CN120814032A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

The substrate processing method of the present invention includes: a hydrophobizing process (step S6), supplying a hydrophobizing agent (SMT) into a groove (R) provided in a stacked structure (L) supported by a substrate (S), wherein the hydrophobizing agent (SMT) hydrophobizes the surfaces of a plurality of first layers (M1) and a plurality of second layers (M2) constituting the stacked structure (L); and an etching process (step S8), supplying an etching liquid (E2) into the groove (R) in a state where the surface of the second layer (M2) is hydrophobized, and selectively etching the first layer (M1); and repeating the hydrophobizing process (step S6) and the etching process (step S8) a predetermined number of times.

Description

Substrate processing method and substrate processing apparatus

Technical Field

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

Background

Conventionally, there is known a substrate processing method for processing a semiconductor substrate having a base material and a plurality of 1 st layers and a plurality of 2 nd layers constituting a laminated structure supported by the base material. As such a substrate processing method, for example, patent document 1 describes a method of selectively etching silicon germanium in a substrate in which silicon and silicon germanium are alternately stacked.

Prior art literature

Patent literature

Patent document 1 Japanese patent application laid-open No. 2018-6405

Disclosure of Invention

Problems to be solved by the invention

Further, as in patent document 1, in the case of selectively etching a specific layer among a plurality of layers, other layers than the specific layer may be etched. Specifically, when a specific layer contains the same substance or a substance having similar chemical properties to other layers, the etching selectivity is lowered. In this case, if a specific layer is to be etched deeper (more), the etching amount of the other layers increases. Thus, for example, the thickness of the other layer becomes thin, and thus, a semiconductor device manufactured using the substrate cannot obtain desired characteristics.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of improving etching selectivity.

Means for solving the problems

According to one aspect of the present invention, a substrate processing method processes a substrate having a base material, a plurality of 1 st layers, and a plurality of 2 nd layers. The substrate processing method includes a hydrophobizing step of supplying a hydrophobizing agent to a recess provided in a laminated structure supported by the substrate, the hydrophobizing agent hydrophobizing surfaces of the 1 st layers and the 2 nd layers constituting the laminated structure, and an etching step of supplying an etching solution to the recess in a state where the surfaces of the 2 nd layers are hydrophobized, and selectively etching the 1 st layers, and repeating the hydrophobizing step and the etching step a predetermined number of times.

In one embodiment, the 1 st layer and the 2 nd layer are laminated in the 1 st direction intersecting one surface of the base material. The groove extends along the 1 st direction. In the etching step, the 1 st layer is selectively etched to form a plurality of recesses connected to the grooves so as to extend in a2 nd direction intersecting the 1 st direction.

In one embodiment, the length of the recess in the 2 nd direction is 20 times or more the length of the recess in the 1 st direction.

In one embodiment, the substrate processing method further includes a post-hydrophobization replacement step of replacing the hydrophobizing agent with the replacement liquid so that the hydrophobizing agent remains at least on the surface of the 2 nd layer by supplying the replacement liquid into the grooves after the hydrophobizing step and before the etching step.

In one embodiment, the substrate processing method further includes a post-etching replacement step of replacing the etching liquid with the rinse liquid by supplying the rinse liquid into the recess after the etching step.

In one embodiment, the rinse solution includes isopropyl alcohol.

In one embodiment, in the hydrophobizing step, the hydrophobizing agent coats at least the surface of the 2 nd layer. Before the hydrophobizing agent is removed from the surface of the 2 nd layer by the etching liquid, the process is transferred from the etching step to the post-etching replacement step.

In one embodiment, the 1 st layer includes silicon germanium. The 2 nd layer contains polycrystalline silicon or monocrystalline silicon.

In one embodiment, in the hydrophobizing step, the hydrophobizing agent silylates at least the surface of the 2 nd layer.

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

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

According to another aspect of the present invention, a substrate processing apparatus includes a hydrophobizing agent supply unit, an etching solution supply unit, and a control unit. The hydrophobizing agent supply unit supplies a hydrophobizing agent to the substrate. The etching liquid supply unit supplies an etching liquid to the substrate. The control unit controls the hydrophobizing agent supply unit and the etching liquid supply unit. The substrate has a base material, and a plurality of 1 st layers and a plurality of 2 nd layers constituting a laminated structure supported by the base material. The hydrophobizing agent hydrophobizes the surface of the layer 2. The etching solution etches the 1 st layer. The control unit controls the hydrophobizing agent supply unit to supply the hydrophobizing agent into the grooves provided in the laminated structure, thereby hydrophobizing the surfaces of the plurality of 2 nd layers. The control unit selectively etches the 1 st layer by controlling the etching liquid supply unit to supply the etching liquid into the grooves in a state where the surface of the 2 nd layer is hydrophobized. The control unit repeatedly performs hydrophobization of the surface of the 2 nd layer and selective etching of the 1 st layer a predetermined number of times.

Effects of the invention

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

Drawings

Fig. 1 is a schematic diagram showing the internal configuration of a processing unit 200 of the substrate processing apparatus according to embodiment 1.

Fig. 2 is a schematic diagram showing a state in which the rinse liquid is discharged from the 1 st nozzle and the 2 nd nozzle.

Fig. 3 is a schematic diagram showing a state in which the replacement liquid is discharged from the 3 rd nozzle and the 4 th nozzle.

Fig. 4 is a schematic view showing a state in which the hydrophobizing agent is discharged from the 5 th nozzle and the 6 th nozzle.

Fig. 5 is a schematic diagram showing the internal configuration of a processing unit 300 of the substrate processing apparatus according to embodiment 1.

Fig. 6 is a schematic view showing a state in which the etching liquid is discharged from the 1 st nozzle and the 2 nd nozzle of the processing unit 300 into the processing bath.

Fig. 7 is a schematic partially enlarged perspective view of a substrate processed using the substrate processing apparatus.

Fig. 8 is a schematic partial enlarged view of a substrate processed using the substrate processing apparatus.

Fig. 9 is a flowchart showing a substrate processing method according to the present embodiment.

Fig. 10 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 11 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 12 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 13 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 14 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 15 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 16 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 17 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 18 is an enlarged cross-sectional view of the periphery of the recess for explaining the substrate processing method of the present embodiment.

Fig. 19 is a flowchart showing a substrate processing method performed by the substrate processing apparatus according to embodiment 2.

Fig. 20 shows experimental results of the relation between the presence or absence of the hydrophobization treatment and the etching amount to Si (silicon).

Fig. 21 is an experimental result showing the relationship between the presence or absence of the hydrophobization treatment and the etching amount of SiGe (silicon germanium).

Fig. 22 is a graph showing experimental results for confirming the effect obtained by using IPA (Isopropyl Alcohol ) as a rinse solution and the effect obtained by using an unused hydrophobizing agent in a post-etching rinse step.

Detailed Description

Embodiments of a substrate processing method and a substrate processing apparatus according to the present invention are described below with reference to the drawings. However, the present invention is not limited to the following embodiments. Note that, in the overlapping description, description may be omitted as appropriate. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and the description thereof will not be repeated.

In the present specification, for ease of understanding, the X direction, the Y direction, and the Z direction orthogonal to each other are sometimes described. Typically, the X-direction and the Y-direction are parallel to the horizontal direction, and the Z-direction is parallel to the vertical direction. However, the direction in which the substrate processing method of the present invention is executed and the direction in which the substrate processing apparatus of the present invention is used are not intended to be limited by the definition of these directions.

The "substrate" in this embodiment mode can be applied to various substrates such as a semiconductor wafer, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for an FED (Field Emission Display ), a substrate for an optical disk, a substrate for a magnetic disk, and a substrate for a magneto-optical disk. The present embodiment will be described below mainly with reference to a substrate processing method and a substrate processing apparatus for processing a disk-shaped semiconductor wafer, but the present embodiment is also applicable to the processing of various substrates as described above. In addition, various shapes can be applied to the shape of the substrate.

[ Embodiment 1]

Embodiment 1 of the present invention will be described below with reference to fig. 1 to 18. First, a substrate processing apparatus 100 according to embodiment 1 will be described with reference to fig. 1 to 6. Fig. 1 is a schematic diagram showing the internal configuration of a processing unit 200 of the substrate processing apparatus 100 according to embodiment 1. The substrate processing apparatus 100 of the present embodiment is a batch type. Accordingly, the substrate processing apparatus 100 processes a plurality of substrates W at a time. Specifically, the substrate processing apparatus 100 processes a plurality of substrates W in a batch unit. The 1 lot contains, for example, 25 substrates W.

As shown in fig. 1, the substrate processing apparatus 100 includes a processing unit 200. The processing unit 200 performs a hydrophobization process on the substrate W. Specifically, the processing unit 200 includes a chamber 202, a liquid receiving member 203, a liquid supply portion 205, a holding portion 250, an opening/closing portion 260, and a lifting portion 270.

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

The liquid receiving member 203 and the liquid supply portion 205 are accommodated in the chamber 202. In addition, the holding portion 250 is housed in the chamber 202 when the substrate W is processed. The chamber 202 has a cover 202a. The cover 202a is attached to an opening in the upper portion of the chamber 202. The cover 202a is movable to open and close the opening.

The liquid supply unit 205 supplies the processing liquid into the chamber 202. The treatment liquid includes, for example, a chemical liquid, a rinse liquid (cleaning liquid), a removing liquid, and/or a hydrophobizing 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 hydrophobizing agent SMT to the substrate W held by the holding unit 250. The liquid supply unit 205 may supply vapor of the rinse liquid to the substrate W. The liquid supply portion 205 may supply the vapor of the replacement liquid to the substrate W. The liquid supply unit 205 may supply the vapor of the hydrophobizing agent SMT to the substrate W.

Fig. 2 is a schematic diagram showing a state in which the rinse liquid is discharged from the 1 st nozzle 211 and the 2 nd nozzle 212. Fig. 3 is a schematic diagram showing a state in which the replacement liquid is discharged from the 3 rd nozzle 213 and the 4 th nozzle 214. Fig. 4 is a schematic diagram showing a state in which the hydrophobizing agent SMT is discharged from the 5 th nozzle 215 and the 6 th nozzle 216. As shown in fig. 1, the liquid supply portion 205 includes 1 st nozzle 211 to 6 th nozzle 216. The 1 st nozzle 211 to the 6 th nozzle 216 are disposed inside the chamber 202 and outside the liquid receiving member 203. Specifically, the 1 st nozzle 211 to the 6 th nozzle 216 are disposed above the liquid receiving member 203. The 1 st nozzle 211 and the 2 nd nozzle 212 spray a mist of rinse liquid. The 3 rd nozzle 213 and the 4 th nozzle 214 discharge a mist of the replacement liquid. The 5 th nozzle 215 and the 6 th nozzle 216 spray the mist of the hydrophobizing agent SMT.

In this embodiment, the rinse solution is DIW (Deionized Water: deionized water). The substitution liquid was IPA (isopropyl alcohol).

The hydrophobizing agent SMT is, for example, a silicon-based rehydrating agent or a metal-based rehydrating agent. Silicon-based hydrating agents dehydrate (hydrophobize) silicon or silicon-containing compounds. The metal-based rehydrating agent causes the metal or metal-containing compound to be rehydrated (hydrophobized).

The silicon-based hydrating agent is, for example, a silane coupling agent. The silane coupling agent includes, for example, at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilanes, alkyldisilazane, and a non-chlorine-based hydrophobizing agent. The non-chlorine-based hydrophobizing agent includes, for example, at least one of dimethylsilyl dimethylamine, dimethylsilyl diethylamine, hexamethyldisilazane, tetramethyldisilazane, bis (dimethylamino) dimethylsilane, N-dimethylaminotrimethylsilane, N- (trimethylsilyl) dimethylamine, and organosilane compounds.

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

The hydrophobizing agent SMT may also be diluted with a solvent having phase solubility to the hydrophilic organic solvent. The solvent is, for example, IPA or PGMEA (Propylene Glycol METHYL ETHER ACETATE, propylene glycol monomethyl ether acetate). In this embodiment, the solvent is PGMEA.

As shown in fig. 1, the liquid receiving member 203 receives the liquid supplied from the liquid supply portion 205 to the substrate W. Specifically, the liquid receiving member 203 receives the rinse liquid, the substitution liquid, and the hydrophobizing agent SMT.

The holding portion 250 holds a plurality of substrates W. Specifically, the holding portion 250 includes a plurality of holding bars 251 and a body plate 252. In the present embodiment, the holding portion 250 has 3 holding bars 251. The main body plate 252 is a plate-like member extending in the vertical direction (Z direction). The holding bars 251 extend in the horizontal direction (X direction) from one principal surface of the body plate 252, respectively. The lower edge of each of the plurality of substrates W is abutted against a plurality of (here, 3) holding bars 251. The plurality of substrates W are held in a standing posture (vertical posture) with an interval in the X direction.

The opening/closing portion 260 opens and closes the cover 202 a. That is, the opening and closing portion 260 switches the cover 202a between the open state and the closed state. The lid 202a is opened and closed, and the opening of the upper portion of the chamber 202 is switched between a closed state and an open state. The opening/closing unit 260 has a drive source and an opening/closing mechanism, and the opening/closing mechanism is driven by the drive source to open and close the lid 202 a. The driving source includes, for example, a motor. The opening and closing mechanism includes, for example, a rack-and-pinion mechanism.

The lifting portion 270 lifts and lowers the holding portion 250. The holding portion 250 is lifted by the lifting portion 270, and the substrate W held by the holding portion 250 is lifted. The lifting unit 270 includes 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 comprises, for example, a rack-and-pinion mechanism or a ball screw.

Specifically, the elevating section 270 moves (elevates) the holding section 250 (substrate W) between the outside and the inside of the chamber 202 through the opening in the upper portion of the chamber 202. That is, the lifting/lowering 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 will be further described with reference to fig. 1. As shown in fig. 1, the substrate processing apparatus 100 further includes a control apparatus 110. The control device 110 controls the operations of the respective units of the substrate processing apparatus 100. Specifically, the control device 110 controls the operations of the respective units of the processing unit 200. The control device 110 includes a control unit 111 and a storage unit 112.

The control unit 111 has a processor. The control unit 111 has, for example, a CPU (Central Processing Unit ) or an MPU (Micro Processing Unit, micro processing unit). Alternatively, the control unit 111 may have a general purpose arithmetic unit.

The storage unit 112 stores data and computer programs. The data comprises protocol data. The protocol data contains information representing a plurality of protocols. Each of the plurality of procedures defines a processing content and a processing order of the substrate W.

The storage unit 112 has a main storage device. The main memory device is, for example, a semiconductor memory. The storage unit 112 may also have an auxiliary storage device. The auxiliary storage device includes, for example, at least one of a semiconductor memory and a hard disk drive. The storage portion 112 may also include removable media. The control unit 111 controls the operations of the respective units of the substrate processing apparatus 100 based on the computer programs and data stored in the storage unit 112.

The control device 110 (control unit 111) controls the opening/closing unit 260 to switch the lid 202a between the open state and the closed state. Specifically, the control device 110 (control unit 111) opens the cover 202a when the substrate W is carried into the chamber 202 and when the substrate W is carried out of the chamber 202. When the lid 202a is opened, the opening in the upper portion of the chamber 202 is opened, so that the substrate W can be carried into the chamber 202 and the substrate W can be carried out of the chamber 202. When the substrate W is processed, the control device 110 (control unit 111) closes the lid 202 a. The lid 202a is closed, and the opening in the upper portion of the chamber 202 is closed. As a result, the interior of the chamber 202 becomes a closed space. The substrate W is processed in the closed space.

The controller 110 (controller 111) controls the lifting/lowering unit 270 to lift and lower the holding unit 250 (substrate W). Specifically, when the substrate W is carried into the chamber 202, the control device 110 (control unit 111) moves the holding unit 250 from the outside to the inside of the chamber 202 through the opening in the upper portion of the chamber 202, and carries the substrate W into the chamber 202. When the substrate W is carried out of 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 in the upper portion of the chamber 202, and carries 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 substitution liquid supply source 222, a hydrophobizing agent supply source 223, 1 st to 3 rd pipes 231 to 233, a drain line 241, and 1 st to 4 th valves V201 to V204.

The rinse liquid supply source 221 supplies rinse liquid. In the present embodiment, the rinse liquid supply source 221 supplies DIW. The substitution liquid supply source 222 supplies substitution liquid. In the present embodiment, the substitution liquid supply source 222 supplies IPA. The hydrophobizing agent supply source 223 supplies a hydrophobizing agent SMT.

The rinse liquid is supplied from the rinse liquid supply source 221 to the 1 st pipe 231. The 1 st pipe 231 circulates the rinse liquid supplied from the rinse liquid supply source 221 to the 1 st nozzle 211 and the 2 nd nozzle 212.

The 1 st nozzle 211 and the 2 nd nozzle 212 are hollow tubular members. A plurality of discharge holes are formed in the 1 st nozzle 211 and the 2 nd nozzle 212, respectively. In the present embodiment, the 1 st nozzle 211 and the 2 nd nozzle 212 extend in the X direction. The plurality of ejection holes of the 1 st nozzle 211 are formed at equal intervals in the X direction. Similarly, a plurality of discharge holes of the 2 nd nozzle 212 are formed at equal intervals in the X direction.

When the rinse liquid is supplied to the 1 st nozzle 211 through the 1 st pipe 231, the rinse liquid is discharged from the plurality of discharge holes of the 1 st nozzle 211 into the chamber 202. Similarly, when the rinse liquid is supplied to the 2 nd nozzle 212 through the 1 st pipe 231, the rinse liquid is discharged from the plurality of discharge holes of the 2 nd nozzle 212 into the chamber 202.

The 1 st valve V201 is attached to the 1 st pipe 231. The 1 st valve V201 is an on-off valve for opening and closing the flow path of the 1 st pipe 231. The 1 st valve V201 controls the flow of the rinse liquid flowing through the 1 st pipe 231. Specifically, when the 1 st valve V201 is opened, the rinse liquid flows to the 1 st nozzle 211 and the 2 nd nozzle 212 through the 1 st pipe 231. As a result, the rinse liquid is discharged from the 1 st nozzle 211 and the 2 nd nozzle 212. When the 1 st valve V201 is closed, the flow of the rinse liquid is blocked, and the 1 st nozzle 211 and the 2 nd nozzle 212 stop discharging the rinse liquid.

The 1 st valve V201 also functions as an adjustment valve for adjusting the flow rate of the rinse liquid flowing through the 1 st pipe 231. The 1 st valve V201 is, for example, a solenoid valve. The 1 st valve V201 is controlled by the control device 110 (control unit 111).

In the present embodiment, a heater (not shown) may be attached to the 1 st pipe 231. The heater heats the rinse liquid, so that the rinse liquid can be heated to a high temperature and gasified. That is, the heater can raise the temperature of the rinse liquid and can generate vapor of the rinse liquid. The 1 st nozzle 211 and the 2 nd nozzle 212 may discharge the high-temperature rinse liquid or vapor of the rinse liquid. Further, a heater (not shown) may be provided in the rinse liquid supply source 221, and high-temperature rinse liquid or vapor of rinse liquid may be supplied from the rinse liquid supply source 221 to the 1 st pipe 231. Further, the heater may not be provided, and the rinse liquid at normal temperature may be discharged from the 1 st nozzle 211 and the 2 nd nozzle 212.

IPA is supplied from the substitution liquid supply source 222 to the 2 nd pipe 232. The 2 nd pipe 232 circulates the IPA supplied from the substitution liquid supply source 222 to the 3 rd nozzle 213 and the 4 th nozzle 214.

The 3 rd nozzle 213 and the 4 th nozzle 214 are disposed below the 1 st nozzle 211 and the 2 nd nozzle 212. The 3 rd nozzle 213 and the 4 th nozzle 214 have the same configuration as the 1 st nozzle 211 and the 2 nd nozzle 212. The 3 rd nozzle 213 and the 4 th nozzle 214 eject IPA into the chamber 202 in the same manner as the 1 st nozzle 211 and the 2 nd nozzle 212.

The 2 nd valve V202 is attached to the 2 nd pipe 232. The 2 nd valve V202 is an on-off valve for opening and closing the flow path of the 2 nd pipe 232. The 2 nd valve V202 controls the flow of the IPA flowing through the 2 nd pipe 232 in the same manner as the 1 st valve V201. The 2 nd valve V202 also functions as an adjustment valve for adjusting the flow rate of the IPA flowing through the 2 nd pipe 232. Valve 2V 202 is, for example, a solenoid valve. The 2 nd valve V202 is controlled by the control device 110 (control unit 111).

In the present embodiment, a heater (not shown) is attached to the 2 nd pipe 232. The heater heats the IPA so that the IPA can be heated to a high temperature or the IPA can be gasified. That is, the heater can raise the temperature of the liquid IPA and can generate vapor of IPA. Further, the 3 rd nozzle 213 and the 4 th nozzle 214 may eject high-temperature liquid IPA or vapor of IPA. Further, a heater (not shown) may be provided in the substitution liquid supply source 222, and high-temperature liquid IPA or vapor of IPA may be supplied from the substitution liquid supply source 222 to the 3 rd pipe 233. In addition, a heater may not be provided, and normal temperature liquid IPA may be ejected from the 3 rd nozzle 213 and the 4 th nozzle 214.

The hydrophobizing agent SMT is supplied from the hydrophobizing agent supply source 223 to the 3 rd pipe 233. The 3 rd piping 233 circulates the hydrophobizing agent SMT supplied from the hydrophobizing agent supply source 223 to the 5 th nozzle 215 and the 6 th nozzle 216.

The 5 th nozzle 215 and the 6 th nozzle 216 are disposed below the 3 rd nozzle 213 and the 4 th nozzle 214. The 5 th nozzle 215 and the 6 th nozzle 216 have the same configuration as the 1 st nozzle 211 and the 2 nd nozzle 212. The 5 th nozzle 215 and the 6 th nozzle 216 eject the hydrophobizing agent SMT into the chamber 202 in the same manner as the 1 st nozzle 211 and the 2 nd nozzle 212.

A 3 rd valve V203 is attached to the 3 rd pipe 233. The 3 rd valve V203 is an on-off valve for opening and closing the flow path of the 3 rd pipe 233. The 3 rd valve V203 controls the flow of the hydrophobizing agent SMT flowing through the 3 rd pipe 233 in the same manner as the 1 st valve V201. The 3 rd valve V203 also functions as an adjustment valve for adjusting the flow rate of the hydrophobizing agent SMT flowing through the 3 rd pipe 233. The 3 rd valve V203 is, for example, a solenoid valve. The 3 rd valve V203 is controlled by the control device 110 (control unit 111).

The hydrophobizing agent supply unit 206 for supplying the hydrophobizing agent SMT to the substrate W is constituted by a hydrophobizing agent supply source 223, a 3 rd pipe 233, a 3 rd valve V203, a 5 th nozzle 215, and a 6 th nozzle 216.

In the present embodiment, a heater (not shown) may be attached to the 3 rd pipe 233. The heater heats the hydrophobizing agent SMT, so that the hydrophobizing agent SMT can be high temperature and can be gasified. That is, the heater can make the liquid hydrophobizing agent SMT high temperature, and can also generate vapor of the hydrophobizing agent SMT. Further, the 5 th nozzle 215 and the 6 th nozzle 216 may eject vapor of the high-temperature liquid hydrophobizing agent SMT. Further, a heater (not shown) may be provided in the hydrophobizing agent supply source 223, and the high-temperature liquid hydrophobizing agent SMT or vapor of the hydrophobizing agent SMT may be supplied from the hydrophobizing agent supply source 223 to the 3 rd pipe 233. Further, the liquid hydrophobizing agent SMT at normal temperature may be ejected from the 5 th nozzle 215 and the 6 th nozzle 216 without providing a heater.

A drain line 241 is connected to the bottom of the liquid receiving member 203. A 4 th valve V204 is installed in the drain line 241. The 4 th valve V204 is an on-off valve for opening and closing the flow path of the drain line 241. The 4 th valve V204 is, for example, a solenoid valve. The 4 th valve V204 is controlled by the control device 110 (control unit 111). When the treatment liquid is stored in the liquid receiving member 203, the control device 110 (control unit 111) closes the 4 th valve V204. On the other hand, when the treatment liquid is discharged from the liquid receiving member 203, the control device 110 (control unit 111) opens the 4 th valve V204. When the 4 th valve V204 is opened, the processing liquid stored in the liquid receiving member 203 is discharged from the liquid receiving member 203 to the outside of the chamber 202 through the liquid discharge line 241.

The substrate processing apparatus 100 may further include a pressure reducing portion (not shown) for reducing the pressure in the chamber 202. The pressure reducing portion includes, for example, an exhaust pump. The exhaust pump is, for example, a vacuum pump. The pressure reducing portion may discharge the gas in the chamber 202 when the lid portion 202a is in the closed state, and reduce the pressure in the chamber 202 to less than the atmospheric pressure.

Next, a processing unit 300 of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 5. Fig. 5 is a schematic diagram showing the internal configuration of a processing unit 300 of the substrate processing apparatus 100 according to embodiment 1. Fig. 6 is a schematic diagram showing a state in which the etching liquid is discharged from the 1 st nozzle 311 and the 2 nd nozzle 312 of the processing unit 300 into the processing tank 303.

As shown in fig. 5, the substrate processing apparatus 100 includes a processing unit 300. The processing unit 300 performs etching processing on the substrate W. The substrate W subjected to the hydrophobization by the processing unit 200 is carried (carried in) to the processing unit 300. In the present embodiment, the processing unit 300 performs wet etching on a part of the substrate W. Specifically, the processing unit 300 includes a chamber 302, a processing tank 303, a liquid supply unit 305, an opening/closing unit 360, and a lifting unit 370.

The processing tank 303 and the liquid supply unit 305 are accommodated in the chamber 302. In addition, the holding portion 250 is housed in the chamber 302 when the substrate W is processed. The chamber 302 has a cover 302a. The cover 302a is mounted to an opening in an upper portion of the chamber 302. The cover 302a is movable to open and close the opening.

The treatment tank 303 stores a treatment liquid. The processing liquid contains an etching liquid. Therefore, the processing tank 303 stores the etching solution. In the present embodiment, the etching solution is an aqueous solution in which an ester solvent, ammonium fluoride, and hydrogen peroxide water are mixed. The substrate W is immersed in the processing bath 303, whereby the substrate W is subjected to etching processing.

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

The liquid supply unit 305 supplies an etching liquid to the processing tank 303. Specifically, the liquid supply unit 305 includes a1 st nozzle 311 and a2 nd nozzle 312. The 1 st nozzle 311 and the 2 nd nozzle 312 are disposed in the processing tank 303. As shown in fig. 6, the 1 st nozzle 311 and the 2 nd nozzle 312 discharge the etching liquid into the processing bath 303.

As shown in fig. 5, the opening/closing portion 360 opens and closes the lid portion 302 a. That is, the opening and closing portion 360 switches the cover portion 302a between the open state and the closed state. The lid 302a is opened and closed, whereby the opening of the upper portion of the chamber 302 is switched between a closed state and an open state. The opening/closing unit 360 has a drive source and an opening/closing mechanism, and the opening/closing mechanism is driven by the drive source to open and close the lid 302 a. The driving source includes, for example, a motor. The opening and closing mechanism includes, for example, a rack-and-pinion mechanism.

The lifting portion 370 lifts and lowers the holding portion 250. The holding portion 250 is the holding portion 250 described with reference to fig. 1. The holding portion 250 is movable between the processing unit 200 and the processing unit 300 while holding the substrate W. The holding portion 250 is lifted by the lifting portion 370, and the substrate W held by the holding portion 250 is lifted. The lifting unit 370 includes 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 comprises, for example, a rack-and-pinion mechanism or a ball screw.

Specifically, the elevating section 370 moves (elevates) the holding section 250 (substrate W) between the outside and the inside of the chamber 302 through the opening in the upper portion of the chamber 302. That is, the lifting/lowering unit 370 carries the substrate W into the chamber 302 and carries the substrate W out of the chamber 302.

The lifting/lowering unit 370 moves (lifts) the holding unit 250 (substrate W) in the chamber 302 between a processing position in the processing bath 303 and a standby position outside the processing bath 303. The substrate W is moved into the processing chamber 303 by the holding portion 250 being moved to the processing position. By the holding portion 250 moving to the standby position, the substrate W moves out of the processing bath 303. Specifically, the standby position is a position above the processing position. By the holding portion 250 moving to the standby position, the substrate W moves to a space above the processing bath 303. In fig. 5, the holding portion 250 and the substrate W moved to the processing position are indicated by solid lines, and the holding portion 250 and the substrate W moved to the standby position are indicated by two-dot chain lines.

Next, the substrate processing apparatus 100 will be further described with reference to fig. 5. As shown in fig. 5, the control device 110 controls the operations of the respective units of the processing unit 300.

The control device 110 (control unit 111) controls the opening/closing unit 360 to switch the lid 302a between the open state and the closed state. Specifically, the control device 110 (control unit 111) opens the cover 302a when the substrate W is carried into the chamber 302 and when the substrate W is carried out of the chamber 302. When the lid 302a is opened, the opening in the upper portion of the chamber 302 is opened, and the substrate W can be carried into the chamber 302 and carried out of the chamber 302. When the substrate W is processed, the control device 110 (control unit 111) closes the lid 302 a. The lid 302a is closed, and the opening in the upper portion of the chamber 302 is closed. As a result, the interior of the chamber 302 becomes a closed space. The substrate W is processed in the closed space.

The control device 110 (control unit 111) controls the lifting unit 370 to lift and lower the holding unit 250 (substrate W). Specifically, when the substrate W is carried into the chamber 302, the control device 110 (control unit 111) moves the holding unit 250 from the outside to the inside of the chamber 302 through the opening in the upper portion of the chamber 302, and carries the substrate W into the chamber 302. When the substrate W is carried out of 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 in the upper portion of the chamber 302, and carries the substrate W out of the chamber 302. When the substrate W is processed, the control device 110 (control unit 111) moves (moves up and down) 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 liquid supply source 321, a1 st pipe 331, a drain line 341, a1 st valve V301, and a 2 nd valve V302.

The etching liquid supply source 321 supplies an etching liquid.

The etching liquid is supplied from the etching liquid supply source 321 to the 1 st pipe 331. The 1 st pipe 331 flows the etching liquid supplied from the etching liquid supply source 321 to the 1 st nozzle 311 and the 2 nd nozzle 312.

The 1 st nozzle 311 and the 2 nd nozzle 312 are hollow tubular members. A plurality of ejection holes are formed in each of the 1 st nozzle 311 and the 2 nd nozzle 312. In the present embodiment, the 1 st nozzle 311 and the 2 nd nozzle 312 extend in the X direction. The plurality of ejection holes of the 1 st nozzle 311 are formed at equal intervals in the X direction. Similarly, a plurality of discharge holes of the 2 nd nozzle 312 are formed at equal intervals in the X direction.

When the etching liquid is supplied to the 1 st nozzle 311 through the 1 st pipe 331, the etching liquid is discharged from the plurality of discharge holes of the 1 st nozzle 311 into the processing tank 303. Similarly, when the etching liquid is supplied to the 2 nd nozzle 312 via the 1 st pipe 331, the etching liquid is discharged from the plurality of discharge holes of the 2 nd nozzle 312 into the processing tank 303.

The 1 st valve V301 is attached to the 1 st pipe 331. The 1 st valve V301 is a switching valve for opening and closing the flow path of the 1 st pipe 331. The 1 st valve V301 controls the flow of the etching liquid flowing through the 1 st pipe 331. Specifically, when the 1 st valve V301 is opened, the etching liquid flows to the 1 st nozzle 311 and the 2 nd nozzle 312 via the 1 st pipe 331. As a result, the etching liquid is discharged from the 1 st nozzle 311 and the 2 nd nozzle 312. When the 1 st valve V301 is closed, the flow of the etching liquid is blocked, and the 1 st nozzle 311 and the 2 nd nozzle 312 stop ejecting the etching liquid.

The 1 st valve V301 also functions as an adjustment valve for adjusting the flow rate of the etching liquid flowing through the 1 st pipe 331. The 1 st valve V301 is, for example, a solenoid valve. The 1 st valve V301 is controlled by the control device 110 (control unit 111).

The etching liquid supply unit 306 is configured by an etching liquid supply source 321, a1 st pipe 331, a1 st valve V301, a1 st nozzle 311, and a2 nd nozzle 312, and supplies the etching liquid to the substrate W.

A heater (not shown) may be attached to the 1 st pipe 331. The heater heats the etching liquid so that the etching liquid is at a high temperature. Further, the heater may not be provided, and the etching liquid at normal temperature may be ejected from the 1 st nozzle 311 and the 2 nd nozzle 312.

A drain line 341 is connected to the bottom of the treatment tank 303. A 2 nd valve V302 is installed in the drain line 341. The 2 nd valve V302 is an on-off valve for opening and closing the flow path of the drain line 341. The 2 nd valve V302 is, for example, a solenoid valve. The 2 nd valve V302 is controlled by the control device 110 (control unit 111). When the processing liquid is stored in the processing tank 303, the control device 110 (control unit 111) closes the 2 nd valve V302. On the other hand, when the processing liquid is discharged from the processing tank 303, the control device 110 (control unit 111) opens the 2 nd valve V302. When the 2 nd 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 via the drain line 341.

The substrate processing apparatus 100 may further include a pressure reducing portion (not shown) for reducing the pressure in the chamber 302. The pressure reducing portion includes, for example, an exhaust pump. The exhaust pump is, for example, a vacuum pump. The pressure reducing portion may discharge the gas in the chamber 302 when the lid portion 302a is in the closed state, and reduce the pressure in the chamber 302 to be less than the atmospheric pressure.

Next, a substrate W processed by the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 7 and 8. Fig. 7 is a schematic partially enlarged perspective view of the substrate W processed by the substrate processing apparatus 100. Fig. 8 is a schematic partial enlarged view of the substrate W processed by the substrate processing apparatus 100. In fig. 7, a direction perpendicular to the main surface of the substrate S of the substrate W is denoted as a z direction, and a direction perpendicular to the z direction is denoted as an x direction and a y direction.

As shown in fig. 7 and 8, the substrate W has a base material S and a laminated structure L. The substrate S is in the form of a thin plate extending in the xy plane. The laminated structure L is formed on the main surface Sa of the substrate S. The substrate S supports the laminated structure L. The laminated structure L is formed to extend in the z-direction from the main surface Sa of the substrate S. The substrate S includes, for example, a semiconductor. The material of the substrate S is not particularly limited, and includes, for example, silicon (hereinafter, may be referred to as Si). In this embodiment, the substrate S includes monocrystalline silicon. The main surface Sa is an example of "one surface" of the present invention. The z direction is an example of the "1 st direction" of the present invention.

The laminated structure L has a plurality of 1 st layers M1 and a plurality of 2 nd layers M2. The 1 st layer M1 and the 2 nd layer M2 are alternately laminated. The 1 st layer M1 and the 2 nd layer M2 are stacked in the z-direction intersecting the main surface Sa of the substrate S.

The 1 st layer M1 and the 2 nd layer M2 include, for example, semiconductors. The 1 st layer M1 and the 2 nd layer M2 are not particularly limited, and include the same elements, for example. The 1 st layer M1 and the 2 nd layer M2 contain, for example, silicon element. In this embodiment, the 1 st layer M1 contains silicon germanium (hereinafter, sometimes referred to as SiGe). Layer 2M 2 comprises polysilicon or monocrystalline silicon. As described above, the substrate W having the Si layer and the SiGe layer stacked thereon is used for manufacturing a Semiconductor device such as a MOSFET (Metal-Oxide-Semiconductor FIELD EFFECT Transistor).

The composition ratio of germanium (hereinafter, sometimes referred to as Ge) contained in the 1 st layer M1 is less than 50%. The composition ratio of Ge contained in the 1 st layer M1 is not particularly limited, and is, for example, 5% to 25%. In this embodiment, the composition ratio of Ge contained in the 1 st layer M1 is 20% or less.

Each of the plurality of 1 st layers M1 extends parallel to the main surface Sa of the substrate S. In the thickness direction (z direction) of the substrate S, the 1 st layer M1 is disposed between the 2 nd layers M2 or between the 2 nd layers M2 and the substrate S.

For example, the thickness (length along the z direction) of the 1 st layer M1 is 1nm or more and 50nm or less. For example, the thickness (length along the z direction) of the 2 nd layer M2 is 1nm or more and 50nm or less. The thickness of the 1 st layer M1 is not particularly limited, and may be smaller than that of the 2 nd layer M2, for example. In this embodiment, the thickness of the 1 st layer M1 is, for example, 5nm to 15 nm.

For example, the total of the thickness of the 1 st layer 1M 1 and the thickness of the 1 nd layer 2M 2 is 20nm to 100 nm. The laminated structure L includes, for example, a1 st layer M1 of 2 layers or more and 100 layers or less and a 2 nd layer M2 of 2 layers or more and 100 layers or less.

The substrate W has a recess R. The recess R is provided in the laminated structure L. The recess R is formed by, for example, dry etching the laminated structure L. The grooves R extend in a direction intersecting 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 recess R extends from the surface La of the laminated structure L toward the substrate S. In the present embodiment, the recess R extends from the surface La of the laminated structure L to the substrate S. In the present embodiment, the groove R extends into the substrate S, but an etching stop layer (not shown) may be provided on the main surface Sa of the substrate S, so that the groove R does not reach the inside of the substrate S.

The recess R is formed in an elongated shape having a long side direction and a short side direction when viewed from the thickness direction (z direction) of the substrate W. 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 groove R in the short side direction may be referred to as the width of the groove R.

The width of the groove R is nano-scale. For example, the width of the groove R is 20nm or more and 300nm or less. The width of the groove R may be 50nm or more and 200nm.

The substrate W has a plurality of recesses C. The plurality of recesses C are connected to the recess R. The concave portions C are arranged between the 2 nd layers M2 or between the 2 nd layers M2 and the substrate S in the thickness direction (z direction). The concave portion C is formed so as to extend in the x direction intersecting the thickness direction (z direction). The x-direction is an example of the "2 nd direction" of the present invention.

Hereinafter, the length of the recess C in the z direction may be referred to as the width of the recess C, and the length of the recess C in the x direction may be referred to as the depth of the recess C. The aspect ratio of the concave portion C (the size of the depth of the concave portion C with respect to the width) is not particularly limited, and is, for example, 10 to 100. In the present embodiment, the aspect ratio of the concave portion C is 20 or more. In other words, the depth (length in the x direction) of the concave portion C is 20 times or more the width (length in the z direction) of the concave portion C. In the present embodiment, the aspect ratio of the concave portion C is, for example, 30 to 50.

Here, the recess C is formed by introducing an etching liquid into the recess R to wet-etch the 1 st layer M1. At this time, even if the etching solution has a function of selectively etching the 1 st layer M1 of the 1 st layer M1 and the 2 nd layer M2, the etching selectivity is lowered when a substance having similar chemical properties is contained between the 1 st layer M1 and the 2 nd layer M2. Specifically, it is difficult for the etching solution to etch only the 1 st layer M1, and the 2 nd layer M2 is also etched. Therefore, the greater the aspect ratio of the portion to be etched (the recess C), the thinner the thickness of the 2 nd layer M2 will be etched, so that the semiconductor device manufactured using the substrate W may not obtain the desired characteristics.

As will be described in detail below, according to the present embodiment, the 1 st layer M1 can be selectively etched even in the case where the aspect ratio of the recess C is large. This can suppress the thickness of the 2 nd layer M2 from becoming thin.

Next, a substrate processing method according to the present embodiment will be described with reference to fig. 9 to 18. Fig. 9 is a flowchart showing a substrate processing method according to the present embodiment. Fig. 10 to 18 are enlarged cross-sectional views of the periphery of the recess R for explaining the substrate processing method according to 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. Step S6 is an example of the "hydrophobizing step" of the present invention. In addition, step S7 is an example of the "post-hydrophobization replacement step" of the present invention. In addition, step S8 is an example of the "etching process" of the present invention. In addition, step S9 is an example of the "post-etching replacement process" of the present invention.

As shown in fig. 9, in step S1, the oxide film of the substrate W is removed. Specifically, the natural oxide film (not shown) formed in the recess R of the substrate W shown in fig. 10 is removed. The substrate W processed by the substrate processing apparatus 100 has a base material S, a laminated structure L, and a recess R provided in the laminated structure L. In step S1, the recess C is not yet formed in the substrate W.

In this embodiment, the natural oxide film of the substrate W is removed using the processing unit 300 shown in fig. 5 or a processing unit having the same structure as the processing unit 300. Specifically, the chemical solution is stored in the processing tank 303. The chemical solution is a chemical solution capable of removing a natural oxide film of the substrate W. The chemical solution is not particularly limited, and contains hydrofluoric acid, for example. The chemical solution contains, for example, hydrofluoric acid diluted to several times or more and several times or less than 1000 times (dilute hydrofluoric acid).

For example, the control unit 111 moves the holding unit 250 to the processing position, and thereby immerses the substrate W carried into the chamber 202 in the chemical solution stored in the processing bath 303. Thereby, the natural oxide film formed on the inner surface of the recess R of the substrate W is removed by the chemical solution. When a predetermined time has elapsed since the substrate W was immersed in the chemical solution, the controller 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 the processing unit 200 having the same configuration as the processing unit 200.

For example, the control unit 111 moves the holding unit 250 from the chamber 302 into the chamber 202, and disposes the substrate W in the chamber 202. The control unit 111 supplies a rinse solution from the 1 st nozzle 211 and the 2 nd nozzle 212 to the substrate W. In the present embodiment, the control unit 111 blows a mist of the rinse liquid toward the substrate W from the 1 st nozzle 211 and the 2 nd nozzle 212. Thereby, the chemical solution adhering to the surface of the substrate W is rinsed off by the rinse solution. When a predetermined time has elapsed since the start of the supply of the rinse liquid to the substrate W, the control unit 111 stops the supply of the rinse liquid. In the present embodiment, the rinse solution is DIW.

Next, in step S3, a portion of the 1 st layer M1 is etched. Specifically, a portion of the 1 st layer M1 is etched using the processing unit 300 shown in fig. 5.

The control unit 111 moves the holding unit 250 from the chamber 202 into the chamber 302, and disposes the substrate W in the chamber 302. The control unit 111 supplies the etching liquid E1 from the 1 st nozzle 311 and the 2 nd nozzle 312 to the processing tank 303. Furthermore, the etching solution E1 may be stored in the processing tank 303 before the substrate W is moved into the chamber 302.

The etching liquid E1 is a liquid capable of etching the 1 st layer M1. The etching amount (etching rate) of the etching solution E1 to the 1 st layer M1 is preferably about 5 times or more, more preferably about 10 times or more, as compared with the etching amount (etching rate) of the etching solution E1 to the 2 nd layer M2. In the present embodiment, the etching amount of the etching solution E1 to the 1 st layer M1 is about 20 times as large as the etching amount of the etching solution E1 to the 2 nd layer M2.

The composition of the etching solution E1 is appropriately set according to the material of the 1 st layer M1 and the 2 nd layer M2, and is not particularly limited. In the present embodiment, the etching solution E1 is an aqueous solution obtained by mixing an ester solvent, ammonium fluoride, and hydrogen peroxide water.

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 solution E1.

As shown in fig. 11, the etching liquid E1 flows into the grooves R. Then, the etching solution E1 etches at least the 1 st layer M1. In the present embodiment, the etching liquid E1 etches the 1 st layer M1 at an etching rate about 20 times higher than that of the 2 nd layer M2. Thus, a recess C is formed in the laminated structure L (see fig. 12). Then, when a predetermined time elapses after the holding unit 250 is moved into the processing tank 303, the control unit 111 moves the holding unit 250 from the standby position to the processing position. That is, the control unit 111 pulls the holding unit 250 from the processing tank 303. The depth (length in the x direction) of the concave portion C formed in step S3 is smaller than the depth of the concave portion C shown in fig. 8. The aspect ratio of the recess 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 into the chamber 202, and disposes the substrate W in the chamber 202. The control unit 111 supplies a rinse solution from the 1 st nozzle 211 and the 2 nd nozzle 212 to the substrate W. In the present embodiment, the control unit 111 blows a mist of rinse liquid (DIW here) from the 1 st nozzle 211 and the 2 nd nozzle 212 toward the substrate W (see fig. 2). Thereby, the etching solution E1 adhering to the surface of the substrate W is rinsed off by the rinse solution. When a predetermined time has elapsed since the start of the supply of the rinse liquid to the substrate W, the control unit 111 stops the supply of the rinse liquid.

Next, in step S5, the rinse liquid attached to the substrate W is replaced with a replacement liquid. Specifically, the replacement liquid is a liquid capable of replacing the rinse liquid (here, DIW) present on the surface of the substrate W. In addition, the substitution liquid is preferably a liquid having affinity for the hydrophobizing agent SMT. The displacement liquid may comprise, for example, an organic solvent or an alcohol. In this embodiment, the substitution liquid contains IPA.

For example, the control unit 111 supplies the replacement liquid from the 3 rd nozzle 213 and the 4 th nozzle 214 to the substrate W. In the present embodiment, the control unit 111 blows the atomized replacement liquid from the 3 rd nozzle 213 and the 4 th nozzle 214 toward the substrate W (see fig. 3). Thereby, the rinse liquid adhering to the surface of the substrate W is replaced with the replacement liquid. In the present embodiment, the unused replacement liquid is supplied from the 3 rd nozzle 213 and the 4 th nozzle 214 to the substrate W. Further, the used replacement liquid recovered after being used 1 or more times may be supplied to the substrate W.

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

As shown in fig. 12, in step S5, the replacement liquid blown to the substrate W is preferably evaporated without remaining in the grooves R and the recesses C. In step S5, the replacement liquid may remain in the grooves R and the recesses C.

Next, in step S6, a hydrophobizing agent SMT is supplied to the substrate W to hydrophobize the surface of the 2 nd layer M2.

For example, the control unit 111 supplies the hydrophobizing agent SMT from the 5 th nozzle 215 and the 6 th nozzle 216 to the substrate W. In the present embodiment, the control unit 111 blows the mist-like hydrophobizing agent SMT from the 5 th nozzle 215 and the 6 th nozzle 216 toward the substrate W (see fig. 4). As a result, as shown in fig. 13, the hydrophobizing agent SMT for hydrophobizing the surface of the 2 nd layer M2 flows into the grooves R and the recesses C. Thus, the surface of layer 2M 2 is hydrophobized. Specifically, the hydrophobizing agent SMT coats at least the surface of the 2 nd layer M2. In addition, the hydrophobizing agent SMT silylates at least the surface of layer 2M 2. In this embodiment, the hydrophobizing agent SMT hydrophobizes the surfaces of both the 1 st layer M1 and the 2 nd layer M2. Therefore, the surfaces of both the 1 st layer M1 and the 2 nd layer M2 are rendered hydrophobic. Specifically, the hydrophobizing agent SMT coats the surfaces of both the 1 st layer M1 and the 2 nd layer M2. In addition, the hydrophobizing agent SMT silylates the surfaces of both the 1 st layer M1 and the 2 nd layer M2.

More specifically, the silane groups contained in the hydrophobizing agent SMT are bonded to both Si-O groups and Ge-O groups. That is, the silane groups contained in the hydrophobizing agent SMT are bonded to both the surface of the 1 st layer M1 and the surface of the 2 nd layer M2. A hydrophobic layer Ls to which silane groups of the hydrophobizing agent SMT are bonded is formed on the surface of the 1 st layer M1 and the surface of the 2 nd layer M2 (see fig. 14). In other words, the surface of the 1 st layer M1 and the surface of the 2 nd layer M2 are covered with the hydrophobic layer Ls containing the hydrophobizing agent SMT. Further, for ease of understanding, the water-repellent layer Ls is depicted with a thick solid line in the figure.

In the present embodiment, the unused hydrophobizing agent SMT is supplied from the 5 th nozzle 215 and the 6 th nozzle 216 to the substrate W. Furthermore, an unused hydrophobizing agent SMT is supplied into the recess R. Further, the used hydrophobizing agent SMT recovered after being used 1 or more times may be supplied to the substrate W.

When a predetermined time has elapsed since the start of the supply of the hydrophobizing agent SMT to the substrate W, the control unit 111 stops the supply of the hydrophobizing agent SMT.

Next, in step S7, the hydrophobizing agent SMT present on the substrate W is replaced with the replacement liquid so that the hydrophobizing agent SMT (the hydrophobic layer Ls) remains at least on the surface of the 2 nd layer M2. Specifically, the substitution liquid is a liquid capable of substituting the hydrophobizing agent SMT existing on the substrate W. In addition, the substitution liquid is preferably a liquid having affinity for the hydrophobizing agent SMT. The displacement liquid may comprise, for example, an organic solvent or an alcohol. In this embodiment, the substitution liquid contains IPA.

For example, the control unit 111 supplies the replacement liquid from the 3 rd nozzle 213 and the 4 th nozzle 214 to the substrate W. In the present embodiment, the control unit 111 blows the atomized replacement liquid from the 3 rd nozzle 213 and the 4 th nozzle 214 toward the substrate W (see fig. 3). Thereby, the hydrophobizing agent SMT existing on the substrate W is replaced with the replacement liquid. However, at least the hydrophobizing agent SMT (hydrophobic layer Ls) on the surface of the 2 nd layer M2 remains. In the present embodiment, the hydrophobizing agent SMT is replaced with a replacement liquid so that the hydrophobic layer Ls remains. In the present embodiment, an unused replacement liquid is supplied to the substrate W. Further, the used replacement liquid may be supplied to the substrate W.

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

As shown in fig. 14, in step S7, the replacement liquid blown to the substrate W is preferably evaporated without remaining in the grooves R and the recesses C. In step S7, the replacement liquid may remain in the grooves R and the recesses C.

Next, in step S8, the 1 st layer M1 is selectively etched. Specifically, the 1 st 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 into the chamber 302, and disposes the substrate W in the chamber 302. The control unit 111 supplies the etching liquid E2 from the 1 st nozzle 311 and the 2 nd nozzle 312 to the processing tank 303. The etching liquid E2 is a liquid capable of etching the 1 st layer M1. Furthermore, the etching solution E2 may be stored in the processing tank 303 before the substrate W is moved into the chamber 302.

The etching amount (etching rate) of the etching solution E2 to the 1 st layer M1 is preferably about 5 times or more, more preferably about 10 times or more, as compared with the etching amount (etching rate) of the etching solution E2 to the 2 nd layer M2. In the present embodiment, the etching amount of the etching solution E2 to the 1 st layer M1 is about 20 times as large as the etching amount of the etching solution E2 to the 2 nd layer M2.

The composition of the etching solution E2 is appropriately set according to the material of the 1 st layer M1 and the 2 nd layer M2, and is not particularly limited. In the present embodiment, the etching solution E2 is an aqueous solution obtained by mixing an ester solvent, ammonium fluoride, and hydrogen peroxide water. In the present 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 solution E2.

As shown in fig. 15, in a state where the surface of the 2 nd layer M2 is hydrophobized, the etching liquid E2 flows into the grooves R and the recesses C. At this time, the etching solution E2 selectively etches the 1 st layer M1 of the 1 st layer M1 and the 2 nd layer M2 as described below. Specifically, a part of the inner surface of the concave portion C is not covered with the water-repellent layer Ls. Thus, layer 1M 1 is etched, while layer 2M 2 is not substantially etched. Thereby, the length of the concave portion C in the x direction becomes larger. In other words, the depth of the concave portion C becomes large (see fig. 16).

Then, when a predetermined time elapses after the holding unit 250 is moved into the processing tank 303, the control unit 111 moves the holding unit 250 from the standby position to the processing position. That is, the control unit 111 pulls the holding unit 250 from the processing tank 303. The predetermined time is shorter than the time from the movement of the holding portion 250 into the processing tank 303 until the hydrophobizing agent SMT disappears from the surface of the 2 nd layer M2. That is, the control unit 111 shifts from the etching step (step S8) to the subsequent post-etching replacement step (step S9) before the hydrophobizing agent SMT is disappeared from the surface of the 2 nd layer M2 by the etching liquid E2. The predetermined time is, for example, 1 minute to 60 minutes. The predetermined time may be, for example, 5 minutes to 30 minutes, or 10 minutes to 25 minutes.

In step S8, the 1 st layer M1 is etched, while the 2 nd layer M2 is not substantially etched, which is considered to be the following reason. Specifically, the silane groups are bonded to the si—o groups and also to the ge—o groups, so that the surface of the 1 st layer M1 and the surface of the 2 nd layer M2 are both rendered hydrophobic. However, the Ge-O group is very soluble in water compared to the Si-O group. Thus, the 1 st layer M1 containing Ge-O groups is more easily etched than the 2 nd layer M2 containing no Ge-O groups. Therefore, it is considered that the water-repellent layer Ls is removed by etching in the 1 st layer M1, and the water-repellent layer Ls is easily left in the 2 nd layer M2 because the etching proceeds slowly. Furthermore, the solubility of GeO ₂ in water was 4.47g/L and the solubility of SiO ₂ in water was 0.12g/L. That is, geO ₂ has a solubility in water of about 37 times as compared to 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 into the chamber 202, and disposes the substrate W in the chamber 202. The control unit 111 supplies a rinse solution from the 1 st nozzle 211 and the 2 nd nozzle 212 to the substrate W. In the present embodiment, the control unit 111 blows a mist of rinse liquid (DIW here) toward the substrate W from the 1 st nozzle 211 and the 2 nd nozzle 212. Thereby, the etching solution E2 adhering to the surface of the substrate W is rinsed off by the rinse solution. In the present embodiment, an unused rinse solution is supplied to the substrate W. Further, the used rinse liquid may be supplied to the substrate W.

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

Next, in step S10, the control unit 111 determines whether or not the selective etching of step S8 has been performed a predetermined number of times (for example, 5 times).

When the control unit 111 determines in step S10 that the selective etching of step S8 is not performed a predetermined number of times, the process returns to step S5. Then, after step S5, in step S6, the hydrophobizing agent SMT is flowed into the recess R and the recess C as shown in fig. 17. As a result, as shown in fig. 18, a water repellent layer Ls is formed on the surface of the recess R and the surface of the recess C. In other words, the surface of the 1 st layer M1 and the surface of the 2 nd layer M2 are covered with the hydrophobic layer Ls. The step S7 is then the same as the 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 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.

Embodiment 1 of the present invention has been described above with reference to fig. 1 to 18. In the present embodiment, as described above, the hydrophobizing step (step S6) and the etching step (step S8) are repeated a predetermined number of times, the hydrophobizing step (step S6) supplies the hydrophobizing agent SMT into the grooves R, and the etching step (step S8) supplies the etching liquid E2 into the grooves R in a state where the surface of the 2 nd layer M2 is hydrophobized, thereby selectively etching the 1 st layer M1. Therefore, the 2 nd layer M2 can be suppressed from being etched, and the 1 st layer M1 can be selectively etched. Further, by repeating the hydrophobizing step (step S6) and the etching step (step S8) a predetermined number of times, the concave portion C having a large aspect ratio can be formed. As described above, in the present embodiment, the etching selectivity can be improved.

In addition, as described above, in the etching step (step S8), the 1 st layer M1 is selectively etched, whereby the plurality of recesses C connected to the grooves R are formed so as to extend in the 2 nd direction (y direction). Therefore, the plurality of concave portions C connected to the groove R can be easily formed substantially parallel to the substrate W.

As described above, the length of the recess C in the 2 nd direction (y direction) is 20 times or more the length of the recess C in the 1 st direction (z direction). That is, the aspect ratio of the concave portion C is 20 or more. In general, when the etching liquid has a function of etching both the specific layer (layer 1M 1) and the other layer (layer 2M 2), the larger the aspect ratio of the concave portion C is, the larger the etching amount of the other layer (layer 2M 2) is. However, in the present embodiment, by repeating the hydrophobization step (step S6) and the etching step (step S8), the concave portion C having an aspect ratio of, for example, 20 or more can be easily formed. Therefore, the present invention is particularly effective in forming the concave portion C having a large aspect ratio.

As described above, the post-hydrophobizing replacement step (step S7) is provided, and the post-hydrophobizing replacement step (step S7) replaces the hydrophobizing agent SMT with the replacement liquid so that the hydrophobizing agent SMT remains at least on the surface of the 2 nd layer M2 by supplying the replacement liquid into the grooves R. Therefore, the hydrophobizing agent SMT can be left on the surface of the 2 nd layer M2, and the etching solution E2 can be suppressed from being hard to penetrate into the grooves R.

As described above, the post-etching replacement step (step S9) is provided after the etching step (step S8), and the post-etching replacement step (step S9) replaces the etching solution E2 with the rinse solution by supplying the rinse solution into the recess R. Therefore, the etching liquid E2 can be easily removed from the inside of the groove R.

As described above, before the hydrophobizing agent SMT (hydrophobic layer Ls) is removed from the surface of the 2 nd layer M2 by the etching solution E2, the process shifts from the etching process (step S8) to the post-etching replacement process (step S9). Therefore, the 2 nd layer M2 can be further suppressed from being etched by the etching liquid E2. This can further improve the etching selectivity.

In addition, as described above, layer 1M 1 comprises silicon germanium and layer 2M 2 comprises polysilicon or monocrystalline silicon. Thus, when the 1 st layer and the 2 nd layer contain the same substance or substances having similar chemical properties (here, the same group elements), the etching selectivity tends to be low. The invention is particularly effective in this case to improve etching selectivity.

As described above, the composition ratio of Ge contained in the 1 st layer M1 is 20% or less. Thus, in the case where more than 80% of the 1 st layer and the 2 nd layer are formed of the same substance, the etching selectivity is more likely to be lowered. The invention is very effective in this case to improve the etching selectivity.

In addition, as described above, the hydrophobizing agent SMT silylates at least the surface of the 2 nd layer M2. Therefore, the surface of the 2 nd layer M2 can be easily hydrophobized.

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

In addition, as described above, in the hydrophobizing step (step S6), the 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 the used hydrophobizing agent SMT.

[ Embodiment 2]

Next, embodiment 2 of the present invention will be described with reference to fig. 19. Fig. 19 is a flowchart showing a substrate processing method performed by the substrate processing apparatus 100 according to embodiment 2. In embodiment 2, an example in which IPA is used as the rinse liquid in the post-etching replacement step (step S9) will be described. The substrate processing method of the present embodiment includes steps S1 to S4 and steps S6 to S10.

As shown in fig. 19, steps S1 to S3 are the same as embodiment 1.

Next, in step S4, the substrate W is rinsed. The rinse liquid is preferably a liquid having affinity for the hydrophobizing agent SMT. The rinse solution may comprise, for example, an organic solvent or an alcohol. In the present embodiment, IPA is used as the rinse liquid.

The control unit 111 blows a mist of rinse liquid (IPA here) toward the substrate W from the 1 st nozzle 211 and the 2 nd nozzle 212. Thereby, the etching solution E1 adhering to the surface of the substrate W is rinsed off by the rinse solution. When a predetermined time has elapsed since the start of the supply of the rinse liquid to the substrate W, the control unit 111 stops the supply of the rinse liquid.

Next, step S6 to step S8 are performed in the same manner as in embodiment 1.

Next, in step S9, the substrate W is rinsed. The rinse liquid is preferably a liquid having affinity for the hydrophobizing agent SMT. The rinse solution may comprise, for example, an organic solvent or an alcohol. In the present embodiment, IPA is used as the rinse liquid.

The control unit 111 blows a mist of rinse liquid (IPA here) toward the substrate W from the 1 st nozzle 211 and the 2 nd nozzle 212. Thereby, the etching solution E2 adhering to the surface of the substrate W is rinsed off by the rinse solution. When a predetermined time has elapsed since the start of the supply of the rinse liquid to the substrate W, the control unit 111 stops the supply of the rinse liquid.

Next, step S10 is executed in the same manner as embodiment 1. When the control unit 111 determines in step S10 that the selective etching of step S8 is not performed a predetermined number of times, the process returns to step S6.

As described above, the process on the substrate W is ended.

The structure of the substrate processing apparatus 100 according to embodiment 2 and other substrate processing methods are the same as those according to embodiment 1.

Embodiment 2 of the present invention has been described above with reference to fig. 19. In the present embodiment, as described above, the rinse liquid used in the post-etching replacement step (step S9) contains IPA. Therefore, for example, compared with the case of using DIW as the rinse liquid, the surface tension of the rinse liquid can be reduced. Thus, even when the width (length in the z direction) of the concave portion C is small (for example, 5nm or more and 15nm or less), the rinse liquid is prevented from being difficult to penetrate into the concave portion C. Therefore, by using IPA as the rinse liquid, it is possible to suppress difficulty in removing the etching liquid E2 from the recess C. This can prevent the hydrophobizing agent SMT from being easily permeated into the concave portion C in the subsequent hydrophobizing step (step S6). As a result, the decrease in etching selectivity can be suppressed.

Other effects of embodiment 2 are the same as those of embodiment 1.

Next, a confirmation experiment performed to confirm the effects of the above-described embodiments will be described with reference to fig. 20 to 22. First, an experiment for confirming whether or not there is a relationship between the hydrophobization treatment and the etching amounts of Si and SiGe will be described with reference to fig. 20 and 21. Fig. 20 shows experimental results of the relationship between the presence or absence of the hydrophobization treatment and the etching amount to Si. Fig. 21 is an experimental result showing the relationship between the presence or absence of the hydrophobization treatment and the etching amount of SiGe.

In this verification experiment, the same substrate W as that of the above embodiment was used as the substrate W. Specifically, a substrate W having a base material S including single crystal silicon and a stacked structure L including a1 st layer M1 including SiGe and a2 nd layer M2 including polycrystalline silicon is used. The composition ratio of Ge contained in layer 1M 1 was about 15%.

Then, a plurality of substrates W are prepared, and a hydrophobization treatment is performed on one substrate W, while a hydrophobization treatment is not performed on the other substrate W. In this confirmation experiment, steps S3, S4, and S10 were not performed.

Specifically, the steps S1 to S2, S5 to S9 are performed on a substrate W. The steps S1 to S2, S7 to S9 are performed on the other substrate W.

Then, the relationship between the etching time in step S8 performed on these substrates W and the etching amounts of the 1 st layer M1 (SiGe) and the 2 nd layer M2 (Si) was studied. The results are shown in fig. 20 and 21.

Referring to fig. 20, it was found that the surface of Si was subjected to a hydrophobization treatment, thereby degrading the etching property of Si. Specifically, when the surface of Si is not subjected to the hydrophobization treatment (black dots in fig. 20), si is etched immediately after the substrate W is immersed in the etching solution E2. On the other hand, in the case of performing the hydrophobizing treatment on the surface of Si (white circles in fig. 20), si is not substantially etched until 25 minutes or more pass from the time of immersing the substrate W in the etching solution E2. Then, si is etched after 25 minutes or more from immersion in the etching solution E2. Therefore, it was found that by performing the hydrophobizing treatment on the surface of Si, the etching property for Si can be reduced before a predetermined time (for example, 25 minutes or more) elapses.

On the other hand, referring to fig. 21, it was found that even if the surface of SiGe was subjected to the hydrophobization treatment, the etching property to SiGe was not substantially lowered. Specifically, the SiGe is etched immediately after the substrate W is immersed in the etching liquid E2, both when the surface of the SiGe is subjected to the hydrophobization treatment (white circles in fig. 21) and when the surface of the SiGe is not subjected to the hydrophobization treatment (black dots in fig. 21).

From the results shown in fig. 20 and 21, it was confirmed that the layer 1M 1 can be etched without substantially etching the layer 2M 2 by performing the hydrophobization treatment on the surface of the layer 1M 1 and the surface of the layer 2M 2.

Next, an experiment for confirming the effect obtained by using IPA as a rinse solution in the post-etching rinse step (step S9) and the effect obtained by using unused hydrophobizing agent SMT will be described with reference to fig. 22. Fig. 22 is a graph showing experimental results for confirming the effect obtained by using IPA as a rinse solution in the post-etching rinse step and the effect obtained by using unused hydrophobizing agent SMT. In this confirmation experiment, examples 1 to 3 corresponding to the present embodiment and comparative example 1 not corresponding to the present embodiment were used. The following table 1 shows a comparison of the production conditions of examples 1 to 3 and comparative example 1.

TABLE 1

	Comparative example 1	Example 1	Example 2	Example 3
					Hydrophobization treatment	Without any means for	Has the following components	Has the following components	Has the following components
Hydrophobing agent	-	Used after using	Unused and not used	Unused and not used
					Flushing liquid	DIW	DIW	DIW	IPA

Example 1

Referring to table 1, the same substrate W as that of the above embodiment was used as the substrate W in example 1. Specifically, a substrate W having a base material S including single crystal silicon and a stacked structure L including a1 st layer M1 including SiGe and a2 nd layer M2 including polycrystalline silicon is used. The composition ratio of Ge contained in layer 1M 1 was about 15%.

Then, the steps S1 to S2, S5 to S10 are performed on the substrate W. The etching time in step S8 was set to 5 minutes/time. The predetermined number of times that is the criterion in step S10 is set to "5 times".

In step S6, the used hydrophobizing agent SMT is used and recovered 1 or more times. In step S9, DIW is used as the rinse liquid.

Example 2

In example 2, the same substrate W as in example 1 was used. The same process as in example 1 was performed on the substrate W. However, in example 2, the unused hydrophobizing agent SMT was used in step S6.

Example 3

In example 3, the same substrate W as in example 1 was used. The same process as in example 1 was performed on the substrate W. However, in example 3, unused hydrophobizing agent SMT was used in step S6. In step S9, IPA is used as the rinse liquid.

Comparative example 1

In comparative example 1, the same substrate W as in example 1 was used. The steps S1 to S2, S7 to S10 are performed on the substrate W. That is, in comparative example 1, the hydrophobizing treatment was not performed. In step S9, DIW is used as the rinse liquid.

Thereafter, for examples 1 to 3 and comparative example 1, the etching amount of the 1 st layer M1 (SiGe) with respect to the etching amount of the 2 nd layer M2 (Si) in the recess C was calculated. The value calculated for comparative example 1 was normalized by setting "1". The results are shown in fig. 22.

Referring to fig. 22, it is apparent that the substrate W is subjected to the hydrophobization treatment to improve the etching selectivity. Specifically, the calculated value of the etching amount of the 1 st layer M1 with respect to the etching amount of the 2 nd layer M2 is larger in each of examples 1 to 3 than in comparative example 1.

In addition, it was found that the etching selectivity was improved by using the unused hydrophobizing agent SMT. Specifically, example 2 is larger than example 1 with respect to the calculated value of the etching amount of layer 1M 1 relative to the etching amount of layer 2M 2. The reason for this is considered as follows. That is, the unused hydrophobizing agent SMT has fewer impurities than the used hydrophobizing agent SMT used 1 or more times, and thus the silane groups can be bonded to almost all si—o groups on the surface of the substrate W. It is therefore considered that by using the unused hydrophobizing agent SMT, the etching selectivity is improved.

In addition, it was found that by using IPA as the rinse liquid in step S9, the etching selectivity was improved as compared with the case of using DIW as the rinse liquid. Specifically, example 3 is larger than example 2 with respect to the calculated value of the etching amount of layer 1M 1 relative to the etching amount of layer 2M 2. The reason for this is considered as follows. That is, the thickness of the 1 st layer M1 is very small (for example, 5nm or more and 15nm or less). Therefore, in the case of using DIW as the rinse liquid, the surface tension of DIW is relatively large, so that it is difficult to enter into the concave portion C. On the other hand, in the case of using IPA as the rinse liquid, the surface tension of the IPA is smaller than that of DIW, so that the rinse liquid relatively easily enters into the concave portion C. Therefore, by using IPA as the rinse liquid, the etching liquid E2 is easily removed from the recess C. In this way, in the subsequent hydrophobizing step (step S6), the hydrophobizing agent SMT is likely to infiltrate into the concave portion C. Therefore, by using IPA as the rinse liquid, a decrease in etching selectivity can be suppressed.

The embodiments of the present invention have been described above with reference to the drawings. However, the present invention is not limited to the above embodiments, and may be implemented in various modes within a scope not departing from the gist thereof. The plurality of components disclosed in the above embodiments may be appropriately changed. For example, some of all the components shown in one embodiment may be added to the components of another embodiment, or some of all the components shown in one embodiment may be deleted from the embodiment.

The drawings schematically show the respective components in the main body for the convenience of understanding the invention, and the thickness, length, number, interval, and the like of the components shown in the drawings may be different from those of the actual ones for the convenience of manufacturing the drawings. It should be noted that the configuration of each component shown in the above-described embodiment is not particularly limited, and various modifications may be made without substantially departing from the effects of the present invention.

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

In embodiment 1, for example, the processing liquid is blown onto the substrate W in steps S2, S4 to S7, and S9. For example, in steps S2, S4 to S7, and S9, the substrate W may be immersed in the processing liquid stored in the processing tank 303 by using the processing unit 300 or the like.

In the above embodiment, the surface of both the 1 st layer M1 and the 2 nd layer M2 is covered with the hydrophobizing agent SMT, but the present invention is not limited to this. For example, a hydrophobizing agent SMT covering only the surface of layer 2M 2 may also be used.

In the above embodiment, the etching solution E1 was supplied to the substrate W from the state shown in fig. 10 after the removal of the natural oxide film, but the present invention is not limited to this. For example, the hydrophobizing 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 hydrophobization treatment may be performed after the removal of the natural oxide film and before the etching treatment.

In the above embodiment, the example in which the laminated structure L has the 1 st layer M1 including SiGe and the 2 nd layer M2 including Si has been described, but the present invention is not limited to this. For example, the laminated structure may also have a 1 st layer including SiN and a2 nd layer including SiO ₂. In addition, for example, the stacked structure may have a 1 st layer including GaAs and a2 nd layer including AlGaAs. Further, for example, the laminated structure may have a 1 st layer including GaN and a2 nd layer including AlGaN.

In the above embodiment, the case where the groove R is formed in an elongated shape having the long side direction and the short side direction when viewed from the thickness direction (z direction) of the substrate W has been described, but the present invention is not limited to this. The recess R may have, for example, a circular shape, an elliptical shape, or a square shape when viewed from the thickness direction of the substrate W.

Industrial applicability

The invention is applicable to a method and apparatus for processing a substrate.

[ Description of reference numerals ]

100 Substrate processing apparatus

111 Control part

206 Hydrophobizing agent supply part

306 Etching liquid supply part

C concave part

E2 etching solution

L-layered structure

M1:1 layer 1

M2:2 layer

R is groove

S: substrate

S6 step (hydrophobing procedure)

S7 step (replacement after hydrophobization)

S8 step (etching step)

S9 step (post-etching replacement step)

SMT hydrophobizing agent

Sa major surface (one side)

Claims (12)

1. A substrate processing method for processing a substrate having a base material, a plurality of 1 st layers and a plurality of 2 nd layers, includes:

A hydrophobizing step of supplying a hydrophobizing agent to a recess provided in a laminated structure supported by the base material, the hydrophobizing agent hydrophobizing surfaces of the 1 st layers and the 2 nd layers constituting the laminated structure, and

An etching step of selectively etching the layer 1 by supplying an etching liquid into the grooves in a state where the surface of the layer 2 is hydrophobized;

the hydrophobization step and the etching step are repeated a predetermined number of times.

2. The substrate processing method according to claim 1, wherein,

The 1 st layer and the 2 nd layer are laminated in the 1 st direction crossing one surface of the base material,

The groove extends along the 1 st direction,

In the etching step, the 1 st layer is selectively etched to form a plurality of recesses connected to the grooves so as to extend in a2 nd direction intersecting the 1 st direction.

3. The substrate processing method according to claim 2, wherein,

The length of the recess in the 2 nd direction is 20 times or more the length of the recess in the 1 st direction.

4. The substrate processing method according to any one of claim 1 to 3, wherein,

After the hydrophobizing step and before the etching step,

And a post-hydrophobizing substitution step of supplying a substitution liquid into the grooves to substitute the hydrophobizing agent with the substitution liquid so that the hydrophobizing agent remains at least on the surface of the layer 2.

5. The substrate processing method according to any one of claims 1 to 4, wherein,

After the etching process described above,

And a post-etching replacement step of supplying a rinse liquid into the recess to replace the etching liquid with the rinse liquid.

6. The substrate processing method according to claim 5, wherein,

The rinse solution comprises isopropyl alcohol.

7. The substrate processing method according to claim 5 or 6, wherein,

In the hydrophobizing step, the hydrophobizing agent coats at least the surface of the 2 nd layer,

Before the hydrophobizing agent is removed from the surface of the 2 nd layer by the etching liquid, the process is transferred from the etching step to the post-etching replacement step.

8. The substrate processing method according to any one of claims 1 to 7, wherein,

The layer 1 described above comprises silicon germanium,

The 2 nd layer contains polycrystalline silicon or monocrystalline silicon.

9. The substrate processing method according to any one of claims 1 to 8, wherein,

In the hydrophobizing step, the hydrophobizing agent silylates at least the surface of the 2 nd layer.

10. The substrate processing method according to any one of claims 1 to 9, wherein,

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

11. The substrate processing method according to any one of claims 1 to 10, wherein,

In the hydrophobizing step, the unused hydrophobizing agent is supplied into the grooves.

12. A substrate processing apparatus is provided with:

A hydrophobizing agent supply unit configured to supply a hydrophobizing agent to the substrate;

An etching liquid supply unit for supplying the etching liquid to the substrate, and

A control unit configured to control the hydrophobizing agent supply unit and the etching liquid supply unit;

The substrate has a base material, a plurality of 1 st layers and a plurality of 2 nd layers forming a laminated structure supported by the base material,

The hydrophobizing agent hydrophobizes the surface of the 2 nd layer,

The etching solution etches the 1 st layer,

The control unit controls the hydrophobizing agent supply unit to supply the hydrophobizing agent into the grooves provided in the laminated structure, thereby hydrophobizing the surfaces of the 2 nd layers,

The control part controls the etching liquid supply part to supply the etching liquid into the grooves in a state that the surface of the layer 2 is hydrophobized, thereby selectively etching the layer 1,

The control unit repeatedly performs hydrophobization of the surface of the 2 nd layer and selective etching of the 1 st layer a predetermined number of times.