Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method and a substrate processing apparatus, capable of appropriately processing a substrate.SOLUTION: The present invention relates to a substrate processing method and a substrate processing apparatus. The 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 positioned between the first layer E and the second layer F. The first layer E includes a surface E1. The surface E1 is in surface contact with the third layer G. The second layer F includes a surface F1. The surface F1 is in surface contact with the third layer G. The first layer E has a composition that is different from that of the third layer G. The second layer F has a composition that is different from that of the third layer G. The substrate processing method comprises a cycle step. The cycle step includes a film formation step and an etching step. In the film formation step, a self-organization monomolecular film P is formed in the first layer E and the second layer F. In the etching step, an etching liquid R is supplied to the substrate W, and the third layer G is etched. The cycle step is repeated two or more times.SELECTED DRAWING: Figure 19

Description

[Technical field]

[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 EL (Electroluminescence) 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. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method for processing a substrate. Specifically, the substrate processing method is for etching a 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 a layer to be protected. In the etching step, an etching solution is supplied to a 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP2013-062278A Summary of the Invention [Problem to be solved by the invention]

[0005] Even with conventional substrate processing methods, it may 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 longer, 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 capable of appropriately processing a substrate. [Means for solving the problem]

[0008] In order to achieve the above object, the present invention has the following configuration: That is, the present invention is a substrate processing method for processing a substrate, the substrate includes a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer has a first surface in surface contact with the third layer, the second layer has a second surface in surface contact with the third layer, the first layer has a composition different from a composition of the third layer, and the second layer has a composition different from a composition of the third layer, the substrate processing method includes a cycle process, the cycle process includes 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 a composition of the third layer. The second layer has a composition different from a composition 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 to etch the third layer.

[0011] In the etching process, the self-assembled monolayer protects the first and second layers. Specifically, in 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 a 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 the self-assembled monolayer. Similarly, after a 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 the self-assembled monolayer. After a portion of the third layer is etched, a portion of the first surface and a portion of the second surface are not protected. After a portion of the third layer is etched, a portion of the first surface and a portion of the second surface are exposed. A portion of the first surface and a portion of the second surface are in contact with the etching solution. A portion of the first surface and a portion of the second surface are exposed to the etching solution. Thus, 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 called a "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 are exposed. A cycle step performed after the first cycle step is called a "second cycle step."

[0014] In the film formation process of the second cycle step, new self-assembled monolayers are formed on the first layer and the second layer. New self-assembled monolayers are also formed on parts of the first and second surfaces described above. After the film formation process 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 the first surface and a portion of the second surface described above. While the third layer is being etched in the etching step of the second cycle, the self-assembled monolayer protects the first surface and a portion of the second surface described above.

[0016] As described above, after a portion of the first surface and a portion of the second surface are exposed, a self-assembled monolayer is quickly formed on the portion of the first surface and the portion of the second surface. Therefore, the time during which the portion of the first surface and the portion of the second surface are exposed is short. The time during which the portion of the first surface and the portion of the second surface are in contact with the etching solution is short. Therefore, it is easy to protect the portion of the first surface and the portion of the second surface from the etching solution. Therefore, it is easy to protect the first layer and the second layer 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-mentioned substrate processing method, the third layer is preferably repeatedly etched in a plurality of the etching steps, so that the third layer is appropriately etched.

[0020] In the above-mentioned substrate processing method, it is preferable that the cycle process is repeated 10 times or more. Therefore, the time of one etching process in one cycle process is shorter. Therefore, it is easier to protect the first layer and the second layer from the etching solution. Furthermore, the etching process is repeated 10 times or more. Therefore, the third layer is repeatedly etched 10 times or more. Therefore, the third layer is appropriately etched.

[0021] In the above-mentioned substrate processing method, it is preferable that the etching amount of the third layer in one etching step in one cycle step is smaller than a target value of the total etching amount of the third layer. Therefore, by repeating the cycle step 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.

[0022] In the above-mentioned substrate processing method, the number of times the cycle process 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 above-mentioned substrate processing method, it is preferable that the time of one etching step in one cycle step depends on at least one of the etching rate of the first layer and the etching rate of the second layer. In this case, the time of one etching step in one cycle step does not depend on the etching rate of the third layer. In this case, the time of one etching step in one cycle step does not depend on the target value of the total etching amount of the third layer. Therefore, it is easy to protect the first layer and the second layer.

[0024] In the above-mentioned substrate processing method, it is preferable that the time of one etching step in one 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 of the etching amount of the first layer in one etching step in one cycle step, so that it is easy to protect the first layer.

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

[0026] In the above-mentioned substrate processing method, it is preferable that the time of one etching step in one 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 of the etching amount of the second layer in one etching step in one cycle step, so that it is easy to protect the second layer.

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

[0028] In the above-mentioned substrate processing method, the time for one of the etching steps in one of the cycle steps preferably depends on the etching rate of the third layer, so that it is easy to etch the third layer.

[0029] In the above-mentioned substrate processing method, it is preferable that the time of one etching step in one cycle step 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 of the etching amount of the third layer in one etching step in one cycle step, so that it is easy to etch the third layer.

[0030] In the above-mentioned substrate processing method, it is preferable that the time of each etching step in each of the cycle steps is limited so that the etching amount of the third layer in each of the etching steps in each of the cycle steps is equal to or less than the third threshold value. Therefore, it is easy to control the etching amount of the third layer in each of the etching steps in each of the cycle steps to be equal to or less than the third threshold value.

[0031] In the above-mentioned substrate processing method, the third threshold is preferably 2 nm or less. Therefore, the amount of etching of the third layer in one etching step in one cycle step is small. Therefore, the time of one etching step is short. The cycle step is frequently repeated. Therefore, it is easier to etch the third layer in the etching step.

[0032] In the above-mentioned 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 surface and the second surface, the self-assembled monolayer does not fill the entire space between the first surface and the second surface. Even when the self-assembled monolayer is formed on the first surface and the second surface, the self-assembled monolayer fills only a part of the space between the first surface and the second surface. Therefore, even when the self-assembled monolayer is formed on the first surface and the second surface, at least a part of the third layer is not covered with the self-assembled monolayer. Therefore, even when the self-assembled monolayer is formed on the first surface and the second surface, the self-assembled monolayer allows the third layer to come into contact with the etching solution. As a result, even when the self-assembled monolayer is formed on the first surface and the second surface, it is easy to etch the third layer.

[0033] In the above-mentioned 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 process.

[0034] In the above-mentioned substrate processing method, 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 preferably contains at least one of unsaturated hydrocarbon, peroxide, organic sulfur molecule, alkylating agent, aromatic diazonium salt, alcohol, aldehyde and epoxy. Therefore, it is easy to form the self-assembled monolayer on the first layer and the second layer in the film formation process.

[0035] In the above-mentioned 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 forming step.

[0036] In the above-mentioned substrate processing method, it is preferable that one of the first layer and the second layer is made of at least one of single crystal silicon, polysilicon and amorphous silicon, the other 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, the self-assembled monolayer formed on one of the first layer and the second layer contains at least one of unsaturated hydrocarbon, peroxide, organic sulfur molecule, alkylating agent, aromatic diazonium salt, alcohol, aldehyde and epoxy, and the self-assembled monolayer formed on the other of the first layer and the second layer contains at least one of unsaturated hydrocarbon and alkyl bromide. Therefore, it is easy to form a self-assembled monolayer on the first layer and the second layer in the film formation process.

[0037] In the above-mentioned 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 first layer does not contain silicon nitride, the second layer is made of at least one of single crystal silicon, polysilicon and amorphous silicon, the second layer does not contain silicon nitride, the third layer is made of silicon nitride, the self-assembled monolayer is made of at least one of peroxide, organic sulfur molecule, alkylating agent, 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 the self-assembled monolayer on the first layer and the second layer in the film formation process.

[0038] In the above-mentioned 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 monolayer on the first layer and the second layer in the film formation step.

[0039] In the above-mentioned substrate processing method, the second self-assembled monolayer preferably has the same composition as the first self-assembled monolayer, which simplifies the structure of the self-assembled monolayer.

[0040] In the above-mentioned 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 layer and the second layer 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 layer and the second layer in the film formation process.

[0041] In the above-mentioned substrate processing method, the film forming step preferably includes a first film forming step of forming the first self-assembled monolayer on the first layer, and a second film forming 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 forming step. For example, even if the second self-assembled monolayer has a composition different from that of the first self-assembled monolayer, it is easy to form the self-assembled monolayer in the film forming step.

[0042] In the above-mentioned substrate processing method, in the film forming step, a protective liquid is preferably supplied to the substrate, and the protective liquid contains a material of the self-assembled monolayer, so that it is easy to form the self-assembled monolayer on the first layer and the second layer in the film forming step.

[0043] In the above-mentioned substrate processing method, it is preferable that the protective liquid further contains toluene, so that the toluene can easily limit the thickness of the self-assembled monolayer, and therefore the self-assembled monolayer does not have an excessively large thickness.

[0044] In the above-mentioned substrate processing method, the cycle step includes a first replacement step of supplying a first replacement liquid to the substrate, and the first replacement step is preferably performed before the film formation step. Therefore, it is easy to supply the protection liquid to the substrate in the film formation step. Therefore, it is easy to reduce the amount of protection liquid used.

[0045] In the above-mentioned substrate processing method, the cycle step includes a second replacement step of supplying a second replacement liquid to the substrate, and the second replacement step is preferably performed after the film formation step and before the etching step. For this reason, in the second replacement step, the protective liquid on the substrate is replaced with the second replacement liquid. Therefore, in the second replacement step, it is easy to remove the protective liquid from the substrate. As described above, the protective liquid contains a material of a self-assembled monolayer. A part of the material of the self-assembled monolayer in the protective liquid changes to a self-assembled monolayer, and the other part of the material of the self-assembled monolayer in the protective liquid does not change to a self-assembled monolayer. The other part of the material of the self-assembled monolayer remains in the protective liquid. The other part of the material of the self-assembled monolayer is an "excess part of the material of the self-assembled monolayer". In the second replacement step, it is easy to remove the excess part of the material of the self-assembled monolayer from the substrate. Therefore, it is even easier to supply an etching liquid to the substrate in the etching step. For example, it is easy to reduce the amount of etching solution used.

[0046] In the above-mentioned substrate processing method, the cycle step includes a first drying step of drying the substrate, and the first drying step is preferably performed after the film forming step and before the etching step. Therefore, in the etching step, an etching solution is supplied to a substrate in a dry state. Therefore, it is easier to supply an etching solution to the substrate in the etching step. For example, it is easy to reduce the amount of etching solution used.

[0047] In the above-mentioned substrate processing method, the cycle step includes a first rinsing step of supplying a first rinsing liquid to the substrate, and the first rinsing step is preferably performed after the film forming step and before the first drying step. Therefore, the first rinsing liquid washes away the protective liquid on the substrate. Therefore, in the first rinsing step, it is easy to remove the protective liquid from the substrate. In the first rinsing step, it is easy to remove the excess material of the self-assembled monolayer from the substrate. Therefore, when the substrate is dried in the first drying step, particles are unlikely to be generated on the substrate. The particles are derived from, for example, the protective liquid. The particles are derived from, for example, the excess material of the self-assembled monolayer.

[0048] In the above-mentioned 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 for one cycle process is short. Therefore, it is easier to repeat the cycle process.

[0049] In the above-mentioned substrate processing method, the cycle step includes a third replacement step of supplying a third replacement liquid to the substrate, and the third replacement step is preferably performed after the etching step. Therefore, in the third replacement step, the etching liquid on the substrate is replaced with the third replacement liquid. Therefore, in the third replacement step, it is easy to remove the etching liquid from the substrate. Therefore, it is easy to stop the etching of the third layer in the third replacement step. Furthermore, it is even easier to protect the first layer and the second layer from the etching liquid in the third replacement step.

[0050] In the above-mentioned substrate processing method, the cycle step includes an oxidation step of oxidizing the third layer, and the oxidation step is preferably performed after the film formation step and before the etching step. The cycle step includes an oxidation step. In the oxidation step, the third layer is oxidized. The oxidation step is performed before the etching step. Therefore, after the third layer is oxidized, the third layer is etched. Therefore, it is easier to etch the third layer in the etching step. For example, it is easier to improve the etching rate of the third layer. The oxidation step is performed after the film formation step. Therefore, after a self-assembled monolayer is formed on the first layer and the second layer, the oxidation step is performed. Therefore, it is easy for the self-assembled monolayer to protect the first layer and the second layer in the oxidation step. For example, it is difficult to oxidize the first layer and the second layer in the oxidation step.

[0051] In the above-described substrate processing method, it is preferable that an oxidizing liquid for oxidizing the third layer is supplied in the oxidation step, so that it is easy to oxidize the third layer in the oxidation step.

[0052] In the above-mentioned 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. Therefore, it is easy to oxidize the third layer in the oxidation process.

[0053] In the above-mentioned substrate processing method, the cycle step includes a fourth replacement step of supplying a fourth replacement liquid to the substrate, and the fourth replacement step is preferably performed after the oxidation step and before the etching step. Therefore, in the fourth replacement step, the oxidizing liquid on the substrate is replaced with the fourth replacement liquid. Therefore, in the fourth replacement 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.

[0054] In the above-mentioned 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, an etching solution is supplied to the substrate in a dry state. Therefore, it is easier to supply the etching solution to the substrate in the etching step. For example, it is easier to reduce the amount of etching solution used.

[0055] In the above-mentioned substrate processing method, the cycle step includes a second rinsing step of supplying a second rinsing liquid to the substrate, and 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 oxidizing liquid on the substrate. Therefore, in the second rinsing step, it is easy to remove the oxidizing liquid from the substrate. Therefore, when the substrate is dried in the second drying step, particles are unlikely to be generated on the substrate. The particles are derived from, for example, the oxidizing liquid.

[0056] In the above-mentioned substrate processing method, 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. Therefore, it is easier to etch the third layer in the etching step. For example, it is easier to improve the etching rate of the third layer.

[0057] In the above-mentioned 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.

[0058] In the above-mentioned 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. Therefore, it is easy to oxidize the third layer in the oxidation process.

[0059] In the above-mentioned substrate processing method, it is preferable that the self-assembled monolayer is not removed from the substrate in the cycle step, so that it is easier to protect the first layer and the second layer during the repeated cycle steps.

[0060] In the above-mentioned substrate processing method, the substrate processing method 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 for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0061] In the above-mentioned substrate processing method, 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 preferably has the same composition as that of 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.

[0062] In the above-mentioned substrate processing method, the remover preferably contains toluene, so that the remover can easily remove the self-assembled monolayer from the substrate.

[0063] In the above-mentioned substrate processing method, it is preferable that the first replacement liquid contains a third solvent, and the third solvent has the same composition as the second solvent. Therefore, it is easy to supply the protection liquid to the substrate in the film forming step. Therefore, it is easy to reduce the amount of the protection liquid used.

[0064] In the above-mentioned substrate processing method, the first replacement liquid preferably contains toluene, which makes it easy to supply the protection liquid to the substrate in the film forming step, and therefore makes it easy to reduce the amount of protection liquid used.

[0065] In the above-mentioned substrate processing method, the substrate processing method 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 for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0066] In the above-mentioned substrate processing method, the substrate processing method further includes a final rinsing step of supplying a final rinsing liquid to the substrate, and the cycle step is preferably repeated two or more times before the final rinsing step, and the final rinsing step is performed before the final drying step. Therefore, the cycle step does not include a final rinsing step. The cycle step is repeated without a final rinsing step. Therefore, the time for one cycle step is short. Therefore, it is easier to repeat the cycle step. Furthermore, in the final rinsing step, the substrate is properly cleaned with the final rinsing liquid. Therefore, when the substrate is dried in the final drying step, particles are less likely to be generated on the substrate.

[0067] The present invention is a substrate processing apparatus, the substrate includes a first layer, a second layer, and a third layer located between the first layer and the second layer, the first layer has a first surface in surface contact with the third layer, the second layer has a second surface in surface contact with the third layer, the first layer has a composition different from a composition of the third layer, and the second layer has a composition different from a composition of the third layer, the substrate processing apparatus includes a film forming unit that forms a self-assembled monolayer on the first layer and the second layer, and an etching unit that etches 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 a self-assembled monolayer on a first layer and a second layer, and in which the etching unit supplies an etching liquid to the substrate to etch the third layer, and the control unit causes the film formation unit and the etching unit to repeat the cycle process two or more times.

[0068] 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 a composition of the third layer. The second layer has a composition different from a composition of the third layer.

[0069] 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 liquid to the substrate to etch the third layer.

[0070] In the etching process, the self-assembled monolayer protects the first and second layers. Specifically, in 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.

[0071] Specifically, when the third layer is etched, a portion of the third layer is removed. After a 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 the self-assembled monolayer. Similarly, after a 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 the self-assembled monolayer. After a portion of the third layer is etched, a portion of the first surface and a portion of the second surface are not protected. After a portion of the third layer is etched, a portion of the first surface and a portion of the second surface are exposed. A portion of the first surface and a portion of the second surface are in contact with the etching solution. A portion of the first surface and a portion of the second surface are exposed to the etching solution. Thus, it is difficult to protect the first surface and the second surface after the third layer is etched.

[0072] The cycle step is repeated two or more times. For convenience, one cycle step is called a "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 are exposed. A cycle step performed after the first cycle step is called a "second cycle step."

[0073] In the film formation process of the second cycle step, new self-assembled monolayers are formed on the first layer and the second layer. New self-assembled monolayers are also formed on parts of the first and second surfaces described above. After the film formation process of the second cycle step, the first and second surfaces are not exposed.

[0074] 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 the first surface and a portion of the second surface described above. While the third layer is being etched in the etching step of the second cycle, the self-assembled monolayer protects the first surface and a portion of the second surface described above.

[0075] As described above, after a portion of the first surface and a portion of the second surface are exposed, a self-assembled monolayer is quickly formed on the portion of the first surface and the portion of the second surface. Therefore, the time during which the portion of the first surface and the portion of the second surface are exposed is short. The time during which the portion of the first surface and the portion of the second surface are in contact with the etching solution is short. Therefore, it is easy to protect the portion of the first surface and the portion of the second surface from the etching solution. Therefore, it is easy to protect the first layer and the second layer from the etching solution.

[0076] 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.

[0077] In summary, the present substrate processing apparatus appropriately etches the third layer while appropriately protecting the first and second layers, and therefore appropriately processes the substrate. Effect of the Invention

[0078] According to the substrate processing method and substrate processing apparatus of the present invention, the substrate is appropriately processed. [Brief description of the drawings]

[0079] [Figure 1] FIG. 2 is a plan view showing the inside of the substrate processing apparatus. [Diagram 2]FIG. 2 is a control block diagram of the substrate processing apparatus. [Diagram 3] 3(a) is a side view of the substrate, and FIG. 3(b) is a plan view of the substrate. [Figure 4] 4(a) and 4(b) are detailed views of the first, second and third layers of the substrate, respectively. [Diagram 5] FIG. 2 is a diagram illustrating a configuration of a processing unit according to the first embodiment. [Figure 6] FIG. 1 shows a chemical structure of an example of an organosulfur molecule. [Figure 7] FIG. 2 is a diagram showing the chemical structural formula of another example of an organosulfur molecule. [Figure 8] FIG. 2 is a diagram showing the chemical structural formula of another example of an organosulfur molecule. [Figure 9] FIG. 2 shows the chemical structure of an example of an alkylating reagent. [Figure 10] FIG. 2 is a diagram showing the chemical structure of another example of an alkylating reagent. [Figure 11] FIG. 2 is a diagram showing the chemical structure of another example of an alkylating reagent. [Figure 12] FIG. 2 is a diagram showing the chemical structure of another example of an alkylating reagent. [Figure 13] FIG. 1 is a diagram showing the chemical structural formula of an example of an aromatic diazonium salt. [Figure 14] FIG. 2 is a diagram showing the chemical structural formula of another example of an aromatic diazonium salt. [Figure 15] FIG. 2 is a diagram showing the chemical structural formula of another example of an aromatic diazonium salt. [Figure 16] FIG. 1 is a diagram showing the chemical structure of an example of an epoxy. [Figure 17] FIG. 2 is a diagram showing the chemical structural formula of another example of epoxy. [Figure 18] FIG. 2 is a diagram showing the chemical structural formula of another example of epoxy. [Figure 19] 1 is a flowchart showing a procedure of a substrate processing method. [Figure 20] 4 is a flowchart showing the procedure of a cycle process according to the first embodiment. [Figure 21]4 is a flowchart showing the procedure of a substrate processing method according to a first embodiment. [Figure 22] FIG. 2 is a diagram illustrating a substrate in a film formation step of a first cycle step in the first embodiment. [Diagram 23] FIG. 2 is a diagram illustrating a substrate during an etching step in a first cycle step of the first embodiment. [Figure 24] FIG. 2 is a diagram illustrating a substrate during an etching step in a first cycle step of the first embodiment. [Diagram 25] 4A to 4C are diagrams illustrating the substrate W in a film formation step of the second cycle step in the first embodiment. [Figure 26] FIG. 4 is a diagram illustrating a substrate during an etching step in a second cycle step in the first embodiment. [Figure 27] FIG. 4 is a diagram illustrating a substrate during an etching step in a second cycle step in the first embodiment. [Figure 28] 10 is a flowchart showing a procedure of a substrate processing method of a comparative example. [Figure 29] 1A to 1C are diagrams illustrating a substrate W in an etching process of a comparative example. [Diagram 30] FIG. 13 is a diagram illustrating a configuration of a processing unit according to a second embodiment. [Diagram 31] 10 is a flowchart showing the procedure of a cycle process according to a second embodiment. [Diagram 32] FIG. 13 is a diagram illustrating a configuration of a processing unit according to a third embodiment. [Diagram 33] 13 is a flowchart showing the procedure of a cycle process according to a third embodiment. [Diagram 34] FIG. 13 is a diagram illustrating a configuration of a processing unit according to a fourth embodiment. [Diagram 35] 13 is a flowchart showing the procedure of a cycle process according to a fourth embodiment. [Diagram 36] 10 is a flowchart showing the procedure of a substrate processing method according to a second embodiment. [Figure 37] FIG. 13 is a diagram illustrating a substrate W in a film formation step of a first cycle step in a second embodiment. [Figure 38]FIG. 11 is a diagram illustrating a substrate W in an oxidation step of a first cycle process of a second embodiment. [Figure 39] FIG. 13 is a diagram illustrating a substrate during an etching step in a first cycle step of a second embodiment. [Diagram 40] FIG. 11 is a diagram illustrating a substrate W in a film formation step of a second cycle step in a second embodiment. [Diagram 41] FIG. 11 is a diagram illustrating a substrate W in an oxidation step of a second cycle step in a second embodiment. [Diagram 42] FIG. 13 is a diagram illustrating a substrate during an etching step in a second cycle step in a second embodiment. [Diagram 43] FIG. 13 is a diagram illustrating a configuration of a processing unit according to a fifth embodiment. [Diagram 44] 13 is a flowchart showing the procedure of a cycle process according to a fifth embodiment. [Diagram 45] 13 is a flowchart showing the procedure of a cycle process according to a sixth embodiment. [Diagram 46] 13 is a flowchart showing the procedure of a cycle process according to a sixth embodiment. [Figure 47] 13 is a flowchart showing the procedure of a cycle process according to a seventh embodiment. [Figure 48] FIG. 13 is a diagram showing a configuration of a processing unit according to a modified embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0080] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A substrate processing method and a substrate processing apparatus according to the present invention will now be described with reference to the drawings.

[0081] 1. First embodiment 1-1. Overview of substrate processing equipment 1 is a plan view showing the inside of a substrate processing apparatus 1. The substrate processing apparatus 1 processes a substrate W. The processes in the substrate processing apparatus 1 include a wet etching process. The wet etching process is a process in which the substrate W is etched with an etching liquid.

[0082] 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 a substrate W to the processing block 7. The processing block 7 processes the substrate W. The indexer unit 3 retrieves the substrate W from the processing block 7.

[0083] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is called 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 called the "front." The direction opposite to the front is called the "rear." The direction perpendicular to the front-rear direction X is called the "width direction Y." The width direction Y is horizontal. One direction of the "width direction Y" is appropriately called the "right side." The direction opposite to the right is called the "left side." When the front-rear direction X and the width direction Y are not differentiated, they are simply called the "horizontal direction." The direction perpendicular to the horizontal direction is called the "vertical direction Z." In each figure, for reference, front, back, right, left, top, and bottom are appropriately indicated.

[0084] The indexer unit 3 includes a plurality of (e.g., four) carrier placement units 4. One carrier C is placed on each carrier placement unit 4. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, a FOUP (Front Opening Unified Pod), a SMIF (Standard Mechanical Interface), or an OC (Open Cassette).

[0085] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 transports a substrate W. The transport mechanism 5 transports the substrate 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.

[0086] 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.

[0087] The processing block 7 includes a plurality of processing units 11. Each processing unit 11 performs a process on the substrate W.

[0088] Each processing unit 11 includes a substrate holder 13. The substrate holder 13 holds a substrate W.

[0089] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 is disposed to the side of the processing unit 11. The transport mechanism 8 transports a substrate W. The transport mechanism 8 transports the substrate W between the indexer unit 3 and the processing unit 11. The transport mechanism 8 transports the substrate 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.

[0090] 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.

[0091] 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 connected to the transport mechanisms 5 and 8 and the processing unit 11 so as to be able to communicate with each other.

[0092] 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 working area for the processes, a storage medium such as a fixed disk, etc. The control unit 10 has various types of information that are stored in advance in the storage medium. The information held by the control unit 10 includes, for example, transport condition information and processing condition information. The transport condition information specifies conditions related to the operation of the transport mechanisms 5 and 8. The processing condition information specifies conditions related to the operation of the processing unit 11. The processing condition information is also called a processing recipe.

[0093] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0094] The transport mechanism 5 takes out the substrate W from the carrier C on the carrier platform 4. The transport mechanism 5 delivers the substrate W to the transport mechanism 8.

[0095] 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 holding portion 13. The substrate holding portion 13 holds the substrate W.

[0096] Each processing unit 11 processes the substrate W held by the substrate holding portion 13. Each processing unit 11 performs a wet etching process on the substrate W, for example.

[0097] After the processing unit 11 processes 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 passes the substrate W to the transport mechanism 5.

[0098] The transport mechanism 5 carries the substrate W into the carrier C.

[0099] 1-2. Structure of the substrate W The substrate W is, for example, any one of a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, and a substrate for a solar cell.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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. Surface G2 is located opposite surface G1. Surface E1 is in surface contact with the third layer G. Surface E1 is in surface contact with surface G1. Surface F1 is in surface contact with the third layer G. Surface F1 is in surface contact with surface G2.

[0106] 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.

[0107] 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.

[0108] The space A is located between the faces E1 and F1. The third layer G is located between the faces E1 and F1. The faces E1 and F1 face each other. The faces E1 and F1 are, for example, parallel to each other. The faces E1 and F1 are not in contact with each other.

[0109] Space A is small.

[0110] 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. The separation distance D is, for example, 50 nm or less. The separation distance D is, for example, 20 nm or less. The separation distance D is, for example, 10 nm or less. The separation distance D is, for example, a few nm.

[0111] At least a portion of face E1 is not exposed, e.g., some portions of face E1 are not exposed and other portions of face E1 are exposed.

[0112] The first layer E further has a surface E2. 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.

[0113] At least a portion of face F1 is not exposed, e.g., face F1 has no exposed portion.

[0114] The second layer F further has a face F2. The face F2 is located at an end of the face F1. The face F2 is not in contact with the third layer G. The face F2 is exposed.

[0115] Surface G1 is not exposed. Surface G2 is not exposed.

[0116] The third layer G further has a surface G3. 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.

[0117] FIG. 4(a) shows the third layer G before it is etched. FIG. 4(b) shows the third layer G after it has been etched. The third layer G is etched. Specifically, face 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.

[0118] At least a portion of the third layer G is removed by etching the third layer G. At least a portion of the space A becomes an unoccupied space by removing at least a portion of the third layer G. The third layer G is not present in the unoccupied space.

[0119] 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.

[0120] The third layer G has a length KG in the depth direction J. When the third layer G is etched, the length KG decreases.

[0121] 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.

[0122] 4(b) 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.

[0123] 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.

[0124] The composition of the second layer F may be the same as that of the first layer E. Alternatively, the composition of the second layer F may be different from that of the first layer E.

[0125] The first layer E is composed of, for example, at least any one of single-crystalline silicon, polysilicon, amorphous silicon, and silicon nitride.

[0126] The second layer F is composed of, for example, at least any one of single-crystalline silicon, polysilicon, amorphous silicon, and silicon nitride.

[0127] The third layer is composed of, for example, at least any one of silicon oxide, titanium nitride, titanium, titanium oxide, tungsten, and silicon nitride.

[0128] When the first layer E is composed of silicon nitride, the third layer G does not contain silicon nitride. When the second layer F is composed of silicon nitride, the third layer G does not contain silicon nitride. When the third layer G is composed of silicon nitride, the first layer E does not contain silicon nitride, and the second layer F does not contain silicon nitride.

[0129] Polycrystalline silicon is also called polysilicon.

[0130] Silicon oxide contains, for example, silicon dioxide (SiO 2 ). Silicon oxide contains, for example, silicon suboxide (SiOx, 0 < x < 2). Silicon suboxide is a suboxide of silicon dioxide. Silicon suboxide is also called lower silicon oxide. Silicon suboxide contains, for example, silicon monoxide (SiO).

[0131] Silicon oxide can be obtained by, for example, a thermal oxidation method, a chemical vapor deposition (CVD) method, or an atomic layer deposition (ALD) method. Silicon oxide obtained by a thermal oxidation method is sometimes called a "thermal oxide film."

[0132] 1-3. Configuration of processing unit 11 5 is a diagram showing the configuration of a 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.

[0133] 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.

[0134] The substrate holding part 13 is installed inside the housing 12. The substrate holding part 13 holds only one substrate W at a time. The substrate holding part 13 holds the substrate W in a substantially horizontal position. When the substrate W is held by the substrate holding part 13, a surface W1 is horizontal.

[0135] When the substrate W is held by the substrate holding part 13, the surface W1 faces upward. When the substrate W is held by the substrate holding part 13, the surface W1 corresponds to the upper surface of the substrate W. The substrate holding part 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 holding part 13 is located below the substrate W held by the substrate holding part 13. The substrate holding part 13 does not contact the surface W1.

[0136] 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.

[0137] 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.

[0138] The protective liquid contains a material for a self-assembled monolayer. 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 a self-assembled monolayer.

[0139] The materials for self-assembled monolayers are explained in detail.

[0140] The material of the self-assembled monolayer includes, for example, at least one of an unsaturated hydrocarbon, a peroxide, an organic sulfur molecule, an alkylating agent, an aromatic diazonium salt, an alcohol, an aldehyde, an epoxy, and an alkyl bromide.

[0141] The compounds given as examples of materials for self-assembled monolayers are classified into the first group M, the second group N, and the third group O. Unsaturated hydrocarbons belong to the first group M. Peroxides, organic sulfur molecules, alkylating agents, aromatic diazonium salts, alcohols, aldehydes, and epoxies belong to the second group N. Alkyl bromides belong to the third group O.

[0142] 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.

[0143] 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.

[0144] 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 of the self-assembled monolayer belonging to the first group M. In the first configuration example, it is preferable that the self-assembled monolayer contains an unsaturated hydrocarbon.

[0145] 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 case of the second configuration example, it is preferable to select a material of the self-assembled monolayer belonging to at least one of the first group M and the second group N. In the case of the second configuration example, it is preferable that the self-assembled monolayer contains at least one of unsaturated hydrocarbons, peroxides, organic sulfur molecules, alkylating reagents, aromatic diazonium salts, alcohols, aldehydes, and epoxies.

[0146] 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 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. 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 contains at least one of an unsaturated hydrocarbon and an alkyl bromide.

[0147] 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 material of the self-assembled monolayer 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 case of the fourth configuration example, it is preferable to select a material of 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 case of 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.

[0148] 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 include 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 include silicon nitride. The third layer G is composed of silicon nitride. In the case of the fifth configuration example, it is preferable to select a material of the self-assembled monolayer belonging to the second group N. In the case of the fifth configuration example, it is preferable not to select a material of the self-assembled monolayer belonging to the first group M. In the case of the fifth configuration example, it is preferable not to select a material of the self-assembled monolayer belonging to the third group O. In the case of 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 case of the fifth configuration example, it is preferable that the self-assembled monolayer does not contain unsaturated hydrocarbon. In the case of the fifth configuration example, it is preferable that the self-assembled monolayer does not contain an alkyl bromide.

[0149] The unsaturated hydrocarbon is, for example, at least one of compounds M1-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

[0150] 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.

[0151] The organosulfur molecule is, for example, at least one of the 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 "EG" in compound Nb1 is ethylene glycol. In the chemical formula showing compound Nb1, "m" is 3, 5, 6, 8, or 11. In the chemical formula showing compound Nb1, "n" is 1, 2, 3, 4, 5, 6, 8, or 12. In the chemical formula for compound Nb2, "m" is 3, 5, 6, 8, or 11. In the chemical formula for compound Nb2, "n" is 2, 3, 4, 5, 6, 8, or 12. In the chemical formula for compound Nb3, "m" is 3, 5, 6, 8, or 11. In the chemical formula for the compound Nb3, "n" is 2, 3, 4, 5, 6, 8, or 12.

[0152] The compound Nb1 is represented by the chemical structural formula shown in FIG. The compound Nb2 is represented by the chemical structural formula shown in FIG. The compound Nb3 is represented by the chemical structural formula shown in FIG.

[0153] The alkylating reagent is, for example, at least one of compounds Nc1-Nc3. Compound Nc1) Allylmagnesium Bromide C3H5BrMg Compound Nc2) sec-Butylmagnesium Bromide C4H9BrMg Compound Nc3) CH3(CH2)2CH2Li Compound Nc4) (CH3)3CLii

[0154] The compound Nc1 is represented by the chemical structural formula shown in FIG. The compound Nc2 is represented by the chemical structural formula shown in FIG. The compound Nc3 is represented by the chemical structural formula shown in FIG. Compound Nc4 is represented by the chemical structural formula shown in FIG.

[0155] The aromatic diazonium salt is, for example, at least one of the compounds Nd1-Nd3. Compound Nd1) 4-Methoxybenzenediazonium Tetrafluoroborate C7H7BF4N2O Compound Nd2) 4-(Diazonium)benzenesulfonic acid, fluoroborate C6H5BF4N2O3S Compound Nd3) Azoic Diazo Component 24 (Salt) C30H28Cl2N6O6·ZnCl2 "X-" in the chemical formula for compound Nd1 is BF4-. "X-" in the chemical formula for the compound Nd2 is BF4-. The "X-" in the chemical formula for the compound Nd3 is Cl-.

[0156] The compound Nd1 is represented by the chemical structural formula shown in FIG. The compound Nd2 is represented by the chemical structural formula shown in FIG. The compound Nd3 is represented by the chemical structural formula shown in FIG.

[0157] The alcohol may be, for example, at least one of the compounds Ne1-Ne3. Compound Ne1) Isopropyl alcohol CH3CH(OH)CH3 Compound Ne2) Ethanol CH3CH2OH Compound Ne3) n-butanol CH3CH2CH2CH2OH Compound Ne4) n-Propanol C3H8O

[0158] The aldehyde is, for example, the compound Nf1. Compound Nf1) Formaldehyde HCHO

[0159] The epoxy is, for example, at least one of compounds Ng1-Ng3. Compound Ng1) A compound having the chemical structure shown in FIG. 16 Compound Ng2) A compound having the chemical structure shown in FIG. 17 Compound Ng3) A compound having the chemical structure shown in FIG. 18

[0160] The alkyl bromide may be, for example, at least one of compounds O1-O3. Compound O1) 1-Bromododecane C12H25Br Compound O2) 1-Bromopentadecane C15H31Br Compound O3) 1-Bromoheptadecane C17H35Br

[0161] For example, the protection liquid further includes toluene.

[0162] For example, the protective liquid further includes a solvent. The solvent of the protective liquid is an organic solvent. For example, the solvent of the protective liquid includes 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.

[0163] The supply unit 15a is an example of the film forming unit in the present invention. The solvent of the protective liquid is an example of the second solvent in the present invention.

[0164] 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 a 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.

[0165] The etching solution includes at least one of, for example, 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.

[0166] It is preferable to select the composition of the etching solution according to the composition of the third layer G.

[0167] 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.

[0168] For example, when the third layer G is 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.

[0169] 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.

[0170] 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.

[0171] For example, when the third layer G is 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.

[0172] The supply unit 15b is an example of the etching unit defined in the present invention.

[0173] 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.

[0174] The removal liquid includes, for example, toluene.

[0175] For example, the removal liquid includes a solvent. For example, the solvent of the removal liquid has the same composition as the solvent of the protection liquid.

[0176] 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.

[0177] The solvent of the removal liquid is an example of the first solvent in the present invention.

[0178] The processing unit 11 includes a supply unit 15d. The supply unit 15d supplies a rinsing liquid to the substrate W. The supply unit 15d supplies the rinsing liquid to the substrate W held by the substrate holding unit 13. The supply unit 15d supplies the rinsing liquid to a surface W1 of the substrate W held by the substrate holding unit 13.

[0179] The rinse liquid is, for example, deionized water (DIW) and / or isopropyl alcohol. The rinse liquid is also called a cleaning liquid.

[0180] 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.

[0181] 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.

[0182] The configuration of the supply units 15a, 15b, 15c, 15d, and 15e is 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 ejects 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 ejects an etching liquid. The nozzle 16c ejects a removing liquid. The nozzle 16d ejects a rinsing liquid. The nozzle 16e ejects a drying gas.

[0183] The supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. At least a portion of the pipe 17a may be provided outside the housing 12. The valve 18a is provided in the pipe 17a. The valve 18a may be provided outside the housing 12. When the valve 18a is open, the nozzle 16a ejects the protective liquid. When the valve 18a is closed, the nozzle 16a does not eject the protective liquid. Similarly, the supply units 15b, 15c, 15d, and 15e include pipes 17b, 17c, 17d, and 17e and valves 18b, 18c, 18d, and 18e, respectively. The pipes 17b, 17c, 17d, and 17e are connected to the nozzles 16b, 16c, 16d, and 16e, respectively. Valves 18b, 18c, 18d, and 18e are provided in 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 rinsing liquid from nozzle 16d. Valve 18e controls the discharge of the drying gas from nozzle 16e.

[0184] Supply unit 15a is connected to supply source 19a. Supply source 19a delivers a protection liquid to supply unit 15a. Similarly, supplies 15b, 15c, 15d, and 15e are connected to supplies 19b, 19c, 19d, and 19e, respectively. Supply source 19b delivers an etching liquid to supply unit 15b. Supply source 19c delivers a removal liquid to supply unit 15c. Supply source 19d delivers a rinsing liquid to supply unit 15c. Supply source 19e delivers a drying gas to supply unit 15d.

[0185] The supply source 19a is provided outside the housing 12. Similarly, the supplies 19b, 19c, 19d, and 19e are each provided outside the housing 12.

[0186] The supply source 19a may distribute the protective liquid to the supply parts 15a of multiple processing units 11. Alternatively, the supply source 19a may supply the protective liquid exclusively to the supply part 15a of one processing unit 11. The same applies to the supplies 19b, 19c, 19d, and 19e.

[0187] The supply source 19a may be an element 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 an element 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 an element of the substrate processing apparatus 1. Alternatively, at least one of the supply sources 19b, 19c, 19d, and 19e may not be an element of the substrate processing apparatus 1.

[0188] 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 receives liquid splashed from the substrate W held by the substrate holding part 13.

[0189] Please refer to Fig. 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.

[0190] 1-4. Example of substrate processing method The substrate processing method is executed in the processing unit 11. The substrate processing method is for processing the substrate W held by the substrate holder 13.

[0191] 19 is a flow chart showing a 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] Each step will be described below.

[0197] Step S1: Cycle process The control unit 10 controls the supply units 15a and 15b to execute the cycle process. The control unit 10 causes the supply units 15a and 15b to repeat the cycle process two or more times.

[0198] 20 is a flow chart 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 next to the film formation process.

[0199] 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.

[0200] 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.

[0201] When one cycle step ends, the next cycle step begins. The cycle steps are performed consecutively, i.e., the time when one cycle step ends is the same as the time when the next cycle step begins.

[0202] When the cycle process is repeated, the film formation process and the etching process are performed alternately.

[0203] When the cycle process is repeated two or more times, multiple film formation processes are performed. The self-assembled monolayer is repeatedly formed on 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.

[0204] When the cycle step is repeated two or more times, multiple etching steps are performed. The third layer G is repeatedly etched in multiple etching steps.

[0205] Step S2: Final removal process 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.

[0206] Step S3: Final rinse process In the final rinsing step, a rinsing liquid is supplied to the substrate W. The rinsing liquid supplied to the substrate W in the final rinsing step is called a "final rinsing liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the final rinsing step. In the final rinsing step, the supply unit 15d supplies the final rinsing liquid to the substrate W. As a result, the removing liquid is removed from the substrate W.

[0207] Step S4: Final drying process 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.

[0208] The rotary drive unit 14 may rotate the substrate W held by the substrate holder 13 in at least any one of the cycle step, the final removal step, and the final rinsing step.

[0209] 1-5. Technical significance of repeating the cycle process two or more times The technical significance of repeating the cycle process two or more times will be explained using a first embodiment and a comparative example.

[0210] The conditions of the first embodiment will be described. FIG. 21 is a flow chart 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 film formation process is performed twice. The etching process is performed twice.

[0211] A substrate W to be processed by the substrate processing method of the first embodiment will be described.

[0212] 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.

[0213] Step S11: Film formation process of the first cycle process FIG. 22 is a schematic diagram of a substrate in the film formation step of the first cycle step. In the film formation step of the first cycle step, a protective liquid Q is supplied to a substrate W. The protective liquid Q contains a material for a self-assembled monolayer P. At least a portion of the material for the self-assembled monolayer P changes 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 step of the first cycle step, the first layer E is not exposed. After the film formation step of the first cycle step, the second layer F is not exposed. After the film formation step of the first cycle step, the first layer E and the second layer F are protected.

[0214] The self-assembled monolayer P includes a first self-assembled monolayer P1. The first self-assembled monolayer P1 is formed on a first layer E.

[0215] The first self-assembled monolayer P1 is formed on a portion of the surface E1. Another portion of the surface E1 is in contact with the third layer G. The surface E1 is not exposed. The surface E1 is protected.

[0216] The first self-assembled monolayer P1 is formed on the surface E2. The surface E2 is not exposed. The surface E2 is protected.

[0217] 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.

[0218] The entirety of face F1 is in contact with the third layer G. Face F1 is not exposed. Face F1 is protected.

[0219] The second self-assembled monolayer P2 is formed on face F2. Face F2 is not exposed. Face F2 is protected.

[0220] 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.

[0221] 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.

[0222] For example, the second self-assembled monolayer P2 has the same composition as the first self-assembled monolayer P1.

[0223] Step S21: Etching process of the first cycle process FIG. 23 is a schematic diagram of a substrate in the etching step of the first cycle. FIG. 23 is a schematic diagram of a substrate at the start of the etching step of the first cycle. In the etching step of the first cycle, 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.

[0224] Fig. 24 is a schematic diagram of the substrate in the etching step of the first cycle step. Fig. 24 is a schematic diagram of the substrate at the end of the etching step of the first cycle step. The third layer G is etched. In the etching step of the first cycle step, the third layer G is etched by an etching amount LG1.

[0225] 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 process, it is difficult to protect the faces E1 and F1.

[0226] Step S11: Film formation process of the second cycle process FIG. 25 is a schematic diagram of 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, F1a. The portions E1a, 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.

[0227] Step S21: Etching process of the second cycle process FIG. 26 is a schematic diagram of a substrate in the etching step of the second cycle. FIG. 26 is a schematic diagram of a substrate at the start of the etching step of the second cycle. In the etching step of the second cycle, 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.

[0228] Fig. 27 shows the substrate in the etching step of the second cycle. Fig. 27 shows the substrate at the end of the etching step of the second cycle. The third layer G is etched again. In the etching step of the second cycle, the third layer G is etched by an etching amount LG2.

[0229] 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 in the first embodiment.

[0230] 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.

[0231] 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.

[0232] 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 in 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 are not in 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.

[0233] 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 amount of etching of the portions E1a and F1a is small. For example, the portions E1a and F1a are not substantially etched.

[0234] Similarly, the time during which 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.

[0235] Therefore, it is easy to protect the faces E1 and F1 from the etching solution R. For example, the etching amount of the faces E1 and F1 is small. For example, the faces E1 and F1 are not substantially etched.

[0236] 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.

[0237] The conditions of the comparative example will be described. Fig. 28 is a flow chart 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, the cycle process that is repeated two or more times is not provided.

[0238] A substrate W processed by a substrate processing method of a comparative example will be described.

[0239] For convenience, refer to Fig. 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.

[0240] Step S31: Film formation process of the comparative example For convenience, reference is made to Figure 22. In the film formation step, a self-assembled monolayer P is formed on a first layer E and a second layer F.

[0241] Step S32: Etching process of the comparative example For convenience, reference is made to Figure 23. In the etching process, the third layer G comes into contact with an etching solution R. The self-assembled monolayer P protects the first layer E and the second layer F from the etching solution R.

[0242] For convenience, refer to Fig. 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, the portions E1a and F1a are exposed.

[0243] FIG. 29 is a schematic diagram of the substrate W in 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. The third layer G is then 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, the portions E1a and F1a remain exposed. While the third layer G is etched by the etching amount LG2, the portions E1a and F1a come into contact with the etching solution R. While the third layer G is etched by the etching amount LG2, the portions E1a and F1a are etched. Therefore, the etching amount of the portions E1a and F1a is significantly large.

[0244] After the third layer G is etched by an etching amount LG2, the other portions E1b and F1b are exposed.

[0245] The differences between the first embodiment and the comparative example are summarized below. See FIG. 27 and FIG. 29. The time during which the portions E1a and F1a are in contact with the etching solution R in the first embodiment 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.

[0246] 1-6. Processing conditions for cycle process The processing conditions of the cycle process are exemplified below.

[0247] 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. For example, the target value LGT is 100 nm, and the etching amount LGa is 2 nm.

[0248] 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 target value LGT divided 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 times.

[0249] For example, the etching time TEa depends on at least one of the etching rate UE and RF. The "etching time TEa" is the time of one etching step in one cycle step. The "etching rate UE" is the etching rate of the first layer E. More specifically, the "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. The "etching rate UF" is the etching rate of the second layer F. More specifically, the "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.

[0250] For example, the etching time TEa is determined based on the etching rate UE and a first threshold V1. The "first threshold V1" is an upper limit value 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.

[0251] For example, the etching time TEa is limited so that the etching amount LEa is equal to or smaller than the first threshold value V1.

[0252] 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.

[0253] For example, the etching time TEa is limited so that the etching amount LFa is equal to or smaller than the second threshold value V2.

[0254] Alternatively, the etching time TEa may 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 the third layer G etched per unit time.

[0255] For example, the etching time TEa is determined based on the etching rate UG and a third threshold value V3. The "third threshold value V3" is the upper limit of the etching amount LGa.

[0256] For example, the etching time TEa is limited so that the etching amount LGa is equal to or smaller than the third threshold value V3.

[0257] For example, the third threshold V3 is equal to or less than 2 nm.

[0258] For example, in the cycling process, the substrate W is not dried.

[0259] For example, the self-assembled monolayer P is not removed from the substrate W during the cycling process.

[0260] 1-7. Effects of the 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.

[0261] 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.

[0262] 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.

[0263] The cycle process is repeated two or more times. The film formation process is repeated two or more times. Therefore, after the portions E1a, F1a are exposed, the self-assembled monolayer P is quickly formed on the portions E1a, F1a. Therefore, the time during which the portions E1a, F1a are exposed is short. The time during which the portions E1a, F1a are in contact with the etching solution R is short. Therefore, it is easy to protect the portions E1a, 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.

[0264] 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.

[0265] 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.

[0266] The third layer G is repeatedly etched in a plurality of etching steps, so that the third layer G is properly etched.

[0267] For example, the cycle process is repeated 10 times or more. Therefore, the etching time TEa is shorter. Therefore, it is easier to protect the first layer E and the second layer F from the etching solution R.

[0268] For example, the etching process is repeated 10 or more times. Therefore, the third layer G is repeatedly etched 10 or more times. Thus, the third layer G is properly etched.

[0269] 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.

[0270] 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.

[0271] For example, the etching time TEa depends on at least one of the etching rates UE and UF. In this case, the etching time TEa does not depend on the etching rate UG of the third layer G. In this case, the etching time TEa does not depend on the target value LGT. Therefore, it is easy to protect the first layer E and the second layer F.

[0272] 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.

[0273] 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.

[0274] The etching time TEa is determined based on the etching rate UF and the second threshold value V2. Therefore, it is easy to protect the second layer F.

[0275] The etching time TEa is limited so that the etching amount LFa is equal to or less than the second threshold value V2. Therefore, it is easy to control the etching amount LFa to be equal to or less than the second threshold value V2.

[0276] Alternatively, the etching time TEa depends on the etching rate UG, so that it is easy to etch the third layer G.

[0277] The etching time TEa is determined based on the etching rate UG and the third threshold value V3, so that it is easy to etch the third layer G.

[0278] The etching time TEa is limited so that the etching amount LGa is equal to or less than the third threshold value V3. Therefore, it is easy to control the etching amount LGa to be equal to or less than the third threshold value V3.

[0279] The third threshold V3 is equal to or less than 2 nm. Therefore, the etching amount LGa is small. Therefore, the etching time TEa is short. The cycle process is repeated frequently. Therefore, it is easier to etch the third layer G in the etching process.

[0280] 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 the surface E1 and the surface F1, the self-assembled monolayer P does not fill the entire space A. Even when the self-assembled monolayer P is formed on the surface E1 and the surface F1, the self-assembled monolayer P fills only a part of the space A. Therefore, even when the self-assembled monolayer P is formed on the surface E1 and the surface F1, at least a part 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 the surface E1 and the surface 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 the surface E1 and the surface F1, it is easy to etch the third layer G.

[0281] For example, 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. The self-assembled monolayer P contains an unsaturated hydrocarbon. For this reason, 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.

[0282] 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 agents, 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.

[0283] For example, 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. The self-assembled monolayer P contains at least one of an unsaturated hydrocarbon and an alkyl bromide. For this reason, 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.

[0284] 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. For this reason, 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.

[0285] 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. For this reason, 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.

[0286] 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 a first layer E. The second self-assembled monolayer P2 is formed on a second layer F. For this reason, 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.

[0287] The second self-assembled monolayer P2 has the same composition as the first self-assembled monolayer P1, which allows the structure of the self-assembled monolayer P to be simplified.

[0288] In the film formation step, a protective liquid Q is supplied to the substrate W. The protective liquid Q contains a material for a 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.

[0289] The protection liquid Q further contains toluene, so it is easy for the toluene to limit the thickness PT, so that the thickness PT is not excessively large.

[0290] In the cycle process, the substrate W is not dried. Therefore, the cycle process is simple. Therefore, the time for one cycle process is short. Therefore, it is easier to repeat the cycle process.

[0291] In the cycling process, 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 process is repeated.

[0292] The substrate processing method further includes a final removal step. The final removal step removes the self-assembled monolayer P from the substrate W. The cycle step is 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 for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0293] In the removal process, a removal liquid is supplied to the substrate W. The removal liquid contains a solvent. In the film formation process, 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.

[0294] The removal liquid contains toluene, so that the removal liquid can easily remove the self-assembled monolayer P from the substrate W.

[0295] The substrate processing method further includes a final drying step. In the final drying step, 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 for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0296] The substrate processing method further includes a final rinsing step. In the final rinsing step, a final rinsing liquid is supplied to the substrate W. The cycle step is repeated two or more times before the final rinsing step. Therefore, the cycle step does not include a final rinsing step. The cycle step is repeated without a final rinsing step. Therefore, the time for one cycle step is short. Therefore, it is easier to repeat the cycle step.

[0297] 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 rinsing liquid. Therefore, when the substrate W is dried in the final drying step, particles are unlikely to be generated on the substrate W.

[0298] 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. 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 controls the supply unit 15a and the supply unit 15b. The control unit 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 solution R to the substrate W to etch the third layer G.

[0299] The cycle process is repeated two or more times. Therefore, 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.

[0300] The cycle process is repeated two or more times, so that it is easy to etch the third layer G.

[0301] 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.

[0302] 2. Second embodiment A substrate processing apparatus 1 and a substrate processing method according to the second embodiment will be described with reference to the drawings. 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.

[0303] 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.

[0304] 2-1. Configuration of processing unit 11 30 is a diagram showing the configuration of a 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 protection liquid to the substrate W. The supply unit 15a2 supplies a second protection liquid to the substrate W.

[0305] The first protective liquid contains a material for a first self-assembled monolayer P1, and the second protective liquid contains a material for a second self-assembled monolayer P2.

[0306] 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.

[0307] When the material composition of the second self-assembled monolayer P2 is different from the material composition of the first self-assembled monolayer P1, the second self-assembled monolayer P2 has a different composition from the first self-assembled monolayer P1.

[0308] 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.

[0309] When the first protective liquid and the second protective liquid are not differentiated from each other, the first protective liquid and the second protective liquid are called "protective liquid Q." When the first self-assembled monolayer P1 and the second self-assembled monolayer P2 are not differentiated from each other, the first self-assembled monolayer P1 and the second self-assembled monolayer P2 are called "self-assembled monolayer P."

[0310] The processing unit 11 includes supply parts 15f and 15g in addition to the supply parts 15a-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.

[0311] The first replacement liquid is, for example, toluene.

[0312] 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.

[0313] The solvent of the first replacement liquid is an organic solvent, and includes, for example, at least one of ethanol, isopropyl alcohol, toluene, hexane, hexanone, cyclohexane, and benzene.

[0314] The solvent of the first replacement liquid is an example of the third solvent in the present invention.

[0315] The second replacement liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol.

[0316] Each of the supply units 15a1, 15a2, 15f, and 15g has a configuration similar to that of the supply unit 15a.

[0317] Although not shown in the figure, the control unit 10 controls the supply units 15a1, 15a2, 15f, and 15g.

[0318] 2-2. Example of substrate processing method For convenience, FIG. 19 is referred to. 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 substrate processing method of the second embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the second embodiment will be described.

[0319] 31 is a flow chart 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.

[0320] 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.

[0321] Each step will be described below.

[0322] Step S10: First replacement process In the first replacement step, a first replacement liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15f to execute the first replacement step. In the first replacement step, the supply unit 15f supplies the first replacement liquid to the substrate W.

[0323] Step S11: Film formation process In the film-forming step, a self-assembled monolayer P is formed on a first layer E and a second layer F. The film-forming step includes a first film-forming step and a second film-forming step.

[0324] Step S11a: First film formation process In the first film formation step, 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 step. In the first film formation step, the supply unit 15a1 supplies a first protective liquid to the substrate W. In the first film formation step, the supply unit 15a1 forms the first self-assembled monolayer P1 on the first layer E.

[0325] 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 a 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.

[0326] 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.

[0327] 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.

[0328] Step S12: Second replacement process In the second replacement process, a second replacement liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15g to execute the second replacement process. In the second replacement process, the supply unit 15g supplies the second replacement liquid to the substrate W. In the second replacement process, the protection liquid Q on the substrate W is replaced with the second replacement liquid. In the second replacement process, the protection liquid Q is removed from the substrate W.

[0329] 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 does not transform into the self-assembled monolayer P and remains in the protective liquid Q. The other portion of the material of the self-assembled monolayer P is the "surplus material of the self-assembled monolayer." In the second replacement step, the excess material of the self-assembled monolayer P is also removed from the substrate W.

[0330] The second replacement liquid used in the second replacement step may be only one of deionized water and isopropyl alcohol. For example, in the second replacement 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.

[0331] Alternatively, the second replacement liquid used in the second replacement step may be both deionized water and isopropyl alcohol. For example, in the second replacement 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.

[0332] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0333] 2-3. Effects of the second embodiment The second embodiment provides similar effects to those of the first embodiment. Furthermore, the second embodiment provides the following effects.

[0334] 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.

[0335] 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. For this reason, 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.

[0336] The cycle process includes a first replacement process. In the first replacement process, a first replacement liquid is supplied to the substrate W. The first replacement 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.

[0337] The first replacement liquid contains a solvent. The solvent of the first replacement liquid has the same composition as the solvent of the protection liquid Q. For this reason, 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 the protection liquid Q used.

[0338] The first replacement liquid contains toluene. For this reason, it is easy to supply the protection liquid Q to the substrate W in the film forming step. Therefore, it is easy to reduce the amount of the protection liquid Q used.

[0339] 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 the 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.

[0340] 3. Third embodiment A substrate processing apparatus 1 and a substrate processing method according to the third embodiment will be described with reference to the drawings. 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.

[0341] 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.

[0342] 3-1. Configuration of processing unit 11 32 is a diagram showing the configuration of a processing unit 11 according to the third embodiment. The processing unit 11 includes a supply unit 15h in addition to the supply units 15a-15e. The supply unit 15h supplies a third substitute liquid to the substrate W.

[0343] The third replacement liquid is, for example, toluene.

[0344] The third 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.

[0345] The third replacement liquid is, for example, an organic solvent. The organic solvent of the third replacement liquid includes, for example, at least one of ethanol, isopropyl alcohol, toluene, hexane, hexanone, cyclohexane, and benzene.

[0346] Supply unit 15h has a configuration similar to that of supply unit 15a.

[0347] Although not shown in the figure, the control unit 10 controls the supply unit 15h.

[0348] 3-2. Example of substrate processing method For convenience, FIG. 19 is referred to. 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 substrate processing method of the third embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the third embodiment will be described.

[0349] 33 is a flow chart 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 replacement 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 replacement process is performed after the etching process.

[0350] 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.

[0351] Each step will be described below.

[0352] Step S11: Film formation process In the film formation step, a protective liquid Q is supplied to the substrate W. In the film formation step, a self-assembled monolayer P is formed on a first layer E and a second layer F.

[0353] Step S13: First rinsing step In the first rinsing step, a rinsing liquid is supplied to the substrate W. The rinsing liquid supplied to the substrate W in the first rinsing step is called the "first rinsing liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the first rinsing step. In the first rinsing step, the supply unit 15d supplies the first rinsing liquid to the substrate W. In the first rinsing step, the first rinsing liquid washes away the protective liquid Q on the substrate W. In the first rinsing step, the protective liquid Q is removed from the substrate W. In the first rinsing step, excess material of the self-assembled monolayer P is also removed from the substrate W.

[0354] Step S14: First drying process 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 causes the substrate W to be dried.

[0355] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0356] Step S23: Third replacement step In the third replacement process, a third replacement liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15h to execute the third replacement process. In the third replacement process, the supply unit 15h supplies the third replacement liquid to the substrate W. In the third replacement process, the etching liquid R on the substrate W is replaced with the third replacement liquid. In the third replacement process, the etching liquid R is removed from the substrate W. In the third replacement process, etching by the etching liquid R stops.

[0357] 3-3. Effects of the Third Embodiment The third embodiment provides similar effects to those of the first embodiment. Furthermore, the third embodiment provides the following effects.

[0358] 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.

[0359] The cycle process includes a first rinsing process. In the first rinsing process, a first rinsing liquid is supplied to the substrate W. The first rinsing process is performed after the film forming process and before the first drying process. Therefore, the first rinsing liquid washes away the protective liquid Q on the substrate W. Therefore, in the first rinsing process, it is easy to remove the protective liquid Q from the substrate W. In the first rinsing process, 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 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.

[0360] The cycle process includes a third replacement process. In the third replacement process, a third replacement liquid is supplied to the substrate W. The third replacement process is performed after the etching process. Therefore, in the third replacement process, the etching liquid R on the substrate W is replaced with the third replacement liquid. Therefore, in the third replacement process, it is easy to remove the etching liquid R from the substrate W. Therefore, it is easy to stop the etching of the third layer G in the third replacement process. Furthermore, it is even easier to protect the first layer E and the second layer F from the etching liquid R in the third replacement process.

[0361] 4. Fourth embodiment A substrate processing apparatus 1 and a substrate processing method according to the fourth embodiment will be described with reference to the drawings. 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.

[0362] 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.

[0363] 4-1. Configuration of processing unit 11 34 is a diagram showing the configuration of a 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.

[0364] The oxidizing liquid 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.

[0365] The oxidizing liquid is, for example, oxygen water. Oxygen water is water containing dissolved oxygen. Oxygen water is, for example, high-concentration oxygen water. High-concentration oxygen water is water containing oxygen at a higher concentration than normal. The amount of oxygen in high-concentration oxygen water is greater than the amount of oxygen in water placed in normal air. Oxygen water is, for example, saturated oxygen water. Saturated oxygen water is water containing oxygen at a saturated concentration.

[0366] 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 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.

[0367] Supply unit 15i has a configuration similar to that of supply unit 15a.

[0368] Although not shown in the figure, the control unit 10 controls the supply unit 15i.

[0369] 4-2. Example of substrate processing method For convenience, FIG. 19 will be referred to. 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 substrate processing method of the fourth embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the fourth embodiment will be described.

[0370] 35 is a flow chart 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.

[0371] 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.

[0372] Each step will be described below.

[0373] Step S11: Film formation process In the film formation step, a self-assembled monolayer P is formed on the first layer E and the second layer F.

[0374] Step S15: Oxidation process In the oxidation process, the third layer G is oxidized. For example, when 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.

[0375] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0376] 4-3.Technical significance of the oxidation process The technical significance of the oxidation process will be explained by a second example.

[0377] The conditions of the second embodiment will be described. FIG. 36 is a flow chart 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 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.

[0378] A substrate W to be processed by the substrate processing method of the second embodiment will be described.

[0379] Step S11: Film formation process of the first cycle process 37 is a schematic diagram of a substrate W in a film formation step of a first cycle step. In the film formation step of the first cycle step, a self-assembled monolayer P is formed on a first layer E and a second layer F. In the film formation step of the first cycle step, a self-assembled monolayer P is not formed on a third layer G.

[0380] The third layer G includes a superficial portion G4 and a deep portion G5. The superficial portion G4 is located close to the surface G3. The superficial portion G4 includes the surface G3. The deep portion G5 is located far from the surface G3. The deep portion G5 does not include the surface G3.

[0381] The surface layer G4 may include silicon suboxide. The surface layer G4 may not be composed of silicon dioxide alone.

[0382] The deep layer G5 includes at least one of silicon suboxide and silicon dioxide.

[0383] Step S15: Oxidation step of the first cycle FIG. 38 shows a schematic diagram of the substrate W in the oxidation step of the first cycle step. In the oxidation step of the first cycle step, the third layer G is oxidized. It is easy to oxidize the surface layer G4. Oxidizing the surface layer G4 is easier than oxidizing the deep layer G5. Therefore, in the oxidation step of the first cycle step, 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.

[0384] 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.

[0385] 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.

[0386] 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. The second layer F is not oxidized.

[0387] Step S21: Etching process of the first cycle process FIG. 39 is a schematic diagram of a substrate in an etching step of a first cycle process. FIG. 39 is a schematic diagram of a substrate at the end of an etching step of a first cycle process. In an etching step of a first cycle process, an etching solution R is supplied. A third layer G is etched. Specifically, a surface portion G4 of the third layer G is etched. At least a part of the surface portion G4 is etched. However, in an etching step of a first cycle process, a deep portion G5 is not etched.

[0388] 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 to etch silicon suboxide.

[0389] As described above, in the etching process of the first cycle, the surface layer portion G4 is etched. In the etching process of the first cycle, the deep layer portion G5 is not etched. Therefore, it is easy to etch the third layer G in the etching process of the first cycle.

[0390] After the portion of the third layer G is etched, the portions E1a and F1a are exposed.

[0391] Step S11: Film formation process of the second cycle process 40 is a schematic diagram of 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.

[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 second cycle 41 is 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.

[0395] The surface layer G4 is oxidized. As a result, the surface layer G4 is composed of only silicon dioxide. The surface layer G4 does not contain silicon suboxide.

[0396] At least a portion of deep layer G5 may not be oxidized, so that deep layer G5 may include silicon suboxide.

[0397] 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.

[0398] Step S21: Etching process of the second cycle process FIG. 42 is a schematic diagram of a substrate in the etching step of the second cycle process. FIG. 42 is a schematic diagram of a substrate 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 portion G4 of the third layer G is etched. At least a part of the surface portion G4 is etched. However, in the etching step of the second cycle process, the deep portion G5 is not etched. Therefore, it is easy to etch the third layer G in the etching step of the second cycle.

[0399] 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. Therefore, the portion of the third layer G that is etched in the etching process is composed of only silicon dioxide. The portion of the third layer G that is etched in the etching process does not include silicon suboxide. Therefore, it is easy to etch the third layer G.

[0400] In the etching process, only the surface portion G4 of the third layer G is etched. Therefore, it is easy to etch the third layer G.

[0401] The etching step does not etch the deep portion G5 of the third layer G. Even if the deep portion G5 contains silicon suboxide, it is easy to etch the third layer G.

[0402] 4-4. Processing conditions for cycle process The processing conditions of the cycle process are exemplified below.

[0403] The etching amount LGa is smaller than the length of the surface 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.

[0404] For example, the etching amount LGa is 2 nm.

[0405] 4-5. Effects of the Fourth Embodiment The fourth embodiment provides similar effects to those of the first embodiment. Furthermore, the fourth embodiment provides the following effects.

[0406] 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 therefore easy to improve the etching rate of the third layer G.

[0407] 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.

[0408] In the oxidation step, an oxidizing liquid is supplied for oxidizing the third layer G. Therefore, it is easy to oxidize the third layer G in the oxidation step.

[0409] 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.

[0410] 5. Fifth embodiment A substrate processing apparatus 1 and a substrate processing method according to the fifth embodiment will be described with reference to the drawings. 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.

[0411] 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.

[0412] 5-1. Configuration of processing unit 11 43 is a diagram showing the configuration of a processing unit 11 according to the fifth embodiment. The processing unit 11 includes the supply units 15i and 15j in addition to the supply units 15a-15e. The supply unit 15i has been described in the fourth embodiment.

[0413] The supply unit 15j supplies the substrate W with the fourth substitute liquid.

[0414] The fourth replacement liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol.

[0415] Supply unit 15j has a configuration similar to that of supply unit 15a.

[0416] Although not shown in the figure, the control unit 10 controls the supply unit 15j.

[0417] 5-2. Example of substrate processing method For convenience, FIG. 19 will be referred to. 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 fourth embodiment are the same as those of the substrate processing method of the first embodiment. The substrate processing method of the fifth embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the fifth embodiment will be described.

[0418] 44 is a flow chart showing the procedure of the cycle process of the fifth embodiment. In addition to the film formation process and the etching process, the cycle process includes an oxidation process and a fourth replacement process. The oxidation process is performed after the film formation process and before the etching process. The fourth replacement process is performed after the oxidation process and before the etching process.

[0419] 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.

[0420] Each step will be described below.

[0421] Step S11: Film formation process In the film formation step, a self-assembled monolayer P is formed on the first layer E and the second layer F.

[0422] Step S15: Oxidation process In the oxidation step, an oxidizing liquid is supplied to the substrate W. In the oxidation step, the third layer G is oxidized.

[0423] Step S16: Fourth replacement step In the fourth replacement process, a fourth replacement liquid is supplied to the substrate W. Specifically, the control unit 10 controls the supply unit 15j to execute the fourth replacement process. In the fourth replacement process, the supply unit 15j supplies the fourth replacement liquid to the substrate W. In the fourth replacement process, the oxidizing liquid on the substrate W is replaced with the fourth replacement liquid. In the fourth replacement process, the oxidizing liquid is removed from the substrate W.

[0424] The fourth replacement liquid used in the fourth replacement step may be only one of deionized water and isopropyl alcohol. For example, in the fourth replacement 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.

[0425] Alternatively, the fourth replacement liquid used in the fourth replacement step may be both deionized water and isopropyl alcohol. For example, in the fourth replacement 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.

[0426] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0427] 5-3. Effects of the Fifth Embodiment The fifth embodiment provides similar effects to those of the first embodiment. Furthermore, the fifth embodiment provides the following effects.

[0428] The cycle process includes a fourth replacement process. In the fourth replacement process, a fourth replacement liquid is supplied to the substrate W. The fourth replacement process is performed after the oxidation process and before the etching process. Therefore, in the fourth replacement process, the oxidizing liquid on the substrate W is replaced with the fourth replacement liquid. Therefore, in the fourth replacement process, 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 process. For example, it is easy to reduce the amount of etching liquid R used.

[0429] 6. Sixth embodiment A substrate processing apparatus 1 and a substrate processing method according to the sixth embodiment will be described with reference to the drawings. 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.

[0430] 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 similar configuration to the processing unit 11 of the fourth embodiment. The configuration of the processing unit 11 of the fourth embodiment is shown in FIG.

[0431] 6-1. Example of substrate processing method For convenience, FIG. 19 will be referred to. 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 fourth embodiment are the same as those of the substrate processing method of the first embodiment. The substrate processing method of the sixth embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the sixth embodiment will be described.

[0432] 45 is a flow chart 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.

[0433] The control unit 10 controls the supply units 15a, 15b, 15d, 15e, 15i, and 15j to execute the cycle process. The control unit 10 causes the rotation drive unit 14 and the supply units 15a, 15b, 15d, 15e, 15i, and 15j to repeat the cycle process two or more times.

[0434] Each step will be described below.

[0435] Step S11: Film formation process In the film formation step, a self-assembled monolayer P is formed on the first layer E and the second layer F.

[0436] Step S15: Oxidation process In the oxidation step, an oxidizing liquid is supplied to the substrate W. In the oxidation step, the third layer G is oxidized.

[0437] Step S17: Second rinsing step In the second rinsing process, a rinsing liquid is supplied to the substrate W. The rinsing liquid supplied to the substrate W in the second rinsing process is called the "second rinsing liquid." Specifically, the control unit 10 controls the supply unit 15d to execute the second rinsing process. In the second rinsing process, the supply unit 15d supplies the second rinsing liquid to the substrate W. In the second rinsing process, the second rinsing liquid washes away the oxidizing liquid on the substrate W. In the second rinsing process, the oxidizing liquid is removed from the substrate W.

[0438] Step S18: Second drying process 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.

[0439] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0440] 6-2. Effects of the Sixth Embodiment The sixth embodiment provides similar effects to those of the first embodiment. Furthermore, the sixth embodiment provides the following effects.

[0441] 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.

[0442] The cycle process includes a second rinsing process. In the second rinsing process, a second rinsing liquid is supplied to the substrate W. The second rinsing process is performed after the film forming process and before the second drying process. Therefore, in the second rinsing process, the second rinsing liquid washes away the oxidizing liquid on the substrate W. Therefore, in the second rinsing process, it is easy to remove the oxidizing liquid from the substrate W. Therefore, when the substrate W is dried in the second drying process, particles are unlikely to be generated on the substrate W. The particles are derived from, for example, the oxidizing liquid.

[0443] 7. Seventh embodiment A substrate processing apparatus 1 and a substrate processing method according to the seventh embodiment will be described with reference to the drawings. 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.

[0444] 7-1. Configuration of processing unit 11 46 is a diagram showing the configuration of a processing unit 11 according to 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 for oxidizing the substrate W. The additive is also called an oxidizing agent.

[0445] 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.

[0446] Supply unit 15k has a configuration similar to that of supply unit 15a.

[0447] Although not shown in the figure, the control unit 10 controls the supply unit 15k.

[0448] 7-2. Example of substrate processing method For convenience, FIG. 19 will be referred to. 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 fourth embodiment are the same as those of the substrate processing method of the first embodiment. The substrate processing method of the sixth embodiment differs from the substrate processing method of the first embodiment in terms of the cycle step. Therefore, the cycle step of the seventh embodiment will be described.

[0449] 47 is a flow chart 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 part of the period during which the oxidation process is performed may overlap at least a part of the period during which the etching process is performed.

[0450] 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.

[0451] Each step will be described below.

[0452] Step S11: Film formation process In the film formation step, a self-assembled monolayer P is formed on the first layer E and the second layer F.

[0453] 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. 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 of the third layer G changes to silicon dioxide.

[0454] Step S21: Etching process In the etching step, an etchant R is supplied to the substrate W. In the etching step, the third layer G is etched.

[0455] 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 etched by the etching solution R. While the third layer G is oxidized by the additive, the third layer G is etched by the etching solution R.

[0456] 7-3. Effects of the Seventh Embodiment The seventh embodiment provides similar effects to those of the first embodiment. Furthermore, the seventh embodiment provides the following effects.

[0457] 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.

[0458] In the oxidation step, an additive for oxidizing the third layer G is supplied to the substrate W. For this reason, it is easy to perform the oxidation step and the etching step simultaneously.

[0459] 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, so that it is easy to oxidize the third layer G in the oxidation process.

[0460] The present invention is not limited to the embodiments, and can be modified as follows.

[0461] (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 in the first layer E and the second layer F by a liquid phase method. However, the method of 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 Depositon (CVD) method. For example, in the film formation process, a gas of the material of the self-assembled monolayer P may be supplied to the substrate W. The gas of the material of the self-assembled monolayer P is, for example, a vapor of the material of the self-assembled monolayer P. For example, the gas of the material of the self-assembled monolayer P may be prepared by heating the protective liquid Q.

[0462] (2) In the oxidation process of the fourth to seventh embodiments, an oxidizing liquid 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 processing gas is supplied to the substrate W. The plasma process includes at least one of an oxygen plasma and an ozone plasma. The processing 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.

[0463] (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.

[0464] (4) The cycle process of the fourth to sixth embodiments may further include a fifth substitution process. In the fifth substitution process, 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 process is performed after the film formation process and before the etching process. According to this modified embodiment, it is easy to oxidize the substrate W in the oxidation process.

[0465] (5) The cycle process of the fourth to sixth embodiments may further include a third drying process. In the third drying process, the substrate W is dried. The third drying process is performed after the film forming process and before the etching process. According to this modified embodiment, the substrate W is in a dry state when the oxidation process starts. Therefore, it is easy to oxidize the substrate W in the oxidation process.

[0466] In the above-described modified embodiment, the cycle process may further include a third rinsing process. In the third rinsing process, a third rinsing liquid is supplied to the substrate W. The third rinsing liquid is, for example, at least one of deionized water (DIW) and isopropyl alcohol. The third rinsing process is performed after the film forming 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.

[0467] (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.

[0468] (7) In the fifth embodiment, the cycle process includes the second rinse step. However, this is not limited to this. For example, the cycle process does not have to include the second rinse step.

[0469] (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 divided into batch types. That is, the processing unit 11 may process multiple substrates W at once.

[0470] 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 given the same reference numerals and detailed description thereof will be omitted.

[0471] 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.

[0472] The processing unit 11 includes substrate holding parts 22a and 22b. The substrate holding part 22a holds multiple substrates W simultaneously. The substrate holding part 22a holds each substrate W in a substantially vertical position. When the substrate W is held by the substrate holding part 22a, the surface W1 of each substrate W is substantially vertical. The substrate holding part 22b has a configuration similar to that of the substrate holding part 22a. The substrate holding part 22a is provided in the tank 21a. The substrate holding part 22b is provided in the tank 21b.

[0473] The processing unit 11 includes lifting and lowering drive units 23a and 23b. The lifting and lowering drive unit 23a is connected to the substrate holding unit 22a. The lifting and lowering drive unit 23a moves the substrate holding unit 22a in the vertical direction Z. The substrate W held by the substrate holding unit 22a moves up and down together with the substrate holding unit 22a. The lifting and lowering drive unit 23a moves the substrate holding unit 22a to an upper position and a lower position. FIG. 16 shows the substrate holding unit 22a in the upper position with a solid line. FIG. 48 shows the substrate holding unit 22a in the lower position with a dashed line. When the substrate holding unit 22a is in the upper position, the substrate W held by the substrate holding unit 22a is located above the protective liquid Q in the bath 21a. When the substrate holding unit 22a is in the lower position, the substrate W held by the substrate holding unit 22a is immersed in the protective liquid Q in the bath 21a. The lifting drive unit 23b is connected to the substrate holding unit 22b. The lifting drive unit 23b has a configuration similar to that of the lifting drive unit 23a. The lifting drive unit 23b moves the substrate holding unit 22b to 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 located above the etching solution R in the tank 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 tank 21b.

[0474] 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 parts 22a and 22b. When the substrate holding part 22a is in the upper position, the substrate transport mechanism delivers the substrate W to the substrate holding part 22a and receives the substrate W from the substrate holding part 22a. When the substrate holding part 22b is in the upper position, the substrate transport mechanism delivers the substrate W to the substrate holding part 22b and receives the substrate W from the substrate holding part 22b.

[0475] Although not shown in the figure, the control unit 10 controls the tanks 21a and 21b, the substrate holders 22a and 22b, and the lifting and lowering drivers 23a and 23b.

[0476] Tank 21a, substrate holder 22a, and lift driver 23a are examples of the film forming section in the present invention. Tank 21b, substrate holder 22b, and lift driver 23b are examples of the etching section in the present invention.

[0477] The procedure of the substrate processing method according to the modified embodiment will be described with reference to FIG.

[0478] Step S11: Film formation process The substrate holding portion 22a is located at an upper position. The substrate holding portion 22a holds a plurality of substrates W. The substrate holding portion 22a is moved from an upper position to a lower position. The substrates W held by the substrate holding portion 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 portion 22a. As a result, a self-assembled monolayer P is formed on the first layer E and the second layer F.

[0479] Step S21: Etching solution process Substrate holding portion 22a moves from a lower position to an upper position. Substrate holding portion 22b is located at an upper position. The substrate transport mechanism transports substrates W from substrate holding portion 22a to substrate holding portion 22b. Substrate holding portion 22b holds a plurality of substrates W. Substrate holding portion 22b moves from an upper position to a lower position. The substrates W held by substrate holding portion 22b are immersed in the etching liquid R in tank 21b. That is, the etching liquid R in tank 21b is supplied to the substrates W held by substrate holding portion 22b. As a result, the third layer G is etched.

[0480] (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 element isolation film. For example, the third layer G may be an insulator layer.

[0481] (10) The first to seventh embodiments and each of 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. [Explanation of symbols]

[0482] 1 ... Substrate processing equipment 10 ... Control section 11 … Processing unit 13... Board holding part 15a, 15a1, 15a2... Supply section (film forming section) 15b ... Supply section (etching section) 21a … Tank (film forming part) 21b … Tank (etching section) A … Space (space between the first and second layers) E … 1st layer E1 … First layer surface (first surface) F … 2nd layer F1: Second layer face (second face) G … 3rd layer P… Self-assembled monolayer P1…First self-assembled monolayer P2…Second self-assembled monolayer Q … Protective liquid R: Etching solution LEa … Etching amount of the first layer in one etching step in one cycle process LFa: Etching amount of the second layer in one etching step in one cycle process LG: Etching amount of the third layer LGa … Etching amount of the third layer in one etching process in one cycle process LGT: Target value of total etching amount of the third layer TEa … Time for 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…Anteroposterior direction Y: Width direction Z: Vertical direction

Claims

1. A substrate processing method for processing a substrate, comprising the steps of: The substrate is A first layer; A second layer; and a third layer located between the first layer and the second layer; and Including, the first layer has a first surface in surface contact with the third layer; the second layer has a second surface in surface contact with the third layer; the first layer has a composition different from a composition of the third layer; the second layer has a composition different from a composition of the third layer; The substrate processing method includes: A cycle process; Equipped with The cycle process includes: a film forming step of forming a self-assembled monolayer on the first layer and the second layer; an etching step of supplying an etching solution to the substrate and etching the third layer; Including, The cycling steps are repeated two or more times. A method for processing a substrate.

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

3. 2. The substrate processing method according to claim 1, The self-assembled monolayer has a thickness that is less than half the separation distance between the first surface and the second surface. A method for processing a substrate.

4. 2. The substrate processing method according to claim 1, The self-assembled monolayer is A first self-assembled monolayer formed on the first layer; A second self-assembled monolayer formed on the second layer; Includes A method for processing a substrate.

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

6. 6. The substrate processing method according to claim 5, The protection liquid further contains toluene. A method for processing a substrate.

7. 6. The substrate processing method according to claim 5, The cycle process includes: a first replacement step of supplying a first replacement liquid to the substrate; Including, The first replacement step is carried out before the film formation step. A method for processing a substrate.

8. 6. The substrate processing method according to claim 5, The cycle process includes: a second replacement step of supplying a second replacement liquid to the substrate; Including, The second replacement step is performed after the film formation step and before the etching step. A method for processing a substrate.

9. 6. The substrate processing method according to claim 5, The cycle process includes: a first drying step of drying the substrate; Including, The first drying step is performed after the film forming step and before the etching step. A method for processing a substrate.

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

11. 2. The substrate processing method according to claim 1, The cycle process includes: a third replacement step of supplying a third replacement liquid to the substrate; Including, The third replacement step is performed after the etching step. A method for processing a substrate.

12. 2. The substrate processing method according to claim 1, The cycle process includes: an oxidation step of oxidizing the third layer; Including, The oxidation step is carried out after the film formation step and before the etching step. A method for processing a substrate.

13. 13. The method of claim 12, further comprising: In the oxidation step, an oxidizing liquid for oxidizing the third layer is supplied. A method for processing a substrate.

14. 14. The method of claim 13, further comprising: The cycle process includes: a fourth replacement step of supplying a fourth replacement liquid to the substrate; Including, The fourth substitution step is carried out after the oxidation step and before the etching step. A method for processing a substrate.

15. 14. The method of claim 13, further comprising: The cycle process includes: a second drying step of drying the substrate; Including, The second drying step is performed after the oxidation step and before the etching step. A method for processing a substrate.

16. 16. The substrate processing method according to claim 15, The cycle process includes: a second rinsing step of supplying a second rinsing liquid to the substrate; Including, The second rinsing step is performed after the film forming step and before the second drying step. A method for processing a substrate.

17. 2. The substrate processing method according to claim 1, the cycling step includes an oxidation step of oxidizing the third layer; The oxidation step is carried out simultaneously with the etching step. A method for processing a substrate.

18. 18. The method of claim 17, further comprising: In the oxidation step, an additive for oxidizing the third layer is supplied to the substrate. A method for processing a substrate.

19. 2. The substrate processing method according to claim 1, The substrate processing method further comprises: a final removal step of removing the self-assembled monolayer from the substrate; Equipped with The cycling step is repeated two or more times before the final removal step. A method for processing a substrate.

20. 20. The method of claim 19, further comprising: In the final removal step, a removal solution is supplied to the substrate; The removal solution includes a first solvent, In the film forming step, a protective liquid is supplied to the substrate, the protective liquid contains a material for the self-assembled monolayer and a second solvent; The second solvent has the same composition as the first solvent. A method for processing a substrate.

21. 2. The substrate processing method according to claim 1, The substrate processing method further comprises: a final drying step for drying the substrate; Equipped with The cycling step is repeated two or more times before the final drying step. A method for processing a substrate.

22. 22. The method of claim 21, further comprising: The substrate processing method further comprises: a final rinse step of supplying a final rinse solution to the substrate; Equipped with The cycling step is repeated two or more times before the final rinsing step; The final rinsing step is carried out before the final drying step. A method for processing a substrate.

23. A substrate processing apparatus, comprising: The substrate is A first layer; A second layer; and a third layer located between the first layer and the second layer; and Including, the first layer has a first surface in surface contact with the third layer; the second layer has a second surface in surface contact with the third layer; the first layer has a composition different from a composition of the third layer; the second layer has a composition different from a composition of the third layer; The substrate processing apparatus includes: a film forming unit that forms a self-assembled monolayer on the first layer and the second layer; an etching unit that etches the third layer; a control unit that controls the film forming unit and the etching unit to execute a cycle process; Equipped with The cycle process includes: A film forming process; An etching process; Including, In the film forming step, the film forming unit forms a self-assembled monolayer on the first layer and the second layer, In the etching step, the etching unit supplies 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. Substrate processing equipment.

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