Substrate processing method and substrate processing device

Abstract

The present invention relates to a substrate processing method and a substrate processing device. This substrate processing method is for processing a substrate W. The substrate W includes a first layer E, a second layer F, and a third layer G. The third layer G is located between the first layer E and the second layer F. The first layer E has a surface E1. The surface E1 is in surface contact with the third layer G. The second layer F has a surface F1. The surface F1 is in surface contact with the third layer G. The first layer E has a composition different from the composition of the third layer G. The second layer F has a composition different from the composition of the third layer G. The substrate processing method includes a cycle step. The cycle step includes a film formation step and an etching step. In the film formation step, self-assembled monomolecular films P are respectively formed on the first layer E and the second layer F. In the etching step, an etching liquid R is supplied to the substrate W, whereby the third layer G is etched. The cycle step is repeated two or more times.

Description

Substrate processing method and substrate processing apparatus

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus, for example, a semiconductor wafer, a liquid crystal display substrate, an organic electroluminescence (EL) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, or a solar cell substrate.

[0002] Patent Document 1 discloses a substrate processing method for processing a substrate. Specifically, the substrate processing method is for etching the substrate. The substrate includes a layer to be protected and a layer to be etched.

[0003] The etching method includes a film formation step and an etching step. In the film formation step, a self-assembled monolayer is formed on the layer to be protected. In the etching step, an etching solution is supplied to the substrate, and the layer to be etched is etched. In the etching step, the layer to be protected is protected by the self-assembled monolayer.

[0004] JP 2013-062278 A

[0005] Even with conventional substrate processing methods, it can be difficult to properly process a substrate. For example, a layer to be etched may be disposed in a space between two layers to be protected. In this case, the etching rate of the layer to be etched is low. In particular, when the space in which the layer to be etched is disposed is narrow, the etching rate of the layer to be etched is significantly low.

[0006] When the etching rate of the layer to be etched is low, the etching process takes a longer time, and when the etching process takes a long time, it is difficult to protect the layer to be protected from the etching solution.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can process substrates appropriately.

[0008] In order to achieve the above object, the present invention is configured as follows: That is, the present invention is a substrate processing method for processing a substrate, the substrate including a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer having a first surface in surface contact with the third layer, the second layer having a second surface in surface contact with the third layer, the first layer having a composition different from a composition of the third layer, and the second layer having a composition different from a composition of the third layer, the substrate processing method comprising a cycle process including a film formation process of forming a self-assembled monolayer on the first layer and the second layer, and an etching process of supplying an etching solution to the substrate and etching the third layer, the cycle process being repeated two or more times.

[0009] The substrate processing method is for processing a substrate. The substrate includes a first layer, a second layer, and a third layer. The third layer is located between the first layer and the second layer. The first layer has a first surface. The first surface is in surface contact with the third layer. The second layer has a second surface. The second surface is in surface contact with the third layer. The first layer has a composition different from that of the third layer. The second layer has a composition different from that of the third layer.

[0010] The substrate processing method includes a cycle process. The cycle process includes a film formation process and an etching process. In the film formation process, a self-assembled monolayer is formed on the first layer and the second layer. In the etching process, an etching solution is supplied to the substrate, and the third layer is etched.

[0011] During the etching process, the self-assembled monolayer protects the first and second layers from the etching solution. However, after the third layer is etched, it is difficult to protect the first and second layers.

[0012] Specifically, when the third layer is etched, a portion of the third layer is removed. After the portion of the third layer is removed, a portion of the first surface is not in contact with the third layer and is not covered with a self-assembled monolayer. Similarly, after the portion of the third layer is etched, a portion of the second surface is not in contact with the third layer and is not covered with a self-assembled monolayer. After the portion of the third layer is etched, portions of the first surface and the second surface are not protected. After the portion of the third layer is etched, portions of the first surface and the second surface are exposed. The portions of the first surface and the second surface come into contact with the etching solution. The portions of the first surface and the second surface are exposed to the etching solution. Therefore, it is difficult to protect the first surface and the second surface after the third layer is etched.

[0013] The cycle step is repeated two or more times. For convenience, one cycle step is referred to as the "first cycle step." After the film formation step of the first cycle step, the first surface and the second surface are not exposed. After the etching step of the first cycle step, a portion of the first surface and the second surface is exposed. The cycle step performed after the first cycle step is referred to as the "second cycle step."

[0014] In the film formation step of the second cycle step, new self-assembled monolayers are formed on the first and second layers. New self-assembled monolayers are also formed on portions of the first and second surfaces. After the film formation step of the second cycle step, the first and second surfaces are not exposed.

[0015] In the etching step of the second cycle, an etching solution is supplied to the substrate, and the third layer is etched. In the etching step of the second cycle, the self-assembled monolayer protects the first layer and the second layer. In the etching step of the second cycle, the self-assembled monolayer protects a portion of the first surface and a portion of the second surface. While the third layer is being etched in the etching step of the second cycle, the self-assembled monolayer protects a portion of the first surface and a portion of the second surface.

[0016] As described above, after portions of the first and second surfaces are exposed, self-assembled monolayers are quickly formed on the portions of the first and second surfaces. Therefore, the time during which the portions of the first and second surfaces are exposed is short. The time during which the portions of the first and second surfaces are in contact with the etching solution is short. Therefore, it is easy to protect the portions of the first and second surfaces from the etching solution. Therefore, it is easy to protect the first and second layers from the etching solution.

[0017] The cycle process is repeated two or more times. Therefore, the etching process is performed two or more times. Therefore, it is easy to increase the total time of the multiple etching processes. Therefore, it is easy to etch the third layer. Even if the etching rate of the third layer is low, it is easy to increase the etching amount of the third layer.

[0018] In summary, according to the present substrate processing method, the first and second layers are properly protected, and the third layer is properly etched, so that the substrate is properly processed according to the present substrate processing method.

[0019] In the above-described substrate processing method, the third layer is preferably repeatedly etched in a plurality of etching steps, so that the third layer is properly etched.

[0020] In the above-described substrate processing method, the cycle step is preferably repeated 10 or more times. Therefore, the time for each etching step in each cycle step is shorter. Therefore, it is easier to protect the first layer and the second layer from the etching solution. Furthermore, the etching step is repeated 10 or more times. Therefore, the third layer is repeatedly etched 10 or more times. Therefore, the third layer is properly etched.

[0021] In the substrate processing method described above, it is preferable that the etching amount of the third layer in one etching step in one cycle process is smaller than a target value of the total etching amount of the third layer. Therefore, by repeating the cycle process two or more times, it is easy to make the total etching amount of the third layer in multiple etching steps equal to the target value. Here, the total etching amount of the third layer is the sum of the etching amounts of the third layer in all etching steps in all cycle processes.

[0022] In the substrate processing method described above, the number of times the cycle step is repeated is preferably determined based on the target value, so that it is easy to make the total etching amount of the third layer equal to the target value.

[0023] In the substrate processing method, the time for one etching step in one cycle step preferably depends on at least one of the etching rate of the first layer and the etching rate of the second layer, thereby making it easy to protect the first layer and the second layer.

[0024] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle step is determined based on the etching rate of the first layer and a first threshold value, and the first threshold value is an upper limit value for the amount of etching of the first layer in each etching step in each cycle step, thereby making it easy to protect the first layer.

[0025] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle step is limited so that the etching amount of the first layer in each etching step in each cycle step is equal to or less than the first threshold value, thereby making it easy to control the etching amount of the first layer in each etching step in each cycle step to be equal to or less than the first threshold value.

[0026] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle step is determined based on the etching rate of the second layer and a second threshold value, and the second threshold value is an upper limit value for the amount of etching of the second layer in each etching step in each cycle step, thereby making it easy to protect the second layer.

[0027] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle step is limited so that the etching amount of the second layer in each etching step in each cycle step is equal to or less than the second threshold value, thereby making it easy to control the etching amount of the second layer in each etching step in each cycle step to be equal to or less than the second threshold value.

[0028] In the substrate processing method, it is preferable that the time for one etching step in one cycle step does not depend on the etching rate of the third layer, thereby making it easy to protect the first and second layers.

[0029] In the substrate processing method, the time for each etching step in each cycle step preferably depends on the etching rate of the third layer. Therefore, etching the third layer is easy. For example, it is easy to adjust the etching amount of the third layer in each etching step in each cycle step.

[0030] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle is determined based on the etching rate of the third layer and a third threshold value, and the third threshold value is an upper limit value for the etching amount of the third layer in each etching step in each cycle. Therefore, etching the third layer is easy. For example, it is easy to adjust the etching amount of the third layer in each etching step in each cycle.

[0031] In the substrate processing method described above, it is preferable that the time for each etching step in each cycle step is limited so that the etching amount of the third layer in each etching step in each cycle step is equal to or less than the third threshold value, thereby making it easy to control the etching amount of the third layer in each etching step in each cycle step to be equal to or less than the third threshold value.

[0032] In the above-described substrate processing method, the third threshold value is preferably 2 nm or less. Therefore, the etching amount of the third layer in one etching step in one cycle step is small. Therefore, the time for one etching step is short. Therefore, it is easy to protect the first and second layers. The cycle step is frequently repeated. Therefore, it is easier to etch the third layer in the etching step. For example, it is easy to fine-tune the total etching amount of the third layer.

[0033] In the substrate processing method, it is preferable that the time for one etching step in one cycle step does not depend on the target value of the total etching amount of the third layer, thereby making it easy to protect the first and second layers.

[0034] In the above-described substrate processing method, the self-assembled monolayer preferably has a thickness smaller than half the separation distance between the first surface and the second surface. Therefore, even when the self-assembled monolayer is formed on the first and second surfaces, the self-assembled monolayer does not fill the entire space between the first and second surfaces. Even when the self-assembled monolayer is formed on the first and second surfaces, the self-assembled monolayer fills only a portion of the space between the first and second surfaces. Therefore, even when the self-assembled monolayer is formed on the first and second surfaces, at least a portion of the third layer is not covered by the self-assembled monolayer. Therefore, even when the self-assembled monolayer is formed on the first and second surfaces, the self-assembled monolayer allows the third layer to come into contact with an etching solution. As a result, even when the self-assembled monolayer is formed on the first and second surfaces, it is easy to etch the third layer.

[0035] In the above-described substrate processing method, it is preferable that the first layer is made of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride, the second layer is made of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride, the third layer is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten, the third layer does not contain silicon nitride, and the self-assembled monolayer contains an unsaturated hydrocarbon. Therefore, it is easy to form a self-assembled monolayer on the first layer and the second layer in the film formation step.

[0036] In the above-described substrate processing method, it is preferable that the first layer is made of at least one of single crystal silicon, polysilicon, and amorphous silicon, the second layer is made of at least one of single crystal silicon, polysilicon, and amorphous silicon, the third layer is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten, the third layer does not contain silicon nitride, and the self-assembled monolayer contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies. Therefore, it is easy to form self-assembled monolayers on the first and second layers in the film formation step.

[0037] In the above-described substrate processing method, it is preferable that at least one of the first layer and the second layer is made of silicon nitride, the third layer is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten, the third layer does not contain silicon nitride, and the self-assembled monolayer contains at least one of unsaturated hydrocarbon and alkyl bromide. Therefore, it is easy to form a self-assembled monolayer on at least one of the first layer and the second layer in the film formation step.

[0038] In the above-described substrate processing method, it is preferable that one of the first layer and the second layer is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon, the other of the first layer and the second layer is composed of silicon nitride, the third layer is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten, and the third layer does not contain silicon nitride, the self-assembled monolayer formed on one of the first layer and the second layer contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies, and the self-assembled monolayer formed on the other of the first layer and the second layer contains at least one of unsaturated hydrocarbons and alkyl bromides. Therefore, it is easy to form a self-assembled monolayer on the first layer and the second layer in the film formation step.

[0039] In the above-described substrate processing method, it is preferable that the first layer is made of at least one of single crystal silicon, polysilicon, and amorphous silicon, and the first layer does not contain silicon nitride, the second layer is made of at least one of single crystal silicon, polysilicon, and amorphous silicon, and the second layer does not contain silicon nitride, and the third layer is made of silicon nitride, the self-assembled monolayer is made of at least one of peroxide, organic sulfur molecule, alkylating reagent, aromatic diazonium salt, alcohol, aldehyde, and epoxy, the self-assembled monolayer does not contain unsaturated hydrocarbon, and the self-assembled monolayer does not contain alkyl bromide. Therefore, it is easy to form self-assembled monolayers on the first and second layers in the film formation step.

[0040] In the above-described substrate processing method, the self-assembled monolayer preferably includes a first self-assembled monolayer formed on the first layer and a second self-assembled monolayer formed on the second layer, which makes it easy to form the self-assembled monolayers on the first layer and the second layer in the film formation step.

[0041] In the above-described substrate processing method, the second self-assembled monolayer preferably has the same composition as the first self-assembled monolayer, thereby simplifying the structure of the self-assembled monolayer.

[0042] In the above-described substrate processing method, the second self-assembled monolayer preferably has a composition different from that of the first self-assembled monolayer. Therefore, it is easy to form a self-assembled monolayer on the first and second layers in the film formation process. For example, even if the second layer has a composition different from that of the first layer, it is easy to form a self-assembled monolayer on the first and second layers in the film formation process.

[0043] In the above-described substrate processing method, the film formation step preferably includes a first film formation step of forming the first self-assembled monolayer on the first layer and a second film formation step of forming the second self-assembled monolayer on the second layer. Therefore, it is easy to form the self-assembled monolayer on the first layer and the second layer in the film formation step. For example, even if the second self-assembled monolayer has a different composition from the first self-assembled monolayer, it is easy to form the self-assembled monolayer in the film formation step.

[0044] In the above-described substrate processing method, it is preferable that in the film formation step, a protective liquid is supplied to the substrate, and the protective liquid contains a material for the self-assembled monolayer, thereby facilitating the formation of the self-assembled monolayer as the first layer and the second layer in the film formation step.

[0045] In the above-described substrate processing method, the protective liquid preferably further contains toluene, which easily limits the thickness of the self-assembled monolayer, thereby preventing the self-assembled monolayer from becoming excessively thick.

[0046] In the substrate processing method described above, the cycle step preferably includes a first substitution step of supplying a first substitution liquid to the substrate, and the first substitution step is preferably performed before the film formation step. This makes it easy to supply the protection liquid to the substrate in the film formation step, and thus makes it easy to reduce the amount of protection liquid used.

[0047] In the above-described substrate processing method, the cycle process preferably includes a second substitution process of supplying a second substitution liquid to the substrate, and the second substitution process is preferably performed after the film formation process and before the etching process. Therefore, in the second substitution process, the protective liquid on the substrate is replaced with the second substitution liquid. Therefore, in the second substitution process, it is easy to remove the protective liquid from the substrate. As described above, the protective liquid contains a material for a self-assembled monolayer. A portion of the material for the self-assembled monolayer in the protective liquid is converted into a self-assembled monolayer, while the other portion of the material for the self-assembled monolayer in the protective liquid does not convert into a self-assembled monolayer. The other portion of the material for the self-assembled monolayer remains in the protective liquid. The other portion of the material for the self-assembled monolayer is "excess material for the self-assembled monolayer." In the second substitution process, it is easy to remove the excess material for the self-assembled monolayer from the substrate. Therefore, it is even easier to supply an etching liquid to the substrate in the etching process. For example, it is easy to reduce the amount of etching solution used, and it is easy to improve the etching rate of the third layer.

[0048] In the above-described substrate processing method, the cycle process preferably includes a first drying process for drying the substrate, and the first drying process is preferably performed after the film forming process and before the etching process. Therefore, in the etching process, an etching solution is supplied to a dry substrate. Therefore, it is easier to supply an etching solution to the substrate in the etching process. For example, it is easy to reduce the amount of etching solution used. For example, it is easy to improve the etching rate of the third layer.

[0049] In the above-described substrate processing method, the cycle step preferably includes a first rinse step of supplying a first rinse liquid to the substrate, and the first rinse step is preferably performed after the film formation step and before the first drying step. Therefore, the first rinse liquid washes away the protective liquid on the substrate. Therefore, in the first rinse step, it is easy to remove the protective liquid from the substrate. In the first rinse step, it is easy to remove excess self-assembled monolayer material from the substrate. Therefore, when the substrate is dried in the first drying step, particles are less likely to be generated on the substrate. The particles originate, for example, from the protective liquid. The particles originate, for example, from excess self-assembled monolayer material.

[0050] In the above-described substrate processing method, it is preferable that the substrate is not dried in the cycle process. Therefore, the cycle process is simple. Therefore, the time required for one cycle process is short. Therefore, it is easier to repeat the cycle process.

[0051] In the above-described substrate processing method, the cycle step preferably includes a third substitution step of supplying a third substitution liquid to the substrate, and the third substitution step is preferably performed after the etching step. Therefore, in the third substitution step, the etching liquid on the substrate is replaced with the third substitution liquid. Therefore, in the third substitution step, it is easy to remove the etching liquid from the substrate. Therefore, it is easy to stop etching of the third layer in the third substitution step. That is, it is easy to control the etching amount of the third layer. Furthermore, it is even easier to protect the first and second layers from the etching liquid in the third substitution step.

[0052] In the above-described substrate processing method, the cycle process preferably includes an oxidation process for oxidizing the third layer, and the oxidation process is preferably performed after the film formation process and before the etching process. The cycle process includes the oxidation process. In the oxidation process, the third layer is oxidized. The oxidation process is performed before the etching process. Therefore, the third layer is etched after being oxidized. Therefore, it is easier to etch the third layer in the etching process. For example, it is easy to improve the etching rate of the third layer. The oxidation process is performed after the film formation process. Therefore, the oxidation process is performed after a self-assembled monolayer is formed on the first and second layers. Therefore, it is easy for the self-assembled monolayer to protect the first and second layers in the oxidation process. For example, it is difficult to oxidize the first and second layers in the oxidation process.

[0053] In the above-described substrate processing method, it is preferable that an oxidizing solution for oxidizing the third layer is supplied in the oxidation step, so that the third layer can be easily oxidized in the oxidation step.

[0054] In the above-described substrate processing method, the oxidizing solution preferably contains at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide, which makes it easy to oxidize the third layer in the oxidation step.

[0055] In the above-described substrate processing method, the cycle step preferably includes a fourth substitution step of supplying a fourth substitution liquid to the substrate, and the fourth substitution step is preferably performed after the oxidation step and before the etching step. Therefore, in the fourth substitution step, the oxidizing liquid on the substrate is replaced with the fourth substitution liquid. Therefore, in the fourth substitution step, it is easy to remove the oxidizing liquid from the substrate. Therefore, it is even easier to supply the etching liquid to the substrate in the etching step. For example, it is easy to reduce the amount of etching liquid used. For example, it is easy to improve the etching rate of the third layer.

[0056] In the above-described substrate processing method, the cycle step preferably includes a second drying step of drying the substrate, and the second drying step is preferably performed after the oxidation step and before the etching step. Therefore, in the etching step, the etching liquid is supplied to the substrate in a dry state. Therefore, it is easier to supply the etching liquid to the substrate in the etching step. For example, it is easy to reduce the amount of etching liquid used. For example, it is easy to improve the etching rate of the third layer.

[0057] In the above-described substrate processing method, the cycle step preferably includes a second rinse step of supplying a second rinse liquid to the substrate, and the second rinse step is preferably performed after the oxidation step and before the second drying step. Therefore, in the second rinse step, the second rinse liquid washes away the oxidizing liquid from the substrate. Therefore, it is easy to remove the oxidizing liquid from the substrate in the second rinse step. Therefore, when the substrate is dried in the second drying step, particles are less likely to be generated on the substrate. The particles may be derived from, for example, the oxidizing liquid.

[0058] In the above-described substrate processing method, the second rinsing step is preferably performed after the film forming step and before the second drying step. Therefore, in the second rinsing step, the second rinsing liquid washes away the protective liquid on the substrate. Therefore, in the second rinsing step, it is easy to remove the protective liquid from the substrate. In the second rinsing step, it is easy to remove excess self-assembled monolayer material from the substrate. Therefore, when the substrate is dried in the second drying step, particles are less likely to be generated on the substrate. The particles originate, for example, from the protective liquid. The particles originate, for example, from excess self-assembled monolayer material.

[0059] In the substrate processing method described above, the cycle step preferably includes an oxidation step of oxidizing the third layer, and the oxidation step is preferably performed simultaneously with the etching step. This makes it easier to etch the third layer in the etching step. For example, this makes it easier to improve the etching rate of the third layer.

[0060] In the above-described substrate processing method, it is preferable that an additive for oxidizing the third layer is supplied to the substrate in the oxidation step, so that the oxidation step can be easily performed simultaneously with the etching step.

[0061] In the above-described substrate processing method, the additive preferably includes at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide, which makes it easy to oxidize the third layer in the oxidation step.

[0062] In the above-described substrate processing method, it is preferable that the self-assembled monolayer is not removed from the substrate during the cycling step, so that it is easier to protect the first layer and the second layer during the repeated cycling step.

[0063] In the above-described substrate processing method, the substrate processing method preferably further includes a final removal step of removing the self-assembled monolayer from the substrate, and the cycle step is preferably repeated two or more times before the final removal step. Therefore, the cycle step does not include the final removal step. The cycle step is repeated without the final removal step. Therefore, the time required for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0064] In the above-described substrate processing method, it is preferable that in the final removal step, a removal liquid is supplied to the substrate, the removal liquid containing a first solvent, and in the film formation step, a protection liquid is supplied to the substrate, the protection liquid containing a material of the self-assembled monolayer and a second solvent, the second solvent having the same composition as the first solvent. Therefore, it is easy for the second solvent to limit the thickness of the self-assembled monolayer. Therefore, the self-assembled monolayer does not have an excessively large thickness.

[0065] In the above-described substrate processing method, it is preferable that toluene is supplied to the substrate in the final removal step. In other words, in the above-described substrate processing method, it is preferable that a removal liquid is supplied to the substrate in the final removal step, and the removal liquid contains toluene. Therefore, it is easy for the removal liquid to remove the self-assembled monolayer from the substrate.

[0066] In the above-described substrate processing method, the first substitute liquid preferably contains a third solvent, and the third solvent preferably has the same composition as the second solvent. This makes it easy to supply the protective liquid to the substrate in the film forming step. This makes it easy to reduce the amount of protective liquid used.

[0067] In the above-described substrate processing method, the first substitute liquid preferably contains toluene, which makes it easy to supply the protection liquid to the substrate in the film forming step, and thus makes it easy to reduce the amount of protection liquid used.

[0068] In the above-described substrate processing method, the substrate processing method preferably further includes a final drying step of drying the substrate, and the cycle step is preferably repeated two or more times before the final drying step. Therefore, the cycle step does not include the final drying step. The cycle step is repeated without the final drying step. Therefore, the time required for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0069] In the above-described substrate processing method, the substrate processing method further includes a final rinse step of supplying a final rinse solution to the substrate, and the cycle step is preferably repeated two or more times before the final rinse step, and the final rinse step is preferably performed before the final drying step. Therefore, the cycle step does not include a final rinse step. The cycle step is repeated without a final rinse step. Therefore, the time required for one cycle step is short. Therefore, repeating the cycle step is easier. Furthermore, in the final rinse step, the substrate is properly cleaned with the final rinse solution. Therefore, particles are less likely to be generated on the substrate when the substrate is dried in the final drying step.

[0070] The present invention provides a substrate processing apparatus for processing a substrate, the substrate including a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer having a first surface in surface contact with the third layer, the second layer having a second surface in surface contact with the third layer, the first layer having a composition different from a composition of the third layer, and the second layer having a composition different from a composition of the third layer, the substrate processing apparatus including a film forming unit for forming self-assembled monolayers on the first layer and the second layer, and an etching unit for etching the third layer. and a control unit that controls the film formation unit and the etching unit to execute a cycle process, the cycle process including a film formation process and an etching process, in which the film formation unit forms the self-assembled monolayer on the first layer and the second layer in the film formation process, and in which the etching unit supplies an etching solution to the substrate to etch the third layer in the etching process, and the control unit causes the film formation unit and the etching unit to repeat the cycle process two or more times.

[0071] The substrate processing apparatus processes a substrate. The substrate includes a first layer, a second layer, and a third layer. The third layer is located between the first layer and the second layer. The first layer has a first surface. The first surface is in surface contact with the third layer. The second layer has a second surface. The second surface is in surface contact with the third layer. The first layer has a composition different from that of the third layer. The second layer has a composition different from that of the third layer.

[0072] The substrate processing apparatus includes a film forming unit, an etching unit, and a control unit. The film forming unit forms a self-assembled monolayer on the first layer and the second layer. The etching unit etches the third layer. The control unit controls the film forming unit and the etching unit. The control unit executes a cycle process. The cycle process includes a film forming process and an etching process. In the film forming process, the film forming unit forms a self-assembled monolayer on the first layer and the second layer. In the etching process, the etching unit supplies an etching solution to the substrate to etch the third layer.

[0073] During the etching process, the self-assembled monolayer protects the first and second layers from the etching solution. However, after the third layer is etched, it is difficult to protect the first and second layers.

[0074] Specifically, when the third layer is etched, a portion of the third layer is removed. After the portion of the third layer is removed, a portion of the first surface is not in contact with the third layer and is not covered with a self-assembled monolayer. Similarly, after the portion of the third layer is etched, a portion of the second surface is not in contact with the third layer and is not covered with a self-assembled monolayer. After the portion of the third layer is etched, portions of the first surface and the second surface are not protected. After the portion of the third layer is etched, portions of the first surface and the second surface are exposed. The portions of the first surface and the second surface come into contact with the etching solution. The portions of the first surface and the second surface are exposed to the etching solution. Therefore, it is difficult to protect the first surface and the second surface after the third layer is etched.

[0075] The cycle step is repeated two or more times. For convenience, one cycle step is referred to as the "first cycle step." After the film formation step of the first cycle step, the first surface and the second surface are not exposed. After the etching step of the first cycle step, a portion of the first surface and the second surface is exposed. The cycle step performed after the first cycle step is referred to as the "second cycle step."

[0076] In the film formation step of the second cycle step, new self-assembled monolayers are formed on the first and second layers. New self-assembled monolayers are also formed on portions of the first and second surfaces. After the film formation step of the second cycle step, the first and second surfaces are not exposed.

[0077] In the etching step of the second cycle, an etching solution is supplied to the substrate, and the third layer is etched. In the etching step of the second cycle, the self-assembled monolayer protects the first layer and the second layer. In the etching step of the second cycle, the self-assembled monolayer protects a portion of the first surface and a portion of the second surface. While the third layer is being etched in the etching step of the second cycle, the self-assembled monolayer protects a portion of the first surface and a portion of the second surface.

[0078] As described above, after portions of the first and second surfaces are exposed, self-assembled monolayers are quickly formed on the portions of the first and second surfaces. Therefore, the time during which the portions of the first and second surfaces are exposed is short. The time during which the portions of the first and second surfaces are in contact with the etching solution is short. Therefore, it is easy to protect the portions of the first and second surfaces from the etching solution. Therefore, it is easy to protect the first and second layers from the etching solution.

[0079] The cycle process is repeated two or more times. Therefore, the etching process is performed two or more times. Therefore, it is easy to increase the total time of the multiple etching processes. Therefore, it is easy to etch the third layer. Even if the etching rate of the third layer is low, it is easy to increase the etching amount of the third layer.

[0080] In summary, the substrate processing apparatus appropriately protects the first and second layers while appropriately etching the third layer, thereby appropriately processing the substrate.

[0081] According to the substrate processing method and substrate processing apparatus of the present invention, the substrate is processed appropriately.

[0082] 1 is a plan view showing the inside of a substrate processing apparatus; FIG. 3 is a control block diagram of the substrate processing apparatus; FIG. 3( a) is a side view of a substrate; FIG. 3( b) is a plan view of a substrate; FIGS. 4( a) and 4(b) are detailed views of a first layer, a second layer, and a third layer of a substrate, respectively; FIG. 4 is a diagram showing the configuration of a processing unit of a first embodiment; FIG. 5 is a diagram showing the chemical structural formula of an example of an organic sulfur molecule; FIG. 6 is a diagram showing the chemical structural formula of another example of an organic sulfur molecule; FIG. 7 is a diagram showing the chemical structural formula of another example of an organic sulfur molecule; FIG. 8 is a diagram showing the chemical structural formula of another example of an alkylating reagent; FIG. 9 is a diagram showing the chemical structural formula of another example of an alkylating reagent; FIG. 10 is a diagram showing the chemical structural formula of another example of an alkylating reagent; FIG. 11 is a diagram showing the chemical structural formula of another example of an aromatic diazonium salt; FIG. 12 is a diagram showing the chemical structural formula of another example of an aromatic diazonium salt; FIG. 13 is a diagram showing the chemical structural formula of an example of an epoxy; FIG. 14 is a diagram showing the chemical structural formula of another example of an epoxy; FIG. 15 is a flowchart showing the procedure of a substrate processing method; 1 is a flowchart showing the procedure of the cycle process of the first embodiment; FIG. 2 is a flowchart showing the procedure of the substrate processing method of Example 1; FIG. 3 is a diagram showing a substrate in a film formation process of the first cycle process of Example 1; FIG. 4 is a diagram showing a substrate in an etching process of the first cycle process of Example 1; FIG. 5 is a diagram showing a substrate in an etching process of the first cycle process of Example 1; FIG. 6 is a diagram showing a substrate W in a film formation process of the second cycle process of Example 1; FIG. 7 is a diagram showing a substrate W in an etching process of the second cycle process of Example 1; FIG. 8 is a diagram showing a substrate W in an etching process of the second cycle process of Example 1; FIG. 9 is a flowchart showing the procedure of the substrate processing method of Comparative Example; FIG. 10 is a diagram showing the configuration of a processing unit of Example 2; FIG. 11 is a flowchart showing the procedure of the cycle process of Example 1; FIG. 12 is a diagram showing the configuration of a processing unit of Example 1;FIG. 10 is a flowchart showing the procedure of a substrate processing method according to a second embodiment; FIG. 11 is a diagram showing a substrate W in a film formation process of a first cycle process of a second embodiment; FIG. 12 is a diagram showing a substrate W in an oxidation process of a first cycle process of a second embodiment; FIG. 13 is a diagram showing a substrate W in an etching process of a first cycle process of a second embodiment; FIG. 14 is a diagram showing a substrate W in a film formation process of a second cycle process of a second embodiment; FIG. 15 is a diagram showing a substrate W in an oxidation process of a second cycle process of a second embodiment; FIG. 16 is a diagram showing a substrate W in an etching process of a second cycle process of a second embodiment; FIG. 17 is a diagram showing the configuration of a processing unit according to a fifth embodiment; FIG. 18 is a flowchart showing the procedure of a cycle process of a sixth embodiment; FIG. 19 is a diagram showing the configuration of a processing unit according to a seventh embodiment; FIG. 19 is a flowchart showing the procedure of a cycle process of a seventh embodiment; FIG. 20 is a diagram showing the configuration of a processing unit according to a modified embodiment;

[0083] A substrate processing method and a substrate processing apparatus according to the present invention will be described below with reference to the drawings.

[0084] 1. First Embodiment 1-1. Overview of Substrate Processing Apparatus Fig. 1 is a plan view showing the interior of a substrate processing apparatus 1. The substrate processing apparatus 1 processes substrates W. The processes in the substrate processing apparatus 1 include wet etching. The wet etching is a process in which the substrate W is etched with an etching solution.

[0085] The substrate processing apparatus 1 includes an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies substrates W to the processing block 7. The processing block 7 processes the substrates W. The indexer unit 3 retrieves the substrates W from the processing block 7.

[0086] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The direction perpendicular to the front-rear direction X is referred to as the "width direction Y." The width direction Y is horizontal. One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." When the front-rear direction X and the width direction Y are not distinguished, they are simply referred to as the "horizontal direction." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." In each figure, for reference, front, rear, right, left, top, and bottom are indicated as appropriate.

[0087] The indexer unit 3 includes a plurality of (for example, four) carrier platforms 4. Each carrier platform 4 has one carrier C mounted thereon. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, a front-opening unified pod (FOUP), a standard mechanical interface (SMIF), or an open cassette (OC).

[0088] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 transports substrates W. The transport mechanism 5 transports substrates W between a carrier C placed on the carrier platform 4 and a processing block 7. The transport mechanism 5 is disposed behind the carrier platform 4. The transport mechanism 5 is configured to approach the carrier C placed on the carrier platform 4. The transport mechanism 5 is configured to approach the processing block 7.

[0089] The transport mechanism 5 includes a hand 5a and a hand driver 5b. The hand 5a supports the substrate W. The hand driver 5b is connected to the hand 5a. The hand driver 5b moves the hand 5a. The hand driver 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 5b rotates the hand 5a, for example, in a horizontal plane.

[0090] The processing block 7 includes a plurality of processing units 11. Each processing unit 11 performs processing on a substrate W.

[0091] Each processing unit 11 includes a substrate holder 13. The substrate holder 13 holds a substrate W.

[0092] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 is arranged to the side of the processing unit 11. The transport mechanism 8 transports substrates W. The transport mechanism 8 transports substrates W between the indexer unit 3 and the processing unit 11. The transport mechanism 8 transports substrates W between the transport mechanism 5 and the substrate holder 13. The transport mechanism 8 is configured to approach the indexer unit 3. The transport mechanism 8 is configured to approach the processing unit 11.

[0093] The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0094] 2 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11. The control unit 10 is communicatively connected to the transport mechanisms 5 and 8 and the processing unit 11.

[0095] The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a work area for the processes, and a storage medium such as a fixed disk. The control unit 10 has various types of information pre-stored in the storage medium. The information stored in the control unit 10 includes, for example, transport condition information and processing condition information. The transport condition information defines conditions related to the operation of the transport mechanisms 5 and 8. The processing condition information defines conditions related to the operation of the processing unit 11. The processing condition information is also called a processing recipe.

[0096] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0097] The transport mechanism 5 takes out the substrate W from the carrier C on the carrier mount part 4. The transport mechanism 5 hands over the substrate W to the transport mechanism 8.

[0098] The transport mechanism 8 delivers the substrate W to the processing unit 11. Specifically, the transport mechanism 8 places the substrate W on the substrate holder 13. The substrate holder 13 holds the substrate W.

[0099] Each processing unit 11 processes the substrate W held by the substrate holder 13. Each processing unit 11 performs wet etching on the substrate W, for example.

[0100] After the processing unit 11 has processed the substrate W, the transport mechanism 8 takes the substrate W from the processing unit 11. Specifically, the transport mechanism 8 takes the substrate W from the substrate holder 13. The transport mechanism 8 hands the substrate W over to the transport mechanism 5.

[0101] The transport mechanism 5 loads the substrate W into the carrier C.

[0102] 1-2. Structure of the Substrate W The substrate W is, for example, any one of a semiconductor wafer, a liquid crystal display substrate, an organic electroluminescence (EL) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, and a solar cell substrate.

[0103] Fig. 3(a) is a side view of the substrate W. Fig. 3(b) is a plan view of the substrate W. The substrate W has a thin, flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0104] The substrate W has a surface W1. The surface W1 has a substantially circular shape in a plan view. The surface W1 is substantially flat. The surface W1 is substantially flat.

[0105] 4(a) and 4(b) are each a detailed view of a portion of a substrate W. The substrate W includes a first layer E, a second layer F, and a third layer G. The first layer E, the second layer F, and the third layer G are each located on a surface W1. The third layer G is located between the first layer E and the second layer F.

[0106] The first layer E has, for example, a plate shape. The first layer E has, for example, a film shape. The second layer F has, for example, a plate shape. The second layer F has, for example, a film shape. The third layer G has, for example, a plate shape. The third layer G has, for example, a film shape.

[0107] The first layer E, the second layer F, and the third layer G are stacked on top of each other. The first layer E, the second layer F, and the third layer G are stacked in this order.

[0108] The first layer E has a surface E1. The second layer F has a surface F1. The third layer G has a surface G1 and a surface G2. The surface G2 is located opposite the surface G1. The surface E1 is in surface contact with the third layer G. The surface E1 is in surface contact with the surface G1. The surface F1 is in surface contact with the third layer G. The surface F1 is in surface contact with the surface G2.

[0109] The surface E1 is an example of the first surface in the present invention, and the surface F1 is an example of the second surface in the present invention.

[0110] The first layer E and the second layer F form a space A between the first layer E and the second layer F. The third layer G is located in the space A.

[0111] The space A is located between the surface E1 and the surface F1. The third layer G is located between the surface E1 and the surface F1. The surface E1 and the surface F1 face each other. The surface E1 and the surface F1 are, for example, parallel to each other. The surface E1 and the surface F1 do not contact each other.

[0112] Space A is small.

[0113] 4(a) and 4(b) show the separation distance D. The separation distance D is the distance between the first layer E and the second layer F. The separation distance D is the distance between the surface E1 and the surface F1. The separation distance D is small. For example, the separation distance D is 50 nm or less. For example, the separation distance D is 20 nm or less. For example, the separation distance D is 10 nm or less. For example, the separation distance D is several nm.

[0114] At least a portion of the surface E1 is not exposed. At least a portion of the surface E1 is in contact with the third layer G. For example, a portion of the surface E1 is not exposed and another portion of the surface E1 is exposed. A portion of the surface E1 is in contact with the third layer G and another portion of the surface E1 is not in contact with the third layer G.

[0115] The first layer E further has a surface E2. The surface E2 is located at an end of the first layer E. The surface E2 is located at an end of the surface E1. The surface E2 is not in contact with the third layer G. The surface E2 is exposed.

[0116] At least a portion of the surface F1 is not exposed. At least a portion of the surface F1 is in contact with the third layer G. For example, the surface F1 does not have an exposed portion. The entire surface F1 is in contact with the third layer G.

[0117] The second layer F further has a surface F2. The surface F2 is located at an end of the second layer F. The surface F2 is located at an end of the surface F1. The surface F2 is not in contact with the third layer G. The surface F2 is exposed.

[0118] The surface G1 is not exposed. The entire surface G1 is in contact with the first layer E. The surface G2 is not exposed. The entire surface G2 is in contact with the second layer F.

[0119] The third layer G further has a surface G3. The surface G3 is located at an end of the third layer G. The surface G3 is located at an end of the surface G1. The surface G3 is located at an end of the surface G2. The surface G3 is not in contact with the first layer E. The surface G3 is not in contact with the second layer F. The surface G3 is exposed.

[0120] 4(a) shows the third layer G before etching. FIG. 4(b) shows the third layer G after etching. The third layer G is etched. Specifically, the surface G3 is etched. The third layer G is selectively etched. The third layer G is etched while the first layer E and the second layer F are protected. The first layer E is not substantially etched. The second layer F is not substantially etched.

[0121] The third layer G is etched to remove at least a portion of the third layer G. The removal of at least a portion of the third layer G results in at least a portion of the space A becoming an unoccupied space. The third layer G is not present in the unoccupied space.

[0122] The third layer G is etched in a depth direction J. Specifically, the surface G3 is etched in the depth direction J. The depth direction J is, for example, perpendicular to the surface G3.

[0123] The third layer G has a length KG in the depth direction J. When the third layer G is etched, the length KG decreases.

[0124] Specifically, in Fig. 4(a), the third layer G has a length KG1. In Fig. 4(b), the third layer G has a length KG2. The length KG2 is shorter than the length KG1.

[0125] 4B shows the etching amount LG of the third layer G. The etching amount LG is, for example, the difference between the length KG1 and the length KG2.

[0126] The first layer E has a composition different from that of the third layer G. The second layer F has a composition different from that of the third layer G.

[0127] The composition of the second layer F may be the same as the composition of the first layer E. Alternatively, the composition of the second layer F may be different from the composition of the first layer E.

[0128] The first layer E is made of, for example, at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride.

[0129] The second layer F is made of, for example, at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride.

[0130] The third layer is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, tungsten, and silicon nitride.

[0131] When the first layer E is made of silicon nitride, the third layer G does not contain silicon nitride. When the second layer F is made of silicon nitride, the third layer G does not contain silicon nitride. When the third layer G is made of silicon nitride, the first layer E does not contain silicon nitride and the second layer F does not contain silicon nitride.

[0132] Polycrystalline silicon is also called polysilicon.

[0133] Silicon oxide is, for example, silicon dioxide (SiO ２ ) Silicon oxides include, for example, silicon suboxides (SiOx, 0<x<2). Silicon suboxides are suboxides of silicon dioxide. Silicon suboxides are also called lower silicon oxides. Silicon suboxides include, for example, silicon monoxide (SiO).

[0134] Silicon oxide can be obtained by, for example, thermal oxidation, chemical vapor deposition (CVD), or atomic layer deposition (ALD). Silicon oxide obtained by thermal oxidation is sometimes called a "thermal oxide film."

[0135] 1-3. Configuration of Processing Unit 11 Fig. 5 is a diagram showing the configuration of the processing unit 11 in the first embodiment. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units. That is, each processing unit 11 processes only one substrate W at a time.

[0136] The processing unit 11 includes a housing 12. The housing 12 has a substantially box shape. The substrate W is processed inside the housing 12.

[0137] The substrate holder 13 is installed inside the housing 12. The substrate holder 13 holds only one substrate W at a time. The substrate holder 13 holds the substrate W in a substantially horizontal position. When the substrate W is held by the substrate holder 13, the surface W1 is horizontal.

[0138] When the substrate W is held by the substrate holder 13, the surface W1 faces upward. When the substrate W is held by the substrate holder 13, the surface W1 corresponds to the upper surface of the substrate W. The substrate holder 13 contacts at least one of the lower surface of the substrate W and the peripheral edge of the substrate W. The lower surface of the substrate W is also called the backside of the substrate W. The substrate holder 13 is located below the substrate W held by the substrate holder 13. The substrate holder 13 does not contact the surface W1.

[0139] The processing unit 11 includes a rotation drive unit 14. The rotation drive unit 14 is provided below the substrate holding unit 13. The rotation drive unit 14 is connected to the substrate holding unit 13. The rotation drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates integrally with the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates, for example, around a rotation axis B. The rotation axis B passes through the center of the substrate W, for example. The rotation axis B extends, for example, in the vertical direction Z.

[0140] The processing unit 11 includes a supply unit 15a. The supply unit 15a supplies a protective liquid to the substrate W. The supply unit 15a supplies the protective liquid to the substrate W held by the substrate holding unit 13. The supply unit 15a supplies the protective liquid to the surface W1 of the substrate W held by the substrate holding unit 13. In this way, the supply unit 15a forms a self-assembled monolayer (SAM) on the first layer E and the second layer F. The self-assembled monolayer protects the first layer E and the second layer F.

[0141] The protective liquid contains a material for a self-assembled monolayer, and when the protective liquid is supplied to the substrate W, at least a part of the material for the self-assembled monolayer is transformed into the self-assembled monolayer.

[0142] The materials for the self-assembled monolayer are explained in detail.

[0143] The material of the self-assembled monolayer includes, for example, at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, epoxies, and alkyl bromides.

[0144] The compounds exemplified as materials for self-assembled monolayers are classified into Group 1 M, Group 2 N, and Group 3 O. Unsaturated hydrocarbons belong to Group 1 M. Peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies belong to Group 2 N. Alkyl bromides belong to Group 3 O.

[0145] The self-assembled monolayer materials belonging to the first group M form self-assembled monolayers on single crystal silicon, polysilicon, amorphous silicon, and silicon nitride. The self-assembled monolayer materials belonging to the second group N form self-assembled monolayers on single crystal silicon, polysilicon, and amorphous silicon, but do not form self-assembled monolayers on silicon nitride. The self-assembled monolayer materials belonging to the third group O form self-assembled monolayers on silicon nitride, but do not form self-assembled monolayers on single crystal silicon, polysilicon, and amorphous silicon.

[0146] It is preferable to select the composition of the material of the self-assembled monolayer depending on the compositions of the first layer E, the second layer F, and the third layer G.

[0147] A first configuration example of the first layer E, the second layer F, and the third layer G will be described. The first layer E is composed of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride. The second layer F is composed of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. In the first configuration example, it is preferable to select a material for the self-assembled monolayer belonging to the first group M. In the first configuration example, it is preferable that the self-assembled monolayer contain an unsaturated hydrocarbon.

[0148] A second configuration example of the first layer E, the second layer F, and the third layer G will be described. The first layer E is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. In the second configuration example, it is preferable to select a material for the self-assembled monolayer belonging to at least one of the first group M and the second group N. In the second configuration example, it is preferable that the self-assembled monolayer contain at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies.

[0149] A third configuration example of the first layer E, the second layer F, and the third layer G will be described. At least one of the first layer E and the second layer F is composed of silicon nitride. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. In the third configuration example, it is preferable to select a material for the self-assembled monolayer that belongs to at least one of the first group M and the third group O. In the third configuration example, it is preferable that the self-assembled monolayer contain at least one of an unsaturated hydrocarbon and an alkyl bromide.

[0150] A fourth configuration example of the first layer E, the second layer F, and the third layer G will be described. One of the first layer E and the second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The other of the first layer E and the second layer F is composed of silicon nitride. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. In the fourth configuration example, it is preferable to select a self-assembled monolayer material belonging to at least one of the first group M and the second group N for one of the first layer E and the second layer F. In the fourth configuration example, it is preferable that the self-assembled monolayer formed on one of the first layer E and the second layer F contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies. In the fourth configuration example, it is preferable to select a material for the self-assembled monolayer belonging to at least one of the first group M and the third group O for the other of the first layer E and the second layer F. In the fourth configuration example, it is preferable that the self-assembled monolayer formed on the other of the first layer E and the second layer F contains at least one of an unsaturated hydrocarbon and an alkyl bromide.

[0151] A fifth configuration example of the first layer E, the second layer F, and the third layer G will be described. The first layer E is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The first layer E does not contain silicon nitride. The second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The second layer F does not contain silicon nitride. The third layer G is composed of silicon nitride. In the fifth configuration example, it is preferable to select a material for the self-assembled monolayer belonging to the second group N. In the fifth configuration example, it is preferable not to select a material for the self-assembled monolayer belonging to the first group M. In the fifth configuration example, it is preferable not to select a material for the self-assembled monolayer belonging to the third group O. In the fifth configuration example, it is preferable that the self-assembled monolayer contains at least one of peroxide, organic sulfur molecule, alkylating reagent, aromatic diazonium salt, alcohol, aldehyde, and epoxy. In the fifth configuration example, it is preferable that the self-assembled monolayer does not contain unsaturated hydrocarbons. In the case of the fifth configuration example, it is preferable that the self-assembled monolayer does not contain alkyl bromide.

[0152] The unsaturated hydrocarbon is, for example, at least one of compounds M1 to M5. Compound M1) Styrene C6H5CH=CH2 Compound M2) Phenylacetylene C8H6 Compound M3) 1-butyne CH≡C?CH2?CH3 Compound M4) Butene CH2=CHCH2CH3 Compound M5) Propylene CH2=CH-CH3

[0153] The peroxide is, for example, at least one of the compounds Na1-Na3. Compound Na1) [CH3-C(O)O]2 Compound Na2) [CH3-CH2-C(O)O]2 Compound Na3) [CH3-(CH2)nC(O)O]2 In the chemical formula for Compound Na3), "n" is 2, 3, 4, 5, or 6.

[0154] The organic sulfur molecule is, for example, at least one of compounds Nb1-Nb3. Compound Nb1) HS-(CH2)m-EGn-OH Compound Nb2) HS-(CH2)m-EGn-NH3+Cl- Compound Nb3) HS-(CH2)m-EGn-OCH2COOH The "EG" in compound Nb1 is ethylene glycol. In the chemical formula representing compound Nb1, "m" is any of 3, 5, 6, 8, or 11. In the chemical formula representing compound Nb1, "n" is any of 1, 2, 3, 4, 5, 6, 8, or 12. In the chemical formula representing compound Nb2, "m" is any of 3, 5, 6, 8, or 11. In the chemical formula representing compound Nb2, "n" is any of 2, 3, 4, 5, 6, 8, or 12. In the chemical formula representing compound Nb3, "m" is any one of 3, 5, 6, 8, and 11. In the chemical formula representing compound Nb3, "n" is any one of 2, 3, 4, 5, 6, 8, and 12.

[0155] Compound Nb1 is represented by the chemical structural formula shown in Figure 6. Compound Nb2 is represented by the chemical structural formula shown in Figure 7. Compound Nb3 is represented by the chemical structural formula shown in Figure 8.

[0156] The alkylating reagent is, for example, at least one of compounds Nc1 to Nc4. Compound Nc1) Allylmagnesium Bromide C3H5BrMg Compound Nc2) sec-Butylmagnesium Bromide C4H9BrMg Compound Nc3) CH3(CH2)2CH2Li Compound Nc4) (CH3)3CLii

[0157] Compound Nc1 is represented by the chemical structural formula shown in Figure 9. Compound Nc2 is represented by the chemical structural formula shown in Figure 10. Compound Nc3 is represented by the chemical structural formula shown in Figure 11. Compound Nc4 is represented by the chemical structural formula shown in Figure 12.

[0158] The aromatic diazonium salt is, for example, at least one of compounds Nd1 to Nd3. Compound Nd1) 4-Methoxybenzenediazonium Tetrafluoroborate C7H7BF4N2O Compound Nd2) 4-(Diazonium)benzenesulfonic acid, fluoroborate C6H5BF4N2O3S Compound Nd3) Azoic Diazo Component 24 (Salt) C30H28Cl2N6O6.ZnCl2

[0159] Aromatic diazonium salts are salts composed of a diazonium ion and an acid anion. Aromatic diazonium salts are represented by the following chemical formula: Ar-N2 + X-. "Ar-N2" in the chemical formula of an aromatic diazonium salt represents a diazonium ion. "X-" in the chemical formula of an aromatic diazonium salt represents an acid anion. When the aromatic diazonium salt is compound Nd1, "X-" in the chemical formula of the aromatic diazonium salt is BF4-. When the aromatic diazonium salt is compound Nd2, "X-" in the chemical formula of the aromatic diazonium salt is BF4-. When the aromatic diazonium salt is compound Nd3, "X-" in the chemical formula of the aromatic diazonium salt is Cl-.

[0160] The compound Nd1 is represented by the chemical structural formula shown in Figure 13. The compound Nd2 is represented by the chemical structural formula shown in Figure 14. The compound Nd3 is represented by the chemical structural formula shown in Figure 15.

[0161] The alcohol is, for example, at least one of compounds Ne1 to Ne3. Compound Ne1) Isopropyl alcohol CH3CH(OH)CH3 Compound Ne2) Ethanol CH3CH2OH Compound Ne3) n-butanol CH3CH2CH2CH2OH Compound Ne4) n-propanol C3H8O

[0162] The aldehyde is, for example, compound Nf1. Compound Nf1) Formaldehyde HCHO

[0163] The epoxy is, for example, at least one of compounds Ng1 to Ng3. Compound Ng1) A compound having the chemical structural formula shown in FIG. 16 Compound Ng2) A compound having the chemical structural formula shown in FIG. 17 Compound Ng3) A compound having the chemical structural formula shown in FIG. 18

[0164] The alkyl bromide is, for example, at least one of compounds O1 to O3. Compound O1) 1-bromododecane C12H25Br Compound O2) 1-bromopentadecane C15H31Br Compound O3) 1-bromoheptadecane C17H35Br

[0165] For example, the protection liquid further includes toluene.

[0166] For example, the protective liquid further includes a solvent, which is an organic solvent, such as at least one of ethanol, isopropyl alcohol, n-propanol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether (PGEE), toluene, hexane, hexanone, cyclohexane, and benzene.

[0167] The supply unit 15a is an example of the film forming unit in the present invention. The solvent of the protection liquid is an example of the second solvent in the present invention.

[0168] 5 , the processing unit 11 includes a supply unit 15b. The supply unit 15b supplies an etching liquid to the substrate W. The supply unit 15b supplies the etching liquid to the substrate W held by the substrate holding unit 13. The supply unit 15b supplies the etching liquid to the surface W1 of the substrate W held by the substrate holding unit 13. In this way, the supply unit 15b etches the third layer G.

[0169] The etching solution includes, for example, at least one of hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrogen peroxide, hydrochloric acid, a mixture of hydrochloric acid and hydrogen peroxide, ammonium hydroxide, a mixture of ammonium hydroxide and hydrogen peroxide, sulfuric acid, a mixture of sulfuric acid and hydrogen peroxide, phosphoric acid, nitric acid, a mixture of phosphoric acid and nitric acid, and a mixture of hydrofluoric acid and nitric acid.

[0170] It is preferable to select the composition of the etching solution depending on the composition of the third layer G.

[0171] For example, when the third layer G is made of silicon oxide, the etching solution is preferably at least one of hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid, and ammonium hydroxide.

[0172] For example, when the third layer G is made of at least one of titanium nitride and titanium, the etching solution is preferably at least one of hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid, ammonium hydroxide, phosphoric acid, a mixture of phosphoric acid and nitric acid, hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, and a mixture of ammonium hydroxide and hydrogen peroxide.

[0173] For example, when the third layer G is made of titanium oxide, the etching solution is preferably at least one of hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), phosphoric acid, hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of phosphoric acid and nitric acid, ammonium hydroxide, and a mixture of ammonium hydroxide and hydrogen peroxide.

[0174] For example, when the third layer G is made of tungsten, the etching solution is preferably at least one of nitric acid, hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), a mixture of hydrofluoric acid and nitric acid, a mixture of phosphoric acid and nitric acid, hydrogen peroxide, ammonium hydroxide, and a mixture of ammonium hydroxide and hydrogen peroxide.

[0175] For example, when the third layer G is made of silicon nitride, the etching solution is preferably at least one of phosphoric acid, hydrofluoric acid, dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), and ammonium hydroxide.

[0176] The supply unit 15b is an example of the etching unit defined in the present invention.

[0177] The processing unit 11 includes a supply unit 15c. The supply unit 15c supplies a removing liquid to the substrate W. The supply unit 15c supplies the removing liquid to the substrate W held by the substrate holding unit 13. The supply unit 15c supplies the removing liquid to a surface W1 of the substrate W held by the substrate holding unit 13.

[0178] The removal liquid includes, for example, toluene.

[0179] For example, the removal liquid contains a solvent, and the solvent of the removal liquid has the same composition as the solvent of the protection liquid.

[0180] For example, the solvent of the remover is an organic solvent, and the remover contains at least one of toluene, sulfuric acid, a sulfuric acid-hydrogen peroxide mixture (SPM), acetic acid, and hydrochloric acid.

[0181] The solvent of the remover is an example of the first solvent in the present invention.

[0182] The processing unit 11 includes a supply unit 15d. The supply unit 15d supplies a rinse liquid to the substrate W. The supply unit 15d supplies the rinse liquid to the substrate W held by the substrate holder 13. The supply unit 15d supplies the rinse liquid to a surface W1 of the substrate W held by the substrate holder 13.

[0183] The rinse liquid is, for example, deionized water (DIW) and / or isopropyl alcohol. The rinse liquid is also called a cleaning liquid.

[0184] The processing unit 11 includes a supply unit 15e. The supply unit 15e supplies a dry gas to the substrate W. The supply unit 15e supplies the dry gas to the substrate W held by the substrate holding unit 13. The supply unit 15e supplies the dry gas to a surface W1 of the substrate W held by the substrate holding unit 13.

[0185] The dry gas preferably has a dew point lower than the temperature inside the housing 12. The dry gas includes at least one of air and an inert gas. The air is, for example, compressed air. The inert gas is, for example, nitrogen gas.

[0186] The configurations of the supply units 15a, 15b, 15c, 15d, and 15e are illustrated. The supply unit 15a includes a nozzle 16a. The nozzle 16a is installed inside the housing 12. The nozzle 16a is disposed above the substrate W held by the substrate holder 13. The nozzle 16a dispenses a protective liquid. Similarly, the supply units 15b, 15c, 15d, and 15e include nozzles 16b, 16c, 16d, and 16e, respectively. The nozzles 16b, 16c, 16d, and 16e are installed inside the housing 12, respectively. The nozzle 16b dispenses an etching liquid. The nozzle 16c dispenses a removing liquid. The nozzle 16d dispenses a rinsing liquid. The nozzle 16e dispenses a drying gas.

[0187] Supply unit 15a includes pipe 17a and valve 18a. Pipe 17a is connected to nozzle 16a. At least a portion of pipe 17a may be provided outside housing 12. Valve 18a is provided in pipe 17a. Valve 18a may be provided outside housing 12. When valve 18a is open, nozzle 16a ejects protective liquid. When valve 18a is closed, nozzle 16a does not eject protective liquid. Similarly, supply units 15b, 15c, 15d, and 15e include pipes 17b, 17c, 17d, and 17e and valves 18b, 18c, 18d, and 18e, respectively. Pipes 17b, 17c, 17d, and 17e are connected to nozzles 16b, 16c, 16d, and 16e, respectively. Valves 18b, 18c, 18d, and 18e are provided on pipes 17b, 17c, 17d, and 17e, respectively. Valve 18b controls the discharge of the etching liquid from nozzle 16b. Valve 18c controls the discharge of the removal liquid from nozzle 16c. Valve 18d controls the discharge of the rinse liquid from nozzle 16d. Valve 18e controls the discharge of the drying gas from nozzle 16e.

[0188] Supply unit 15a is connected to supply source 19a. Supply source 19a supplies a protection liquid to supply unit 15a. Similarly, supply units 15b, 15c, 15d, and 15e are connected to supply sources 19b, 19c, 19d, and 19e, respectively. Supply source 19b supplies an etching liquid to supply unit 15b. Supply source 19c supplies a removal liquid to supply unit 15c. Supply source 19d supplies a rinsing liquid to supply unit 15d. Supply source 19e supplies a drying gas to supply unit 15e.

[0189] The supply source 19a is provided outside the housing 12. Similarly, the supply sources 19b, 19c, 19d, and 19e are each provided outside the housing 12.

[0190] The supply source 19a may distribute the protective liquid to the supply portions 15a of multiple processing units 11. Alternatively, the supply source 19a may supply the protective liquid exclusively to the supply portion 15a of one processing unit 11. The same applies to the supply sources 19b, 19c, 19d, and 19e.

[0191] The supply source 19a may be a component of the substrate processing apparatus 1. For example, the supply source 19a may be installed inside the substrate processing apparatus 1. Alternatively, the supply source 19a may not be a component of the substrate processing apparatus 1. For example, the supply source 19a may be installed outside the substrate processing apparatus 1. Similarly, at least one of the supply sources 19b, 19c, 19d, and 19e may be a component of the substrate processing apparatus 1. Alternatively, at least one of the supply sources 19b, 19c, 19d, and 19e may not be a component of the substrate processing apparatus 1.

[0192] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is disposed on the side of the substrate holding part 13. The cup surrounds the substrate holding part 13. The cup catches liquid splashed from the substrate W held by the substrate holding part 13.

[0193] 2, the control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply units 15a-15e. The control unit 10 controls the valves 18a-18e.

[0194] 1-4. Example of Procedure of Substrate Processing Method The substrate processing method is performed in the processing unit 11. The substrate processing method is for processing the substrate W held by the substrate holder 13.

[0195] 19 is a flowchart showing the procedure of a substrate processing method. The substrate processing method includes a cycle process. The cycle process is repeated two or more times. For example, the cycle process is repeated ten or more times.

[0196] The substrate processing method includes a final removal step. The final removal step is performed after the cycle step is repeated two or more times. In other words, the cycle step is repeated two or more times before the final removal step.

[0197] The substrate processing method includes a final rinse step, which is performed after the cycle step is repeated two or more times. In other words, the cycle step is repeated two or more times before the final rinse step.

[0198] The substrate processing method includes a final drying step, which is performed after the cycle step is repeated two or more times. In other words, the cycle step is repeated two or more times before the final drying step.

[0199] After the final removal step, a final drying step is performed. After the final removal step, a final rinsing step is performed. Before the final drying step, a final rinsing step is performed.

[0200] Each step will be described below.

[0201] Step S1: Cycling Process The control unit 10 controls the supply units 15a and 15b to execute the cycling process. The control unit 10 causes the supply units 15a and 15b to repeat the cycling process two or more times.

[0202] 20 is a flowchart showing the procedure of the cycle process of the first embodiment. The cycle process includes a film formation process and an etching process. The film formation process is performed before the etching process. The etching process is performed after the film formation process. For example, the etching process is performed after the film formation process.

[0203] Step S11: Film Formation Process In the film formation process, a self-assembled monolayer is formed on the first layer E and the second layer F. Specifically, the control unit 10 controls the supply unit 15a to execute the film formation process. In the film formation process, the supply unit 15a supplies a protective liquid to the substrate W. In the film formation process, the supply unit 15a forms a self-assembled monolayer on the first layer E and the second layer F.

[0204] Step S21: Etching Process In the etching process, an etching liquid is supplied to the substrate W, and the third layer G is etched. Specifically, the control unit 10 controls the supply unit 15b to execute the etching process. In the etching process, the supply unit 15b supplies the etching liquid to the substrate W. In the etching process, the supply unit 15b etches the third layer G.

[0205] When one cycle step ends, the next cycle step begins. Multiple cycle steps are performed consecutively. For example, the time when one cycle step ends is the same time when the next cycle step begins.

[0206] When the cycle process is repeated, the film formation process and the etching process are performed alternately.

[0207] When the cycle process is repeated two or more times, multiple film formation processes are performed. The self-assembled monolayer is repeatedly formed into the first layer E and the second layer F in the multiple film formation processes. The first layer E and the second layer F are repeatedly covered with the self-assembled monolayer in the multiple film formation processes.

[0208] When the cycle process is repeated two or more times, multiple etching steps are performed. The third layer G is repeatedly etched in multiple etching steps.

[0209] Step S2: Final Removal Step In the final removal step, the self-assembled monolayer is removed from the substrate W. Specifically, the control unit 10 controls the supply unit 15c to execute the final removal step. In the final removal step, the supply unit 15c supplies a removal liquid to the substrate W. This separates the self-assembled monolayer from the first layer E and the second layer F. The self-assembled monolayer is removed from the substrate W. As a result, the first layer E is not covered with the self-assembled monolayer. The second layer F is not covered with the self-assembled monolayer.

[0210] Step S3: Final Rinse Process In the final rinse process, a rinse liquid is supplied to the substrate W. The rinse liquid supplied to the substrate W in the final rinse process is called the "final rinse liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the final rinse process. In the final rinse process, the supply unit 15d supplies the final rinse liquid to the substrate W. As a result, the removing liquid is removed from the substrate W.

[0211] Step S4: Final Drying Step In the final drying step, the substrate W is dried. Specifically, the control unit 10 controls at least one of the rotation drive unit 14 and the supply unit 15e to execute the final drying step. For example, in the final drying step, the rotation drive unit 14 rotates the substrate W held by the substrate holder 13. For example, in the final drying step, the supply unit 15e supplies a drying gas to the substrate W. This dries the substrate W.

[0212] In addition, the rotation driver 14 may rotate the substrate W held by the substrate holder 13 in at least one of the cycle step, the final removal step, and the final rinsing step.

[0213] 1-5. Technical Significance of Repeating the Cyclic Process Two or More Times The technical significance of repeating the cyclic process two or more times will be explained using the first example and a comparative example.

[0214] The conditions of the first embodiment will be explained. FIG. 21 is a flowchart showing the procedure of the substrate processing method of the first embodiment. In the first embodiment, the cycle process is repeated twice. Specifically, in the first embodiment, the cycle process includes a first cycle process and a second cycle process. The first cycle process is performed, and then the second cycle process is performed. The cycle process includes a film formation process and an etching process. The first cycle process includes a film formation process and an etching process. The second cycle process includes a film formation process and an etching process. The film formation process is performed twice. The etching process is performed twice.

[0215] A substrate W to be processed by the substrate processing method of the first embodiment will be described.

[0216] For convenience, refer to Figure 4(a). Before the first cycle step, the first layer E is exposed. Before the first cycle step, the second layer F is exposed. Before the first cycle step, the third layer G is exposed.

[0217] Step S11: Film Formation Process of First Cycle Step Figure 22 schematically shows a substrate in the film formation process of the first cycle step. In the film formation process of the first cycle step, a protective liquid Q is supplied to the substrate W. The protective liquid Q contains materials for a self-assembled monolayer P. At least a portion of the materials for the self-assembled monolayer P is transformed into a self-assembled monolayer P. The self-assembled monolayer P is formed into a first layer E and a second layer F. The first layer E and the second layer F are covered with the self-assembled monolayer P. After the film formation process of the first cycle step, the first layer E is not exposed. After the film formation process of the first cycle step, the second layer F is not exposed. After the film formation process of the first cycle step, the first layer E and the second layer F are protected.

[0218] The self-assembled monolayer P includes a first self-assembled monolayer P1. The first self-assembled monolayer P1 is formed on the first layer E.

[0219] The first self-assembled monolayer P1 is formed on a portion of the surface E1. The other portion of the surface E1 is in contact with the third layer G. The surface E1 is not exposed. The surface E1 is protected.

[0220] The first self-assembled monolayer P1 is formed on the surface E2. The surface E2 is not exposed. The surface E2 is protected.

[0221] The self-assembled monolayer P includes a second self-assembled monolayer P2. The second self-assembled monolayer P2 is formed on the second layer F.

[0222] The entire surface F1 is in contact with the third layer G. The surface F1 is not exposed. The surface F1 is protected.

[0223] The second self-assembled monolayer P2 is formed on the surface F2. The surface F2 is not exposed. The surface F2 is protected.

[0224] A self-assembled monolayer P is not formed on the third layer G. A self-assembled monolayer P is not formed on the surface G3. After the film formation process of the first cycle step, the third layer G is still exposed. After the film formation process of the first cycle step, the surface G3 is still exposed.

[0225] The self-assembled monolayer P is sufficiently thin. Specifically, the self-assembled monolayer P has a thickness PT. The thickness PT is smaller than half the separation distance D. Therefore, even after the self-assembled monolayer P is formed on the surface E1 and the surface F1, at least a portion of the surface G3 is not covered with the self-assembled monolayer P. At least a portion of the surface G3 is exposed.

[0226] For example, the second self-assembled monolayer P2 has the same composition as the first self-assembled monolayer P1.

[0227] Step S21: Etching step of first cycle process Figure 23 schematically shows the substrate W in the etching step of the first cycle process. Figure 23 schematically shows the substrate W at the start of the etching step of the first cycle process. In the etching step of the first cycle process, an etching solution R is supplied to the substrate W. The third layer G comes into contact with the etching solution R. The self-assembled monolayer P protects the first layer E and the second layer F from the etching solution R. The first layer E and the second layer F do not come into contact with the etching solution R.

[0228] 24 is a schematic diagram of the substrate W in the etching step of the first cycle process. Also, FIG. 24 is a schematic diagram of the substrate W at the end of the etching step of the first cycle process. The third layer G is etched. In the etching step of the first cycle process, the third layer G is etched by an etching amount LG1.

[0229] When the third layer G is etched, a portion of the third layer G is removed. After a portion of the third layer G is removed in the etching step of the first cycle step, a portion E1a of the surface E1 is not in contact with the third layer G and is not covered with the self-assembled monolayer P. Similarly, after a portion of the third layer G is etched in the etching step of the first cycle step, a portion F1a of the surface F1 is not in contact with the third layer G and is not covered with the self-assembled monolayer P. After a portion of the third layer G is etched in the etching step of the first cycle step, the portions E1a and F1a are not protected. After a portion of the third layer G is etched in the etching step of the first cycle step, the portions E1a and F1a are exposed. The portions E1a and F1a come into contact with the etching solution R. The portions E1a and F1a are exposed to the etching solution R. The portions E1a and F1a may be etched by the etching solution R. Therefore, after a portion of the third layer G is etched in the etching step of the first cycle step, it is difficult to protect the surface E1 and the surface F1.

[0230] Step S11: Film Formation Step of Second Cycle Step Figure 25 schematically shows the substrate W in the film formation step of the second cycle step. In the film formation step of the second cycle step, a protective liquid Q is supplied to the substrate W. A new self-assembled monolayer P is formed on the first layer E and the second layer F. The new self-assembled monolayer P is also formed on portions E1a and F1a. The portions E1a and F1a are covered with the self-assembled monolayer P. After the film formation step of the second cycle step, the first layer E is not exposed. After the film formation step of the second cycle step, the second layer F is not exposed. After the film formation step of the second cycle step, the first layer E and the second layer F are protected again.

[0231] Step S21: Etching step of second cycle process Figure 26 schematically shows a substrate in the etching step of the second cycle process. Figure 26 schematically shows a substrate at the start of the etching step of the second cycle process. In the etching step of the second cycle process, etching solution R is supplied to the substrate W. The third layer G again comes into contact with the etching solution R. The self-assembled monolayer P protects the first layer E and the second layer F from the etching solution R. The self-assembled monolayer P protects portions E1a and F1a from the etching solution R. The first layer E and the second layer F do not come into contact with the etching solution R. The portions E1a and F1a do not come into contact with the etching solution R.

[0232] 27 is a schematic diagram of the substrate during the etching step of the second cycle. Also, FIG. 27 is a schematic diagram of the substrate at the end of the etching step of the second cycle. The third layer G is etched again. During the etching step of the second cycle, the third layer G is etched by an etching amount LG2.

[0233] The sum of the etching amount LG1 and the etching amount LG2 corresponds to the total etching amount of the third layer G in the multiple etching steps of the first embodiment.

[0234] When the third layer G is etched, a portion of the third layer G is removed. After a portion of the third layer G is etched in the etching step of the second cycle step, another portion E1b of the surface E1 is not in contact with the third layer G and is not covered with the self-assembled monolayer P. Similarly, after a portion of the third layer G is etched in the etching step of the second cycle step, another portion F1b of the surface F1 is not in contact with the third layer G and is not covered with the self-assembled monolayer P. After a portion of the third layer G is etched in the etching step of the second cycle step, the portions E1b, F1b are not protected. After a portion of the third layer G is etched in the etching step of the second cycle step, the portions E1b, F1b are exposed.

[0235] However, the portion E1b is located at a different position from the portion E1a, and the portion F1b is located at a different position from the portion F1a.

[0236] During the etching step of the second cycle step, while a portion of the third layer G is etched, the self-assembled monolayer P is formed into portions E1a and F1a. During the etching step of the second cycle step, while a portion of the third layer G is etched, the portions E1a and F1a are not exposed. During the etching step of the second cycle step, while a portion of the third layer G is etched, the portions E1a and F1a do not come into contact with the etching solution R. During the etching step of the second cycle step, while a portion of the third layer G is etched, the self-assembled monolayer P protects the portions E1a and F1a. During the etching step of the second cycle step, while a portion of the third layer G is etched, the portions E1a and F1a are not etched.

[0237] As described above, after the portions E1a and F1a are exposed, the self-assembled monolayer P is quickly formed on the portions E1a and F1a. For example, the portions E1a and F1a are exposed in the etching step of the first cycle process. In this case, the self-assembled monolayer P is quickly formed on the portions E1a and F1a before the etching step of the second cycle process. Therefore, the time during which the portions E1a and F1a are exposed is short. The time during which the portions E1a and F1a are in contact with the etching solution R is short. Therefore, it is easy to protect the portions E1a and F1a from the etching solution R. For example, the etching amount of the portions E1a and F1a is small. For example, the portions E1a and F1a are not substantially etched.

[0238] Similarly, the time that the portions E1b and F1b are in contact with the etching solution R is short. Therefore, it is easy to protect the portions E1b and F1b from the etching solution R. For example, the etching amount of the portions E1b and F1b is small. For example, the portions E1b and F1b are not substantially etched.

[0239] Therefore, it is easy to protect the surfaces E1 and F1 from the etching solution R. For example, the etching amount of the surfaces E1 and F1 is small. For example, the surfaces E1 and F1 are not substantially etched.

[0240] Therefore, it is easy to protect the first layer E and the second layer F from the etching solution R. For example, the etching amount of the first layer E and the second layer F is small. For example, the first layer E and the second layer F are not substantially etched.

[0241] The conditions of the comparative example will be described. Fig. 28 is a flowchart showing the procedure of the substrate processing method of the comparative example. In the comparative example, the film forming process is performed only once. In the comparative example, the etching process is performed only once. In the comparative example, there is no cycle process that is repeated two or more times.

[0242] A substrate W processed by a substrate processing method of a comparative example will be described.

[0243] For convenience, refer to Figure 4(a). Before the film formation process, the first layer E is exposed. Before the film formation process, the second layer F is exposed. Before the film formation process, the third layer G is exposed.

[0244] Step S31: Film Forming Step of Comparative Example For convenience, refer to Fig. 22. In the film forming step, the self-assembled monolayer P is formed into a first layer E and a second layer F.

[0245] Step S32: Etching Step of Comparative Example For convenience, refer to Fig. 23. In the etching step, the third layer G comes into contact with the etching solution R. The self-assembled monolayer P protects the first layer E and the second layer F from the etching solution R.

[0246] For convenience, refer to Figure 24. The third layer G is etched. The third layer G is etched by an etching amount LG1. After the third layer G is etched by the etching amount LG1, portions E1a and F1a are exposed.

[0247] 29 is a schematic diagram of the substrate W during the etching process of the comparative example. FIG. 29 is a schematic diagram of the substrate W at the end of the etching process of the comparative example. Subsequently, the third layer G is etched. The third layer G is further etched by an etching amount LG2. While the third layer G is etched by the etching amount LG2, portions E1a and F1a remain exposed. While the third layer G is etched by the etching amount LG2, portions E1a and F1a come into contact with the etching solution R. While the third layer G is etched by the etching amount LG2, portions E1a and F1a are etched. Therefore, the etching amounts of portions E1a and F1a are significantly large.

[0248] After the third layer G is etched by an etching amount LG2, the other portions E1b and F1b are exposed.

[0249] The differences between the first embodiment and the comparative example are summarized below. See FIGS. 27 and 29. In the first embodiment, the time during which the portions E1a and F1a are in contact with the etching solution R is shorter than the time during which the portions E1a and F1a are in contact with the etching solution R in the comparative example. Therefore, the etching amount of the portions E1a and F1a in the first embodiment is smaller than the etching amount of the portions E1a and F1a in the comparative example. Therefore, the etching amount of the surfaces E1 and F1 in the first embodiment is smaller than the etching amount of the surfaces E1 and F1 in the comparative example. The etching amount of the first layer E and the second layer F in the first embodiment is smaller than the etching amount of the first layer E and the second layer F in the comparative example.

[0250] 1-6. Processing conditions for the cycle process Examples of processing conditions for the cycle process are given below.

[0251] The etching amount LGa is smaller than the target value LGT. The "etching amount LGa" is the etching amount of the third layer G in one etching step in one cycle process. More specifically, the "etching amount LGa" is the etching amount of the third layer G in one etching step in one cycle process when the third layer G is not protected by the self-assembled monolayer P. The "target value LGT" is the target value of the total etching amount of the third layer G. More specifically, the "target value LGT" is the target value of the total etching amount of the third layer G in multiple etching steps. Here, the total etching amount of the third layer G is the sum of the etching amounts of the third layer G in all etching steps in all cycle processes. For example, the total etching amount of the third layer G is the sum of all etching amounts LGa. For example, the target value LGT is 100 nm, and the etching amount LGa is 2 nm.

[0252] The number of times the cycle process is repeated is determined by the target value LGT. For example, the number of times the cycle process is repeated is determined by the target value LGT and the etching amount LGa. For example, the number of times the cycle process is repeated is the value obtained by dividing the target value LGT by the etching amount LGa. For example, when the target value LGT is 100 nm and the etching amount LGa is 2 nm, the number of times the cycle process is repeated is 50.

[0253] The "etching time TEa" is the time required for one etching step in one cycle process. The etching time TEa is, for example, the time required for the portions E1a and F1a to come into contact with the etching solution R.

[0254] For example, the etching time TEa depends on at least one of the etching rate UE and RF. "Etching rate UE" is the etching rate of the first layer E. More specifically, "etching rate UE" is the etching rate of the first layer E when the first layer E is not protected by the self-assembled monolayer P. The etching rate of the first layer E is the amount of etching of the first layer E per unit time. "Etching rate UF" is the etching rate of the second layer F. More specifically, "etching rate UF" is the etching rate of the second layer F when the second layer F is not protected by the self-assembled monolayer P. The etching rate of the second layer F is the amount of etching of the second layer F per unit time.

[0255] For example, the etching time TEa is determined based on the etching rate UE and a first threshold V1. The "first threshold V1" is the upper limit of the etching amount LEa. The "etching amount LEa" is the etching amount of the first layer E in one etching step in one cycle process. More specifically, the "etching amount LEa" is the etching amount of the first layer E in one etching step in one cycle process when the first layer E is not protected by the self-assembled monolayer P.

[0256] For example, the etching time TEa is limited so that the etching amount LEa is equal to or less than the first threshold value V1.

[0257] For example, the etching time TEa is determined based on the etching rate UF and the first threshold V2. The "second threshold V2" is the upper limit of the etching amount LFa. The "etching amount LFa" is the etching amount of the second layer F in one etching step in one cycle process. More specifically, the "etching amount LFa" is the etching amount of the second layer F in one etching step in one cycle process when the second layer F is not protected by the self-assembled monolayer P.

[0258] For example, the etching time TEa is limited so that the etching amount LFa is equal to or less than the second threshold value V2.

[0259] For example, the etching time TEa does not depend on the etching rate UG. The "etching rate UG" is the etching rate of the third layer G. More specifically, the "etching rate UG" is the etching rate of the third layer G when the third layer G is not protected by the self-assembled monolayer P. The etching rate of the third layer G is the amount of etching of the third layer G per unit time.

[0260] Alternatively, the etching time TEa may depend on the etching rate UG.

[0261] For example, the etching time TEa is determined based on the etching rate UG and a third threshold V3, which is the upper limit of the etching amount LGa.

[0262] For example, the etching time TEa is limited so that the etching amount LGa is equal to or less than the third threshold value V3.

[0263] For example, the third threshold V3 is equal to or less than 2 nm.

[0264] For example, the etching time TEa does not depend on the target value LGT.

[0265] For example, in the cycling process, the substrate W is not dried.

[0266] For example, the self-assembled monolayer P is not removed from the substrate W in the cycling process.

[0267] 1-7. Effects of First Embodiment The substrate processing method of the first embodiment is for processing a substrate W. The substrate W includes a first layer E, a second layer F, and a third layer G. The third layer G is located between the first layer E and the second layer F. The first layer E has a surface E1. The surface E1 is in surface contact with the third layer G. The second layer F has a surface F1. The surface F1 is in surface contact with the third layer G. The first layer E has a composition different from the composition of the third layer G. The second layer F has a composition different from the composition of the third layer G.

[0268] The substrate processing method includes a cycle process. The cycle process includes a film formation process and an etching process. In the film formation process, a self-assembled monolayer P is formed on a first layer E and a second layer F. In the etching process, an etching solution R is supplied to the substrate W, and the third layer G is etched.

[0269] In the etching step, the self-assembled monolayer P protects the first layer E and the second layer F. Specifically, in the etching step, the self-assembled monolayer P protects the first layer E and the second layer F from the etching solution R. However, after the third layer G is etched, a portion E1a of the surface E1 and a portion F1a of the surface F1 are exposed.

[0270] The cycle process is repeated two or more times. The film formation process is repeated two or more times. Therefore, after the portions E1a and F1a are exposed, the self-assembled monolayer P is quickly formed on the portions E1a and F1a. Therefore, the time during which the portions E1a and F1a are exposed is short. The time during which the portions E1a and F1a are in contact with the etching solution R is short. Therefore, it is easy to protect the portions E1a and F1a from the etching solution R. Therefore, it is easy to protect the first layer E and the second layer F from the etching solution R.

[0271] The cycle process is repeated two or more times. Therefore, the etching process is performed two or more times. Therefore, it is easy to increase the total time of the multiple etching processes. Therefore, it is easy to etch the third layer G. Even if the etching rate UG of the third layer G is low, it is easy to increase the etching amount LG of the third layer G. For example, even if the etching amount LGa is small, it is easy to increase the total etching amount of the third layer G.

[0272] In summary, according to the substrate processing method of the first embodiment, the first layer E and the second layer F are appropriately protected, and the third layer G is appropriately etched. Therefore, according to the substrate processing method, the substrate W is appropriately processed.

[0273] The third layer G is repeatedly etched in a plurality of etching steps, so that the third layer G is properly etched.

[0274] For example, the cycle process is repeated 10 or more times, so that the etching time TEa is shorter, and it is therefore easier to protect the first layer E and the second layer F from the etching solution R.

[0275] For example, the etching process is repeated 10 or more times. Therefore, the third layer G is repeatedly etched 10 or more times. Therefore, the third layer G is properly etched.

[0276] The etching amount LGa is smaller than the target value LGT. Therefore, by repeating the cycle process two or more times, it is easy to make the total etching amount of the third layer G in the multiple etching processes equal to the target value LGT.

[0277] The number of times the cycle process is repeated is determined by the target value LGT, so it is easy to make the total etching amount of the third layer G equal to the target value.

[0278] For example, the etching time TEa depends on at least one of the etching rates UE and UF, so that it is easy to protect the first layer E and the second layer F.

[0279] The etching time TEa is determined based on the etching rate UE and the first threshold value V1, so that it is easy to protect the first layer E.

[0280] The etching time TEa is limited so that the etching amount LEa is equal to or less than the first threshold value V1. Therefore, it is easy to control the etching amount LEa to be equal to or less than the first threshold value V1.

[0281] The etching time TEa is determined based on the etching rate UF and the second threshold value V2, so that it is easy to protect the second layer F.

[0282] The etching time TEa is limited so that the etching amount LFa is equal to or less than the second threshold value V2, so that it is easy to control the etching amount LFa to be equal to or less than the second threshold value V2.

[0283] For example, the etching time TEa does not depend on the etching rate UG of the third layer G. Therefore, it is easy to protect the first layer E and the second layer F.

[0284] Alternatively, the etching time TEa depends on the etching rate UG, so it is easy to etch the third layer G. For example, it is easy to adjust the etching amount LGa.

[0285] The etching time TEa is determined based on the etching rate UG and the third threshold V3, which makes it easy to etch the third layer G. For example, it is easy to adjust the etching amount LGa.

[0286] The etching time TEa is limited so that the etching amount LGa is equal to or less than the third threshold value V3, so that it is easy to control the etching amount LGa to be equal to or less than the third threshold value V3.

[0287] The third threshold V3 is 2 nm or less. Therefore, the etching amount LGa is small. Therefore, the etching time TEa is short. Therefore, it is easy to protect the first layer E and the second layer F. The cycle process is frequently repeated. Therefore, it is easier to etch the third layer G in the etching process. For example, it is easy to fine-tune the total etching amount of the third layer G.

[0288] For example, the etching time TEa does not depend on the target value LGT, so it is easy to protect the first and second layers.

[0289] The self-assembled monolayer P has a thickness PT. The thickness PT is smaller than half the separation distance D. Therefore, even when the self-assembled monolayer P is formed on surfaces E1 and F1, the self-assembled monolayer P does not fill the entire space A. Even when the self-assembled monolayer P is formed on surfaces E1 and F1, the self-assembled monolayer P fills only a portion of the space A. Therefore, even when the self-assembled monolayer P is formed on surfaces E1 and F1, at least a portion of the third layer G is not covered with the self-assembled monolayer P. Therefore, even when the self-assembled monolayer P is formed on surfaces E1 and F1, the self-assembled monolayer P allows the third layer G to come into contact with the etching solution R. As a result, even when the self-assembled monolayer P is formed on surfaces E1 and F1, it is easy to etch the third layer G.

[0290] For example, the first layer E is made of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride. The second layer F is made of at least one of single crystal silicon, polysilicon, amorphous silicon, and silicon nitride. The third layer G is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. The self-assembled monolayer P contains an unsaturated hydrocarbon. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0291] For example, the first layer E is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. The self-assembled monolayer P contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0292] For example, at least one of the first layer E and the second layer F is made of silicon nitride. The third layer G is made of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. The self-assembled monolayer P contains at least one of unsaturated hydrocarbon and alkyl bromide. Therefore, it is easy to form the self-assembled monolayer P on at least one of the first layer E and the second layer F in the film formation process.

[0293] For example, one of the first layer E and the second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The other of the first layer E and the second layer F is composed of silicon nitride. The third layer G is composed of at least one of silicon oxide, titanium nitride, titanium, titanium oxide, and tungsten. The third layer G does not contain silicon nitride. The self-assembled monolayer P formed on one of the first layer E and the second layer F contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies. The self-assembled monolayer P formed on the other of the first layer E and the second layer F contains at least one of unsaturated hydrocarbons and alkyl bromides. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0294] For example, the first layer E is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The first layer E does not contain silicon nitride. The second layer F is composed of at least one of single crystal silicon, polysilicon, and amorphous silicon. The second layer F does not contain silicon nitride. The third layer G is composed of silicon nitride. The self-assembled monolayer P is composed of at least one of peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies. The self-assembled monolayer P does not contain unsaturated hydrocarbons. The self-assembled monolayer P does not contain alkyl bromides. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0295] The self-assembled monolayer P includes a first self-assembled monolayer P1 and a second self-assembled monolayer P2. The first self-assembled monolayer P1 is formed on the first layer E. The second self-assembled monolayer P2 is formed on the second layer F. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0296] The second self-assembled monolayer P2 has the same composition as the first self-assembled monolayer P1, which simplifies the structure of the self-assembled monolayer P.

[0297] In the film formation step, a protective liquid Q is supplied to the substrate W. The protective liquid Q contains materials for the self-assembled monolayer P. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation step.

[0298] The protection liquid Q further contains toluene, so that the toluene easily limits the thickness PT, and therefore the thickness PT is not excessively large.

[0299] In the cycle process, the substrate W is not dried. Therefore, the cycle process is simple. Therefore, the time required for one cycle process is short. Therefore, it is easier to repeat the cycle process.

[0300] In the cycling step, the self-assembled monolayer P is not removed from the substrate W. Therefore, it is easier to protect the first layer E and the second layer F while the cycling step is repeated.

[0301] The substrate processing method further includes a final removal step. In the final removal step, the self-assembled monolayer P is removed from the substrate W. This makes it difficult for particles to be generated on the substrate W. The particles originate from the self-assembled monolayer P, for example.

[0302] The cycle process is repeated two or more times before the final removal step. Therefore, the cycle process does not include the final removal step. The cycle process is repeated without the final removal step. Therefore, the time for one cycle process is short. Therefore, it is easier to repeat the cycle process.

[0303] In the removal step, a removal liquid is supplied to the substrate W. The removal liquid contains a solvent. In the film formation step, a protection liquid Q is supplied to the substrate W. The protection liquid Q contains the material of the self-assembled monolayer P and a solvent. The solvent of the protection liquid Q has the same composition as the solvent of the removal liquid. Therefore, it is easy for the solvent of the protection liquid Q to limit the thickness PT. Therefore, the thickness PT is not excessively large.

[0304] In the removal step, toluene is supplied to the substrate W. Specifically, in the removal step, a removal liquid is supplied to the substrate W. The removal liquid contains toluene. Therefore, it is easy for the removal liquid to remove the self-assembled monolayer P from the substrate W.

[0305] The substrate processing method further includes a final drying step, in which the substrate W is dried. The cycle step is repeated two or more times before the final drying step. Therefore, the cycle step does not include the final drying step. The cycle step is repeated without the final drying step. Therefore, the time required for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0306] The substrate processing method further includes a final rinse step. In the final rinse step, a final rinse liquid is supplied to the substrate W. The cycle step is repeated two or more times before the final rinse step. Therefore, the cycle step does not include the final rinse step. The cycle step is repeated without the final rinse step. Therefore, the time required for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0307] The final rinsing step is performed before the final drying step. In the final rinsing step, the substrate W is properly cleaned with the final rinse liquid. Therefore, when the substrate W is dried in the final drying step, particles are less likely to be generated on the substrate W.

[0308] The substrate processing apparatus 1 processes a substrate W. The substrate processing apparatus 1 includes a supply unit 15a, a supply unit 15b, and a control unit 10. The supply unit 15a forms a self-assembled monolayer P on the first layer E and the second layer F. The supply unit 15b etches the third layer G. The control unit 10 controls the supply units 15a and 15b. The control unit 10 executes a cycle process. The cycle process includes a film formation process and an etching process. In the film formation process, the supply unit 15a forms a self-assembled monolayer P on the first layer E and the second layer F. In the etching process, the supply unit 15b supplies an etching liquid R to the substrate W to etch the third layer G.

[0309] The cycle process is repeated two or more times, so that it is easy to protect the first layer E and the second layer F from the etching solution R. For example, it is easy to protect the surfaces E1 and F1 from the etching solution R.

[0310] The cycle process is repeated two or more times, so that etching the third layer G is easy.

[0311] In summary, the substrate processing apparatus 1 properly protects the first layer E and the second layer F, and also properly etches the third layer G. Therefore, the substrate processing apparatus 1 properly processes the substrate W.

[0312] 2. Second Embodiment A substrate processing apparatus 1 and a substrate processing method according to a second embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0313] The second embodiment is the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the structure of the substrate W.

[0314] 30 is a diagram showing the configuration of the processing unit 11 of the second embodiment. The supply unit 15a includes a supply unit 15a1 and a supply unit 15a2. The supply unit 15a1 supplies a first protective liquid to the substrate W. The supply unit 15a2 supplies a second protective liquid to the substrate W.

[0315] The first protective liquid contains the material of the first self-assembled monolayer P1, and the second protective liquid contains the material of the second self-assembled monolayer P2.

[0316] For example, the material of the second self-assembled monolayer P2 has a different composition from the material of the first self-assembled monolayer P1. For example, the material of the first self-assembled monolayer P1 belongs to one of the second group N and the third group O. The material of the second self-assembled monolayer P2 belongs to the other of the second group N and the third group O.

[0317] When the composition of the material of the second self-assembled monolayer P2 is different from the composition of the material of the first self-assembled monolayer P1, the second self-assembled monolayer P2 has a composition different from the composition of the first self-assembled monolayer P1.

[0318] Alternatively, the material of the second self-assembled monolayer P2 may have the same composition as the material of the first self-assembled monolayer P1.

[0319] When the first protective liquid and the second protective liquid are not distinguished from each other, the first protective liquid and the second protective liquid are referred to as "protective liquid Q." When the first self-assembled monolayer P1 and the second self-assembled monolayer P2 are not distinguished from each other, the first self-assembled monolayer P1 and the second self-assembled monolayer P2 are referred to as "self-assembled monolayer P."

[0320] The processing unit 11 includes supply parts 15f and 15g in addition to the supply parts 15a to 15e. The supply part 15f supplies a first substitute liquid to the substrate W. The supply part 15g supplies a second substitute liquid to the substrate W.

[0321] The first substitution liquid is, for example, toluene.

[0322] The first replacement liquid contains, for example, a solvent. The solvent of the first replacement liquid has the same composition as the solvent of the protection liquid Q.

[0323] The solvent of the first substitute liquid is an organic solvent, and the solvent of the first substitute liquid contains, for example, at least one of ethanol, isopropyl alcohol, toluene, hexane, hexanone, cyclohexane, and benzene.

[0324] The solvent of the first displacement liquid is an example of the third solvent in the present invention.

[0325] The second substitution liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol.

[0326] Each of the supply units 15a1, 15a2, 15f, and 15g has a configuration similar to that of the supply unit 15a.

[0327] Although not shown in the figure, the control unit 10 controls the supply units 15a1, 15a2, 15f, and 15g.

[0328] 2-2. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the second embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the second embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the second embodiment is different from that of the substrate processing method of the first embodiment. Therefore, the cycle step of the second embodiment will be described.

[0329] 31 is a flowchart showing the procedure of the cycle process of the second embodiment. The cycle process includes a first replacement process and a second replacement process in addition to a film formation process and an etching process. The first replacement process is performed before the film formation process. The second replacement process is performed after the film formation process and before the etching process.

[0330] The control unit 10 controls the supply units 15a1, 15a2, 15b, 15f, and 15g to execute the cycle process. The control unit 10 causes the supply units 15a1, 15a2, 15b, 15f, and 15g to repeat the cycle process two or more times.

[0331] Each step will be described below.

[0332] Step S10: First Substitution Step In the first substitution step, a first substitute liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15f to execute the first substitution step. In the first substitution step, the supply unit 15f supplies the first substitute liquid to the substrate W.

[0333] Step S11: Film Formation Step In the film formation step, a self-assembled monolayer P is formed on a first layer E and a second layer F. The film formation step includes a first film formation step and a second film formation step. For example, in the film formation step, a protective liquid Q is supplied to the substrate W.

[0334] Step S11a: First Film Formation Process In the first film formation process, a first self-assembled monolayer P1 is formed on the first layer E. Specifically, the control unit 10 controls the supply unit 15a1 to execute the first film formation process. In the first film formation process, the supply unit 15a1 supplies a first protective liquid to the substrate W. In the first film formation process, the supply unit 15a1 forms the first self-assembled monolayer P1 on the first layer E.

[0335] Step S11b: Second Film Formation Process In the second film formation process, a second self-assembled monolayer P2 is formed on the second layer F. Specifically, the control unit 10 controls the supply unit 15a2 to execute the second film formation process. In the second film formation process, the supply unit 15a2 supplies the second protective liquid to the substrate W. In the second film formation process, the supply unit 15a2 forms the second self-assembled monolayer P2 on the second layer F.

[0336] At least a part of the period during which the second film formation step is performed may overlap at least a part of the period during which the first film formation step is performed. For example, the second film formation step is performed simultaneously with the first film formation step.

[0337] Alternatively, the period during which the second film formation process is performed does not have to overlap with the period during which the first film formation process is performed. For example, the second film formation process is performed after the first film formation process. For example, the second film formation process is performed before the first film formation process.

[0338] Step S12: Second Substitution Step In the second substitution step, a second substitution liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15g to execute the second substitution step. In the second substitution step, the supply unit 15g supplies the second substitution liquid to the substrate W. In the second substitution step, the protection liquid Q on the substrate W is replaced with the second substitution liquid. In the second substitution step, the protection liquid Q is removed from the substrate W.

[0339] As described above, the protective liquid Q contains the material of the self-assembled monolayer P. A portion of the material of the self-assembled monolayer P is transformed into the self-assembled monolayer P. The other portion of the material of the self-assembled monolayer P remains in the protective liquid Q without being transformed into the self-assembled monolayer P. The other portion of the material of the self-assembled monolayer P is the "excess material of the self-assembled monolayer." In the second substitution step, the excess material of the self-assembled monolayer P is also removed from the substrate W.

[0340] The second substitution liquid used in the second substitution step may be only one of deionized water and isopropyl alcohol. For example, in the second substitution step, deionized water may be supplied to the substrate W. In this case, the protection liquid Q on the substrate W is directly replaced with deionized water.

[0341] Alternatively, the second substitution liquid used in the second substitution step may be both deionized water and isopropyl alcohol. For example, in the second substitution step, isopropyl alcohol may be supplied to the substrate W, and then deionized water may be supplied to the substrate W. In this case, the protection liquid Q on the substrate W is replaced with isopropyl alcohol, and then the isopropyl alcohol on the substrate W is replaced with deionized water. The protection liquid Q on the substrate W is indirectly replaced with deionized water.

[0342] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0343] 2-3. Advantages of the Second Embodiment The second embodiment has advantages similar to those of the first embodiment. Furthermore, the second embodiment has the following advantages.

[0344] The second self-assembled monolayer P2 has a composition different from that of the first self-assembled monolayer P1. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process. For example, even if the second layer F has a composition different from that of the first layer E, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process.

[0345] The film formation process includes a first film formation process and a second film formation process. In the first film formation process, a first self-assembled monolayer P1 is formed on the first layer E. In the second film formation process, a second self-assembled monolayer P2 is formed on the second layer F. Therefore, it is easy to form the self-assembled monolayer P on the first layer E and the second layer F in the film formation process. For example, even if the second self-assembled monolayer P2 has a composition different from that of the first self-assembled monolayer P1, it is easy to form the self-assembled monolayer P in the film formation process.

[0346] The cycle process includes a first substitution process. In the first substitution process, a first substitution liquid is supplied to the substrate W. The first substitution process is performed before the film formation process. Therefore, it is easy to supply the protection liquid Q to the substrate W in the film formation process. Therefore, it is easy to reduce the amount of protection liquid Q used.

[0347] The first replacement liquid contains a solvent. The solvent in the first replacement liquid has the same composition as the solvent in the protection liquid Q. This makes it easy to supply the protection liquid Q to the substrate W in the film formation step. This makes it easy to reduce the amount of protection liquid Q used.

[0348] The first substitute liquid contains toluene, which makes it easy to supply the protection liquid Q to the substrate W in the film forming step, and therefore makes it easy to reduce the amount of protection liquid Q used.

[0349] The cycle process includes a second replacement process. In the second replacement process, a second replacement liquid is supplied to the substrate W. The second replacement process is performed after the film formation process and before the etching process. Therefore, in the second replacement process, the protective liquid Q on the substrate W is replaced with the second replacement liquid. Therefore, in the second replacement process, it is easy to remove the protective liquid Q from the substrate W. In the second replacement process, it is easy to remove excess material of the self-assembled monolayer P from the substrate W. Therefore, it is even easier to supply the etching liquid R to the substrate W in the etching process. For example, it is easy to reduce the amount of etching liquid R used. For example, it is easy to improve the etching rate UG.

[0350] 3. Third Embodiment A substrate processing apparatus 1 and a substrate processing method according to a third embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0351] The third embodiment is the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the structure of the substrate W.

[0352] 32 is a diagram showing the configuration of the processing unit 11 according to the third embodiment. The processing unit 11 includes a supply unit 15h in addition to the supply units 15a to 15e. The supply unit 15h supplies a third substitute liquid to the substrate W.

[0353] The third substitution liquid is, for example, toluene.

[0354] The third substitution liquid contains, for example, a solvent. The solvent of the third substitution liquid has the same composition as the solvent of the protection liquid Q.

[0355] The third substitution liquid is, for example, an organic solvent, and the organic solvent of the third substitution liquid includes, for example, at least one of ethanol, isopropyl alcohol, toluene, hexane, hexanone, cyclohexane, and benzene.

[0356] The supply unit 15h has a configuration similar to that of the supply unit 15a.

[0357] Although not shown in the figure, the control unit 10 controls the supply unit 15h.

[0358] 3-2. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the third embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the third embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the third embodiment is different from that of the first embodiment. Therefore, the cycle step of the third embodiment will be described.

[0359] 33 is a flowchart showing the procedure of the cycle process of the third embodiment. In addition to the film formation process and the etching process, the cycle process includes a first rinsing process, a first drying process, and a third substitution process. The first drying process is performed after the film formation process and before the etching process. The first rinsing process is performed after the film formation process and before the first drying process. The third substitution process is performed after the etching process.

[0360] The control unit 10 controls the supply units 15a, 15b, 15d, 15e, and 15h to execute the cycle process. The control unit 10 causes the supply units 15a, 15b, 15d, 15e, and 15h to repeat the cycle process two or more times.

[0361] Each step will be described below.

[0362] Step S11: Film Forming Step In the film forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. For example, a protective liquid Q is supplied to the substrate W in the film forming step.

[0363] Step S13: First Rinse Step In the first rinse step, a rinse liquid is supplied to the substrate W. The rinse liquid supplied to the substrate W in the first rinse step is called the "first rinse liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the first rinse step. In the first rinse step, the supply unit 15d supplies the first rinse liquid to the substrate W. In the first rinse step, the first rinse liquid washes away the protective liquid Q on the substrate W. In the first rinse step, the protective liquid Q is removed from the substrate W. In the first rinse step, excess material of the self-assembled monolayer P is also removed from the substrate W.

[0364] Step S14: First Drying Step In the first drying step, the substrate W is dried. Specifically, the control unit 10 controls at least one of the rotation drive unit 14 and the supply unit 15e to execute the first drying step. For example, in the first drying step, the rotation drive unit 14 rotates the substrate W. For example, in the first drying step, the supply unit 15e supplies a drying gas to the substrate W. This dries the substrate W.

[0365] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0366] Step S23: Third Substitution Step In the third substitution step, a third substitution liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15h to execute the third substitution step. In the third substitution step, the supply unit 15h supplies the third substitution liquid to the substrate W. In the third substitution step, the etching liquid R on the substrate W is replaced with the third substitution liquid. In the third substitution step, the etching liquid R is removed from the substrate W. In the third substitution step, etching with the etching liquid R stops.

[0367] 3-3. Advantages of the Third Embodiment The third embodiment has advantages similar to those of the first embodiment. Furthermore, the third embodiment has the following advantages.

[0368] The cycle process includes a first drying process. In the first drying process, the substrate W is dried. The first drying process is performed after the film forming process and before the etching process. Therefore, in the etching process, the etching liquid R is supplied to the substrate W in a dry state. Therefore, it is easier to supply the etching liquid R to the substrate W in the etching process. For example, it is easy to reduce the amount of etching liquid R used. For example, it is easy to improve the etching rate UG.

[0369] The cycle process includes a first rinse process. In the first rinse process, a first rinse liquid is supplied to the substrate W. The first rinse process is performed after the film formation process and before the first drying process. Therefore, the first rinse liquid washes away the protective liquid Q on the substrate W. Therefore, in the first rinse process, it is easy to remove the protective liquid Q from the substrate W. In the first rinse process, it is easy to remove excess material of the self-assembled monolayer P from the substrate W. Therefore, when the substrate W is dried in the first drying process, particles are unlikely to be generated on the substrate W. The particles originate from, for example, the protective liquid Q. The particles originate from, for example, the excess material of the self-assembled monolayer P.

[0370] The cycle process includes a third substitution process. In the third substitution process, a third substitution liquid is supplied to the substrate W. The third substitution process is performed after the etching process. Therefore, in the third substitution process, the etching liquid R on the substrate W is replaced with the third substitution liquid. Therefore, in the third substitution process, it is easy to remove the etching liquid R from the substrate W. Therefore, it is easy to stop etching of the third layer G in the third substitution process. That is, it is easy to control the etching amount LG. For example, it is easy to control the etching amount LGa. Furthermore, it is even easier to protect the first layer E and the second layer F from the etching liquid R in the third substitution process.

[0371] 4. Fourth Embodiment A substrate processing apparatus 1 and a substrate processing method according to a fourth embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0372] The fourth embodiment is the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the structure of the substrate W.

[0373] 34 is a diagram showing the configuration of the processing unit 11 according to the fourth embodiment. The processing unit 11 includes a supply unit 15i in addition to the supply units 15a-15e. The supply unit 15i supplies an oxidizing liquid to the substrate W. The oxidizing liquid is a processing liquid for oxidizing the substrate W.

[0374] The oxidizing solution contains at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide.

[0375] The oxidizing liquid is, for example, oxygenated water. Oxygenated water is water containing dissolved oxygen. Oxygenated water is, for example, high-concentration oxygenated water. High-concentration oxygenated water is water containing oxygen at a higher concentration than normal. The concentration of oxygen in high-concentration oxygenated water is higher than the concentration of oxygen in water exposed to air. The amount of oxygen in high-concentration oxygenated water is greater than the amount of oxygen in water placed in normal air. Oxygenated water is, for example, saturated oxygenated water. Saturated oxygenated water is water containing oxygen at a saturated concentration.

[0376] The oxidizing liquid is, for example, ozone water. Ozone water is water containing dissolved ozone. The ozone water is, for example, high-concentration ozone water. High-concentration ozone water is water containing ozone at a higher concentration than normal. The concentration of ozone in high-concentration ozone water is higher than the concentration of ozone in water exposed to air. The amount of ozone in high-concentration ozone water is greater than the amount of ozone in water placed in normal air. The ozone water is, for example, saturated ozone water. Saturated ozone water is water containing ozone at a saturated concentration.

[0377] The supply unit 15i has a configuration similar to that of the supply unit 15a.

[0378] Although not shown in the figure, the control unit 10 controls the supply unit 15i.

[0379] 4-2. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the fourth embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the fourth embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the fourth embodiment is different from that of the first embodiment. Therefore, the cycle step of the fourth embodiment will be described.

[0380] 35 is a flowchart showing the procedure of the cycle process of the fourth embodiment. The cycle process includes an oxidation process in addition to a film formation process and an etching process. The oxidation process is performed after the film formation process and before the etching process.

[0381] The control unit 10 controls the supply units 15a, 15b, and 15i to execute the cycle process. The control unit 10 causes the supply units 15a, 15b, and 15i to repeat the cycle process two or more times.

[0382] Each step will be described below.

[0383] Step S11: Film Forming Step In the film forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. For example, a protective liquid Q is supplied to the substrate W in the film forming step.

[0384] Step S15: Oxidation Process In the oxidation process, the third layer G is oxidized. For example, if the third layer G is made of silicon oxide, the silicon oxide is oxidized. Specifically, the control unit 10 controls the supply unit 15i to execute the oxidation process. In the oxidation process, the supply unit 15i supplies an oxidizing liquid to the substrate W. In the oxidation process, the third layer G comes into contact with the oxidizing liquid. In the oxidation process, the oxidizing liquid oxidizes the third layer G.

[0385] In the oxidation step, the surface G3 comes into contact with an oxidizing liquid, which oxidizes the surface G3.

[0386] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0387] 4-3. Technical Significance of the Oxidation Process The technical significance of the oxidation process will be explained using a second example.

[0388] The conditions of the second embodiment will be explained. FIG. 36 is a flowchart showing the procedure of the substrate processing method of the second embodiment. In the second embodiment, the cycle process is repeated twice. Specifically, in the second embodiment, the cycle process includes a first cycle process and a second cycle process. The first cycle process is performed, and then the second cycle process is performed. The cycle process includes a film formation process, an oxidation process, and an etching process. The first cycle process includes a film formation process, an oxidation process, and an etching process. The second cycle process includes a film formation process, an oxidation process, and an etching process. The film formation process is performed twice. The oxidation process is performed twice. The etching process is performed twice. The third layer G is made of silicon oxide.

[0389] A substrate W to be processed by the substrate processing method of the second embodiment will now be described.

[0390] 37 schematically shows the substrate W in the film formation step of the first cycle step. In the film formation step of the first cycle step, a self-assembled monolayer P is formed on the first layer E and the second layer F. In the film formation step of the first cycle step, a self-assembled monolayer P is not formed on the third layer G.

[0391] The third layer G includes a surface portion G4 and a deep portion G5. The surface portion G4 is located close to the surface G3. The surface portion G4 includes the surface G3. As described above, the surface G3 is exposed. Therefore, the surface portion G4 is exposed. The deep portion G5 is located deeper than the surface portion G4. The deep portion G5 is located deeper in the depth direction J than the surface portion G4. The deep portion G5 is located farther from the surface G3. The deep portion G5 does not include the surface G3. The deep portion G5 is not exposed.

[0392] The surface layer G4 may include silicon suboxide. The surface layer G4 may not be composed of silicon dioxide alone.

[0393] The deep layer G5 includes at least one of silicon suboxide and silicon dioxide.

[0394] Step S15: Oxidation step of the first cycle process Figure 38 schematically shows the substrate W in the oxidation step of the first cycle process. In the oxidation step of the first cycle process, the third layer G is oxidized. The surface layer G4 comes into contact with the oxidizing solution. The deep layer G5 does not come into contact with the oxidizing solution. It is easy to oxidize the surface layer G4. It is easier to oxidize the surface layer G4 than the deep layer G5. Therefore, in the oxidation step of the first cycle process, at least the surface layer G4 is oxidized. As a result, the surface layer G4 is composed only of silicon dioxide. The surface layer G4 does not contain silicon suboxide.

[0395] The surface layer portion G4 is defined as follows: The surface layer portion G4 is a portion of the third layer G that is oxidized in the oxidation process. The surface layer portion G4 is a portion of the third layer G that is composed only of silicon dioxide after the oxidation process. The surface layer portion G4 is a portion of the third layer G that does not contain silicon suboxide after the oxidation process.

[0396] It is difficult to oxidize the deep layer G5. Therefore, at least a part of the deep layer G5 may not be oxidized in the oxidation step of the first cycle. Even after the oxidation step, the deep layer G5 may contain silicon suboxide.

[0397] In the oxidation step of the first cycle step, the self-assembled monolayer P protects the first layer E and the second layer F. Therefore, the first layer E is not oxidized, and the second layer F is not oxidized.

[0398] Step S21: Etching step of first cycle process Figure 39 schematically shows the substrate W in the etching step of the first cycle process. Figure 39 schematically shows the substrate W at the end of the etching step of the first cycle process. In the etching step of the first cycle process, an etching solution R is supplied. The third layer G is etched. The third layer G is etched in the depth direction J. Specifically, the surface portion G4 of the third layer G is etched. At least a portion of the surface portion G4 is etched. For example, the entire surface portion G4 is etched. However, in the etching step of the first cycle process, the deep layer portion G5 is not etched.

[0399] As described above, the surface layer G4 is made of silicon dioxide. It is easy to etch silicon dioxide. It is easier to etch silicon dioxide than silicon suboxide.

[0400] As described above, in the first cycle etching step, the surface layer portion G4 is etched. In the first cycle etching step, the deep layer portion G5 is not etched. Therefore, it is easy to etch the third layer G in the first cycle etching step.

[0401] After the portion of the third layer G is etched, the portions E1a and F1a are exposed.

[0402] Step S11: Film Formation Step of Second Cycle Process Figure 40 schematically shows the substrate W in the film formation step of the second cycle process. In the film formation step of the second cycle process, a protective liquid Q is supplied to the substrate W. A new self-assembled monolayer P is formed on the first layer E and the second layer F. The new self-assembled monolayer P is also formed on portions E1a and F1a.

[0403] As the third layer G is etched in the depth direction J, the position of the surface layer G4 shifts in the depth direction J. The new surface layer G4 may not have been sufficiently oxidized in the oxidation step of the first cycle process. Therefore, the surface layer G4 may contain silicon suboxide. The surface layer G4 may not be composed of silicon dioxide only.

[0404] The deep layer G5 includes at least one of silicon suboxide and silicon dioxide.

[0405] Step S15: Oxidation step of the second cycle process Figure 41 shows a schematic diagram of the substrate W in the oxidation step of the second cycle process. In the oxidation step of the second cycle process, the third layer G is oxidized.

[0406] The surface layer G4 is oxidized. As a result, the surface layer G4 is made of only silicon dioxide. The surface layer G4 does not contain silicon suboxide.

[0407] At least a portion of the deep layer G5 may not be oxidized, and as a result, the deep layer G5 may include silicon suboxide.

[0408] In the oxidation step of the second cycle step, the self-assembled monolayer P protects the first layer E and the second layer F. In the oxidation step of the second cycle step, the self-assembled monolayer P protects the portions E1a and F1a. Therefore, in the oxidation step of the second cycle step, the first layer E is not oxidized. In the oxidation step of the second cycle step, the portion E1a is not oxidized. In the oxidation step of the second cycle step, the second layer F is not oxidized. In the oxidation step of the second cycle step, the portion F1a is not oxidized.

[0409] Step S21: Etching step of second cycle process Figure 42 schematically shows the substrate W in the etching step of the second cycle process. Figure 42 schematically shows the substrate W at the end of the etching step of the second cycle process. In the etching step of the second cycle process, an etching solution R is supplied. The third layer G is etched. Specifically, the surface layer G4 of the third layer G is etched. At least a portion of the surface layer G4 is etched. However, in the etching step of the second cycle process, the deep layer G5 is not etched. Therefore, it is easy to etch the third layer G in the etching step of the second cycle.

[0410] As described above, according to the second embodiment, the cycle process includes the oxidation process. Therefore, the oxidation process is repeatedly performed. The third layer G is repeatedly oxidized. The third layer G is frequently oxidized. Specifically, the surface layer G4 is frequently oxidized. The surface layer G4 is the portion of the third layer G that is etched in the etching process. Therefore, the portion of the third layer G that is etched in the etching process is composed only of silicon dioxide. The portion of the third layer G that is etched in the etching process does not contain silicon suboxide. Therefore, it is easy to etch the third layer G.

[0411] In the etching step, only the surface layer G4 of the third layer G is etched, so that the third layer G can be easily etched.

[0412] The etching step does not etch the deep layer portion G5 of the third layer G. Therefore, even if the deep layer portion G5 contains silicon suboxide, it is easy to etch the third layer G.

[0413] 4-4. Processing conditions for the cycle process Examples of processing conditions for the cycle process are given below.

[0414] The etching amount LGa is smaller than the length of the surface layer portion G4 in the depth direction J. As described above, the "etching amount LGa" is the etching amount LG of the third layer G in one etching step in one cycle process.

[0415] For example, the etching amount LGa is 2 nm.

[0416] 4-5. Advantages of the Fourth Embodiment The fourth embodiment has advantages similar to those of the first embodiment. Furthermore, the fourth embodiment has the following advantages.

[0417] The cycle process includes an oxidation process. In the oxidation process, the third layer G is oxidized. The oxidation process is performed after the film formation process and before the etching process. Therefore, after the third layer G is oxidized, the third layer G is etched. Therefore, it is easier to etch the third layer G in the etching process. For example, it is easy to improve the etching rate of the third layer G.

[0418] The oxidation step is performed after the film formation step. Therefore, the oxidation step is performed after the self-assembled monolayer P is formed on the first layer E and the second layer F. Therefore, it is easy for the self-assembled monolayer P to protect the first layer E and the second layer F in the oxidation step. For example, it is difficult to oxidize the first layer E and the second layer F in the oxidation step.

[0419] In the oxidation step, an oxidizing liquid is supplied to oxidize the third layer G. Therefore, it is easy to oxidize the third layer G in the oxidation step.

[0420] The oxidizing solution contains at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide, making it easy to oxidize the third layer G in the oxidation process.

[0421] 5. Fifth Embodiment A substrate processing apparatus 1 and a substrate processing method according to a fifth embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0422] The fifth embodiment is the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the structure of the substrate W.

[0423] 43 is a diagram showing the configuration of the processing unit 11 according to the fifth embodiment. The processing unit 11 includes supply units 15i and 15j in addition to supply units 15a-15e. Supply unit 15i has been described in the fourth embodiment.

[0424] The supply unit 15j supplies the substrate W with the fourth substitute liquid.

[0425] The fourth substitution liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol.

[0426] The supply unit 15j has a configuration similar to that of the supply unit 15a.

[0427] Although not shown in the figure, the control unit 10 controls the supply unit 15j.

[0428] 5-2. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the fifth embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the fifth embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the fifth embodiment is different from that of the first embodiment. Therefore, the cycle step of the fifth embodiment will be described.

[0429] 44 is a flowchart showing the procedure of the cycle process of the fifth embodiment. The cycle process includes an oxidation process and a fourth substitution process in addition to a film formation process and an etching process. The oxidation process is performed after the film formation process and before the etching process. The fourth substitution process is performed after the oxidation process and before the etching process.

[0430] The control unit 10 controls the supply units 15a, 15b, 15i, and 15j to execute the cycle process. The control unit 10 causes the supply units 15a, 15b, 15i, and 15j to repeat the cycle process two or more times.

[0431] Each step will be described below.

[0432] Step S11: Film Forming Step In the film forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. For example, a protective liquid Q is supplied to the substrate W in the film forming step.

[0433] Step S15: Oxidation Step In the oxidation step, an oxidizing liquid is supplied to the substrate W. In the oxidation step, the third layer G is oxidized.

[0434] Step S16: Fourth Substitution Step In the fourth substitution step, a fourth substitute liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15j to execute the fourth substitution step. In the fourth substitution step, the supply unit 15j supplies the fourth substitute liquid to the substrate W. In the fourth substitution step, the oxidizing liquid on the substrate W is replaced with the fourth substitute liquid. In the fourth substitution step, the oxidizing liquid is removed from the substrate W.

[0435] The fourth substitution liquid used in the fourth substitution step may be only one of deionized water and isopropyl alcohol. For example, in the fourth substitution step, deionized water may be supplied to the substrate W. In this case, the oxidizing liquid on the substrate W is directly replaced with deionized water.

[0436] Alternatively, the fourth substitution liquid used in the fourth substitution step may be both deionized water and isopropyl alcohol. For example, in the fourth substitution step, isopropyl alcohol may be supplied to the substrate W, and then deionized water may be supplied to the substrate W. In this case, the oxidizing liquid on the substrate W is replaced with isopropyl alcohol, and then the isopropyl alcohol on the substrate W is replaced with deionized water. The oxidizing liquid on the substrate W is indirectly replaced with deionized water.

[0437] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0438] 5-3. Advantages of the Fifth Embodiment The fifth embodiment has advantages similar to those of the first embodiment. Furthermore, the fifth embodiment has the following advantages.

[0439] The cycle process includes a fourth substitution step. In the fourth substitution step, a fourth substitution liquid is supplied to the substrate W. The fourth substitution step is performed after the oxidation step and before the etching step. Therefore, in the fourth substitution step, the oxidizing liquid on the substrate W is replaced with the fourth substitution liquid. Therefore, in the fourth substitution step, it is easy to remove the oxidizing liquid from the substrate W. Therefore, it is even easier to supply the etching liquid R to the substrate W in the etching step. For example, it is easy to reduce the amount of etching liquid R used. For example, it is easy to improve the etching rate UG.

[0440] 6. Sixth Embodiment A substrate processing apparatus 1 and a substrate processing method according to a sixth embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0441] The sixth embodiment is the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the structure of the substrate W. The processing unit 11 of the sixth embodiment has a configuration similar to that of the processing unit 11 of the fourth embodiment. The configuration of the processing unit 11 of the fourth embodiment is shown in FIG.

[0442] 6-1. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the sixth embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the sixth embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the sixth embodiment is different from that of the first embodiment. Therefore, the cycle step of the sixth embodiment will be described.

[0443] 45 is a flowchart showing the procedure of the cycle process of the sixth embodiment. In addition to the film formation process and the etching process, the cycle process includes an oxidation process, a second rinsing process, and a second drying process. The oxidation process is performed after the film formation process and before the etching process. The second drying process is performed after the oxidation process and before the etching process. The second rinsing process is performed after the oxidation process and before the second drying process. The second rinsing process is performed after the film formation process and before the second drying process.

[0444] The control unit 10 controls the supply units 15a, 15b, 15d, 15e, and 15i to execute the cycle process. The control unit 10 causes the rotation drive unit 14 and the supply units 15a, 15b, 15d, 15e, and 15i to repeat the cycle process two or more times.

[0445] Each step will be described below.

[0446] Step S11: Film Forming Step In the film forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. For example, a protective liquid Q is supplied to the substrate W in the film forming step.

[0447] Step S15: Oxidation Step In the oxidation step, an oxidizing liquid is supplied to the substrate W. In the oxidation step, the third layer G is oxidized.

[0448] Step S17: Second Rinse Process In the second rinse process, a rinse liquid is supplied to the substrate W. The rinse liquid supplied to the substrate W in the second rinse process is called the "second rinse liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the second rinse process. In the second rinse process, the supply unit 15d supplies the second rinse liquid to the substrate W. In the second rinse process, the second rinse liquid washes away the oxidizing liquid on the substrate W. In the second rinse process, the oxidizing liquid is removed from the substrate W.

[0449] Step S18: Second Drying Step In the second drying step, the substrate W is dried. Specifically, the control unit 10 controls at least one of the rotation drive unit 14 and the supply unit 15e to execute the second drying step. For example, in the second drying step, the rotation drive unit 14 rotates the substrate W. For example, in the second drying step, the supply unit 15e supplies a drying gas to the substrate W. This dries the substrate W.

[0450] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0451] 6-2. Advantages of the Sixth Embodiment The sixth embodiment has advantages similar to those of the first embodiment. Furthermore, the sixth embodiment has the following advantages.

[0452] The cycle process includes a second drying process. In the second drying process, the substrate W is dried. The second drying process is performed after the oxidation process and before the etching process. Therefore, in the etching process, the etching liquid R is supplied to the substrate W in a dry state. Therefore, it is easier to supply the etching liquid R to the substrate W in the etching process. For example, it is easy to reduce the amount of etching liquid R used. For example, it is easy to improve the etching rate UG.

[0453] The cycle process includes a second rinse process. In the second rinse process, a second rinse liquid is supplied to the substrate W. The second rinse process is performed after the oxidation process and before the second drying process. Therefore, in the second rinse process, the second rinse liquid washes away the oxidizing liquid on the substrate W. Therefore, it is easy to remove the oxidizing liquid from the substrate W in the second rinse process. Therefore, when the substrate W is dried in the second drying process, particles are less likely to be generated on the substrate W. The particles originate from, for example, the oxidizing liquid.

[0454] The second rinsing step is performed after the film forming step and before the second drying step. Therefore, in the second rinsing step, the second rinsing liquid washes away the protective liquid Q on the substrate W. Therefore, in the second rinsing step, it is easy to remove the protective liquid Q from the substrate W. In the second rinsing step, it is easy to remove the excess material of the self-assembled monolayer P from the substrate W. Therefore, when the substrate W is dried in the second drying step, particles are less likely to be generated on the substrate W. The particles originate from, for example, the protective liquid Q. The particles originate from, for example, the excess material of the self-assembled monolayer P.

[0455] 7. Seventh Embodiment A substrate processing apparatus 1 and a substrate processing method according to a seventh embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.

[0456] 7-1. Configuration of Processing Unit 11 Fig. 46 is a diagram showing the configuration of the processing unit 11 of the seventh embodiment. The processing unit 11 includes a supply unit 15k in addition to the supply units 15a-15e. The supply unit 15k supplies an additive to the substrate W. The additive is used to oxidize the substrate W. The additive is also called an oxidizing agent.

[0457] The additive includes at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide.

[0458] The supply unit 15k has a configuration similar to that of the supply unit 15a.

[0459] Although not shown in the figure, the control unit 10 controls the supply unit 15k.

[0460] 7-2. Example of Procedure of Substrate Processing Method For convenience, reference will be made to FIG. 19. The substrate processing method of the seventh embodiment includes a cycle step, a final removal step, a final rinsing step, and a final drying step. The final removal step, the final rinsing step, and the final drying step of the substrate processing method of the seventh embodiment are the same as those of the substrate processing method of the first embodiment. The cycle step of the substrate processing method of the seventh embodiment is different from that of the first embodiment. Therefore, the cycle step of the seventh embodiment will be described.

[0461] 47 is a flowchart showing the procedure of the cycle process of the seventh embodiment. The cycle process includes an oxidation process in addition to a film formation process and an etching process. The oxidation process is performed simultaneously with the etching process. For example, at least a portion of the period during which the oxidation process is performed may overlap at least a portion of the period during which the etching process is performed.

[0462] The control unit 10 controls the supply units 15a, 15b, and 15k to execute the cycle process. The control unit 10 causes the supply units 15a, 15b, and 15k to repeat the cycle process two or more times.

[0463] Each step will be described below.

[0464] Step S11: Film Forming Step In the film forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. For example, a protective liquid Q is supplied to the substrate W in the film forming step.

[0465] Step S19: Oxidation Process In the oxidation process, the third layer G is oxidized. Specifically, the control unit 10 controls the supply unit 15k to execute the oxidation process. In the oxidation process, the supply unit 15k supplies an additive to the substrate W. In the oxidation process, the third layer G comes into contact with the additive. The surface G3 comes into contact with the additive. In the oxidation process, the additive oxidizes the third layer G. For example, if the third layer G is made of silicon oxide, the additive oxidizes the silicon oxide. As a result, the silicon suboxide in the third layer G changes to silicon dioxide. For example, the silicon suboxide on the surface G3 changes to silicon dioxide.

[0466] Step S21: Etching Step In the etching step, the etching liquid R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0467] As described above, the oxidation step is performed simultaneously with the etching step. For this purpose, the etching solution R and the additive are supplied to the substrate W. The third layer G is oxidized by the additive and is then etched by the etching solution R. While the third layer G is being oxidized by the additive, the third layer G is also etched by the etching solution R.

[0468] 7-3. Advantages of the Seventh Embodiment The seventh embodiment has advantages similar to those of the first embodiment. Furthermore, the seventh embodiment has the following advantages.

[0469] The cycle process includes an oxidation process, in which the third layer G is oxidized. The oxidation process is performed simultaneously with the etching process. Therefore, it is easier to etch the third layer G in the etching process. For example, it is therefore easier to improve the etching rate of the third layer G.

[0470] In the oxidation step, an additive for oxidizing the third layer G is supplied to the substrate W. Therefore, it is easy to perform the oxidation step and the etching step simultaneously.

[0471] The additive includes at least one of oxygen, ozone, hydrogen peroxide, nitric acid, iodine molecules, tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, hydrogen iodide, nitrogen triiodide, phosphorus triiodide, and ammonium triiodide, making it easy to oxidize the third layer G in the oxidation step.

[0472] The present invention is not limited to the embodiments, and can be modified as follows.

[0473] (1) In the film formation process of the first to seventh embodiments, the protective liquid Q is supplied to the substrate W to form the self-assembled monolayer P. That is, in the film formation process of the first to seventh embodiments, the self-assembled monolayer P is formed into the first layer E and the second layer F by a liquid-phase method. However, the method for forming the self-assembled monolayer P is not limited to the liquid-phase method. For example, in the film formation process, the self-assembled monolayer P may be formed by a gas-phase method. For example, in the film formation process, the self-assembled monolayer P may be formed by a chemical vapor deposition (CVD) method. For example, in the film formation process, gas of the material for the self-assembled monolayer P may be supplied to the substrate W. The gas of the material for the self-assembled monolayer P is, for example, vapor of the material for the self-assembled monolayer P. For example, the gas of the material for the self-assembled monolayer P may be prepared by heating the protective liquid Q.

[0474] (2) In the oxidation process of the fourth to seventh embodiments, an oxidizing liquid or an oxidizing agent is supplied to the substrate W to oxidize the substrate W. That is, in the oxidation process of the fourth to seventh embodiments, a wet process is performed to oxidize the substrate W. However, the method of oxidizing the substrate W is not limited to the wet process. For example, in the oxidation process, a dry process may be performed on the substrate W to oxidize the substrate W. For example, the dry process includes at least one of a UV process, a plasma process, and an ozone bake process. In the UV process, the substrate W is irradiated with ultraviolet light. In the plasma process, plasma of a process gas is supplied to the substrate W. The plasma process includes at least one of an oxygen plasma and an ozone plasma. The process gas includes at least one of oxygen and ozone. In the ozone bake process, ozone gas is supplied to the substrate W while the substrate W is heated.

[0475] (3) In the seventh embodiment, the supply unit 15b supplies the etching liquid R to the substrate W, and the supply unit 15k supplies the additive to the substrate W. That is, in the seventh embodiment, the supply unit 15b that supplies the etching liquid R is different from the supply unit 15k that supplies the additive. However, the configuration for supplying the etching liquid R and the additive is not limited to the supply units 15b and 15k. For example, the supply unit 15b may supply both the etching liquid R and the additive to the substrate W. For example, the supply unit 15b may supply a mixed liquid of the etching liquid R and the additive to the substrate W. For example, the supply unit 15k may be omitted.

[0476] (4) The cycle steps of the fourth to sixth embodiments may further include a fifth substitution step. For example, the cycle steps shown in Figures 35, 44, and 45 may further include a fifth substitution step. In the fifth substitution step, a fifth substitution liquid is supplied to the substrate W. The fifth substitution liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol.

[0477] For example, the fifth substitution step is performed after the film formation step and before the etching step. According to this modified embodiment, it is easy to supply the etching liquid R to the substrate W in the etching step.

[0478] For example, the fifth replacement step is performed after the film formation step and before the oxidation step (step S15). According to this modified embodiment, it is easy to oxidize the substrate W in the oxidation step.

[0479] Similarly, the cycle process of the seventh embodiment may further include a fifth substitution step. For example, the cycle process shown in FIG. 47 may further include a fifth substitution step. In the fifth substitution step, a fifth substitution liquid is supplied to the substrate W. The fifth substitution liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol. The fifth substitution step is performed after the film formation step and before the etching step and the oxidation step (step S19). According to this modified embodiment, it is easy to supply the etching liquid R to the substrate W in the etching step. Furthermore, according to this modified embodiment, it is easy to oxidize the substrate W in the oxidation step (step S19).

[0480] (5) The cycle process of the fourth to sixth embodiments may further include a third drying step. For example, the cycle process shown in Figures 35, 44, and 45 may further include a third drying step. In the third drying step, the substrate W is dried.

[0481] For example, the third drying step is performed after the film forming step and before the etching step. According to this modified embodiment, in the etching step, the etching liquid R is supplied to the substrate W in a dry state. Therefore, it is easy to supply the etching liquid R to the substrate W in the etching step.

[0482] For example, the third drying step is performed after the film formation step and before the oxidation step (step S15). According to this modified embodiment, the substrate W is in a dry state when the oxidation step (step S15) begins. Therefore, it is easy to oxidize the substrate W in the oxidation step.

[0483] Similarly, the cycle process of the seventh embodiment may further include a third drying step. For example, the cycle process shown in FIG. 47 may further include a third drying step. In the third drying step, the substrate W is dried. The third drying step is performed after the film formation step and before the etching step and the oxidation step (step S19). According to this modified embodiment, in the etching step, the etching liquid R is supplied to the substrate W in a dry state. Therefore, it is easy to supply the etching liquid R to the substrate W in the etching step. Furthermore, according to this modified embodiment, the substrate W is in a dry state when the oxidation step (step S19) starts. Therefore, it is easy to oxidize the substrate W in the oxidation step (step S19).

[0484] In the above-described modified embodiment, the cycle process may further include a third rinse process. In the third rinse process, a third rinse liquid is supplied to the substrate W. The third rinse liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol. The third rinse process is performed after the film formation process and before the third drying process. This makes it difficult for particles to be generated on the substrate when the substrate is dried in the third drying process.

[0485] (6) In the second embodiment, the cycle process includes the first rinse step. However, this is not limited to this. For example, the cycle process does not have to include the first rinse step.

[0486] (7) In the fifth embodiment, the cycle process includes the second rinse step. However, this is not limiting. For example, the cycle process does not have to include the second rinse step.

[0487] (8) In the first to seventh embodiments, the processing units 11 are classified as single-wafer processing units. However, the processing units 11 are not limited to single-wafer processing units. For example, the processing units 11 may be classified as batch processing units. In other words, the processing units 11 may process multiple substrates W at once.

[0488] 48 is a diagram showing the configuration of a processing unit 11 of the modified embodiment. Note that the same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0489] The processing unit 11 includes tanks 21a and 21b. The tank 21a stores a protective liquid Q. The tank 21b stores an etching liquid R.

[0490] The processing unit 11 includes substrate holders 22a and 22b. The substrate holder 22a holds multiple substrates W simultaneously. The substrate holder 22a holds each substrate W in a substantially vertical position. When a substrate W is held by the substrate holder 22a, the surface W1 of each substrate W is substantially vertical. The substrate holder 22b has a configuration similar to that of the substrate holder 22a. The substrate holder 22a is provided in the bath 21a. The substrate holder 22b is provided in the bath 21b.

[0491] The processing unit 11 includes lifting / lowering drivers 23a and 23b. The lifting / lowering driver 23a is connected to the substrate holder 22a. The lifting / lowering driver 23a moves the substrate holder 22a in the vertical direction Z. The substrate W held by the substrate holder 22a moves up and down integrally with the substrate holder 22a. The lifting / lowering driver 23a moves the substrate holder 22a between an upper position and a lower position. Figure 48 shows the substrate holder 22a in the upper position with a solid line. Figure 48 shows the substrate holder 22a in the lower position with a dashed line. When the substrate holder 22a is in the upper position, the substrate W held by the substrate holder 22a is positioned above the protective liquid Q in the bath 21a. When the substrate holder 22a is in the lower position, the substrate W held by the substrate holder 22a is immersed in the protective liquid Q in the bath 21a. The lifting / lowering drive unit 23b is connected to the substrate holding unit 22b. The lifting / lowering drive unit 23b has a configuration similar to that of the lifting / lowering drive unit 23a. The lifting / lowering drive unit 23b moves the substrate holding unit 22b between an upper position and a lower position. When the substrate holding unit 22b is in the upper position, the substrate W held by the substrate holding unit 22b is positioned above the etching solution R in the bath 21b. When the substrate holding unit 22b is in the lower position, the substrate W held by the substrate holding unit 22b is immersed in the etching solution R in the bath 21b.

[0492] The processing unit 11 further includes a substrate transport mechanism (not shown). The substrate transport mechanism transports a plurality of substrates W between the substrate holding part 22a and the substrate holding part 22b. When the substrate holding part 22a is in the upper position, the substrate transport mechanism transfers a substrate W to the substrate holding part 22a and receives a substrate W from the substrate holding part 22a. When the substrate holding part 22b is in the upper position, the substrate transport mechanism transfers a substrate W to the substrate holding part 22b and receives a substrate W from the substrate holding part 22b.

[0493] Although not shown, the control unit 10 controls the baths 21a and 21b, the substrate holders 22a and 22b, and the lifting and lowering drive units 23a and 23b.

[0494] The tank 21a, the substrate holder 22a, and the lifting / lowering drive unit 23a are examples of the film forming unit in the present invention, and the tank 21b, the substrate holder 22b, and the lifting / lowering drive unit 23b are examples of the etching unit in the present invention.

[0495] The procedure of the substrate processing method of the modified embodiment will be described with reference to FIG.

[0496] Step S11: Film Formation Process The substrate holding part 22a is positioned at the upper position. The substrate holding part 22a holds a plurality of substrates W. The substrate holding part 22a is moved from the upper position to the lower position. The substrates W held by the substrate holding part 22a are immersed in the protective liquid Q in the tank 21a. That is, the protective liquid Q in the tank 21a is supplied to the substrates W held by the substrate holding part 22a. As a result, a self-assembled monolayer P is formed on a first layer E and a second layer F.

[0497] Step S21: Etching liquid process The substrate holding part 22a moves from the lower position to the upper position. The substrate holding part 22b is positioned at the upper position. The substrate transport mechanism transports the substrates W from the substrate holding part 22a to the substrate holding part 22b. The substrate holding part 22b holds multiple substrates W. The substrate holding part 22b moves from the upper position to the lower position. The substrates W held by the substrate holding part 22b are immersed in the etching liquid R in the bath 21b. That is, the etching liquid R in the bath 21b is supplied to the substrates W held by the substrate holding part 22b. As a result, the third layer G is etched.

[0498] (9) The substrate processing methods of the first to seventh embodiments may be applied to the manufacture of various semiconductor products. For example, the substrate processing methods of the first to seventh embodiments may be applied to the manufacture of a Fin Field-Effect Transistor (FinFET). For example, the substrate processing methods of the first to seventh embodiments may be applied to the formation of a recess structure. For example, the third layer G may be disposed in a trench. For example, the third layer G may be an isolation film. For example, the third layer G may be an insulator layer.

[0499] (10) The first to seventh embodiments and the modified embodiments described above in (1) to (9) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment.

[0500] REFERENCE SIGNS LIST 1 ... substrate processing apparatus 10 ... control unit 11 ... processing unit 13 ... substrate holder 15a, 15a1, 15a2 ... supply unit (film forming unit) 15b ... supply unit (etching unit) 21a ... tank (film forming unit) 21b ... tank (etching unit) A ... space (space between first layer and second layer) E ... first layer E1 ... surface of first layer (first surface) F ... second layer F1 ... surface of second layer (second surface) G ... third layer P ... self-assembled monolayer P1 ... first self-assembled monolayer P2 ... second self-assembled monolayer Q ... protective liquid R ... etchant LEa ... etching amount of first layer in one etching step in one cycle process LFa ... etching amount of second layer in one etching step in one cycle process LG ... etching amount of third layer LGa ... etching amount of the third layer in one etching step in one cycle process LGT ... target value of the total etching amount of the third layer TEa ... time of one etching step in one cycle process UE ... etching rate of the first layer UF ... etching rate of the second layer UG ... etching rate of the third layer V1 ... first threshold (upper limit of etching amount LEa) V2 ... second threshold (upper limit of etching amount LFa) V3 ... third threshold (upper limit of etching amount LGa) W ... substrate X ... front-rear direction Y ... width direction Z ... vertical direction

Claims

1. A substrate processing method for processing a substrate, the substrate comprising: a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer having a first surface in surface contact with the third layer, the second layer having a second surface in surface contact with the third layer, the first layer having a composition different from a composition of the third layer, and the second layer having a composition different from a composition of the third layer, the substrate processing method comprising: a cycle process including: a film formation process for forming a self-assembled monolayer on the first layer and the second layer; and an etching process for supplying an etching liquid to the substrate and etching the third layer, the cycle process being repeated two or more times.

2. A substrate processing method according to claim 1, wherein the time for one of said etching steps in one of said cycle steps depends on at least one of the etching rate of said first layer and the etching rate of said second layer.

3. A substrate processing method according to claim 1, wherein the self-assembled monolayer has a thickness smaller than half the separation distance between the first surface and the second surface.

4. A substrate processing method according to claim 1, wherein the self-assembled monolayer includes a first self-assembled monolayer formed on the first layer, and a second self-assembled monolayer formed on the second layer.

5. The substrate processing method according to claim 1, wherein in the film forming step, a protective liquid is supplied to the substrate, and the protective liquid contains a material for the self-assembled monolayer.

6. The substrate processing method according to claim 5, wherein the protective liquid further contains toluene.

7. A substrate processing method according to claim 5, wherein the cycle process includes a first replacement process of supplying a first replacement liquid to the substrate, and the first replacement process is performed before the film formation process.

8. A substrate processing method according to claim 5, wherein the cycle process includes a second replacement process of supplying a second replacement liquid to the substrate, and the second replacement process is performed after the film formation process and before the etching process.

9. A substrate processing method according to claim 5, wherein the cycle process includes a first drying process for drying the substrate, the first drying process being performed after the film forming process and before the etching process.

10. A substrate processing method according to claim 9, wherein the cycle process includes a first rinsing process of supplying a first rinsing liquid to the substrate, and the first rinsing process is performed after the film forming process and before the first drying process.

11. The substrate processing method according to claim 1, wherein the cycle step includes a third replacement step of supplying a third replacement liquid to the substrate, and the third replacement step is performed after the etching step.

12. A substrate processing method according to claim 1, wherein the cycle step includes an oxidation step of oxidizing the third layer, the oxidation step being performed after the film formation step and before the etching step.

13. The substrate processing method according to claim 12, wherein in the oxidation step, an oxidizing liquid for oxidizing the third layer is supplied.

14. A substrate processing method according to claim 13, wherein the cycle step includes a fourth replacement step of supplying a fourth replacement liquid to the substrate, and the fourth replacement step is performed after the oxidation step and before the etching step.

15. A substrate processing method according to claim 13, wherein the cycle step includes a second drying step of drying the substrate, the second drying step being performed after the oxidation step and before the etching step.

16. A substrate processing method according to claim 15, wherein the cycle step includes a second rinsing step of supplying a second rinsing liquid to the substrate, the second rinsing step being performed after the oxidation step and before the second drying step.

17. The substrate processing method according to claim 1, wherein the cycle step includes an oxidation step of oxidizing the third layer, and the oxidation step is performed simultaneously with the etching step.

18. The substrate processing method according to claim 17, wherein in the oxidation step, an additive for oxidizing the third layer is supplied to the substrate.

19. A substrate processing method according to claim 1, further comprising a final removal step of removing the self-assembled monolayer from the substrate, and the cycle step is repeated two or more times before the final removal step.

20. A substrate processing method as described in claim 19, wherein in the final removal step, a removal liquid is supplied to the substrate, the removal liquid containing a first solvent, and in the film formation step, a protection liquid is supplied to the substrate, the protection liquid containing a material of the self-assembled monolayer and a second solvent, and the second solvent has the same composition as the composition of the first solvent.

21. The substrate processing method according to claim 1, further comprising a final drying step of drying the substrate, and the cycle step is repeated two or more times before the final drying step.

22. A substrate processing method according to claim 21, further comprising a final rinsing step of supplying a final rinsing liquid to the substrate, wherein the cycle step is repeated two or more times before the final rinsing step, and the final rinsing step is performed before the final drying step.

23. A substrate processing apparatus for processing a substrate, the substrate comprising: a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer having a first surface in surface contact with the third layer, the second layer having a second surface in surface contact with the third layer, the first layer having a composition different from a composition of the third layer, and the second layer having a composition different from a composition of the third layer, the substrate processing apparatus comprising: a film forming unit for forming a self-assembled monolayer on the first layer and the second layer; an etching unit for etching the third layer; and a control unit for controlling the film forming unit and the etching unit to execute a cycle process, the cycle process comprising: a film forming process; and an etching process, the film forming unit forming the self-assembled monolayer on the first layer and the second layer, and the etching unit supplying an etching solution to the substrate to etch the third layer, The control unit causes the film forming unit and the etching unit to repeat the cycle process two or more times.

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