means for Solving the Problems

[0006] One embodiment of the present invention provides a substrate processing method comprising: supplying a rinse liquid to the surface of a substrate; while the rinse liquid is in contact with the surface of the substrate, supplying a first polymer liquid containing ions of a first polymer having an electrical charge opposite to the polarity of the surface of the substrate in contact with the rinse liquid to the surface of the substrate, thereby forming a first adsorption film containing the first polymer adsorbed on the surface of the substrate; removing the first polymer liquid from the surface of the substrate while leaving the first adsorption film on the surface of the substrate; and, after removing the first polymer liquid from the surface of the substrate while leaving the first adsorption film on the surface of the substrate, supplying a second polymer liquid containing ions of a second polymer having an electrical charge opposite to the polarity of the ions of the first polymer to the surface of the substrate, thereby forming a second adsorption film containing the second polymer adsorbed on the first adsorption film to the surface of the substrate.

[0007] In the above embodiment, at least one of the following features may be added to the substrate processing method.

[0008] Supplying the rinse liquid to the surface of the substrate includes supplying the rinse liquid to the surface on which a pattern including a plurality of protrusions and a plurality of recesses is formed; forming the first adsorption film on the surface of the substrate includes forming the first adsorption film on the side surface of the protrusions; and forming the second adsorption film on the surface of the substrate includes forming the second adsorption film on the side surface of the protrusions via the first adsorption film.

[0009] The substrate processing method further includes removing the second polymer liquid from the surface of the substrate while leaving the first adsorption film and the second adsorption film on the surface of the substrate, and, after removing the second polymer liquid from the surface of the substrate while leaving the first adsorption film and the second adsorption film on the surface of the substrate, performing one or more cycles including supplying the first polymer liquid, removing the first polymer liquid, supplying the second polymer liquid, and removing the second polymer liquid.

[0010] A laminated film comprising at least one pair of the first adsorption film and the second adsorption film forms a gap within the recess that is recessed in the height direction of the protrusion toward the bottom of the recess, and performing the cycle once or more times includes performing the cycle multiple times until a portion of the gap is filled in at least one of the first polymer and the second polymer.

[0011] A laminated film comprising at least one pair of the first adsorption film and the second adsorption film forms a gap within the recess that is recessed in the height direction of the protrusion toward the bottom of the recess, and performing the cycle once or more times includes terminating the cycle after performing the cycle once or more times, before a portion of the gap is filled in at least one of the first polymer and the second polymer.

[0012] The substrate processing method further includes drying the substrate while a laminated film comprising at least one pair of the first adsorption film and the second adsorption film is located on the side surface of the protrusion.

[0013] The substrate processing method further includes maintaining the end faces of the protrusions covered with the processing liquid from the time the supply of the rinsing liquid to the surface of the substrate is started until the drying of the substrate is started.

[0014] The substrate processing method further includes removing the laminated film from the dried substrate by ashing.

[0015] Another embodiment of the present invention provides a substrate processing apparatus comprising a substrate holder for holding a substrate, at least one nozzle for supplying a processing liquid to the surface of the substrate held in the substrate holder, and a control unit for controlling the supply of the processing liquid from the at least one nozzle to the substrate. The control unit supplies a rinse liquid to the surface of the substrate held in the substrate holder via the at least one nozzle, and while the rinse liquid is in contact with the surface of the substrate, it supplies a first polymer liquid containing ions of a first polymer charged with an electrical polarity opposite to that of the surface of the substrate in contact with the rinse liquid to the surface of the substrate held in the substrate holder, thereby forming a first adsorbed film containing the first polymer adsorbed on the surface of the substrate, and by supplying a replacement liquid to the surface of the substrate held in the substrate holder, the surface of the substrate The first polymer solution is replaced with the displacement solution, the first polymer solution is removed from the surface of the substrate while leaving the first adsorption film on the surface of the substrate, and after removing the first polymer solution from the surface of the substrate while leaving the first adsorption film on the surface of the substrate, the second polymer solution containing ions of the second polymer having an electrical charge opposite to that of the ions of the first polymer is supplied to the surface of the substrate held in the substrate holder, thereby controlling the at least one nozzle to form a second adsorption film containing the second polymer adsorbed on the first adsorption film on the surface of the substrate. At least one of the features of the substrate processing method described above may be added to the substrate processing apparatus. [Brief explanation of the drawing]

[0016] [Figure 1A-C] This is a schematic cross-sectional view illustrating a substrate processing method according to one embodiment. [Figure 2A-D] This is a schematic cross-sectional view illustrating a substrate processing method according to one embodiment. [Figure 3A-F] This is a schematic cross-sectional view illustrating a substrate processing method according to one embodiment. [Figure 4A] This is a schematic plan view showing the layout of a substrate processing apparatus according to one embodiment. [Figure 4B] It is a schematic side view of a substrate processing apparatus. [Figure 5] It is a schematic view of the inside of a wet processing chamber seen horizontally. [Figure 6] It is a schematic view of the inside of a dry processing chamber seen horizontally. [Figure 7] It is a schematic diagram for explaining an example of the processing of a substrate performed by a substrate processing apparatus. [Figure 8] It is a schematic diagram for explaining a configuration for charging the surface of a substrate held by a spin chuck.

Mode for Carrying Out the Invention

[0017] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0018] FIGS. 1A, 1B, 1C, 2A, 2B, 2C, 2D, 3A, 3B, 3C, 3D, 3E, and 3F are schematic cross-sectional views for explaining a substrate processing method according to an embodiment.

[0019] FIGS. 1A to 1C show the steps until the chemical solution is washed away with a rinse solution. FIGS. 2A to 2D show the steps until the laminated film F3 is deposited on the surface of the substrate W. FIGS. 3A to 3F show the steps until the laminated film F3 is removed from the surface of the substrate W. FIGS. 1A to 3F show an example of a cross-section of the substrate W cut along a plane perpendicular to the flat surface of the substrate W before the pattern PA is formed. In FIGS. 1A to 3F, the vertical direction of the paper surface corresponds to the height direction of the convex portion P1 and the depth direction of the concave portion Q1, and the horizontal direction of the paper surface corresponds to the width direction of the convex portion P1 and the concave portion Q1.

[0020] The substrate W includes a front and back surface that are parallel to each other, and an annular end face that connects the outer edges of the front and back surfaces along the entire circumference of the front and back surfaces. Figure 1A shows the substrate W with the front surface facing upwards. The front surface of the substrate W corresponds to the top surface of the substrate W. The front surface of the substrate W is the device-forming surface on which devices are formed. The back surface of the substrate W is a non-device-forming surface on which no devices are formed. Both the front and back surfaces of the substrate W may be device-forming surfaces.

[0021] The front and back surfaces of the substrate W are flat surfaces parallel to each other. When the pattern PA is formed on the surface of the substrate W, the surface of the substrate W is, strictly speaking, an uneven surface. The thickness direction of the substrate W is perpendicular to the flat surface of the substrate W before the pattern PA is formed, and the plane direction of the substrate W is parallel to that surface. In Figure 1A, the vertical direction of the paper corresponds to the thickness direction of the substrate W, and the horizontal direction of the paper corresponds to the plane direction of the substrate W. The pattern PA may be formed before the substrate processing apparatus 1 processes the substrate W, or it may be formed while the substrate processing apparatus 1 is processing the substrate W.

[0022] Figure 1A shows an example of a cross-section of a substrate W cut with a plane perpendicular to the flat surface of the substrate W before the pattern PA is formed. In this example, a plurality of protrusions P1 are formed extending in the thickness direction of the substrate W from the surface of the base layer s4 of the substrate W. The base layer s4 may be part of a disc-shaped semiconductor substrate or a thin film formed on the substrate. The pattern PA includes a plurality of protrusions P1 and a plurality of recesses Q1. The plurality of protrusions P1 are spaced apart from each other in the plane direction of the substrate W. Two protrusions P1 that are spaced apart and facing each other in the plane direction of the substrate W form a recess Q1 that is recessed in the thickness direction of the substrate W from the tips of the two protrusions P1.

[0023] Figure 1A shows an example where the cross-section of the protrusion P1 is rectangular and extends in the thickness direction of the substrate W. The protrusion P1 may be cylindrical, prismatic, or plate-shaped, or it may have any other shape. The recess Q1 may be a hole or a groove. The protrusion P1 and recess Q1 may extend in the plane direction of the substrate W, rather than in the thickness direction of the substrate W. The width of the protrusion P1 may be constant from the base to the tip of the protrusion P1, or it may vary. The width of the recess Q1 may be constant from the bottom to the entrance of the recess Q1, or it may vary.

[0024] The protrusion P1 may consist of a single layer, or it may consist of multiple layers stacked in the height direction of the protrusion P1. Figure 1A shows an example of the former. In the latter case, all layers included in a single protrusion P1 may be made of the same or different materials, or some of all the layers may be made of the same material but different from the rest of all the layers. The material of the protrusion P1 may be one or more of semiconductors, insulators, and metals, or other materials. The material of the end face s1 of the protrusion P1 may be a silicon-containing material such as silicon dioxide, or other materials.

[0025] The surface of pattern PA includes the surface of the protrusion P1 and the inner surface of the recess Q1. The surface of the protrusion P1 includes an end face s1 corresponding to the tip of the protrusion P1 and a side surface s2 extending from the end face s1 to the base of the protrusion P1. The end face s1 of the protrusion P1 corresponds to the tip and top surfaces of the protrusion P1. Multiple end faces s1 of the protrusion P1 are arranged on a single plane. Multiple end faces s1 of the protrusion P1 correspond to part or all of the upper surface of the substrate W. The inner surface of the recess Q1 includes a bottom surface s3 corresponding to the bottom of the recess Q1 and a side surface extending from the bottom surface s3 to the entrance of the recess Q1. The side surface of the recess Q1 may also be the side surface s2 of the protrusion P1, or it may be different from the side surface s2. Figure 1A shows an example of the former. The side surface of the recess Q1 forms the entrance of the recess Q1.

[0026] Next, a substrate processing method according to one embodiment will be described.

[0027] When processing the substrate W shown in Figure 1A, a chemical supply step is performed in which the chemical solution is supplied to the entire surface of the substrate W. When supplying the chemical solution to the substrate W, the chemical solution may be supplied to the upper surface of the substrate W, which corresponds to the surface of the substrate W, while the substrate W is held horizontally, or the substrate W may be immersed in the chemical solution in the immersion tank while the substrate W is held vertically. In the former case, the chemical solution may be supplied to the upper surface of the substrate W while the substrate W is rotated around a vertical axis of rotation passing through the center of the substrate W, or the chemical solution may be supplied to the upper surface of the substrate W without rotating the substrate W. The contents of this paragraph also apply when supplying processing liquids other than chemical solutions to the surface of the substrate W.

[0028] When supplying a chemical solution to the upper surface of a substrate W while rotating the substrate W around a vertical axis of rotation passing through the center of the substrate W, the chemical solution may be discharged toward the upper surface of the substrate W while the treatment solution is discharged toward the lower surface of the substrate W. In this case, the treatment solution discharged toward the lower surface of the substrate W may have the same components, concentration, and temperature as the treatment solution discharged toward the upper surface of the substrate W, or at least one of the components, concentration, and temperature may be different. For example, the chemical solution may be discharged toward the upper surface of the substrate W while the rinse solution described later is discharged toward the lower surface of the substrate W. The contents of this paragraph also apply when supplying a treatment solution other than a chemical solution to the surface of the substrate W.

[0029] As shown in Figure 1B, when the chemical solution is supplied to the substrate W, the chemical solution enters the recess Q1 and fills the recess Q1 with the chemical solution. Therefore, the chemical solution comes into contact not only with the end face s1 of the convex portion P1, but also with the side surface s2 of the recess Q1 (the side surface s2 of the convex portion P1) and the bottom surface s3 of the recess Q1. The chemical solution may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, aqueous hydrogen peroxide, organic acids (e.g., citric acid, oxalic acid, etc.), organic alkalis (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactants, and corrosion inhibitors, or it may be any other liquid.

[0030] After supplying the chemical solution to the substrate W, a rinsing solution supply step is performed in which the rinsing solution is supplied to the entire surface of the substrate W while the chemical solution is in contact with the surface of the substrate W. As shown in Figure 1C, when the rinsing solution is supplied to the surface of the substrate W, the rinsing solution enters the recesses Q1 and fills the recesses Q1 with the rinsing solution. As a result, the chemical solution in contact with the substrate W is washed away by the rinsing solution. The rinsing solution may be any of the following: pure water (deionized water: DIW), carbonated water, electrolyzed ionized water, hydrogen water, ozonated water, hydrochloric acid water at a dilution concentration (e.g., about 1 to 100 ppm), or ammonia water at a dilution concentration (e.g., about 1 to 100 ppm), or any other liquid.

[0031] After supplying the rinse solution to the substrate W, a laminated film F3 (see Figure 2C) containing at least one pair of first adsorption films F1 and second adsorption films F2 is deposited on the surface of the substrate W by the LbL (Layer-by-Layer) method, also known as the alternating lamination method or alternating adsorption method. Before depositing the laminated film F3 on the surface of the substrate W, the aforementioned chemical solution supply step and rinse solution supply step may be performed multiple times. For example, HF (hydrofluoric acid) and DIW (pure water) may be supplied to the surface of the substrate W, and then SC1 (a mixture of ammonia, hydrogen peroxide, and water) and DIW may be supplied to the surface of the substrate W (see Figure 7). Hydrofluoric acid and SC1 are both examples of chemical solutions.

[0032] When depositing a multilayer film F3 on the surface of a substrate W using the LbL method, a first polymer solution supply step is performed in which the first polymer solution containing ions of the first polymer is supplied to the entire surface of the substrate W while the rinse solution is in contact with the surface of the substrate W. As shown in Figure 2A, when the first polymer solution is supplied to the surface of the substrate W, the first polymer solution enters the recesses Q1, and the recesses Q1 are filled with the first polymer solution. As a result, the rinse solution in contact with the substrate W is replaced by the first polymer solution. The first polymer solution is a liquid containing cations p1 of the first polymer (see Figure 2A). Details of the first polymer solution will be described later.

[0033] The rinsing solution is a liquid with a pH (hydrogen ion concentration) of 7 or near 7. When the rinsing solution is in contact with the surface of a solid silicon (Si), the zeta potential of that surface is negative. This is also true when the rinsing solution is in contact with the surface of solid silicon dioxide (SiO2) and silicon nitride (Si3N4). At least a portion of the surface of the substrate W is made of a silicon-containing material. The silicon-containing material may be at least one of silicon, silicon dioxide, and silicon nitride, or it may be other materials. When the rinsing solution is in contact with the surface of the substrate W, the zeta potential of at least a portion of the surface of the substrate W is negative.

[0034] When the first polymer solution is supplied to the surface of the substrate W, it mixes with the rinse solution and diffuses through it. Subsequently, all or almost all of the rinse solution is removed from the substrate W, and the first polymer solution comes into contact with the entire surface of the substrate W. Since at least a portion of the surface of the substrate W is negatively charged, the cations of the first polymer are adsorbed onto at least a portion of the surface of the substrate W by electrostatic interaction. As a result, as shown in Figure 2A, with the recess Q1 filled with the first polymer solution, a first adsorbed film F1 containing the adsorbed first polymer is formed on at least a portion of the surface of the substrate W.

[0035] Note that although Figure 2A depicts a boundary between the first polymer solution and the first adsorption film F1, no such boundary actually exists. In Figure 2A, the ratio of the thickness of the first adsorption film F1 to the width of the protrusion P1 (length in the left-right direction of the paper) is not necessarily the same as the actual ratio. The same applies to the second adsorption film F2, which will be described later. The thickness of the first adsorption film F1 may be equal to or different from the thickness of one molecule of the first polymer. The thickness of the second adsorption film F2 may be equal to or different from the thickness of one molecule of the second polymer, which will be described later.

[0036] After supplying the first polymer solution to the substrate W, a first polymer solution removal step is performed to remove the first polymer solution from the surface of the substrate W while leaving the first adsorption film F1 on the surface of the substrate W. For example, the first polymer solution in contact with the surface of the substrate W may be removed from the surface of the substrate W by replacing it with a replacement liquid such as a rinsing solution. Alternatively, when immersing the substrate W in the first polymer solution in an immersion tank, the first polymer solution may be removed from the surface of the substrate W by moving the substrate W above the liquid level of the first polymer solution in the immersion tank, or by draining all of the first polymer solution from the immersion tank while the substrate W is placed in the immersion tank. The contents of this paragraph also apply to the second polymer solution removal step described later.

[0037] Figure 2B shows an example of replacing the first polymer liquid in contact with the surface of the substrate W by supplying a rinse solution, which is an example of a replacement solution, to the entire surface of the substrate W. As a result, the first polymer liquid in contact with the substrate W is washed away by the rinse solution while the first adsorbent film F1 remains on the surface of the substrate W. The rinse solution supplied to the substrate W in the first polymer liquid removal step may have the same components, concentration, and temperature as the rinse solution supplied to the substrate W in the rinse solution supply step, or at least one of the components, concentration, and temperature may be different.

[0038] After supplying a rinse solution, which is an example of a replacement solution, to the substrate W, a second polymer solution supply step is performed in which the second polymer solution, containing ions of the second polymer, is supplied to the entire surface of the substrate W while the rinse solution is in contact with the surface of the substrate W. As shown in Figure 2C, when the second polymer solution is supplied to the surface of the substrate W, the second polymer solution enters the recess Q1, and the recess Q1 is filled with the second polymer solution. As a result, the rinse solution in contact with the substrate W is replaced by the second polymer solution. The second polymer solution is a liquid containing the anion p2 of the second polymer (see Figure 2C). Details of the second polymer solution will be described later.

[0039] Since the first adsorption film F1 is positively charged, the anions of the second polymer are adsorbed onto the first adsorption film F1. If a portion of the surface of the substrate W is exposed from the first adsorption film F1 and is positively charged, the anions of the second polymer are adsorbed onto the same portion. As a result, with the recess Q1 filled with the second polymer liquid, a second adsorption film F2 containing the second polymer adsorbed on at least one of the first adsorption film F1 and the substrate W is formed on at least a portion of the surface of the substrate W. Note that Figure 2C depicts a boundary between the second polymer liquid and the second adsorption film F2, and a boundary between the first adsorption film F1 and the second adsorption film F2, but in reality, such boundaries do not exist.

[0040] After supplying the second polymer solution to the substrate W, a second polymer solution removal step is performed to remove the second polymer solution from the surface of the substrate W while leaving the first adsorption film F1 and the second adsorption film F2 on the surface of the substrate W. Figure 2D shows an example in which the second polymer solution in contact with the surface of the substrate W is replaced with the rinse solution by supplying a rinse solution, which is an example of a replacement solution, to the entire surface of the substrate W. As a result, the second polymer solution in contact with the substrate W is washed away by the rinse solution while the first adsorption film F1 and the second adsorption film F2 remain on the surface of the substrate W.

[0041] The first polymer solution is a solution in which the first polymer, which corresponds to the solute, is dissolved in a solvent. Preferably, the first polymer and the solvent are compounds that do not contain metal elements. The first polymer is a cationic synthetic polymer electrolyte. The cationic synthetic polymer electrolyte is an organic compound. When the cationic synthetic polymer electrolyte dissolves in the solvent, it separates into cations and anions of the polymer compound. These cations correspond to the cations of the first polymer. The cations of the first polymer may be polycations having multiple cationic groups.

[0042] The cationic synthetic polymer electrolyte may be one or more of polydiallyldimethylammonium chloride (PDDA), polyacrylic acid salts, polyvinyl sulfonic acid, and polyvinyl alcohol, or it may be any other polymer electrolyte.

[0043] The solvent for the first polymer solution may be water such as pure water, alcohol such as glycerin, ethanol, or IPA, or an organic solvent other than alcohol. The solvent may contain water and a liquid (such as IPA) that has a lower surface tension than water and dissolves with the first polymer.

[0044] The second polymer solution is a solution in which the second polymer, which corresponds to the solute, is dissolved in a solvent. Preferably, the second polymer and the solvent are compounds that do not contain metal elements. The second polymer is an anionic synthetic polymer electrolyte. An anionic synthetic polymer electrolyte is an organic compound. When an anionic synthetic polymer electrolyte dissolves in a solvent, it separates into anions and cations of the polymer compound. These anions correspond to the anions of the second polymer. The anions of the second molecular compound may be polyanions having multiple anionic groups.

[0045] The anionic synthetic polymer electrolyte may be one or more of the following: polyvinyl alcohol (PVA), polyvinyl sulfonic acid (PVS), polyallylamine hydrochloride, polyethyleneimine, polydiallyldimethylammonium chloride, quaternary ammonium, or protonated amine, or it may be any other polymer electrolyte.

[0046] The solvent for the second polymer solution may be water such as pure water, alcohol such as glycerin, ethanol, or IPA, or an organic solvent other than alcohol. The solvent may also contain water and a liquid (such as IPA) that has a lower surface tension than water and dissolves with the second polymer.

[0047] The temperature of the first polymer solution before it is supplied to the substrate W may be room temperature (e.g., 20-30°C), or it may be higher or lower than room temperature. The same applies to the temperature of the second polymer solution before it is supplied to the substrate W. The temperature of the first polymer solution or the second polymer solution may be changed to a temperature higher or lower than room temperature by heating or cooling the first polymer solution or the second polymer solution while they are in contact with the substrate W. Raising the temperature of the first polymer solution makes the cations of the first polymer in the first polymer solution more active, making it easier for them to reach the surface of the substrate W. The same applies to the second polymer solution.

[0048] After the first adsorption film F1 and the second adsorption film F2 are formed on the surface of the substrate W, the first polymer liquid supply step, the first polymer liquid removal step, the second polymer liquid supply step, and the second polymer liquid removal step described above are repeated. In other words, after the first first polymer liquid supply step, the first polymer liquid removal step, the second polymer liquid supply step, and the second polymer liquid removal step are performed once or more times, a repeating step is performed in which one LbL (Layer-by-Layer) cycle including the first polymer liquid supply step, the first polymer liquid removal step, the second polymer liquid supply step, and the second polymer liquid removal step is repeated. In Figures 2A to 2D, "repeated" indicates the repetition of the LbL cycle.

[0049] When the first polymer liquid supply process and the second polymer liquid supply process are performed for the first time, a laminated film F3 including the first adsorption film F1 and the second adsorption film F2 is formed on the surface of the substrate W, as described above. When the second polymer liquid supply process is performed for the second time, cations of the first polymer are adsorbed onto the second adsorption film F2, and another first adsorption film F1 is laminated onto the second adsorption film F2. Therefore, three films are laminated on the surface of the substrate W in the order of first adsorption film F1, second adsorption film F2, and first adsorption film F1 from the surface side of the substrate W. When the second polymer liquid supply process is performed for the second time, four films are laminated on the surface of the substrate W in the order of first adsorption film F1, second adsorption film F2, first adsorption film F1, and second adsorption film F2 from the surface side of the substrate W. Therefore, with each LbL cycle described above, the number of first adsorption films F1 and second adsorption films F2 increases, and the thickness of the laminated film F3 increases.

[0050] As shown in Figure 2D, the laminated film F3 includes at least a plurality of side films F5 arranged on the side surfaces s2 of a plurality of protrusions P1. The laminated film F3 may further include at least one of a plurality of end films F4 arranged on the end faces s1 of a plurality of protrusions P1, and a plurality of bottom films F6 arranged on the bottom faces s3 of a plurality of recesses Q1. Figure 2D shows an example in which the laminated film F3 includes a plurality of side films F5, a plurality of end films F4, and a plurality of bottom films F6. The side films F5 extend from the bottom films F6 to the end films F4 along the side surfaces s2 of the protrusions P1.

[0051] Two adjacent side films F5 in the width direction of the protrusion P1 are positioned within the recess Q1. As shown in Figure 2D, the two adjacent side films F5 form a gap G1 within the recess Q1 that is recessed in the height direction of the protrusion P1 toward the bottom of the recess Q1. The two adjacent side films F5 face each other in the width direction of the protrusion P1 with a gap between them. The gap between the two adjacent side films F5 corresponds to the width W1 of the gap G1 (see Figure 2D). The width W1 of the gap G1 may be constant from the entrance to the bottom of the gap G1, or it may vary. As the thickness of the laminated film F3 increases, the width W1 of the gap G1 decreases. The LbL cycle may be repeated until the width W1 of the gap G1 decreases to or less than the thickness T1 of the side films F5 in the width direction of the protrusion P1 (see Figure 2D), or the LbL cycle may be repeated so that the width W1 does not decrease to or less than the thickness T1. Figures 3A and 3D show an example of the former.

[0052] One approach is to fill the recesses Q1 with a polymer film by converting a polymer liquid supplied to the surface of the substrate W into a solid or semi-solid polymer film. Another approach is to fill the recesses Q1 with a solid film by converting a sublimable substance-containing liquid supplied to the surface of the substrate W into a solidified film containing a sublimable substance.

[0053] However, if the viscosity of the polymer liquid or sublimable substance-containing liquid is high, it will be difficult for the polymer liquid or sublimable substance-containing liquid to enter the recess Q1, and the recess Q1 will not be filled with a polymer film or solidified film. If the concentration of the polymer liquid or sublimable substance-containing liquid is reduced, the viscosity of the polymer liquid or sublimable substance-containing liquid will decrease, but the thickness of the polymer film or solidified film may fall below the required thickness. Cavities may form within the polymer film or solidified film, which may cause the pattern PA to collapse.

[0054] The cations of the first polymer in the first polymer solution are large enough to enter the space between two adjacent protrusions P1 (the recess Q1). The same applies to the anions of the second polymer in the second polymer solution. Therefore, each of the cations of the first polymer and the anions of the second polymer enters the recess Q1. This allows a laminated film F3, containing at least one pair of first adsorption films F1 and second adsorption films F2, to be deposited on the inner surface of the recess Q1. The distance between two adjacent protrusions P1 (the width of the recess Q1) may be within the range of 3 to 50 nm, or it may be outside this range.

[0055] Since the cations of the first polymer and the anions of the second polymer each enter the recess Q1, the laminated film F3 can be deposited on the inner surface of the recess Q1 even if the width of the recess Q1 is narrow, that is, even if the pattern PA is fine. Although the first adsorption film F1 and the second adsorption film F2 are each thin, the thickness of the laminated film F3 can be increased by increasing the number of the first and second adsorption films F1 and F2. This allows the recess Q1 to be filled with the laminated film F3. In other words, the volume of the portion of the recess Q1 occupied by the laminated film F3 can be increased. Furthermore, since the first adsorption film F1 or the second adsorption film F2 adheres closely to the substrate W, and the first and second adsorption films F1 and F2 adhere closely to each other, voids are less likely to occur within the laminated film F3.

[0056] After the final second polymer liquid removal step, the substrate W is dried by removing the liquid from the substrate W. Figures 3B and 3E show two examples of cross-sections of the dried substrate W. The method for drying the substrate W may be spin drying, which removes the liquid from the substrate W by rotating the substrate W, or it may be a method other than spin drying, such as vacuum drying, which evaporates the liquid in contact with the substrate W by lowering the air pressure in the containment space containing the substrate W.

[0057] The liquid adhering to the substrate W when drying the substrate W may be a rinse solution such as pure water, or a liquid with a lower surface tension than pure water, such as IPA (isopropyl alcohol). In the latter case, the pure water adhering to the substrate W can be replaced with IPA before drying the substrate W. From the start of supplying the treatment solution to the surface of the substrate W until the start of drying the substrate W, the end face s1 of the protrusion P1 may be kept from being exposed to the treatment solution, or it may be temporarily exposed to the treatment solution.

[0058] Before drying the substrate W, the entrance to the gap G1 between two adjacent side films F5 in the width direction of the protrusion P1 may or may not be blocked by at least one of the first polymer and the second polymer. In other words, the two adjacent side films F5 may be separated from each other at any position, or they may be connected to each other via at least one of the first polymer and the second polymer at a position away from the bottom of the recess Q1.

[0059] Figure 3A shows an example where the second adsorption membrane F2 enters the interior of gap G1 from the entrance, and a portion of gap G1, including the entrance, is filled with the second adsorption membrane F2. Figure 3D shows an example where two side membranes F5 within a single recess Q1 are separated from each other at any position. In the example shown in Figure 3A, a portion of gap G1, including the entrance, is filled with the second polymer, and the rest of gap G1 is filled with liquid. In the example shown in Figure 3A, the entrance to gap G1 is closed by the second adsorption membrane F2, which acts as a lid.

[0060] When the multilayer film F3 is deposited on the surface of the substrate W, the protrusions P1 are reinforced by the multilayer film F3. Furthermore, the electrical polarity of the surfaces of the two side films F5 within a single recess Q1 is the same. As the distance between two adjacent side films F5 decreases, the repulsive force pushing the two adjacent side films F5 away from each other increases. Therefore, by forming a multilayer film F3 containing multiple pairs of first adsorption films F1 and second adsorption films F2 on the surface of the substrate W, the collapse of the pattern PA (collapse of the protrusions P1) can be reduced.

[0061] In particular, as shown in Figure 3B, if the entrance to the gap G1 formed in the recess Q1 by the laminated film F3 is blocked by at least one of the first and second polymers, the inclination of the protrusions P1 can be maintained at zero or nearly zero even after the substrate W is dried. If the entrance to the gap G1 is not blocked, as shown in Figure 3E, even if the protrusions P1 tilt when the substrate W is dried, the inclination of the protrusions P1 can be reduced compared to when there is no laminated film F3. Figure 3E shows an example where the protrusions P1 tilt when the substrate W is dried, and two regions within the laminated film F3 touch each other at the tips of two adjacent protrusions P1. Even if the protrusions P1 tilt when the substrate W is dried, the laminated film F3 may be separated from each other at the tips of two adjacent protrusions P1.

[0062] After drying the substrate W, the laminated film F3 may be removed from the substrate W, or the next processing may be performed on the substrate W without removing the laminated film F3. In the former case, an ashing process may be performed to remove the laminated film F3 from the substrate W by ashing, which decomposes the solid or semi-solid laminated film F3 into a gas. Figures 3C and 3F show two examples of cross-sections of the substrate W after the ashing process. The ashing may be plasma ashing, which decomposes the laminated film F3 into a gas using oxygen plasma, or ozone ashing, which decomposes the laminated film F3 into a gas using ozone gas, or any other type of ashing. In any case, when ashing is performed, the laminated film F3 changes into a gas such as carbon dioxide or water vapor and is removed from the substrate W.

[0063] When a series of processes from the chemical supply process to the drying process are performed in one substrate processing apparatus 1 (see Figure 4A), the ashing process may be performed in the same substrate processing apparatus 1 or in a different substrate processing apparatus 1. In the former case, that is, when a series of processes from the chemical supply process to the ashing process are performed in one substrate processing apparatus 1, the ashing process may be performed in a chamber 4 (see Figure 5) in which one or more processes other than the ashing process are performed, or in a different chamber 41 (see Figure 6).

[0064] As shown in Figures 3C and 3F, when the laminated film F3 is removed from the substrate W by ashing, the surface of the pattern PA, that is, the end face s1 of the protrusions P1, the side surface s2 of the protrusions P1, and the bottom surface s3 of the recesses Q1 are exposed and come into contact with the atmosphere in the space in which the substrate W is placed. Therefore, the laminated film F3 can be removed from the substrate W without creating a surface of liquid (a gas-liquid interface) in the recesses Q1 that spans the side surfaces s2 of two adjacent protrusions P1. As shown in Figures 3E and 3F, even if the protrusions P1 tilt when the substrate W is dried, the tilt of the protrusions P1 is small, so when the laminated film F3 is removed, the protrusions P1 return to a state perpendicular to the base layer s4 by the restorative force of the protrusions P1 themselves.

[0065] Next, we will describe the substrate processing apparatus 1 that performs the aforementioned processing on the substrate W.

[0066] Figure 4A is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment. Figure 4B is a schematic side view of the substrate processing apparatus 1.

[0067] The substrate processing apparatus 1 is a single-wafer type apparatus that processes disc-shaped substrates W, such as semiconductor wafers, one at a time. The substrate processing apparatus 1 comprises a load port LP that holds carriers CA that contain substrates W, a plurality of processing chambers 2 that process the substrates W transported from the carriers CA on the load port LP with processing fluids such as processing liquid and processing gas, a transport system TS that transports the substrates W between the carriers CA on the load port LP and the plurality of processing chambers 2, and a control unit 3 that controls the substrate processing apparatus 1.

[0068] Multiple processing chambers 2 form multiple towers TW. Figure 4A shows an example where four towers TW are formed. As shown in Figure 4B, the multiple processing chambers 2 contained in one tower TW are stacked vertically. As shown in Figure 4A, the multiple towers TW form two rows extending in the depth direction of the substrate processing apparatus 1 in a plan view. In a plan view, the two rows face each other via a transport path TP.

[0069] The multiple processing chambers 2 may include a wet processing chamber 2w (see Figure 5) that performs a series of processes from the chemical supply process to the drying process and a dry processing chamber 2d (see Figure 6) that performs the ashing process, or they may include a multi-processing chamber that performs a series of processes from the chemical supply process to the ashing process. Figures 5 and 6, described later, show examples of the former. Specifically, Figure 5 shows an example of a wet processing chamber 2w, and Figure 6 shows an example of a dry processing chamber 2d.

[0070] The transport system TS includes an indexer robot IR that loads and unloads substrates W to and from a carrier CA on a load port LP, and a center robot CR that loads and unloads substrates W to and from multiple processing chambers 2. The center robot CR is located on the transport path TP. The indexer robot IR is located between the load port LP and the center robot CR in a plan view. The indexer robot IR passes the substrates W to the center robot CR and receives the substrates W from the center robot CR. The center robot CR does the same.

[0071] The indexer robot IR includes one or more hands Hi that horizontally support the substrate W. The hands Hi are movable parallel to both the horizontal and vertical directions. The hands Hi are rotatable around a vertical line. The hands Hi can load and unload the substrate W to and from the carrier CA on any load port LP, and can transfer the substrate W to and from the center robot CR.

[0072] The central robot CR includes one or more hands Hc that horizontally support the substrate W. The hands Hc are movable parallel to both the horizontal and vertical directions. The hands Hc are rotatable around a vertical line. The hands Hc can transfer the substrate W to and from the indexer robot IR, and can load and unload the substrate W into and out of any processing chamber 2.

[0073] The control unit 3 controls the electrical and electronic equipment provided in the substrate processing apparatus 1. The control unit 3 includes at least one computer capable of communicating with each other. The computer has one or more processors or circuits and may include a plurality of separate computers or a network of a plurality of separate processors or circuits to read and execute computer executable instructions. The computer includes a memory 3b for storing information such as programs, and a processor that controls the substrate processing apparatus 1 according to the programs stored in the memory 3b. The processor is, for example, a CPU 3a (central processing unit). The control unit 3 performs the aforementioned processing of the substrate W by controlling the substrate processing apparatus 1. In other words, the control unit 3 is programmed to perform the aforementioned processing of the substrate W.

[0074] The program may be supplied to a system or device via a network or storage medium, and one or more processors in the computer of that system or device may read and execute the program to perform the processing on the aforementioned board W. It can also be implemented by a circuit (e.g., an ASIC) that implements one or more functions. Furthermore, the present invention may be constructed by appropriately combining elements of the embodiments described above.

[0075] Next, we will describe the wet processing chamber 2w.

[0076] Figure 5 is a schematic diagram of the inside of the wet processing chamber 2w viewed horizontally. As shown in Figure 5, the wet processing chamber 2w includes a chamber 4 for housing the substrate W and a spin chuck 10 that holds one substrate W horizontally within the chamber 4 and rotates it around a vertical rotation axis A1 passing through the center of the substrate W.

[0077] Chamber 4 includes a box-shaped partition wall 5 with a passage 5b through which the substrate W passes, and a door 6 that opens and closes the passage 5b. The FFU 7 (Fan Filter Unit 7) is positioned above an air outlet 5a located at the top of the partition wall 5. The FFU 7 constantly supplies clean air (air filtered by the filter) into Chamber 4 from the air outlet 5a. The gas inside Chamber 4 is discharged from Chamber 4 through an exhaust duct 8 connected to the bottom of a processing cup 21, which will be described later. This constantly creates a downflow of clean air inside Chamber 4. The flow rate of the exhaust discharged into the exhaust duct 8 is changed according to the opening degree of the exhaust valve 9 located inside the exhaust duct 8.

[0078] The spin chuck 10 includes a horizontally held disc-shaped spin base 12, a plurality of chuck pins 11 that horizontally hold the substrate W above the spin base 12, and a spin motor 13 that rotates the spin base 12 and the plurality of chuck pins 11 around a rotation axis A1. The spin chuck 10 is not limited to a mechanical chuck in which the plurality of chuck pins 11 contact the end face of the substrate W, but may also be a vacuum chuck that horizontally holds the substrate W by adsorbing the back surface (bottom surface) of the substrate W, which is a non-device forming surface, to the upper surface 12u of the spin base 12. When the spin chuck 10 is a mechanical chuck, the plurality of chuck pins 11 correspond to a substrate holder. When the spin chuck 10 is a vacuum chuck, the spin base 12 corresponds to a substrate holder.

[0079] The wet processing chamber 2w includes a cylindrical processing cup 21 for receiving processing liquid splashed from the substrate W. The processing cup 21 includes a plurality of guards 24 for receiving processing liquid discharged outward from the substrate W held by the spin chuck 10, a plurality of cups 23 for receiving processing liquid guided downward by the plurality of guards 24, and a cylindrical outer wall 22 surrounding the plurality of guards 24 and the plurality of cups 23. Figure 5 shows an example in which four guards 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third guard 24 from the top.

[0080] The guard 24 includes a cylindrical portion 25 surrounding the spin chuck 10 and an annular ceiling portion 26 extending diagonally upward toward the rotation axis A1 from the upper end of the cylindrical portion 25. Multiple ceiling portions 26 are stacked vertically, and multiple cylindrical portions 25 are arranged concentrically. The annular upper end of the ceiling portion 26 corresponds to the upper end 24u of the guard 24 surrounding the substrate W and spin base 12 in a plan view. Multiple cups 23 are each located below the multiple cylindrical portions 25. The cups 23 form annular grooves that receive the processing liquid guided downward by the guard 24.

[0081] The wet processing chamber 2w includes a lifting actuator 27 that individually raises and lowers multiple guards 24. The lifting actuator 27 can hold the guards 24 stationary at any position within the range from the upper position to the lower position. Figure 5 shows a state where two guards 24 are positioned in the upper position and the remaining two guards 24 are positioned in the lower position. The upper position is a position where the upper end 24u of the guard 24 is positioned above the holding position where the substrate W held by the spin chuck 10 is placed. The lower position is a position where the upper end 24u of the guard 24 is positioned below the holding position.

[0082] An actuator is a device that converts driving energy, represented by electricity, fluid, magnetic, thermal, or chemical energy, into mechanical work, i.e., the motion of a tangible object. Actuators include electric motors (rotary motors), linear motors, air cylinders, and other devices. When the motion of the actuator differs from the motion of the object, a motion converter may be provided to convert the actuator's motion into linear motion or rotation. For example, if the actuator is an electric motor and the object is to move in a linear motion, a motion converter such as a ball screw and ball nut may be used to convert the rotation of the electric motor into linear motion.

[0083] The wet processing chamber 2w includes a plurality of nozzles that discharge processing fluids such as processing liquid and processing gas toward the substrate W held by the spin chuck 10. The plurality of nozzles include a first chemical nozzle 31a, a first rinse nozzle 31b, a second chemical nozzle 31c, a second rinse nozzle 31d, a first polymer liquid nozzle 31e, and the like.

[0084] The first chemical nozzle 31a and the second chemical nozzle 31c are nozzles that discharge the chemical solution toward the upper surface of the substrate W. The first rinse solution nozzle 31b, the second rinse solution nozzle 31d, and the third rinse solution nozzle 31g are nozzles that discharge the rinse solution toward the upper surface of the substrate W. The first polymer solution nozzle 31e is a nozzle that discharges the first polymer solution toward the upper surface of the substrate W. The second polymer solution nozzle 31f is a nozzle that discharges the second polymer solution toward the upper surface of the substrate W. Figure 5 shows an example where the first chemical solution is HF (hydrofluoric acid), the second chemical solution is SC1, and the rinse solution is DIW (pure water).

[0085] The first chemical nozzle 31a may be a scanning nozzle that moves the collision position of the chemical with respect to the substrate W within the upper surface of the substrate W, or it may be a fixed nozzle that cannot move the collision position of the chemical with respect to the substrate W. The same applies to the other nozzles. Figure 5 shows an example in which the first chemical nozzle 31a, the first rinse nozzle 31b, the second chemical nozzle 31c, the second rinse nozzle 31d, the first polymer nozzle 31e, etc., are scanning nozzles.

[0086] The first chemical nozzle 31a and the first rinse nozzle 31b are connected to a first nozzle actuator 35a that moves the first chemical nozzle 31a and the first rinse nozzle 31b in at least one of the vertical and horizontal directions. The first chemical nozzle 31a and the first rinse nozzle 31b extend downward from a first nozzle arm 34a that extends horizontally within the chamber 4. The first nozzle actuator 35a moves the first chemical nozzle 31a and the first rinse nozzle 31b by moving the first nozzle arm 34a.

[0087] The second chemical nozzle 31c and the second rinse nozzle 31d are connected to a second nozzle actuator 35b that moves the second chemical nozzle 31c and the second rinse nozzle 31d in at least one of the vertical and horizontal directions. The second chemical nozzle 31c and the second rinse nozzle 31d extend downward from a second nozzle arm 34b that extends horizontally within the chamber 4. The second nozzle actuator 35b moves the second chemical nozzle 31c and the second rinse nozzle 31d by moving the second nozzle arm 34b.

[0088] The first polymer liquid nozzle 31e, the second polymer liquid nozzle 31f, and the third rinse liquid nozzle 31g (also referred to as "first polymer liquid nozzle 31e, etc.") are connected to a third nozzle actuator 35c that moves the first polymer liquid nozzle 31e, etc. in at least one of the vertical and horizontal directions. The first polymer liquid nozzle 31e, etc. extends downward from a third nozzle arm 34c that extends horizontally within the chamber 4. The third nozzle actuator 35c moves the first polymer liquid nozzle 31e, etc. by moving the third nozzle arm 34c.

[0089] The first nozzle actuator 35a moves the first chemical nozzle 31a and the first rinse nozzle 31b horizontally between a processing position in which the processing liquid discharged from the first chemical nozzle 31a or the first rinse nozzle 31b is supplied to the upper surface of the substrate W, and a standby position in which the first chemical nozzle 31a and the first rinse nozzle 31b are positioned around the processing cup 21 in a plan view. The same applies to the second nozzle actuator 35b and the third nozzle actuator 35c. Figure 5 shows the state in which the first polymer liquid nozzle 31e, etc., are positioned in the processing position.

[0090] The first chemical nozzle 31a is connected to the first chemical pipe 32a that guides the first chemical. When the first chemical valve 33a attached to the first chemical pipe 32a is opened, the discharge port of the first chemical nozzle 31a continuously discharges the first chemical downwards. Similarly, the second chemical nozzle 31c is connected to the second chemical pipe 32c that guides the second chemical. When the second chemical valve 33c attached to the second chemical pipe 32c is opened, the discharge port of the second chemical nozzle 31c continuously discharges the second chemical downwards.

[0091] Although not shown in the diagram, the first chemical solution valve 33a includes a valve body provided with an annular valve seat through which the chemical solution passes, a valve element movable relative to the valve seat, and an actuator that moves the valve element between a closed position where the valve element is in contact with the valve seat and an open position where the valve element is away from the valve seat. The same applies to the other valves. The actuator may be a pneumatic actuator or an electric actuator, or any other type of actuator. The control unit 3 opens and closes the first chemical solution valve 33a, etc., by controlling the actuator.

[0092] The first rinse liquid nozzle 31b is connected to the first rinse liquid piping 32b that guides the first rinse liquid. When the first rinse liquid valve 33b attached to the first rinse liquid piping 32b is opened, the discharge port of the first rinse liquid nozzle 31b continuously discharges the first rinse liquid downwards. Similarly, the second rinse liquid nozzle 31d is connected to the second rinse liquid piping 32d that guides the second rinse liquid. When the second rinse liquid valve 33d attached to the second rinse liquid piping 32d is opened, the discharge port of the second rinse liquid nozzle 31d continuously discharges the second rinse liquid downwards.

[0093] The first polymer liquid nozzle 31e is connected to the first polymer liquid piping 32e that guides the first polymer liquid. When the first polymer liquid valve 33e attached to the first polymer liquid piping 32e is opened, the outlet of the first polymer liquid nozzle 31e continuously discharges the first polymer liquid downwards. Similarly, the second polymer liquid nozzle 31f is connected to the second polymer liquid piping 32f that guides the second polymer liquid. When the second polymer liquid valve 33f attached to the second polymer liquid piping 32f is opened, the outlet of the second polymer liquid nozzle 31f continuously discharges the second polymer liquid downwards. The third rinse liquid nozzle 31g is connected to the rinse liquid piping 32g that guides the rinse liquid. When the rinse liquid valve 33g attached to the rinse liquid piping 32g is opened, the outlet of the third rinse liquid nozzle 31g continuously discharges the rinse liquid downwards.

[0094] The multiple nozzles include a first chemical nozzle 31a, etc., as well as a bottom nozzle 31h that discharges the processing liquid toward the center of the lower surface of the substrate W. The bottom nozzle 31h includes a disc portion positioned between the upper surface 12u of the spin base 12 and the lower surface of the substrate W, and a cylindrical portion extending downward from the disc portion. The discharge port of the bottom nozzle 31h opens at the center of the upper surface of the disc portion. When the substrate W is held in the spin chuck 10, the discharge port of the bottom nozzle 31h faces the center of the lower surface of the substrate W in an upward and downward direction.

[0095] The lower nozzle 31h is connected to a rinse fluid pipe 32h that guides the rinse fluid. Figure 5 shows an example where the rinse fluid is pure water. When the rinse fluid valve 33h attached to the rinse fluid pipe 32h is opened, the rinse fluid is continuously discharged upward from the outlet of the lower nozzle 31h. The temperature of the rinse fluid discharged from the lower nozzle 31h may be room temperature, or it may be higher or lower than room temperature.

[0096] The outer circumferential surface of the lower nozzle 31h and the inner circumferential surface of the spin base 12 form a cylindrical gas flow path extending vertically. The gas flow path includes a central opening 31i that opens in the center of the upper surface 12u of the spin base 12. The gas flow path is connected to an inert gas pipe 32i that guides an inert gas. When an inert gas valve 33i attached to the inert gas pipe 32i is opened, the inert gas is continuously discharged upward from the central opening 31i of the spin base 12.

[0097] When the substrate W is held in the spin chuck 10, the central opening 31i of the spin base 12 discharges inert gas, causing the inert gas to flow radially in all directions between the lower surface of the substrate W and the upper surface 12u of the spin base 12. This fills the space between the substrate W and the spin base 12 with inert gas. The inert gas discharged from the central opening 31i of the spin base 12 is nitrogen gas. The inert gas may be a gas other than nitrogen gas, such as helium gas or argon gas. The temperature of the inert gas discharged from the central opening 31i of the spin base 12 may be room temperature, or it may be higher or lower than room temperature.

[0098] Next, we will describe the dry processing chamber 2d.

[0099] Figure 6 is a schematic diagram of the inside of the dry processing chamber 2d viewed horizontally. The dry processing chamber 2d includes a chamber 41 that forms the internal space of the dry processing chamber 2d, a door 43 that opens and closes a passage 42 formed in the chamber 41, an oxidation unit 44o that supplies a processing gas such as ozone gas to the substrate W while heating the substrate W inside the chamber 41, a cooling unit 44c that cools the substrate W heated by the oxidation unit 44o inside the chamber 41, and a local transport robot 45 that transports the substrate W inside the chamber 41.

[0100] The cooling unit 44c and the oxidation unit 44o are located inside the chamber 41. The cooling unit 44c is closer to the passage 42 than the oxidation unit 44o. The central robot CR (see Figure 4A) moves the substrate W into and out of the chamber 41 through the passage 42. The local transport robot 45 receives the substrate W from the central robot CR and passes the substrate W back to the central robot CR. The local transport robot 45 then transports the substrate W between the cooling unit 44c and the oxidation unit 44o.

[0101] The cooling unit 44c includes a cooling plate 46 for cooling the substrate W, a lift pin 47 that moves up and down through the cooling plate 46, and a pin lifting actuator 48 that moves the lift pin 47 up and down. The cooling plate 46 has a cooling surface 46a on which the substrate W is placed. Inside the cooling plate 46, a refrigerant path (not shown) is formed through which a refrigerant (typically cooling water) circulates. The lift pin 47 moves up and down between an upper position that supports the substrate W above the cooling surface 46a and a lower position where the tip of the lift pin 47 is located below the cooling surface 46a.

[0102] The oxidation unit 44o includes a hot plate 49 for heating the substrate W, an inner chamber 50 housing the hot plate 49, a lift pin 54 that moves up and down through the hot plate 49, and a pin lifting actuator 55 for moving the lift pin 54 up and down. The hot plate 49 has a heating surface 49a on which the substrate W is placed. A heating element 49b that generates heat when power is supplied is built into the hot plate 49. When the substrate W is placed on the heating surface 49a, the substrate W is surrounded by the outer periphery of the heating surface 49a in a plan view.

[0103] The inner chamber 50 forms the containment space SP1. The inner chamber 50 comprises a fixed housing 52 fixed to the chamber 41 and a hood 51 that moves up and down above the fixed housing 52. The hot plate 49 is positioned between the hood 51 and the fixed housing 52. The hood 51 includes a disc-shaped plate portion 51p held horizontally above the hot plate 49 and a cylindrical portion 51t extending downward from the outer circumference of the plate portion 51p. The lower end of the cylindrical portion 51t is perpendicular to the upper end of the fixed housing 52.

[0104] The oxidation unit 44o is equipped with a hood lifting actuator 53 that raises and lowers the hood 51. The fixed housing 52 has an opening 52a that opens upward, and the hood 51 opens and closes this opening 52a. The hood 51 moves up and down between a closed position (lower position) in which a sealed containment space SP1 is formed between the hood 51 and the fixed housing 52, and an open position (upper position) in which the lower end of the cylindrical portion 51t is located above the upper end of the fixed housing 52. Figure 6 shows the state in which the hood 51 is in the upper position. The lift pin 54 moves up and down between an upper position in which it supports the substrate W above the heating surface 49a, and a lower position in which the tip of the lift pin 54 is located below the heating surface 49a.

[0105] The oxidation unit 44o includes a gas supply port 56a for supplying ozone gas to the containment space SP1. Figure 6 shows an example in which the gas supply port 56a is opened on the lower surface of the plate portion 51p of the hood 51. The oxidation unit 44o further includes an ozone gas generator 59a that generates ozone gas to be supplied to the gas supply port 56a, an ozone gas piping 57a that guides the ozone gas generated by the ozone gas generator 59a toward the gas supply port 56a, and an ozone gas valve 58a that opens and closes between an open state in which ozone gas flows from the ozone gas piping 57a to the gas supply port 56a and a closed state in which ozone gas does not flow from the ozone gas piping 57a to the gas supply port 56a.

[0106] The oxidation unit 44o further includes an exhaust port 60a for discharging gas from the containment space SP1, and an exhaust pipe 60b for guiding the gas flowing into the exhaust port 60a away from the containment space SP1. When the ozone gas valve 58a is opened, ozone gas flows out from the gas supply port 56a and is supplied to the containment space SP1. If the supply of ozone gas continues, the containment space SP1 is filled with ozone gas. The supply of ozone gas to the containment space SP1 may be carried out while discharging the gas in the containment space SP1 to the exhaust port 60a, or after discharging the gas in the containment space SP1 to the exhaust port 60a.

[0107] The oxidation unit 44o includes an inert gas pipe 57b that guides nitrogen gas, which is an example of an inert gas to be supplied to the containment space SP1, and an inert gas valve 58b that opens and closes between an open state in which nitrogen gas flows from the inert gas pipe 57b to the containment space SP1 and a closed state in which nitrogen gas does not flow from the inert gas pipe 57b to the containment space SP1. Figure 6 shows an example in which nitrogen gas in the inert gas pipe 57b is supplied to the containment space SP1 via a gas supply port 56a. The nitrogen gas in the inert gas pipe 57b may also be supplied to the containment space SP1 via a supply port other than the gas supply port 56a.

[0108] The local transport robot 45 is equipped with a hand 45h for transporting the substrate W between the cooling unit 44c and the oxidation unit 44o. The hand 45h is configured to be able to transfer the substrate W to and from the lift pin 47 of the cooling unit 44c, and to transfer the substrate W to and from the lift pin 54 of the oxidation unit 44o. As a result, the hand 45h can operate to receive the substrate W from the lift pin 47 of the cooling unit 44c and transfer the substrate W to the lift pin 54 of the oxidation unit 44o. Furthermore, the hand 45h can operate to receive the substrate W from the lift pin 54 of the oxidation unit 44o and transfer the substrate W to the lift pin 47 of the cooling unit 44c.

[0109] When performing the ashing process, the door 43 is positioned in the open position, opening the passage opening 42. In this state, the hand Hc of the center robot CR (see Figure 4A) enters the chamber 41 and places the substrate W above the cooling plate 46. Then, the lift pin 47 rises to the upper position and receives the substrate W from the hand Hc of the center robot CR. After that, the hand Hc of the center robot CR retracts out of the chamber 41.

[0110] Next, the hand 45h of the local transport robot 45 receives the substrate W from the lift pin 47 and transports the substrate W to the lift pin 54 of the oxidation unit 44o. At this time, the hood 51 is in the open position (upper position), and the lift pin 54 supports the received substrate W in the upper position. After the hand 45h retracts from the inner chamber 50, the lift pin 54 descends to the lower position and places the substrate W on the heating surface 49a. Meanwhile, the hood 51 descends to the closed position (lower position), forming a sealed containment space SP1 that encloses the hot plate 49. In this state, the ashing process is performed on the substrate W.

[0111] In the ashing process, ozone gas flowing out from the gas supply port 56a is supplied to the substrate W on the hot plate 49, while the hot plate 49 heats the substrate W. Specifically, when the lift pin 54 receives the substrate W from the hand 45h of the local transport robot 45 and places it on the heating surface 49a of the hot plate 49, heating of the substrate W by the hot plate 49 begins. After the hood 51 is set to the closed position (lower position), ozone gas is supplied from the gas supply port 56a to the containment space SP1, that is, the internal space of the inner chamber 50, and the gas in the containment space SP1 is discharged through the exhaust port 60a. As a result, the containment space SP1 is filled with ozone gas and supplied to the substrate W on the hot plate 49. After the ashing process, the gas in the containment space SP1, such as ozone gas, is discharged through the exhaust port 60a, and the containment space SP1 is filled with gases other than ozone gas, such as inert gas.

[0112] After the ashing process is complete, the hood 51 rises to the open position (upper position), opening the inner chamber 50. Furthermore, the lift pin 54 rises to the upper position, pushing the substrate W upwards above the heating surface 49a. In this state, the hand 45h of the local transport robot 45 receives the substrate W from the lift pin 54 and transports it to the lift pin 47 of the cooling unit 44c. The lift pin 47 supports the received substrate W in the upper position. After waiting for the hand 45h to retract, the lift pin 47 descends to the lower position, thereby placing the substrate W on the cooling surface 46a of the cooling plate 46. As a result, the substrate W is cooled.

[0113] Once the substrate W has finished cooling, the lift pin 47 rises to its upper position, thereby pushing the substrate W upwards onto the cooling surface 46a. In this state, the door 43 opens, and the hand Hc of the center robot CR enters the chamber 41 and is positioned below the substrate W, which is supported by the lift pin 47 in its upper position. In this state, the lift pin 47 descends, and the substrate W is handed to the hand Hc of the center robot CR. The hand Hc, holding the substrate W, retracts out of the chamber 41, and then the door 43 closes the passage opening 42.

[0114] Next, an example of the processing of the substrate W performed by the substrate processing apparatus 1 will be described.

[0115] Figure 7 is a schematic diagram illustrating the same example. Figures 5 to 7 will be referenced below. When processing the substrate W with the substrate processing apparatus 1, the substrate W is loaded into the wet processing chamber 2w and held in the spin chuck 10. Then, while the substrate W is held in the spin chuck 10, the spin motor 13 rotates the substrate W.

[0116] Next, as shown in the upper part of Figure 7, while rotating the substrate W, HF (hydrofluoric acid), DIW (pure water), SC1, and DIW are sequentially supplied to the upper surface of the substrate W. Specifically, hydrofluoric acid, DIW, SC1, and DIW are sequentially discharged from the first chemical nozzle 31a, the first rinse nozzle 31b, the second chemical nozzle 31c, and the second rinse nozzle 31d. Figure 7 shows an example in which these processing liquids are supplied to the upper surface of the substrate W while DIW is supplied to the lower surface of the substrate W. The DIW supplied to the lower surface of the substrate W is the DIW discharged from the lower nozzle 31h. The supply of DIW discharged from the lower nozzle 31h to the lower surface of the substrate W is the same in subsequent steps.

[0117] Next, as shown in the middle section of Figure 7, the first polymer liquid is supplied to the upper surface of the substrate W covered with DIW. Subsequently, DIW, the second polymer liquid, and DIW are supplied sequentially to the upper surface of the substrate W. Specifically, the first polymer liquid and DIW are sequentially discharged from the first polymer liquid nozzle 31e and the third rinse liquid nozzle 31g, and then the second polymer liquid and DIW are sequentially discharged from the second polymer liquid nozzle 31f and the third rinse liquid nozzle 31g. Figure 7 shows an example of supplying DIW to the lower surface of the substrate W while supplying DIW to the upper surface of the substrate W.

[0118] When supplying the first polymer liquid to the upper surface of the substrate W while rotating the substrate W, a paddle process may or may not be performed to stagnate the first polymer liquid on the upper surface of the substrate W while maintaining a state in which the entire upper surface of the substrate W is covered with a liquid film of the first polymer liquid. The same applies when supplying the second polymer liquid to the upper surface of the substrate W.

[0119] When forming a puddle of the first polymer liquid on the upper surface of the substrate W by performing a puddling process, the rotation speed of the substrate W may be reduced from the displacement speed to the puddling speed (for example, a speed greater than 0 and less than or equal to 30 rpm) while discharging the first polymer liquid toward the upper surface of the substrate W. Subsequently, when the entire upper surface of the substrate W is covered with a liquid film of the first polymer liquid, the discharge of the first polymer liquid toward the upper surface of the substrate W may be stopped while maintaining the rotation speed of the substrate W at the puddling speed.

[0120] The time for maintaining the rotation speed of the substrate W at the paddle speed may be equal to or different from the time for decreasing the rotation speed of the substrate W from the displacement speed to the paddle speed. Maintaining the rotation speed of the substrate W at the paddle speed reduces the amount of the first polymer liquid discharged from the upper surface of the substrate W to zero or nearly zero, and the thickness of the liquid film of the first polymer liquid on the substrate W stabilizes at a value corresponding to the paddle speed. As a result, the first polymer liquid stagnates on the upper surface of the substrate W, allowing for more reliable adsorption of cations of the first polymer in the first polymer liquid onto the surface of the substrate W.

[0121] When DIW is supplied to the upper surface of a substrate W covered with a liquid film of the first polymer liquid, the first polymer liquid on the substrate W is replaced by the DIW, and the first polymer liquid is removed from the upper surface of the substrate W. The same occurs when DIW is supplied to the upper surface of a substrate W covered with a liquid film of the second polymer liquid. After sequentially supplying the first polymer liquid, DIW, second polymer liquid, and DIW to the upper surface of the substrate W, the process is repeated sequentially, supplying the first polymer liquid, DIW, second polymer liquid, and DIW to the upper surface of the substrate W again. In other words, one LbL cycle, which includes supplying the first polymer liquid, removing the first polymer liquid, supplying the second polymer liquid, and removing the second polymer liquid, is performed multiple times. The "repeat" in Figure 7 represents the repetition of the LbL cycle.

[0122] After repeating the LbL cycle, that is, after the final supply of DIW, the substrate W is dried by rotating it, as shown in the lower part of Figure 7. Then, the laminated film F3 (see Figure 3A) is removed from the substrate W by ashing. Specifically, the substrate W is removed from the wet processing chamber 2w and transferred to the dry processing chamber 2d. Then, ozone gas is supplied to the top surface of the substrate W. After that, the substrate W is removed from the dry processing chamber 2d.

[0123] Next, the effects of this embodiment will be described.

[0124] In this embodiment, by supplying a rinse solution to the surface of the substrate W, the zeta potential of the surface of the substrate W is changed to a value other than 0, corresponding to the pH (hydrogen ion concentration) of the rinse solution. Then, while the rinse solution is in contact with the surface of the substrate W, the first polymer solution is supplied to the surface of the substrate W. The first polymer solution contains ions of the first polymer that are electrically charged with a polarity opposite to that of the surface of the substrate W in contact with the rinse solution. The ions of the first polymer are adsorbed onto the surface of the substrate W. As a result, a first adsorption film F1 containing the first polymer adsorbed onto the surface of the substrate W is formed on the surface of the substrate W.

[0125] After forming the first adsorption film F1 on the surface of the substrate W, the first polymer liquid is removed from the surface of the substrate W while leaving the first adsorption film F1 on the substrate W. Then, the second polymer liquid is supplied to the surface of the substrate W. The second polymer liquid contains ions of the second polymer that are electrically charged with the opposite polarity to the ions of the first polymer. The ions of the second polymer are adsorbed onto the first adsorption film F1. As a result, a second adsorption film F2 containing the second polymer adsorbed on the first adsorption film F1 is formed on the surface of the substrate W.

[0126] In this way, the rinsing solution is in contact with the surface of the substrate W, and the first polymer solution is supplied to the surface of the substrate W while the substrate W surface is positively or negatively charged. This ensures that ions of the first polymer are reliably adsorbed onto the surface of the substrate W. Furthermore, since ions of polymers such as the first polymer and the second polymer are adsorbed onto the surface of the substrate W, the number of ions that need to be adsorbed onto the surface of the substrate W can be reduced compared to the case where ions of compounds other than polymers are adsorbed onto the surface of the substrate W, and the time required for ion adsorption can be shortened.

[0127] In this embodiment, ions of the first polymer are adsorbed onto the side surface s2 of the protrusions P1 of the pattern PA. This forms a first adsorption film F1 on the side surface s2 of the protrusions P1. Subsequently, ions of the second polymer are adsorbed onto the first adsorption film F1. This forms a second adsorption film F2 on the side surface s2 of the protrusions P1 via the first adsorption film F1. Since the first adsorption film F1 is positively or negatively charged, if two adjacent side surfaces s2 of protrusions P1 in the width direction of the protrusions P1 are covered by the first adsorption film F1, an electrical repulsive force is applied to the two side surfaces s2 of the protrusions P1. The same applies if two adjacent side surfaces s2 of protrusions P1 are covered by the second adsorption film F2. Therefore, collapse of the pattern PA (collapse of the protrusions P1) can be reduced.

[0128] In this embodiment, the second polymer liquid is removed from the surface of the substrate W while leaving the first adsorption film F1 and the second adsorption film F2 on the surface of the substrate W, and then the first polymer liquid is supplied to the surface of the substrate W. As a result, ions of the first polymer are adsorbed onto the second adsorption film F2, and a second first adsorption film F1 is formed on the surface of the substrate W. Subsequently, the first polymer liquid is removed from the surface of the substrate W while leaving three adsorption films (two first adsorption films F1 and one second adsorption film F2) on the surface of the substrate W. Then, the second polymer liquid is supplied to the surface of the substrate W. As a result, a second second adsorption film F2 is formed on top of the second first adsorption film F1. Subsequently, the second polymer liquid is removed from the surface of the substrate W while leaving four adsorption films (two first adsorption films F1 and two second adsorption films F2) on the surface of the substrate W. Then, the LbL cycle from supplying the first polymer liquid to removing the second polymer liquid is performed one or more times as needed. Performing a LbL cycle increases the number of first adsorption films F1 and second adsorption films F2, and increases the thickness of the laminated film F3, which contains at least one pair of first and second adsorption films F1 and F2. This allows the protrusions P1 to be reinforced by the laminated film F3, reducing the collapse of the pattern PA.

[0129] In this embodiment, one LbL cycle, including supplying a first polymer liquid, removing the first polymer liquid, supplying a second polymer liquid, and removing the second polymer liquid, is performed multiple times. The laminated film F3, which includes at least one pair of first adsorption films F1 and second adsorption films F2, forms a gap G1 (see Figures 3A and 3D) in the recess Q1 that is recessed in the height direction of the convex P1 toward the bottom of the recess Q1. The LbL cycle is repeated until a portion of the gap G1 formed by the laminated film F3 is filled with at least one of the first and second polymers (see Figure 3A). Once a portion of the gap G1 is filled with at least one of the first and second polymers, the area near the entrance of the recess Q1 is filled with the first and second polymers. Even if a force is generated that tilts the convex P1, the first and second polymers restrict the tilting of the convex P1. This reduces the collapse of the pattern PA.

[0130] In this embodiment, after the first adsorption film F1 and the second adsorption film F2 are formed on the side surface s2 of the protrusion P1 of the pattern PA, one or more LbL cycles are performed from the supply of the first polymer liquid to the removal of the second polymer liquid. Therefore, at least two pairs of first adsorption films F1 and second adsorption films F2 are formed on the side surface s2 of the protrusion P1. This reinforces the protrusion P1. The LbL cycle ends before a portion of the gap G1 formed by the laminated film F3 is filled by at least one of the first polymer and the second polymer (see Figure 3D). Therefore, the processing time for the substrate W can be shortened compared to repeating the LbL cycle until a portion of the gap G1 is filled by at least one of the first polymer and the second polymer.

[0131] In this embodiment, the substrate W is dried with a laminated film F3, which includes at least one pair of first adsorption films F1 and second adsorption films F2, on the side surface s2 of the protrusions P1 of the pattern PA. The protrusions P1 are reinforced by the laminated film F3. Furthermore, because the laminated film F3 is on the side surface s2 of the protrusions P1, an electrical repulsive force is applied to the side surfaces s2 of two adjacent protrusions P1. Therefore, the collapse of the pattern PA that occurs when the substrate W is dried can be reduced.

[0132] In this embodiment, the end face s1 of the protrusion P1 is kept covered with a processing liquid, such as the rinsing liquid or the first polymer liquid, from the start of supplying the rinsing liquid to the surface of the substrate W until the start of drying the substrate W. If the end face s1 of the protrusion P1 is exposed from the processing liquid, a surface of the processing liquid (interface between gas and processing liquid) that spans the sides s2 of two adjacent protrusions P1 may be generated within the recess Q1. When such a surface of processing liquid is generated, a force that tilts the protrusion P1 is applied to the protrusion P1 from the processing liquid. By keeping the end face s1 of the protrusion P1 covered with the processing liquid from the start of supplying the rinsing liquid until the start of drying the substrate W, such a force can be prevented from being applied to the protrusion P1.

[0133] In this embodiment, the substrate W is dried while leaving a laminated film F3 containing at least one pair of first adsorption films F1 and second adsorption films F2 on the side surface s2 of the protrusion P1 of the pattern PA, and then the laminated film F3 is removed from the substrate W by ashing. When ashing is performed, the laminated film F3 changes into a gas with little to no liquid phase. When the surface of the processing liquid is generated in the recess Q1, a force that tilts the protrusion P1 is applied from the processing liquid to the protrusion P1. By removing the laminated film F3 by ashing, such a force can be eliminated or weakened, and the collapse of the pattern PA that occurs when the laminated film F3 is removed can be reduced.

[0134] Next, other embodiments will be described.

[0135] Instead of dispensing the chemical solution, rinse solution, first polymer solution, and second polymer solution from separate nozzles, two or more of these may be dispensed from a single nozzle.

[0136] Rather than forming a laminated film F3 containing at least one pair of first adsorption films F1 and second adsorption films F2 on the surface of the substrate W on which the pattern PA is formed, the laminated film F3 may be formed on the flat surface of the substrate W before the pattern PA is formed.

[0137] When supplying the first polymer liquid to the surface of the substrate W, the surface of the substrate W may be positively or negatively charged by applying a voltage to the substrate W. Specifically, as shown in Figure 8, a DC power supply 71 may be connected to the chuck pin 11 via wiring 72 and a rotary connector (not shown). In this case, when the on / off switch 73 is closed, the DC power supply 71 is connected to the substrate W via wiring 72, the rotary connector, and the chuck pin 11, and the voltage of the DC power supply 71 is applied to the substrate W. As a result, the surface of the substrate W becomes positively or negatively charged.

[0138] The substrate processing apparatus 1 is not limited to an apparatus for processing a disc-shaped substrate W, but may also be an apparatus for processing a polygonal substrate W.

[0139] The substrate processing apparatus 1 may be a batch-type apparatus that processes multiple substrates W at once.

[0140] You may combine two or more of the above-mentioned configurations. You may also combine two or more of the above-mentioned processes.

[0141] Although embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical content of the present invention, and the present invention should not be construed as being limited to these specific examples. The spirit and scope of the present invention are limited only by the appended claims. [Explanation of Symbols]

[0142] 1: Substrate processing device, 2d: Dry processing chamber, 2w: Wet processing chamber, 3: Control unit, 10: Spin chuck, 11: Chuck pin, 13: Spin motor, 31a: First chemical nozzle, 31b: First rinse nozzle, 31c: Second chemical nozzle, 31d: Second rinse nozzle, 31e: First polymer nozzle, 31f: Second polymer nozzle, 31g: Third rinse nozzle, 3 1h: Bottom nozzle, 44o: Oxidation unit, 49: Hot plate, 56a: Gas supply port, 57a: Ozone gas piping, 58a: Ozone gas valve, 59a: Ozone gas generator, F1: First adsorption film, F2: Second adsorption film, F3: Laminated film, F4: End film, F5: Side film, F6: Bottom film, G1: Gap, P1: Protrusion, PA: Pattern, Q1: Recess, W: Substrate, p1: Cation, p2: Anion

Claims

1. The rinsing solution is supplied to the surface of the substrate, With the rinse liquid in contact with the surface of the substrate, a first polymer liquid containing ions of the first polymer having an electrical charge opposite to the polarity of the surface of the substrate in contact with the rinse liquid is supplied to the surface of the substrate, thereby forming a first adsorbed film containing the first polymer adsorbed on the surface of the substrate. Removing the first polymer liquid from the surface of the substrate while leaving the first adsorption film on the surface of the substrate, A substrate processing method comprising: removing the first polymer solution from the surface of the substrate while leaving the first adsorption film on the surface of the substrate; and then supplying the surface of the substrate with a second polymer solution containing ions of the second polymer having an electrical charge opposite to that of the ions of the first polymer, thereby forming a second adsorption film on the surface of the substrate containing the second polymer adsorbed on the first adsorption film.

2. Supplying the rinse liquid to the surface of the substrate includes supplying the rinse liquid to the surface on which a pattern including a plurality of protrusions and a plurality of recesses is formed, Forming the first adsorption film on the surface of the substrate includes forming the first adsorption film on the side surface of the protrusion, The substrate processing method according to claim 1, wherein forming the second adsorption film on the surface of the substrate includes forming the second adsorption film on the side surface of the protrusion via the first adsorption film.

3. The substrate processing method according to claim 2, further comprising removing the second polymer liquid from the surface of the substrate while leaving the first adsorption film and the second adsorption film on the surface of the substrate, and, after removing the second polymer liquid from the surface of the substrate while leaving the first adsorption film and the second adsorption film on the surface of the substrate, performing one or more cycles including supplying the first polymer liquid, removing the first polymer liquid, supplying the second polymer liquid, and removing the second polymer liquid.

4. The laminated film, which includes at least one pair of the first adsorption film and the second adsorption film, has a gap formed within the recess that is recessed in the height direction of the protrusion toward the bottom of the recess. The substrate processing method according to claim 3, wherein performing the cycle once or more times includes performing the cycle multiple times until a portion of the gap is filled with at least one of the first polymer and the second polymer.

5. The laminated film, which includes at least one pair of the first adsorption film and the second adsorption film, has a gap formed within the recess that is recessed in the height direction of the protrusion toward the bottom of the recess. The substrate processing method according to claim 3, wherein performing the cycle once or more times includes terminating the cycle after performing the cycle once or more times, before a portion of the gap is filled with at least one of the first polymer and the second polymer.

6. A substrate processing method according to any one of claims 2 to 5, further comprising drying the substrate while a laminated film including at least one pair of the first adsorption film and the second adsorption film is on the side surface of the protrusion.

7. The substrate processing method according to claim 6, further comprising maintaining the end face of the protrusion covered with the processing liquid from the time the supply of the rinsing liquid to the surface of the substrate is started until the drying of the substrate is started.

8. The substrate processing method according to claim 6, further comprising removing the laminated film from the dried substrate by ashing.

9. The substrate processing method according to claim 7, further comprising removing the laminated film from the dried substrate by ashing.

10. A substrate holder that holds the substrate, At least one nozzle for supplying a processing liquid to the surface of the substrate held in the substrate holder, The set includes a control unit that controls the supply of processing liquid from at least one nozzle to the substrate, The control unit, The at least one nozzle is A rinse liquid is supplied to the surface of the substrate held in the substrate holder. With the rinse liquid in contact with the surface of the substrate, a first polymer liquid containing ions of the first polymer having an electrical charge opposite to the polarity of the surface of the substrate in contact with the rinse liquid is supplied to the surface of the substrate held in the substrate holder, thereby forming a first adsorbent film containing the first polymer adsorbed on the surface of the substrate. By supplying a replacement liquid to the surface of the substrate held in the substrate holder, the first polymer liquid on the surface of the substrate is replaced with the replacement liquid, and the first polymer liquid is removed from the surface of the substrate while leaving the first adsorbent film on the surface of the substrate. After removing the first polymer solution from the surface of the substrate while leaving the first adsorption film on the surface of the substrate, a second polymer solution containing ions of the second polymer having an electrical charge opposite to that of the ions of the first polymer is supplied to the surface of the substrate held in the substrate holder, thereby forming a second adsorption film on the surface of the substrate containing the second polymer adsorbed on the first adsorption film. Control the at least one nozzle in such a way Circuit board processing equipment.

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