TWI878006B - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

A substrate processing method includes: a hydrophobization step (Step S6) of supplying a hydrophobizing agent (SMT) to a recess (R) formed in a layered structure (L) supported by a base (S), the layered structure (L) being formed of a plurality of first layers (M1) and a plurality of second layers (M2), the hydrophbizing agent hydrophobizing the surface of the second layers (M2); and an etching step (Step S8) of selectively etching the first layers (M1) by supplying an etching solution (E2) to the recess (R) in a state in which the surface of the second layers (M2) is hydrophobized. The hydrophobization step (Step S6) and the etching step (Step S8) are repeated a predetermined times.

Description

Substrate processing method and substrate processing device

The present invention relates to a substrate processing method and a substrate processing device.

In the past, a substrate processing method is known, which processes a semiconductor substrate having a substrate and a plurality of first layers and a plurality of second layers constituting a layered structure supported by the substrate. As such a substrate processing method, for example, Patent Document 1 describes a method for selectively etching silicon germanium in a substrate on which silicon and silicon germanium are alternately layered. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2018-6405

[The problem the invention is trying to solve]

For example, as described in Patent Document 1, when a specific layer among a plurality of layers is selectively etched, other layers different from the specific layer may also be etched. Specifically, when the specific layer and other layers contain the same substance or contain substances with similar chemical properties, the etching selectivity decreases. In this case, if the specific layer is to be etched deeper (more), the etching amount of other layers will increase. As a result, for example, the thickness of other layers becomes thinner, and therefore, the semiconductor device manufactured using the substrate cannot obtain the desired characteristics.

The present invention is completed in view of the above-mentioned subject, and its purpose is to provide a substrate processing method and substrate processing device that can improve etching selectivity. [Technical means to solve the problem]

According to one aspect of the present invention, a substrate processing method is to process a substrate having a substrate and a plurality of first layers and a plurality of second layers. The substrate processing method includes: a hydrophobic process, which is to supply a hydrophobic agent into a groove provided in a layered structure supported by the substrate, and the hydrophobic agent makes the surface of the plurality of first layers and the plurality of second layers constituting the layered structure hydrophobic; and an etching process, which is to supply an etching liquid into the groove in a state where the surface of the second layer is hydrophobic, and selectively etches the first layer; and the hydrophobic process and the etching process are repeated for a specified number of times.

In one embodiment, the first layer and the second layer are stacked in a first direction intersecting one surface of the substrate. The groove extends along the first direction. In the etching step, the first layer is selectively etched to form a plurality of recesses connected to the groove in a manner extending along a second direction intersecting the first direction.

In one embodiment, the length of the recess in the second direction is 20 times or more the length of the recess in the first direction.

In a certain embodiment, the above-mentioned substrate processing method further includes a post-hydrophobicization replacement process after the above-mentioned hydrophobicization process and before the above-mentioned etching process. The post-hydrophobicization replacement process is to supply a replacement liquid into the above-mentioned groove to replace the above-mentioned hydrophobicization agent with the above-mentioned replacement liquid in a manner that the above-mentioned hydrophobicization agent remains on the surface of at least the above-mentioned second layer.

In a certain embodiment, the substrate processing method further includes a post-etching replacement process after the etching process, wherein the post-etching replacement process replaces the etching liquid with the rinse liquid by supplying the rinse liquid into the groove.

In one embodiment, the rinse solution comprises isopropyl alcohol.

In one embodiment, in the hydrophobizing step, the hydrophobizing agent at least covers the surface of the second layer. Before the hydrophobizing agent disappears from the surface of the second layer by the etching liquid, the etching step is transferred to the post-etching replacement step.

In one embodiment, the first layer includes silicon germanium, and the second layer includes polycrystalline silicon or single crystal silicon.

In one embodiment, in the hydrophobizing step, the hydrophobizing agent silanes at least the surface of the second layer.

In one embodiment, in the hydrophobizing step, the hydrophobizing agent or the vapor of the hydrophobizing agent is supplied to the substrate in a mist form.

In one embodiment, in the hydrophobizing step, unused hydrophobizing agent is supplied into the groove.

According to another aspect of the present invention, a substrate processing device includes a hydrophobic agent supply unit, an etching liquid supply unit and a control unit. The hydrophobic agent supply unit supplies a hydrophobic agent to a substrate. The etching liquid supply unit supplies an etching liquid to the substrate. The control unit controls the hydrophobic agent supply unit and the etching liquid supply unit. The substrate has a substrate and a plurality of first layers and a plurality of second layers constituting a layered structure supported by the substrate. The hydrophobic agent makes the surface of the second layer hydrophobic. The etching liquid etches the first layer. The control unit controls the hydrophobizing agent supply unit to supply the hydrophobizing agent into the grooves provided in the layered structure, thereby hydrophobizing the surfaces of the plurality of second layers. The control unit selectively etches the first layer by controlling the etching liquid supply unit to supply the etching liquid into the grooves in a state where the surfaces of the second layers are hydrophobized. The control unit repeatedly performs the hydrophobizing of the surfaces of the second layers and the selective etching of the first layer a predetermined number of times. [Effect of the invention]

According to the present invention, a substrate processing method and a substrate processing device capable of improving etching selectivity can be provided.

Hereinafter, the implementation of the substrate processing method and substrate processing device of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following implementation. Furthermore, the description of the repeated descriptions may be omitted appropriately. In addition, the same reference symbols are used for the same or equivalent parts in the drawings, and the descriptions are not repeated.

In this specification, for ease of understanding, mutually orthogonal X, Y, and Z directions are sometimes described. Typically, the X and Y directions are parallel to the horizontal direction, and the Z direction is parallel to the vertical direction. However, the definitions of these directions are not intended to limit the directions when executing the substrate processing method of the present invention or the directions when using the substrate processing apparatus of the present invention.

The "substrate" in this embodiment can be applied to various substrates such as semiconductor wafers, glass substrates for masks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FED (Field Emission Display), substrates for optical disks, substrates for magnetic disks, and substrates for magneto-optical disks. In the following, this embodiment is mainly described by taking a substrate processing method and a substrate processing device for processing a disc-shaped semiconductor wafer as an example, but it can also be applied to the processing of various substrates exemplified above. In addition, various shapes of substrates can also be applied.

[First embodiment] Hereinafter, the first embodiment of the present invention will be described with reference to FIGS. 1 to 18. First, the substrate processing device 100 of the first embodiment will be described with reference to FIGS. 1 to 6. FIG. 1 is a schematic diagram showing the internal structure of the processing unit 200 of the substrate processing device 100 of the first embodiment. The substrate processing device 100 of this embodiment is a batch type. Therefore, the substrate processing device 100 processes a plurality of substrates W together. Specifically, the substrate processing device 100 processes a plurality of substrates W in batches. One batch includes, for example, 25 substrates W.

1 , the substrate processing apparatus 100 includes a processing unit 200 . The processing unit 200 performs hydrophobic treatment on the substrate W. Specifically, the processing unit 200 includes a chamber 202 , a liquid receiving member 203 , a liquid supply unit 205 , a holding unit 250 , an opening and closing unit 260 , and a lifting unit 270 .

The substrate W has the following grooves. The grooves are formed on the surface of the substrate W by dry etching. Specifically, the substrate processing apparatus 100 has a processing unit for dry etching the substrate W in addition to the processing unit 200. The substrate W after dry etching by the processing unit is transported (carried in) to the processing unit 200.

The chamber 202 contains a liquid receiving member 203 and a liquid supply unit 205. When processing a substrate W, a holding unit 250 is contained in the chamber 202. The chamber 202 has a cover 202a. The cover 202a is attached to an opening at the upper portion of the chamber 202. The cover 202a can move to open and close the opening.

The liquid supply unit 205 supplies a processing liquid into the chamber 202. The processing liquid includes, for example, a chemical solution, a rinse liquid (cleaning liquid), a removal liquid and/or a hydrophobic agent. Specifically, the liquid supply unit 205 supplies a mist of a rinse liquid, a mist of a replacement liquid and a mist of a hydrophobic agent SMT to the substrate W held by the holding unit 250. Furthermore, the liquid supply unit 205 can also supply the vapor of the rinse liquid to the substrate W. Furthermore, the liquid supply unit 205 can also supply the vapor of the replacement liquid to the substrate W. Furthermore, the liquid supply unit 205 can also supply the vapor of the hydrophobic agent SMT to the substrate W.

FIG. 2 is a schematic diagram showing a state where a rinse liquid is sprayed from the first nozzle 211 and the second nozzle 212. FIG. 3 is a schematic diagram showing a state where a replacement liquid is sprayed from the third nozzle 213 and the fourth nozzle 214. FIG. 4 is a schematic diagram showing a state where a hydrophobic agent SMT is sprayed from the fifth nozzle 215 and the sixth nozzle 216. As shown in FIG. 1 , the liquid supply unit 205 has the first nozzle 211 to the sixth nozzle 216. The first nozzle 211 to the sixth nozzle 216 are arranged inside the chamber 202 and outside the liquid receiving member 203. Specifically, the first nozzle 211 to the sixth nozzle 216 are arranged above the liquid receiving member 203. The first nozzle 211 and the second nozzle 212 spray a mist of the rinsing liquid. The third nozzle 213 and the fourth nozzle 214 spray a mist of the replacement liquid. The fifth nozzle 215 and the sixth nozzle 216 spray a mist of the hydrophobic agent SMT.

In this embodiment, the rinse solution is DIW (Deionized Water) and the replacement solution is IPA (isopropyl alcohol).

The hydrophobizing agent SMT is, for example, a silicon-based hydrophobizing agent or a metal-based hydrophobizing agent. The silicon-based hydrophobizing agent hydrophobizes (hydrophobizes) silicon or a compound containing silicon. The metal-based hydrophobizing agent hydrophobizes (hydrophobizes) metal or a compound containing metal.

The silane-based hydrophobic agent is, for example, a silane coupling agent. The silane coupling agent includes, for example, at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilane, alkyldisilazane, and non-chlorine-based hydrophobic agents. The non-chlorine-based hydrophobic agent includes, for example, at least one of dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethylaminotrimethylsilane, N-(trimethylsilyl)dimethylamine, and an organic silane compound.

The metal-based hydrophobic agent includes, for example, at least one of an amine having a hydrophobic group and an organic silicon compound.

The hydrophobic agent SMT can also be diluted with a solvent that is soluble in the hydrophilic organic solvent. The solvent is, for example, IPA or PGMEA (Propylene Glycol Methyl Ether Acetate). In this embodiment, the solvent is PGMEA.

1 , the liquid receiving member 203 receives the liquid supplied from the liquid supplying section 205 to the substrate W. Specifically, the liquid receiving member 203 receives the rinse liquid, the replacement liquid, and the hydrophobic agent SMT.

The holding portion 250 holds a plurality of substrates W. Specifically, the holding portion 250 has a plurality of holding rods 251 and a main body plate 252. In the present embodiment, the holding portion 250 has three holding rods 251. The main body plate 252 is a plate-shaped member extending in the vertical direction (Z direction). The holding rods 251 extend in the horizontal direction (X direction) from one main surface of the main body plate 252. The lower edge of each of the plurality of substrates W abuts against the plurality (here, 3) holding rods 251. The plurality of substrates W are arranged at intervals in the X direction and are held in a vertical posture (vertical posture).

The opening and closing part 260 opens and closes the cover part 202a. That is, the opening and closing part 260 switches the cover part 202a between an open state and a closed state. By opening and closing the cover part 202a, the opening of the upper part of the chamber 202 switches between a closed state and an open state. The opening and closing part 260 has a driving source and an opening and closing mechanism, and the driving source drives the opening and closing mechanism to open and close the cover part 202a. The driving source includes, for example, a motor. The opening and closing mechanism includes, for example, a gear-gear mechanism.

The lifting unit 270 lifts and lowers the holding unit 250. The lifting unit 270 lifts and lowers the holding unit 250, and the substrate W held by the holding unit 250 is lifted and lowered. The lifting unit 270 has a driving source and a lifting mechanism, and the lifting mechanism is driven by the driving source to raise and lower the holding unit 250. The driving source includes, for example, a motor. The lifting mechanism includes, for example, a gear-gear mechanism or a ball screw.

Specifically, the lifting unit 270 moves (lifts and lowers) the holding unit 250 (substrate W) between the outside and the inside of the chamber 202 through the opening of the upper portion of the chamber 202. That is, the lifting unit 270 carries the substrate W into the chamber 202 and carries the substrate W out of the chamber 202.

Next, the substrate processing apparatus 100 is further described with reference to FIG1 . As shown in FIG1 , the substrate processing apparatus 100 further includes a control device 110 . The control device 110 controls the operation of each part of the substrate processing apparatus 100 . Specifically, the control device 110 controls the operation of each part of the processing unit 200 . The control device 110 includes a control unit 111 and a memory unit 112 .

The control unit 111 has a processor. For example, the control unit 111 has a CPU (Central Processing Unit) or an MPU (Micro Processing Unit). Alternatively, the control unit 111 may also have a general-purpose calculator.

The memory unit 112 stores data and computer programs. The data includes recipe data. The recipe data includes information indicating a plurality of recipes. Each of the plurality of recipes specifies the processing content and processing sequence of the substrate W.

The memory unit 112 has a main memory device. The main memory device is, for example, a semiconductor memory. The memory unit 112 may further have an auxiliary memory device. The auxiliary memory device includes, for example, at least one of a semiconductor memory and a hard disk. The memory unit 112 may also include a removable medium. The control unit 111 controls the operation of each unit of the substrate processing device 100 based on the computer program and data stored in the memory unit 112.

The control device 110 (control unit 111) controls the opening and closing unit 260 to switch the cover 202a between an open state and a closed state. Specifically, when the substrate W is loaded into the chamber 202 or unloaded from the chamber 202, the control device 110 (control unit 111) puts the cover 202a in an open state. When the cover 202a is in an open state, the opening of the upper part of the chamber 202 is opened, and the substrate W can be loaded into the chamber 202 or unloaded from the chamber 202. When the substrate W is processed, the control device 110 (control unit 111) puts the cover 202a in a closed state. When the cover 202a is in a closed state, the opening of the upper part of the chamber 202 is closed. As a result, the interior of the chamber 202 becomes a closed space, and the substrate W is processed in the closed space.

The control device 110 (control unit 111) controls the lifting unit 270 to lift the holding unit 250 (substrate W). Specifically, when the substrate W is loaded into the chamber 202, the control device 110 (control unit 111) moves the holding unit 250 from the outside of the chamber 202 to the inside through the opening at the upper part of the chamber 202, thereby loading the substrate W into the chamber 202. When the substrate W is unloaded from the chamber 202, the control device 110 (control unit 111) moves the holding unit 250 from the inside of the chamber 202 to the outside through the opening at the upper part of the chamber 202, thereby loading the substrate W out of the chamber 202. When the substrate W is processed, the control device 110 (control unit 111) holds the holding unit 250 above the liquid receiving member 203 in the chamber 202.

The substrate processing apparatus 100 further includes a rinse liquid supply source 221, a replacement liquid supply source 222, a hydrophobic agent supply source 223, first to third pipes 231 to 233, a drain line 241, and first to fourth valves V201 to V204.

The rinse liquid supply source 221 supplies rinse liquid. In this embodiment, the rinse liquid supply source 221 supplies DIW. The replacement liquid supply source 222 supplies replacement liquid. In this embodiment, the replacement liquid supply source 222 supplies IPA. The hydrophobizing agent supply source 223 supplies hydrophobizing agent SMT.

The rinse liquid is supplied from the rinse liquid supply source 221 to the first pipe 231. The first pipe 231 allows the rinse liquid supplied from the rinse liquid supply source 221 to flow to the first nozzle 211 and the second nozzle 212.

The first nozzle 211 and the second nozzle 212 are hollow tubular members. A plurality of ejection holes are formed in the first nozzle 211 and the second nozzle 212, respectively. In this embodiment, the first nozzle 211 and the second nozzle 212 extend along the X direction. The plurality of ejection holes of the first nozzle 211 are formed at equal intervals in the X direction. Similarly, the plurality of ejection holes of the second nozzle 212 are formed at equal intervals in the X direction.

When the rinse liquid is supplied to the first nozzle 211 through the first pipe 231, the rinse liquid is sprayed into the chamber 202 from the plurality of spray holes of the first nozzle 211. Similarly, when the rinse liquid is supplied to the second nozzle 212 through the first pipe 231, the rinse liquid is sprayed into the chamber 202 from the plurality of spray holes of the second nozzle 212.

The first valve V201 is installed in the first pipe 231. The first valve V201 is an on-off valve that opens and closes the flow path of the first pipe 231. The first valve V201 controls the flow of the flushing liquid flowing through the first pipe 231. In detail, when the first valve V201 is opened, the flushing liquid flows through the first pipe 231 to the first nozzle 211 and the second nozzle 212. As a result, the flushing liquid is sprayed from the first nozzle 211 and the second nozzle 212. When the first valve V201 is closed, the flow of the flushing liquid is blocked, and the first nozzle 211 and the second nozzle 212 stop spraying the flushing liquid.

The first valve V201 also functions as a regulating valve for regulating the flow rate of the flushing liquid flowing through the first pipe 231. The first valve V201 is, for example, an electromagnetic valve. The first valve V201 is controlled by the control device 110 (control unit 111).

In this embodiment, a heater (not shown) may be installed in the first pipe 231. The heater heats the rinse liquid, thereby making the rinse liquid high-temperature or vaporizing the rinse liquid. That is, the heater can make the rinse liquid high-temperature or generate the steam of the rinse liquid. Moreover, the first nozzle 211 and the second nozzle 212 can also spray the high-temperature rinse liquid or the steam of the rinse liquid. Furthermore, a heater (not shown) may be installed in the rinse liquid supply source 221, and the high-temperature rinse liquid or the steam of the rinse liquid may be supplied from the rinse liquid supply source 221 to the first pipe 231. Furthermore, it is also possible to not provide a heater and spray the rinsing liquid at room temperature from the first nozzle 211 and the second nozzle 212.

IPA is supplied from the replacement liquid supply source 222 to the second pipe 232. The second pipe 232 allows the IPA supplied from the replacement liquid supply source 222 to flow to the third nozzle 213 and the fourth nozzle 214.

The third nozzle 213 and the fourth nozzle 214 are disposed below the first nozzle 211 and the second nozzle 212. The third nozzle 213 and the fourth nozzle 214 have the same structure as the first nozzle 211 and the second nozzle 212. The third nozzle 213 and the fourth nozzle 214 spray IPA into the chamber 202 in the same manner as the first nozzle 211 and the second nozzle 212.

The second valve V202 is installed in the second pipe 232. The second valve V202 is an on-off valve that opens and closes the flow path of the second pipe 232. The second valve V202 controls the flow of IPA flowing through the second pipe 232 in the same manner as the first valve V201. The second valve V202 also functions as a regulating valve that adjusts the flow rate of IPA flowing through the second pipe 232. The second valve V202 is, for example, an electromagnetic valve. The second valve V202 is controlled by the control device 110 (control unit 111).

In the present embodiment, a heater (not shown) is installed in the second pipe 232. The heater heats the IPA, thereby making the IPA high temperature, and also can vaporize the IPA. That is, the heater can make the liquid IPA high temperature, and can also generate the vapor of IPA. Moreover, the third nozzle 213 and the fourth nozzle 214 can also spray high-temperature liquid IPA or IPA vapor. Furthermore, a heater (not shown) can also be provided at the replacement liquid supply source 222, and high-temperature liquid IPA or IPA vapor can be supplied from the replacement liquid supply source 222 to the third pipe 233. Moreover, it is also possible not to provide a heater, and spray liquid IPA at normal temperature from the third nozzle 213 and the fourth nozzle 214.

The hydrophobizing agent SMT is supplied from the hydrophobizing agent supply source 223 to the third pipe 233. The third pipe 233 allows the hydrophobizing agent SMT supplied from the hydrophobizing agent supply source 223 to flow to the fifth nozzle 215 and the sixth nozzle 216.

The fifth nozzle 215 and the sixth nozzle 216 are disposed below the third nozzle 213 and the fourth nozzle 214. The fifth nozzle 215 and the sixth nozzle 216 have the same structure as the first nozzle 211 and the second nozzle 212. The fifth nozzle 215 and the sixth nozzle 216 spray the hydrophobic agent SMT into the interior of the chamber 202 in the same manner as the first nozzle 211 and the second nozzle 212.

The third valve V203 is installed in the third pipe 233. The third valve V203 is an on-off valve that opens and closes the flow path of the third pipe 233. The third valve V203 controls the flow of the hydrophobic agent SMT flowing through the third pipe 233 in the same manner as the first valve V201. The third valve V203 also functions as an adjusting valve that adjusts the flow rate of the hydrophobic agent SMT flowing through the third pipe 233. The third valve V203 is, for example, an electromagnetic valve. The third valve V203 is controlled by the control device 110 (control unit 111).

Furthermore, the hydrophobic agent supply source 223 , the third pipe 233 , the third valve V203 , the fifth nozzle 215 , and the sixth nozzle 216 constitute a hydrophobic agent supply unit 206 for supplying the hydrophobic agent SMT to the substrate W.

In this embodiment, a heater (not shown) may be installed in the third pipe 233. The heater heats the hydrophobic agent SMT, thereby making the hydrophobic agent SMT high temperature and also gasifying the hydrophobic agent SMT. That is, the heater can make the liquid hydrophobic agent SMT high temperature and also generate the steam of the hydrophobic agent SMT. Moreover, the fifth nozzle 215 and the sixth nozzle 216 can also spray the steam of the high temperature liquid hydrophobic agent SMT. Furthermore, a heater (not shown) may be provided at the hydrophobic agent supply source 223 to supply high-temperature liquid hydrophobic agent SMT or steam of the hydrophobic agent SMT from the hydrophobic agent supply source 223 to the third pipe 233. Alternatively, the fifth nozzle 215 and the sixth nozzle 216 may spray liquid hydrophobic agent SMT at room temperature without providing a heater.

The drain line 241 is connected to the bottom of the liquid receiving component 203. The fourth valve V204 is installed in the drain line 241. The fourth valve V204 is an on-off valve that opens and closes the flow path of the drain line 241. The fourth valve V204 is, for example, an electromagnetic valve. The fourth valve V204 is controlled by the control device 110 (control unit 111). When the treatment liquid is stored in the liquid receiving component 203, the control device 110 (control unit 111) closes the fourth valve V204. On the other hand, when the treatment liquid is discharged from the liquid receiving component 203, the control device 110 (control unit 111) opens the fourth valve V204. When the fourth valve V204 is opened, the processing liquid stored in the liquid receiving component 203 is discharged from the liquid receiving component 203 to the outside of the chamber 202 through the drain line 241.

Furthermore, the substrate processing apparatus 100 may also include a depressurizing unit (not shown) for reducing the pressure in the chamber 202. The depressurizing unit includes, for example, an exhaust pump. The exhaust pump is, for example, a vacuum pump. The depressurizing unit can exhaust the gas in the chamber 202 when the cover 202a is in a closed state, and reduce the pressure in the chamber 202 to below atmospheric pressure.

Next, the processing unit 300 of the substrate processing apparatus 100 of the present embodiment will be described with reference to Fig. 5. Fig. 5 is a schematic diagram showing the internal structure of the processing unit 300 of the substrate processing apparatus 100 of the first embodiment. Fig. 6 is a schematic diagram showing the state of ejecting etching liquid from the first nozzle 311 and the second nozzle 312 of the processing unit 300 into the processing tank 303.

As shown in FIG5 , the substrate processing apparatus 100 includes a processing unit 300. The processing unit 300 performs etching processing on the substrate W. The substrate W that has been subjected to hydrophobic treatment by the processing unit 200 is transported (carried in) to the processing unit 300. In this embodiment, the processing unit 300 performs wet etching on a portion of the substrate W. Specifically, the processing unit 300 includes a chamber 302, a processing tank 303, a liquid supply unit 305, an opening and closing unit 360, and a lifting unit 370.

The processing tank 303 and the liquid supply unit 305 are housed in the chamber 302. When the substrate W is processed, the holding unit 250 is housed in the chamber 302. The chamber 302 has a cover 302a. The cover 302a is attached to the opening of the upper part of the chamber 302. The cover 302a can move so as to open and close the opening.

The processing tank 303 stores the processing liquid. The processing liquid includes an etching liquid. Therefore, the processing tank 303 stores the etching liquid. In this embodiment, the etching liquid is an aqueous solution of an ester solvent, ammonium fluoride and hydrogen peroxide. By immersing the substrate W in the processing tank 303, the substrate W is etched.

The liquid supply unit 305 supplies a processing liquid into the chamber 302. Specifically, the liquid supply unit 305 supplies an etching liquid into the chamber 302.

The liquid supply unit 305 supplies the etching liquid to the processing tank 303. Specifically, the liquid supply unit 305 includes a first nozzle 311 and a second nozzle 312. The first nozzle 311 and the second nozzle 312 are disposed in the processing tank 303. As shown in FIG. 6 , the first nozzle 311 and the second nozzle 312 spray the etching liquid into the processing tank 303.

As shown in FIG5 , the opening and closing section 360 opens and closes the cover section 302a. That is, the opening and closing section 360 switches the cover section 302a between an open state and a closed state. By opening and closing the cover section 302a, the opening of the upper portion of the chamber 302 switches between a closed state and an open state. The opening and closing section 360 has a driving source and an opening and closing mechanism, and the driving source drives the opening and closing mechanism to open and close the cover section 302a. The driving source includes, for example, a motor. The opening and closing mechanism includes, for example, a gear-gear mechanism.

The lifting unit 370 lifts and lowers the holding unit 250. The holding unit 250 is the holding unit 250 described using FIG. 1 . The holding unit 250 can move between the processing unit 200 and the processing unit 300 while holding the substrate W. The holding unit 250 is lifted and lowered by the lifting unit 370, and the substrate W held by the holding unit 250 is lifted and lowered. The lifting unit 370 has a driving source and a lifting mechanism, and the lifting mechanism is driven by the driving source to raise and lower the holding unit 250. The driving source includes, for example, a motor. The lifting mechanism includes, for example, a rack-and-pinion mechanism or a ball screw.

Specifically, the lifting unit 370 moves (lifts and lowers) the holding unit 250 (substrate W) between the outside and the inside of the chamber 302 through the opening of the upper portion of the chamber 302. That is, the lifting unit 370 carries the substrate W into the chamber 302 and carries the substrate W out of the chamber 302.

Furthermore, the lifting unit 370 moves (lifts and lowers) the holding unit 250 (substrate W) between the processing position in the processing tank 303 and the standby position outside the processing tank 303 in the chamber 302. When the holding unit 250 moves to the processing position, the substrate W moves into the processing tank 303. When the holding unit 250 moves to the standby position, the substrate W moves outside the processing tank 303. Specifically, the standby position is a position above the processing position. When the holding unit 250 moves to the standby position, the substrate W moves to the space above the processing tank 303. Furthermore, in FIG. 5 , the holding unit 250 and the substrate W moved to the processing position are indicated by a solid line, and the holding unit 250 and the substrate W moved to the standby position are indicated by a double-dot chain line.

Next, the substrate processing apparatus 100 will be further described with reference to FIG5 . As shown in FIG5 , the control device 110 controls the operation of each part of the processing unit 300 .

The control device 110 (control unit 111) controls the opening and closing unit 360 to switch the cover 302a between an open state and a closed state. Specifically, when the substrate W is loaded into the chamber 302 or unloaded from the chamber 302, the control device 110 (control unit 111) puts the cover 302a in an open state. When the cover 302a is in an open state, the opening of the upper part of the chamber 302 is opened, and the substrate W can be loaded into the chamber 302 or unloaded from the chamber 302. When the substrate W is processed, the control device 110 (control unit 111) puts the cover 302a in a closed state. When the cover 302a is in a closed state, the opening of the upper part of the chamber 302 is closed. As a result, the interior of the chamber 302 becomes a closed space, and the substrate W is processed in the closed space.

The control device 110 (control unit 111) controls the lifting unit 370 to lift the holding unit 250 (substrate W). Specifically, when the substrate W is loaded into the chamber 302, the control device 110 (control unit 111) moves the holding unit 250 from the outside of the chamber 302 to the inside through the opening at the upper part of the chamber 302, thereby loading the substrate W into the chamber 302. When the substrate W is unloaded from the chamber 302, the control device 110 (control unit 111) moves the holding unit 250 from the inside of the chamber 302 to the outside through the opening at the upper part of the chamber 302, thereby loading the substrate W out of the chamber 302. When the substrate W is processed, the control device 110 (control unit 111) moves (lifts) the holding unit 250 between the processing position and the standby position in the chamber 302.

The substrate processing apparatus 100 further includes an etching solution supply source 321 , a first pipe 331 , a drain line 341 , a first valve V301 , and a second valve V302 .

The etching liquid supply source 321 supplies etching liquid.

The etching liquid is supplied from the etching liquid supply source 321 to the first pipe 331. The first pipe 331 allows the etching liquid supplied from the etching liquid supply source 321 to flow to the first nozzle 311 and the second nozzle 312.

The first nozzle 311 and the second nozzle 312 are hollow tubular members. A plurality of ejection holes are formed in the first nozzle 311 and the second nozzle 312, respectively. In this embodiment, the first nozzle 311 and the second nozzle 312 extend along the X direction. The plurality of ejection holes of the first nozzle 311 are formed at equal intervals in the X direction. Similarly, the plurality of ejection holes of the second nozzle 312 are formed at equal intervals in the X direction.

When the etching liquid is supplied to the first nozzle 311 through the first pipe 331, the etching liquid is ejected from the plurality of ejection holes of the first nozzle 311 into the processing tank 303. Similarly, when the etching liquid is supplied to the second nozzle 312 through the first pipe 331, the etching liquid is ejected from the plurality of ejection holes of the second nozzle 312 into the processing tank 303.

The first valve V301 is installed in the first pipe 331. The first valve V301 is an on-off valve that opens and closes the flow path of the first pipe 331. The first valve V301 controls the flow of the etching liquid flowing through the first pipe 331. In detail, when the first valve V301 is opened, the etching liquid flows through the first pipe 331 to the first nozzle 311 and the second nozzle 312. As a result, the etching liquid is sprayed from the first nozzle 311 and the second nozzle 312. When the first valve V301 is closed, the flow of the etching liquid is blocked, and the first nozzle 311 and the second nozzle 312 stop spraying the etching liquid.

The first valve V301 also functions as a regulating valve for regulating the flow rate of the etching solution flowing through the first pipe 331. The first valve V301 is, for example, an electromagnetic valve. The first valve V301 is controlled by the control device 110 (control unit 111).

Furthermore, an etching liquid supply unit 306 for supplying etching liquid to the substrate W is constituted by the etching liquid supply source 321 , the first pipe 331 , the first valve V301 , the first nozzle 311 , and the second nozzle 312 .

Furthermore, a heater (not shown) may be installed in the first pipe 331. The heater heats the etching liquid to make the etching liquid high in temperature. Furthermore, the first nozzle 311 and the second nozzle 312 may eject the etching liquid at room temperature without installing a heater.

The drain line 341 is connected to the bottom of the treatment tank 303. The second valve V302 is installed in the drain line 341. The second valve V302 is an on-off valve that opens and closes the flow path of the drain line 341. The second valve V302 is, for example, an electromagnetic valve. The second valve V302 is controlled by the control device 110 (control unit 111). When the treatment liquid is stored in the treatment tank 303, the control device 110 (control unit 111) closes the second valve V302. On the other hand, when the treatment liquid is discharged from the treatment tank 303, the control device 110 (control unit 111) opens the second valve V302. When the second valve V302 is opened, the processing liquid stored in the processing tank 303 is discharged from the processing tank 303 to the outside of the chamber 302 through the drain line 341.

Furthermore, the substrate processing apparatus 100 may also include a depressurizing unit (not shown) for reducing the pressure in the chamber 302. The depressurizing unit includes, for example, an exhaust pump. The exhaust pump is, for example, a vacuum pump. The depressurizing unit can exhaust the gas in the chamber 302 when the cover 302a is in a closed state, and reduce the pressure in the chamber 302 to below atmospheric pressure.

Next, the substrate W processed by the substrate processing apparatus 100 of the present embodiment will be described with reference to FIG7 and FIG8. FIG7 is a schematic partial enlarged three-dimensional view of the substrate W processed by the substrate processing apparatus 100. FIG8 is a schematic partial enlarged view of the substrate W processed by the substrate processing apparatus 100. Furthermore, in FIG7, the direction perpendicular to the main surface of the base material S of the substrate W is represented as the z direction, and the directions perpendicular to the z direction are represented as the x direction and the y direction.

As shown in Figures 7 and 8, the substrate W has a base material S and a multilayer structure L. The base material S is in the shape of a thin plate extending on the xy plane. The multilayer structure L is formed on the main surface Sa of the base material S. The base material S supports the multilayer structure L. The multilayer structure L is formed in a manner extending from the main surface Sa of the base material S along the z direction. The base material S includes, for example, a semiconductor. The material of the base material S is not particularly limited, and for example includes silicon (hereinafter, sometimes recorded as Si). In the present embodiment, the base material S includes single crystal silicon. Furthermore, the main surface Sa is an example of the "one side" of the present invention. Furthermore, the z direction is an example of the "first direction" of the present invention.

The layered structure L has a plurality of first layers M1 and a plurality of second layers M2. The first layers M1 and the second layers M2 are alternately layered. The first layers M1 and the second layers M2 are layered in the z direction intersecting the main surface Sa of the substrate S.

The first layer M1 and the second layer M2 include, for example, semiconductors. The first layer M1 and the second layer M2 are not particularly limited, and may include, for example, the same element. The first layer M1 and the second layer M2 include, for example, silicon elements. In the present embodiment, the first layer M1 includes silicon germanium (hereinafter, sometimes described as SiGe). The second layer M2 includes polycrystalline silicon or single crystal silicon. In this way, the substrate W having the Si layer and the SiGe layer stacked thereon is used, for example, to manufacture semiconductor elements such as MOSFET (Metal-Oxide-Semiconductor Field Effect Transistor).

The composition ratio of germanium (hereinafter sometimes referred to as Ge) contained in the first layer M1 is less than 50%. The composition ratio of Ge contained in the first layer M1 is not particularly limited, and is, for example, 5% or more and 25% or less. In this embodiment, the composition ratio of Ge contained in the first layer M1 is 20% or less.

Each of the plurality of first layers M1 extends parallel to the main surface Sa of the substrate S. In the thickness direction of the substrate S (z direction), the first layer M1 is disposed between the second layers M2 or between the second layer M2 and the substrate S.

For example, the thickness of the first layer M1 (the length along the z direction) is greater than 1 nm and less than 50 nm. Also, for example, the thickness of the second layer M2 (the length along the z direction) is greater than 1 nm and less than 50 nm. The thickness of the first layer M1 is not particularly limited, and may be less than the thickness of the second layer M2. In the present embodiment, the thickness of the first layer M1 is, for example, greater than 5 nm and less than 15 nm.

For example, the total thickness of one first layer M1 and one second layer M2 is 20 nm to 100 nm. The layered structure L includes, for example, 2 to 100 first layers M1 and 2 to 100 second layers M2.

The substrate W has a groove R. The groove R is provided in the multilayer structure L. The groove R is formed by, for example, dry etching the multilayer structure L. The groove R extends in a direction intersecting with the main surface Sa of the substrate S. Specifically, the groove R extends in a direction (z direction) perpendicular to the main surface Sa of the substrate S. The groove R extends from the surface La of the multilayer structure L toward the substrate S. In the present embodiment, the groove R extends from the surface La of the multilayer structure L to the substrate S. Furthermore, in the present embodiment, the groove R extends to the interior of the substrate S, but it may also be configured such that an etching stop layer (not shown) is provided on the main surface Sa of the substrate S, and the groove R does not reach the interior of the substrate S.

When viewed from the thickness direction (z direction) of the substrate W, the groove R is formed into an elongated shape having a long side direction and a short side direction. In the present embodiment, the long side direction is the y direction and the short side direction is the x direction. Hereinafter, the length of the short side direction of the groove R is sometimes recorded as the width of the groove R.

The width of the groove R is in the nanometer range. For example, the width of the groove R is greater than 20 nm and less than 300 nm. The width of the groove R may also be greater than 50 nm and less than 200 nm.

The substrate W has a plurality of recesses C. The plurality of recesses C are connected to the groove R. The recesses C are arranged between the second layers M2 or between the second layer M2 and the substrate S in the thickness direction (z direction). The recesses C are formed in a manner extending along the x direction intersecting the thickness direction (z direction). Furthermore, the x direction is an example of the "second direction" of the present invention.

Hereinafter, the length of the recess C in the z direction is sometimes described as the width of the recess C, and the length of the recess C in the x direction is sometimes described as the depth of the recess C. The aspect ratio of the recess C (the size of the depth of the recess C relative to the width) is not particularly limited, and is, for example, 10 or more and 100 or less. In the present embodiment, the aspect ratio of the recess C is 20 or more. In other words, the depth of the recess C (the length in the x direction) is 20 times or more of the width of the recess C (the length in the z direction). In addition, in the present embodiment, the aspect ratio of the recess C is, for example, 30 or more and 50 or less.

Here, the concave portion C is formed by wet etching the first layer M1 by introducing an etching liquid into the groove R. At this time, even if the etching liquid has the function of selectively etching the first layer M1 between the first layer M1 and the second layer M2, when a substance with similar chemical properties is included between the first layer M1 and the second layer M2, the etching selectivity will also decrease. Specifically, it is difficult for the etching liquid to etch only the first layer M1, and the second layer M2 will also be etched. Therefore, the greater the aspect ratio of the portion to be etched (the concave portion C), the thinner the thickness of the second layer M2 will be etched, so the semiconductor device manufactured using the substrate W may not obtain the desired characteristics.

As will be described in detail below, according to this embodiment, even when the depth and width of the concave portion C are relatively large, the first layer M1 can be selectively etched. Thereby, the thickness of the second layer M2 can be suppressed from being thinned.

Next, the substrate processing method of the present embodiment is described with reference to FIGS. 9 to 18. FIG. 9 is a flow chart showing the substrate processing method of the present embodiment. FIGS. 10 to 18 are enlarged cross-sectional views of the periphery of the groove R for describing the substrate processing method of the present embodiment. The substrate processing method of the present embodiment includes steps S1 to S10. Steps S1 to S10 are executed by the control unit 111. Furthermore, step S6 is an example of the "hydrophobicization process" of the present invention. Furthermore, step S7 is an example of the "post-hydrophobicization replacement process" of the present invention. Furthermore, step S8 is an example of the "etching process" of the present invention. Furthermore, step S9 is an example of the "post-etching replacement process" of the present invention.

As shown in FIG9 , in step S1 , the oxide film of the substrate W is removed. Specifically, the natural oxide film (not shown) formed in the groove R of the substrate W shown in FIG10 is removed. The substrate W processed by the substrate processing apparatus 100 has a base material S, a multilayer structure L, and a groove R provided in the multilayer structure L. Furthermore, in step S1 , the concave portion C has not yet been formed in the substrate W.

In this embodiment, the processing unit 300 shown in FIG. 5 or a processing unit having the same structure as the processing unit 300 is used to remove the natural oxide film of the substrate W. Specifically, a chemical solution is stored in the processing tank 303. The chemical solution is a chemical solution that can remove the natural oxide film of the substrate W. The chemical solution is not particularly limited, and for example, includes hydrofluoric acid. For example, the chemical solution includes hydrofluoric acid diluted to more than several 10 times and less than several 1000 times (diluted hydrofluoric acid).

For example, the control unit 111 moves the holding unit 250 to the processing position, thereby immersing the substrate W carried into the chamber 202 in the chemical solution stored in the processing tank 303. In this way, the natural oxide film formed on the inner surface of the groove R of the substrate W is removed by the chemical solution. When a predetermined time has passed since the substrate W was immersed in the chemical solution, the control unit 111 moves the holding unit 250 to the standby position.

Next, in step S2 , the substrate W is rinsed. Specifically, the substrate W is rinsed using the processing unit 200 shown in FIG. 1 , or a processing unit 200 having the same structure as the processing unit 200 .

For example, the control unit 111 moves the holding unit 250 from the chamber 302 to the chamber 202, thereby arranging the substrate W in the chamber 202. The control unit 111 supplies the rinsing liquid to the substrate W from the first nozzle 211 and the second nozzle 212. In this embodiment, the control unit 111 blows the mist-like rinsing liquid toward the substrate W from the first nozzle 211 and the second nozzle 212. Thereby, the chemical solution attached to the surface of the substrate W is washed away by the rinsing liquid. When a specified time has passed since the start of supplying the rinsing liquid to the substrate W, the control unit 111 stops supplying the rinsing liquid. Furthermore, in this embodiment, the rinsing liquid is DIW.

Next, in step S3, a portion of the first layer M1 is etched. Specifically, the processing unit 300 shown in FIG. 5 is used to etch a portion of the first layer M1.

The control unit 111 moves the holder 250 from the chamber 202 to the chamber 302, thereby placing the substrate W in the chamber 302. The control unit 111 supplies the etching liquid E1 to the processing tank 303 from the first nozzle 311 and the second nozzle 312. Before the substrate W is moved into the chamber 302, the etching liquid E1 may be stored in the processing tank 303.

The etching liquid E1 is a liquid capable of etching the first layer M1. The etching amount (etching speed) of the etching liquid E1 on the first layer M1 is preferably about 5 times or more, and more preferably about 10 times or more, compared to the etching amount (etching speed) of the etching liquid E1 on the second layer M2. In this embodiment, the etching amount of the etching liquid E1 on the first layer M1 is about 20 times the etching amount of the etching liquid E1 on the second layer M2.

The components of the etching solution E1 are appropriately set according to the materials of the first layer M1 and the second layer M2, and are not particularly limited. In this embodiment, the etching solution E1 is an aqueous solution of an ester solvent, ammonium fluoride, and hydrogen peroxide.

The control unit 111 moves the holding unit 250 from the standby position to the processing position. That is, the control unit 111 moves the holding unit 250 into the processing tank 303. Thereby, the substrate W is immersed in the etching liquid E1.

As shown in FIG11 , the etching liquid E1 flows into the groove R. Then, the etching liquid E1 etches at least the first layer M1. In the present embodiment, the etching liquid E1 etches the first layer M1 at an etching speed approximately 20 times that of the second layer M2. Thereby, a recess C is formed in the layered structure L (refer to FIG12 ). Then, when a prescribed time has passed since the holding portion 250 was moved into the processing tank 303, the control portion 111 moves the holding portion 250 from the standby position to the processing position. That is, the control portion 111 pulls the holding portion 250 from the processing tank 303. Furthermore, the depth of the recess C formed in step S3 (the length in the x direction) is smaller than the depth of the recess C shown in FIG8 . The aspect ratio of the concave portion C formed in step S3 is, for example, less than 10.

Next, in step S4, the substrate W is rinsed. Specifically, the substrate W is rinsed using the processing unit 200 shown in FIG. 1 .

For example, the control unit 111 moves the holding unit 250 from the chamber 302 to the chamber 202, thereby arranging the substrate W in the chamber 202. The control unit 111 supplies the rinsing liquid to the substrate W from the first nozzle 211 and the second nozzle 212. In this embodiment, the control unit 111 blows the mist-like rinsing liquid (here, DIW) toward the substrate W from the first nozzle 211 and the second nozzle 212 (refer to FIG. 2). Thereby, the etching liquid E1 attached to the surface of the substrate W is washed away by the rinsing liquid. When a predetermined time has passed since the start of supplying the rinsing liquid to the substrate W, the control unit 111 stops supplying the rinsing liquid.

Next, in step S5, the rinsing liquid attached to the substrate W is replaced with a replacement liquid. Specifically, the replacement liquid is a liquid that can replace the rinsing liquid (here, DIW) on the surface of the substrate W. In addition, the replacement liquid is preferably a liquid that has an affinity for the hydrophobic agent SMT. The replacement liquid may include, for example, an organic solvent or an alcohol. In this embodiment, the replacement liquid includes IPA.

For example, the control unit 111 supplies the replacement liquid from the third nozzle 213 and the fourth nozzle 214 to the substrate W. In this embodiment, the control unit 111 blows the replacement liquid in a mist form from the third nozzle 213 and the fourth nozzle 214 toward the substrate W (see FIG. 3 ). Thereby, the rinsing liquid attached to the surface of the substrate W is replaced with the replacement liquid. In this embodiment, the unused replacement liquid is supplied to the substrate W from the third nozzle 213 and the fourth nozzle 214. Furthermore, the used replacement liquid that is recovered after being used more than once may also be supplied to the substrate W.

When a predetermined time has passed since the start of supplying the replacement liquid to the substrate W, the control unit 111 stops supplying the replacement liquid.

12 , in step S5 , the replacement liquid blown onto the substrate W is preferably evaporated without remaining in the recess R and the recess C. Furthermore, in step S5 , the replacement liquid may also remain in the recess R and the recess C.

Next, in step S6, a hydrophobic agent SMT is supplied to the substrate W to make the surface of the second layer M2 hydrophobic.

For example, the control unit 111 supplies the hydrophobic agent SMT from the 5th nozzle 215 and the 6th nozzle 216 to the substrate W. In this embodiment, the control unit 111 blows the hydrophobic agent SMT in a mist form from the 5th nozzle 215 and the 6th nozzle 216 toward the substrate W (refer to FIG. 4 ). As a result, as shown in FIG. 13 , the hydrophobic agent SMT that makes the surface of the second layer M2 hydrophobic flows into the groove R and the recess C. Therefore, the surface of the second layer M2 is hydrophobic. Specifically, the hydrophobic agent SMT at least coats the surface of the second layer M2. Furthermore, the hydrophobic agent SMT at least silanes the surface of the second layer M2. In this embodiment, the hydrophobizing agent SMT hydrophobizes the surfaces of both the first layer M1 and the second layer M2. Therefore, the surfaces of both the first layer M1 and the second layer M2 are hydrophobized. Specifically, the hydrophobizing agent SMT coats the surfaces of both the first layer M1 and the second layer M2. Furthermore, the hydrophobizing agent SMT silanes the surfaces of both the first layer M1 and the second layer M2.

More specifically, the silyl groups contained in the hydrophobic agent SMT are bonded to both the Si-O group and the Ge-O group. That is, the silyl groups contained in the hydrophobic agent SMT are bonded to both the surface of the first layer M1 and the surface of the second layer M2. Moreover, a hydrophobic layer Ls is formed on the surface of the first layer M1 and the surface of the second layer M2 to which the silyl groups of the hydrophobic agent SMT are bonded (see FIG. 14 ). In other words, the surface of the first layer M1 and the surface of the second layer M2 are covered by the hydrophobic layer Ls containing the hydrophobic agent SMT. Furthermore, for ease of understanding, the hydrophobic layer Ls is depicted with a thick solid line in the figure.

Furthermore, in this embodiment, unused hydrophobic agent SMT is supplied to the substrate W from the fifth nozzle 215 and the sixth nozzle 216. Also, unused hydrophobic agent SMT is supplied to the recess R. Furthermore, used hydrophobic agent SMT that is recycled after being used once or more may be supplied to the substrate W.

When a predetermined time has passed since the start of supplying the hydrophobic agent SMT to the substrate W, the control unit 111 stops supplying the hydrophobic agent SMT.

Next, in step S7, the hydrophobic agent SMT present on the substrate W is replaced with a replacement liquid in such a manner that the hydrophobic agent SMT (hydrophobic layer Ls) remains on the surface of at least the second layer M2. Specifically, the replacement liquid is a liquid capable of replacing the hydrophobic agent SMT present on the substrate W. In addition, the replacement liquid is preferably a liquid having an affinity for the hydrophobic agent SMT. The replacement liquid may include, for example, an organic solvent or an alcohol. In the present embodiment, the replacement liquid includes IPA.

For example, the control unit 111 supplies the replacement liquid from the third nozzle 213 and the fourth nozzle 214 to the substrate W. In this embodiment, the control unit 111 blows the replacement liquid in a mist form from the third nozzle 213 and the fourth nozzle 214 toward the substrate W (refer to FIG. 3 ). Thereby, the hydrophobic agent SMT present on the substrate W is replaced with the replacement liquid. However, at least the hydrophobic agent SMT (hydrophobic layer Ls) on the surface of the second layer M2 is left. In this embodiment, the hydrophobic agent SMT is replaced with the replacement liquid in a manner that the hydrophobic layer Ls remains. In this embodiment, unused replacement liquid is supplied to the substrate W. Furthermore, used replacement liquid may also be supplied to the substrate W.

When a predetermined time has passed since the start of supplying the replacement liquid to the substrate W, the control unit 111 stops supplying the replacement liquid.

14 , in step S7 , the replacement liquid blown onto the substrate W is preferably evaporated without remaining in the recess R and the recess C. Furthermore, in step S7 , the replacement liquid may also remain in the recess R and the recess C.

Next, in step S8, the first layer M1 is selectively etched. Specifically, the first layer M1 is selectively etched using the processing unit 300 shown in FIG. 5 .

The control unit 111 moves the holding unit 250 from the chamber 202 to the chamber 302, thereby placing the substrate W in the chamber 302. The control unit 111 supplies the etching liquid E2 to the processing tank 303 from the first nozzle 311 and the second nozzle 312. The etching liquid E2 is a liquid capable of etching the first layer M1. In addition, before the substrate W is moved into the chamber 302, the etching liquid E2 may be stored in the processing tank 303.

The etching amount (etching rate) of the etchant E2 on the first layer M1 is preferably about 5 times or more, and more preferably about 10 times or more, compared to the etching amount (etching rate) of the etchant E2 on the second layer M2. In this embodiment, the etching amount of the etchant E2 on the first layer M1 is about 20 times the etching amount of the etchant E2 on the second layer M2.

The composition of the etching solution E2 is appropriately set according to the materials of the first layer M1 and the second layer M2, and is not particularly limited. In this embodiment, the etching solution E2 is an aqueous solution of an ester solvent, ammonium fluoride and hydrogen peroxide. Furthermore, in this embodiment, the etching solution E2 has the same composition as the etching solution E1.

The control unit 111 moves the holding unit 250 from the standby position to the processing position. That is, the control unit 111 moves the holding unit 250 into the processing tank 303. Thereby, the substrate W is immersed in the etching liquid E2.

As shown in FIG. 15 , in a state where the surface of the second layer M2 is hydrophobized, the etching liquid E2 flows into the groove R and the concave portion C. At this time, as described below, the etching liquid E2 selectively etches the first layer M1 of the first layer M1 and the second layer M2. Specifically, a portion of the inner surface of the concave portion C is not covered by the hydrophobic layer Ls. Therefore, the first layer M1 is etched, while the second layer M2 is basically not etched. As a result, the length of the concave portion C in the x direction becomes larger. In other words, the depth of the concave portion C becomes larger (refer to FIG. 16 ).

Then, when a predetermined time has passed since the holding part 250 was moved into the processing tank 303, the control part 111 moves the holding part 250 from the standby position to the processing position. That is, the control part 111 pulls the holding part 250 from the processing tank 303. The predetermined time is a time shorter than the time from when the holding part 250 is moved into the processing tank 303 to when the hydrophobic agent SMT disappears from the surface of the second layer M2. That is, the control part 111 moves from the etching process (step S8) to the subsequent post-etching replacement process (step S9) before the hydrophobic agent SMT disappears from the surface of the second layer M2 by the etching liquid E2. The predetermined time is, for example, more than 1 minute and less than 60 minutes. The predetermined time may be, for example, not less than 5 minutes and not more than 30 minutes, or not less than 10 minutes and not more than 25 minutes.

In step S8, the first layer M1 is etched, while the second layer M2 is basically not etched. The reason is considered to be as follows. Specifically, the surface of the first layer M1 and the surface of the second layer M2 are both hydrophobized by the silyl group bonding with the Si-O group and also with the Ge-O group. However, the Ge-O group is much more soluble in water than the Si-O group. Therefore, the first layer M1 containing the Ge-O group is more easily etched than the second layer M2 not containing the Ge-O group. Therefore, it is considered that in the first layer M1, the hydrophobic layer Ls is removed along with the etching, while in the second layer M2, the etching progresses slowly, so the hydrophobic layer Ls is easily left. Furthermore, the solubility of GeO ₂ in water is 4.47 g/L, and the solubility of SiO ₂ in water is 0.12 g/L. That is, the solubility of GeO ₂ in water is about 37 times that of SiO ₂ .

Next, in step S9, the substrate W is rinsed. Specifically, the substrate W is rinsed using the processing unit 200 shown in FIG. 1 .

For example, the control unit 111 moves the holding unit 250 from the chamber 302 to the chamber 202, thereby arranging the substrate W in the chamber 202. The control unit 111 supplies the rinsing liquid to the substrate W from the first nozzle 211 and the second nozzle 212. In this embodiment, the control unit 111 blows the mist-like rinsing liquid (here, DIW) toward the substrate W from the first nozzle 211 and the second nozzle 212. Thereby, the etching liquid E2 attached to the surface of the substrate W is washed away by the rinsing liquid. In this embodiment, the unused rinsing liquid is supplied to the substrate W. Furthermore, the used rinsing liquid may also be supplied to the substrate W.

When a predetermined time has passed since the start of supplying the rinse liquid to the substrate W, the control unit 111 stops supplying the rinse liquid.

Next, in step S10, the control unit 111 determines whether the selective etching of step S8 has been performed a specified number of times (for example, 5 times).

In step S10, when the control unit 111 determines that the selective etching of step S8 has not been performed for the specified number of times, the process returns to step S5. Then, after step S5, in step S6, as shown in FIG. 17, the hydrophobic agent SMT is made to flow into the groove R and the concave portion C. Thereby, as shown in FIG. 18, a hydrophobic layer Ls is formed on the surface of the groove R and the surface of the concave portion C. In other words, the surface of the first layer M1 and the surface of the second layer M2 are covered with the hydrophobic layer Ls. The process after step S7 is the same as the process after step S7 described above.

On the other hand, when the control unit 111 determines in step S10 that the selective etching of step S8 has been performed for a predetermined number of times (for example, 5 times), the process ends. Thus, a substrate W having the structure shown in FIG. 8 is obtained.

The first embodiment of the present invention is described above with reference to FIGS. 1 to 18. In this embodiment, as described above, the hydrophobic process (step S6) and the etching process (step S8) are repeated for a predetermined number of times. The hydrophobic process (step S6) is to supply the hydrophobic agent SMT into the groove R. The etching process (step S8) is to supply the etching liquid E2 into the groove R in a state where the surface of the second layer M2 is hydrophobicized, and selectively etch the first layer M1. Therefore, the second layer M2 can be suppressed from being etched, while the first layer M1 can be selectively etched. Furthermore, by repeating the hydrophobicization process (step S6) and the etching process (step S8) for a predetermined number of times, a relatively large depth and width recess C can be formed. In this way, in this embodiment, the etching selectivity can be improved.

As described above, in the etching process (step S8), the first layer M1 is selectively etched to form a plurality of recesses C connected to the recess R so as to extend in the second direction (y direction). Therefore, the plurality of recesses C connected to the recess R can be easily formed substantially parallel to the substrate W.

Furthermore, as described above, the length of the recess C in the second direction (y direction) is more than 20 times the length of the recess C in the first direction (z direction). That is, the aspect ratio of the recess C is more than 20. Generally, when the etching liquid has the function of etching both a specific layer (the first layer M1) and other layers (the second layer M2), the larger the aspect ratio of the recess C, the more the etching amount of the other layer (the second layer M2) will be. However, in the present embodiment, by repeatedly performing the hydrophobicization process (step S6) and the etching process (step S8), it is possible to easily form a recess C with an aspect ratio of, for example, more than 20. Therefore, the application of the present invention is particularly effective in the case of forming a recess C with a larger aspect ratio.

Furthermore, as described above, a post-hydrophobization replacement step (step S7) is provided, and the post-hydrophobization replacement step (step S7) replaces the hydrophobic agent SMT with the replacement liquid in such a manner that the hydrophobic agent SMT remains on at least the surface of the second layer M2 by supplying the replacement liquid into the recess R. Therefore, the hydrophobic agent SMT can be retained on the surface of the second layer M2, and the etching liquid E2 can be inhibited from penetrating into the recess R.

Furthermore, as described above, after the etching process (step S8), a post-etching replacement process (step S9) is provided, and the post-etching replacement process (step S9) replaces the etching liquid E2 with the rinse liquid by supplying the rinse liquid into the groove R. Therefore, the etching liquid E2 can be easily removed from the groove R.

Furthermore, as described above, before the hydrophobic agent SMT (hydrophobic layer Ls) disappears from the surface of the second layer M2 by the etching liquid E2, the etching process (step S8) is transferred to the post-etching replacement process (step S9). Therefore, the etching of the second layer M2 by the etching liquid E2 can be further suppressed. Thus, the etching selectivity can be further improved.

Furthermore, as described above, the first layer M1 includes silicon germanium, and the second layer M2 includes polycrystalline silicon or single crystal silicon. In this case, when the first layer and the second layer include the same substance or substances with similar chemical properties (here, elements of the same group), the etching selectivity is likely to decrease. In this case, it is particularly effective to apply the present invention to improve the etching selectivity.

Furthermore, as described above, the composition ratio of Ge contained in the first layer M1 is less than 20%. Thus, when more than 80% of the first layer and the second layer are formed of the same material, the etching selectivity is more likely to decrease. In this case, it is very effective to apply the present invention to improve the etching selectivity.

Furthermore, as described above, the hydrophobizing agent SMT silanes at least the surface of the second layer M2. Therefore, the surface of the second layer M2 can be easily hydrophobized.

Furthermore, as described above, the hydrophobizing agent SMT or the vapor of the hydrophobizing agent SMT is supplied to the substrate W in a mist state. Therefore, compared with the case where the hydrophobizing agent SMT is supplied to the substrate W in a so-called continuous flow, for example, the amount of the hydrophobizing agent SMT used can be reduced.

Furthermore, as described above, in the hydrophobizing step (step S6), unused hydrophobizing agent SMT is supplied into the recess R. Therefore, as described below, the etching selectivity can be further improved compared to the case of using used hydrophobizing agent SMT.

[Second embodiment] Next, the second embodiment of the present invention is described with reference to FIG. 19. FIG. 19 is a flow chart showing a substrate processing method performed using the substrate processing apparatus 100 of the second embodiment. In the second embodiment, an example of using IPA as a rinse liquid in the post-etching replacement process (step S9) is described. The substrate processing method of this embodiment includes steps S1 to S4 and steps S6 to S10.

As shown in FIG19 , steps S1 to S3 are the same as those in the first embodiment.

Next, in step S4, the substrate W is rinsed. The rinsing liquid is preferably a liquid having affinity to the hydrophobic agent SMT. The rinsing liquid may include, for example, an organic solvent or alcohol. In this embodiment, IPA is used as the rinsing liquid.

The control unit 111 blows a mist of rinsing liquid (IPA in this case) toward the substrate W from the first nozzle 211 and the second nozzle 212. Thus, the etching liquid E1 attached to the surface of the substrate W is washed away by the rinsing liquid. When a predetermined time has passed since the start of supplying the rinsing liquid to the substrate W, the control unit 111 stops supplying the rinsing liquid.

Next, steps S6 to S8 are performed in the same manner as in the first embodiment.

Next, in step S9, the substrate W is rinsed. The rinsing liquid is preferably a liquid having affinity to the hydrophobic agent SMT. The rinsing liquid may include, for example, an organic solvent or alcohol. In this embodiment, IPA is used as the rinsing liquid.

The control unit 111 blows a mist of rinsing liquid (IPA in this case) from the first nozzle 211 and the second nozzle 212 toward the substrate W. Thus, the etching liquid E2 attached to the surface of the substrate W is washed away by the rinsing liquid. When a predetermined time has passed since the start of supplying the rinsing liquid to the substrate W, the control unit 111 stops supplying the rinsing liquid.

Next, step S10 is executed in the same manner as in the first embodiment. If the control unit 111 determines in step S10 that the selective etching of step S8 has not been executed for a predetermined number of times, the process returns to step S6.

As described above, the processing of the substrate W is completed.

The structure of the substrate processing apparatus 100 and other substrate processing methods of the second embodiment are the same as those of the first embodiment.

The second embodiment of the present invention has been described above with reference to FIG. 19 . In this embodiment, as described above, the rinsing liquid used in the post-etching replacement process (step S9) includes IPA. Therefore, for example, compared with the case where DIW is used as the rinsing liquid, the surface tension of the rinsing liquid can be reduced. Thus, even when the width (length in the z direction) of the recess C is small (for example, greater than 5 nm and less than 15 nm), it is possible to suppress the difficulty of the rinsing liquid from penetrating into the recess C. Therefore, by using IPA as the rinsing liquid, it is possible to suppress the difficulty of removing the etching liquid E2 from the recess C. Thus, it is possible to suppress the difficulty of the hydrophobizing agent SMT from penetrating into the recess C in the subsequent hydrophobizing process (step S6). As a result, it is possible to suppress a decrease in etching selectivity.

The other effects of the second implementation method are the same as those of the first implementation method.

Next, referring to FIG. 20 to FIG. 22, the confirmation experiment conducted to confirm the effect of the above-mentioned implementation method is described. First, referring to FIG. 20 and FIG. 21, the experiment for confirming the relationship between the presence or absence of hydrophobic treatment and the etching amount of Si and SiGe is described. FIG. 20 shows the experimental results of the relationship between the presence or absence of hydrophobic treatment and the etching amount of Si. FIG. 21 shows the experimental results of the relationship between the presence or absence of hydrophobic treatment and the etching amount of SiGe.

In the confirmation experiment, the same substrate W as that in the above-mentioned embodiment was used as the substrate W. Specifically, a substrate W having a base material S and a layered structure L was used. The base material S included single crystal silicon, and the layered structure L included a first layer M1 including SiGe and a second layer M2 including polycrystalline silicon. In addition, the composition ratio of Ge contained in the first layer M1 was about 15%.

Then, a plurality of substrates W are prepared, one substrate W is subjected to a hydrophobic treatment, and the other substrate W is not subjected to a hydrophobic treatment. In addition, in the confirmation experiment, steps S3, S4, and S10 are not performed.

Specifically, the above steps S1 to S2 and S5 to S9 are performed on one substrate W. Also, the above steps S1 to S2 and S7 to S9 are performed on another substrate W.

Then, the relationship between the etching time of step S8 performed on the substrates W and the etching amount of the first layer M1 (SiGe) and the second layer M2 (Si) was studied. The results are shown in FIG. 20 and FIG. 21 .

Referring to FIG. 20 , it is found that by performing a hydrophobic treatment on the surface of Si, the etching property of Si is reduced. Specifically, when the surface of Si is not subjected to a hydrophobic treatment (black dots in FIG. 20 ), Si is etched immediately after the substrate W is immersed in the etching liquid E2. On the other hand, when the surface of Si is subjected to a hydrophobic treatment (white circles in FIG. 20 ), Si is basically not etched from the time when the substrate W is immersed in the etching liquid E2 until more than 25 minutes have passed. Moreover, Si is etched after more than 25 minutes have passed since the immersion in the etching liquid E2. Therefore, it is found that by performing a hydrophobic treatment on the surface of Si, the etching property of Si can be reduced before a specified time (e.g., more than 25 minutes) has passed.

On the other hand, referring to FIG21, it is found that even if the surface of SiGe is subjected to hydrophobic treatment, the etching property of SiGe is basically not reduced. Specifically, whether the surface of SiGe is subjected to hydrophobic treatment (white circle in FIG21) or not subjected to hydrophobic treatment (black dot in FIG21), SiGe is etched immediately after the substrate W is immersed in the etching solution E2.

According to the results shown in FIG. 20 and FIG. 21 , it can be confirmed that by performing a hydrophobic treatment on the surface of the first layer M1 and the surface of the second layer M2, the first layer M1 can be etched without substantially etching the second layer M2.

Next, referring to FIG. 22 , an experiment for confirming the effect obtained by using IPA as a rinsing liquid in the post-etching rinsing process (step S9) and the effect obtained by using an unused hydrophobic agent SMT will be described. FIG. 22 is a graph showing the experimental results for confirming the effect obtained by using IPA as a rinsing liquid in the post-etching rinsing process and the effect obtained by using an unused hydrophobic agent SMT. In the confirmation experiment, Examples 1 to 3 corresponding to the present embodiment and Comparative Example 1 not corresponding to the present embodiment were used. A comparison of the manufacturing conditions of Examples 1 to 3 and Comparative Example 1 is shown in Table 1 below.

[Table 1] Comparison Example 1 Embodiment 1 Embodiment 2 Embodiment 3 Hydrophobic treatment without have have have Hydrophobic Agent - Used Not used Not used Rinse fluid DIW DIW DIW IPA

(Example 1) Referring to Table 1, in Example 1, as a substrate W, the same substrate W as in the above-mentioned embodiment is used. Specifically, a substrate W having a base material S and a layered structure L is used, the base material S comprises single crystal silicon, and the layered structure L comprises a first layer M1 comprising SiGe and a second layer M2 comprising polycrystalline silicon. In addition, the composition ratio of Ge contained in the first layer M1 is approximately 15%.

Then, the above-mentioned steps S1 to S2 and S5 to S10 are performed on the substrate W. Furthermore, the etching time of step S8 is set to 5 minutes/time. Moreover, the prescribed number of times as the judgment standard in step S10 is set to "5 times".

Furthermore, in step S6, the used hydrophobic agent SMT which has been used more than once and recovered is used. Furthermore, in step S9, DIW is used as the rinse liquid.

(Example 2) In Example 2, the same substrate W as in Example 1 is used. Furthermore, the substrate W is treated in the same manner as in Example 1. However, in Example 2, an unused hydrophobic agent SMT is used in step S6.

(Example 3) In Example 3, the same substrate W as in Example 1 is used. Furthermore, the substrate W is treated in the same manner as in Example 1. However, in Example 3, an unused hydrophobic agent SMT is used in step S6. In addition, IPA is used as a rinse liquid in step S9.

(Comparative Example 1) In Comparative Example 1, the same substrate W as in Example 1 is used. Furthermore, the above-mentioned steps S1 to S2 and steps S7 to S10 are performed on the substrate W. That is, in Comparative Example 1, no hydrophobic treatment is performed. In addition, DIW is used as a rinse liquid in step S9.

Then, the etching amount of the first layer M1 (SiGe) relative to the etching amount of the second layer M2 (Si) in the concave portion C was calculated for Examples 1 to 3 and Comparative Example 1. The value calculated for Comparative Example 1 was normalized by setting it to "1". The results are shown in FIG. 22 .

22 , it is found that etching selectivity is improved by performing hydrophobic treatment on the substrate W. Specifically, regarding the etching amount of the first layer M1 relative to the etching amount of the second layer M2, that is, the calculated value, Examples 1 to 3 are all greater than Comparative Example 1.

Furthermore, it was found that the etching selectivity was improved by using the unused hydrophobic agent SMT. Specifically, the etching amount of the first layer M1 relative to the etching amount of the second layer M2, i.e., the calculated value, was greater in Example 2 than in Example 1. The reason is considered to be as follows. That is, the unused hydrophobic agent SMT has fewer impurities than the used hydrophobic agent SMT that has been used more than once, so the silane group can bond with almost all Si-O groups on the surface of the substrate W. Therefore, it is considered that the etching selectivity is improved by using the unused hydrophobic agent SMT.

Furthermore, it was found that by using IPA as the rinsing liquid in step S9, the etching selectivity was improved compared with the case where DIW was used as the rinsing liquid. Specifically, regarding the etching amount of the first layer M1 relative to the etching amount of the second layer M2, that is, the calculated value, Example 3 was greater than Example 2. The reason is considered to be as follows. That is, the thickness of the first layer M1 is very small (for example, more than 5 nm and less than 15 nm). Therefore, when DIW is used as the rinsing liquid, the surface tension of DIW is relatively large, so it is difficult to enter the recess C. On the other hand, when IPA is used as the rinsing liquid, the surface tension of IPA is smaller than the surface tension of DIW, so the rinsing liquid is relatively easy to enter the recess C. Therefore, by using IPA as the rinse liquid, the etching liquid E2 can be easily removed from the recessed portion C. Therefore, in the subsequent hydrophobic process (step S6), the hydrophobic agent SMT can easily penetrate into the recessed portion C. Therefore, by using IPA as the rinse liquid, the reduction of etching selectivity can be suppressed.

The embodiments of the present invention are described above with reference to the drawings. However, the present invention is not limited to the embodiments described above, and can be implemented in various forms within the scope of the gist thereof. In addition, the plurality of components disclosed in the embodiments described above can be appropriately changed. For example, a component of all components shown in a certain embodiment can be added to the components of another embodiment, or some components of all components shown in a certain embodiment can be deleted from the embodiment.

The drawings schematically show each component in the main body for the purpose of facilitating the understanding of the invention. For the convenience of drawing, the thickness, length, number, spacing, etc. of each component shown in the drawings may be different from the actual ones. Moreover, it is obvious that the configuration of each component shown in the above-mentioned embodiment is an example and is not particularly limited. Various changes can be made within the scope of the effect of the present invention.

For example, in the above-mentioned embodiment, an example of using a batch type substrate processing apparatus as the substrate processing apparatus is shown, but the present invention is not limited thereto. For example, a single-wafer type substrate processing apparatus that processes substrates one by one may also be used as the substrate processing apparatus.

In the first embodiment, for example, the processing liquid is blown onto the substrate W in steps S2, S4 to S7, and S9, but the present invention is not limited thereto. For example, the substrate W may be immersed in the processing liquid stored in the processing tank 303 using the processing unit 300 in steps S2, S4 to S7, and S9.

In the above embodiment, the hydrophobic agent SMT covers the surfaces of both the first layer M1 and the second layer M2, but the present invention is not limited thereto. For example, the hydrophobic agent SMT may cover only the surface of the second layer M2.

Furthermore, in the above-mentioned embodiment, an example is shown in which the etching liquid E1 is supplied to the substrate W from the state shown in FIG. 10 after the natural oxide film is removed, but the present invention is not limited thereto. For example, the hydrophobic agent SMT may be supplied to the substrate W from the state shown in FIG. 10 after the natural oxide film is removed. That is, the hydrophobic treatment may be performed after the natural oxide film is removed and before the etching treatment.

Furthermore, in the above-mentioned embodiment, an example is shown in which the stacked structure L has the first layer M1 including SiGe and the second layer M2 including Si, but the present invention is not limited thereto. For example, the stacked structure may also have the first layer including SiN and the second layer including _SiO2 . Furthermore, for example, the stacked structure may also have the first layer including GaAs and the second layer including AlGaAs. Furthermore, for example, the stacked structure may also have the first layer including GaN and the second layer including AlGaN.

In the above embodiment, when viewed from the thickness direction (z direction) of the substrate W, the groove R is formed into an example of an elongated shape having a long side direction and a short side direction, but the present invention is not limited thereto. When viewed from the thickness direction of the substrate W, the groove R may have a circular, elliptical or square shape, for example.

Furthermore, in the above description, for example, the expression "Above A and below B" means "Above A and below B". The expression "greater than A and less than B" means "greater than A and less than B". The expression "higher than A and lower than B" means "higher than A and lower than B". Similarly, other expressions such as "higher than the concentration of A and lower than the concentration of B" also mean "higher than the concentration of A and lower than the concentration of B". [Industrial Applicability]

The present invention can be used in a method and apparatus for processing a substrate.

100: substrate processing device 110: control device 111: control unit 112: memory unit 200: processing unit 202: chamber 202a: cover unit 203: liquid receiving member 205: liquid supply unit 206: hydrophobic agent supply unit 211: first nozzle 212: second nozzle 213: third nozzle 214: fourth nozzle 215: fifth nozzle 216: sixth nozzle 221: rinse liquid supply source 222: replacement liquid supply source 223: hydrophobic agent supply source 231: first pipe 232: second pipe 233: third pipe 241: Drainage pipeline 250: Holding part 251: Holding rod 252: Main body plate 260: Opening and closing part 270: Lifting part 300: Processing unit 302: Chamber 302a: Cover part 303: Processing tank 305: Liquid supply part 306: Etching liquid supply part 311: First nozzle 312: Second nozzle 321: Etching liquid supply source 331: First piping 341: Drainage pipeline 360: Opening and closing part 370: Lifting part C: Concave part E1: Etching liquid E2: Etching liquid L: Layered structure La: Surface Ls: Hydrophobic layer M1: Layer 1 M2: Layer 2 R: Groove S: Substrate S1: Step S2: Step S3: Step S4: Step S5: Step S6: Step (hydrophobic process) S7: Step (hydrophobic post-replacement process) S8: Step (etching process) S9: Step (etching post-replacement process) S10: Step Sa: Main surface (one side) SMT: Hydrophobic agent V201: Valve 1 V202: Valve 2 V203: Valve 3 V204: Valve 4 V301: Valve 1 V302: Valve 2 W: Substrate X: Direction Y: Direction Z: Direction

FIG. 1 is a schematic diagram showing the internal structure of a processing unit 200 of a substrate processing device of the first embodiment. FIG. 2 is a schematic diagram showing the state of spraying a rinse liquid from the first nozzle and the second nozzle. FIG. 3 is a schematic diagram showing the state of spraying a replacement liquid from the third nozzle and the fourth nozzle. FIG. 4 is a schematic diagram showing the state of spraying a hydrophobic agent from the fifth nozzle and the sixth nozzle. FIG. 5 is a schematic diagram showing the internal structure of a processing unit 300 of a substrate processing device of the first embodiment. FIG. 6 is a schematic diagram showing the state of spraying an etching liquid from the first nozzle and the second nozzle of the processing unit 300 into a processing tank. FIG. 7 is a schematic partial enlarged three-dimensional view of a substrate after being processed by a substrate processing device. FIG. 8 is a schematic partial enlarged view of a substrate after being processed by a substrate processing device. FIG. 9 is a flow chart showing the substrate processing method of the present embodiment. FIG. 10 is an enlarged cross-sectional view of the periphery of a groove for illustrating the substrate processing method of the present embodiment. FIG. 11 is an enlarged cross-sectional view of the periphery of a groove for illustrating the substrate processing method of the present embodiment. FIG. 12 is an enlarged cross-sectional view of the periphery of a groove for illustrating the substrate processing method of the present embodiment. FIG. 13 is an enlarged cross-sectional view of the periphery of a groove for illustrating the substrate processing method of the present embodiment. FIG. 14 is an enlarged cross-sectional view of the periphery of a groove for illustrating the substrate processing method of the present embodiment. FIG. 15 is an enlarged cross-sectional view of the groove periphery for illustrating the substrate processing method of the present embodiment. FIG. 16 is an enlarged cross-sectional view of the groove periphery for illustrating the substrate processing method of the present embodiment. FIG. 17 is an enlarged cross-sectional view of the groove periphery for illustrating the substrate processing method of the present embodiment. FIG. 18 is an enlarged cross-sectional view of the groove periphery for illustrating the substrate processing method of the present embodiment. FIG. 19 is a flow chart showing a substrate processing method performed using a substrate processing apparatus of the second embodiment. FIG. 20 is an experimental result showing the relationship between the presence or absence of hydrophobic treatment and the etching amount of Si (silicon). FIG. 21 is an experimental result showing the relationship between the presence or absence of hydrophobic treatment and the etching amount of SiGe (silicon germanium). Figure 22 is a graph showing the experimental results of confirming the effect of using IPA (Isopropyl Alcohol) as a rinse liquid in the rinse process after etching and the effect of using no hydrophobic agent.

S1: Steps

S2: Step

S3: Step

S4: Step

S5: Step

S6: Step (hydrophobic process)

S7: Step (hydrophobic post-replacement process)

S8: Step (etching process)

S9: Step (post-etching replacement process)

S10: Step

Claims (12)

A substrate processing method is for processing a substrate having a substrate and a plurality of first layers and a plurality of second layers, and includes: a hydrophobic process, which is to supply a hydrophobic agent into a groove provided in a layered structure supported by the substrate, and the hydrophobic agent makes the surface of the plurality of first layers and the plurality of second layers constituting the layered structure hydrophobic; and an etching process, which is to supply an etching liquid into the groove in a state where the surface of the second layer is hydrophobic, and selectively etches the first layer; and the hydrophobic process and the etching process are repeated for a specified number of times. The substrate processing method of claim 1, wherein the first layer and the second layer are laminated in a first direction intersecting one surface of the substrate, the groove extends along the first direction, and in the etching process, the first layer is selectively etched to form a plurality of recesses connected to the groove in a manner extending along a second direction intersecting the first direction. As in claim 2, the substrate processing method, wherein the length of the above-mentioned recess in the above-mentioned second direction is more than 20 times the length of the above-mentioned recess in the above-mentioned first direction. A substrate processing method as claimed in any one of claims 1 to 3, wherein after the hydrophobizing step and before the etching step, a post-hydrophobizing replacement step is further included, wherein the post-hydrophobizing replacement step is to replace the hydrophobizing agent with the replacement liquid by supplying a replacement liquid into the groove so that the hydrophobizing agent remains on at least the surface of the second layer. A substrate processing method as claimed in any one of claims 1 to 3, wherein after the etching process, a post-etching replacement process is further included, wherein the post-etching replacement process replaces the etching liquid with the rinse liquid by supplying a rinse liquid into the groove. A substrate processing method as claimed in claim 5, wherein the rinse solution contains isopropyl alcohol. The substrate processing method of claim 5, wherein in the hydrophobizing step, the hydrophobizing agent at least coats the surface of the second layer, and before the hydrophobizing agent disappears from the surface of the second layer by the etching liquid, the etching step is transferred to the post-etching replacement step. A substrate processing method as claimed in any one of claims 1 to 3, wherein the first layer comprises silicon germanium, and the second layer comprises polycrystalline silicon or single crystal silicon. A substrate processing method as claimed in any one of claims 1 to 3, wherein in the hydrophobizing step, the hydrophobizing agent at least silanes the surface of the second layer. A substrate processing method as claimed in any one of claims 1 to 3, wherein in the hydrophobizing step, the hydrophobizing agent or the vapor of the hydrophobizing agent is supplied to the substrate in a mist form. A substrate processing method as claimed in any one of claims 1 to 3, wherein in the hydrophobizing step, unused hydrophobizing agent is supplied into the groove. A substrate processing device comprises: a hydrophobic agent supplying unit, which supplies a hydrophobic agent to a substrate; an etching liquid supplying unit, which supplies an etching liquid to the substrate; and a control unit, which controls the hydrophobic agent supplying unit and the etching liquid supplying unit; wherein the substrate has a substrate and a plurality of first layers and a plurality of second layers constituting a layered structure supported by the substrate, the hydrophobic agent makes the surface of the second layer hydrophobic, the etching liquid etches the first layer, and the control unit controls the hydrophobic agent supplying unit and the etching liquid supplying unit to control the hydrophobic agent supplying unit and the etching liquid supplying unit. The hydrophobizing agent supplying unit supplies the hydrophobizing agent into the groove provided in the layered structure to hydrophobize the surface of the plurality of first layers and the plurality of second layers. The etching liquid supplying unit is controlled to supply the etching liquid into the groove in a state where the surface of the second layer is hydrophobized, thereby selectively etching the first layer. The control unit repeatedly performs the hydrophobizing of the surface of the second layer and the selective etching of the first layer for a predetermined number of times.