JP2020132440A - Generator, substrate processing device, and substrate processing method - Google Patents

Abstract

To provide a generator, a substrate processing device, and a substrate processing method, which can efficiently generate a processing fluid from a processing liquid.SOLUTION: A generator 30 generates Caro's acid used in the processing of a substrate W from sulfuric acid. The generator 30 is provided with an exhaust part 311 and a generation part 35. The exhaust part 311 exhausts sulfuric acid. The generation part 35 generates plasma. A generation region E of the plasma is located above a transfer route R of sulfuric acid exhausted from the exhaust part 311. The exhaust part 311 preferably generates a liquid drop a of sulfuric acid by mixing sulfuric acid and a gas.SELECTED DRAWING: Figure 7

Description

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

The caroic acid generator described in Patent Document 1 includes a plasma generating means and a plasma irradiation chamber. The plasma generating means generates oxygen plasma. The plasma irradiation chamber produces caroic acid by irradiating a solution containing sulfuric acid stored in a resist removing tank with oxygen plasma.

JP-A-2002-53312

However, in the caroic acid generator described in Patent Document 1, oxygen plasma is irradiated only to a specific portion of sulfuric acid (treatment liquid) stored in the resist removing tank. The specific location is a location located on the surface layer of the sulfuric acid stored in the resist removing tank. Therefore, it is difficult to efficiently produce caroic acid because it does not contribute to the production of caroic acid (treatment fluid) other than sulfuric acid located on the surface layer.

An object of the present invention is to provide a generator, a substrate processing apparatus, and a substrate processing method capable of efficiently generating a processing fluid from a processing liquid.

According to the first aspect of the present invention, the generator produces the processing fluid used for processing the substrate from the processing liquid. The generator includes a discharge unit and a generator unit. The discharge unit discharges the treatment liquid. The generating part generates plasma. The plasma generation region is located on the movement path of the treatment liquid discharged from the discharge portion.

In the generator of the present invention, the processing fluid contains caroic acid. The treatment liquid contains sulfuric acid.

In the generator of the present invention, the discharge unit generates droplets of the treatment liquid by mixing the treatment liquid and a gas.

In the generator of the present invention, the discharge unit has a first supply port, a second supply port, a third supply port, a discharge port, a first passage, and a second passage. The gas is supplied to the first supply port. The treatment liquid is supplied to the second supply port. The gas is supplied to the third supply port. The discharge port communicates with the third supply port. The first passage communicates with the first supply port and also communicates with the discharge port. The second passage communicates with the second supply port and also communicates with the first passage.

In the generator of the present invention, the discharge unit has a first supply port, a second supply port, a first discharge port, and a second discharge port. The gas is supplied to the first supply port. The treatment liquid is supplied to the second supply port. The first outlet communicates with the second supply port. The second discharge port is formed so as to surround the first discharge port and communicates with the first supply port.

In the generator of the present invention, the gas comprises at least one of oxygen, nitrogen, argon and helium.

The generator of the present invention further includes a tube portion. The pipe portion protrudes from the discharge portion. The plasma generation region is located inside the tube portion.

In the generator of the present invention, the plasma is an inductively coupled plasma.

In the generator of the present invention, the generator generates oxygen plasma at normal pressure.

The generator of the present invention further includes a temperature control mechanism. The temperature control mechanism controls the temperature of the plasma generation region.

According to the second aspect of the present invention, the substrate processing apparatus includes the above-mentioned generation apparatus. The substrate processing apparatus supplies the processing fluid generated by the generation apparatus to the substrate.

According to the third aspect of the present invention, the substrate processing method includes a step of producing the sulfuric acid droplets by mixing the gas and sulfuric acid. The substrate processing method includes a step of producing caroic acid by moving the sulfuric acid droplets in the plasma generation region. The substrate processing method includes a step of supplying the caroic acid to the substrate.

According to the generator, the substrate processing apparatus, and the substrate processing method of the present invention, the processing fluid can be efficiently generated from the processing liquid.

It is a top view which shows typically the structure of the substrate processing apparatus which concerns on embodiment of this invention. It is a side view which shows typically the structure of the processing unit. It is a figure which shows typically the structure of the generator. It is a flow diagram which shows an example of the processing with respect to the substrate executed by the substrate processing apparatus. It is a flow chart which shows the caroic acid supply process. FIG. 1 is a diagram showing the operation of the generator. FIG. 2 is a diagram showing the operation of the generator. It is a figure which shows the modification of the generator. It is a figure which shows the 1st example of the apparatus configuration of the generator which generates SC1. It is a figure which shows the 2nd example of the apparatus configuration of the generator which generates SC1. It is a schematic diagram which shows the discharge part which is a modification of the discharge part.

An embodiment of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference numerals and the description is not repeated.

The substrate processing apparatus 100 according to the embodiment of the present invention will be described with reference to FIG. FIG. 1 is a plan view schematically showing the configuration of the substrate processing apparatus 100 according to the embodiment of the present invention.

As shown in FIG. 1, the substrate processing apparatus 100 is a single-wafer processing apparatus that processes substrates W one by one. The substrate processing apparatus 100 processes the substrate W so as to perform at least one of etching, surface treatment, character imparting, treatment film formation, removal of at least a part of the film, and cleaning of the substrate W.

The substrate W has a thin plate shape. Typically, the substrate W has a thin substantially disc shape. The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a field emission display (Field Display Display: FED), an optical disk substrate, a magnetic disk substrate, a magneto-optical disk substrate, a photomask substrate, and a ceramic substrate. And a substrate for solar cells.

The substrate processing device 100 includes a plurality of load port LPs, a plurality of processing units 1, a storage unit 2, and a control unit 3.

The load port LP holds the carrier C accommodating the substrate W. The processing unit 1 processes the substrate W conveyed from the load port LP.

The storage unit 2 includes a main storage device (for example, a semiconductor memory) such as a ROM (Read Only Memory) and a RAM (Random Access Memory), and may further include an auxiliary storage device (for example, a hard disk drive). The main storage device and / or the auxiliary storage device stores various computer programs executed by the control unit 3.

The control unit 3 includes processors such as a CPU (Central Processing Unit) and an MPU (Micro Processing Unit). The control unit 3 controls each element of the substrate processing device 100.

The substrate processing device 100 further includes a transfer robot. The transfer robot transfers the substrate W between the load port LP and the processing unit 1. The transfer robot includes an indexer robot IR and a center robot CR. The indexer robot IR conveys the substrate W between the load port LP and the center robot CR. The center robot CR conveys the substrate W between the indexer robot IR and the processing unit 1. Each of the indexer robot IR and the center robot CR includes a hand that supports the substrate W.

The plurality of processing units 1 are stacked one above the other to form a tower U. The substrate processing apparatus 100 includes a plurality of towers U. The plurality of towers U are arranged so as to surround the center robot CR in a plan view.

In this embodiment, each tower U includes three processing units 1. In addition, four towers U are provided. The number of processing units 1 constituting the tower U is not particularly limited. Further, the number of towers U is not particularly limited.

The processing unit 1 will be described with reference to FIG. FIG. 2 is a side view schematically showing the configuration of the processing unit 1.

As shown in FIG. 2, the processing unit 1 includes a chamber 6, a spin chuck 10, and a cup 14.

The chamber 6 includes a partition wall 8, a shutter 9, and an FFU 7 (fan filter unit). The partition wall 8 has a hollow shape. The partition wall 8 is provided with a transport port. The shutter 9 opens and closes the transport port. The FFU 7 forms a downflow of clean air in the chamber 6. Clean air is air that has been filtered by a filter.

The center robot CR (see FIG. 1) carries the substrate W into the chamber 6 through the transport port, and carries out the substrate W from the chamber 6 through the transport port.

The spin chuck 10 is arranged in the chamber 6. The spin chuck 10 rotates the substrate W around the rotation axis A1 while holding the substrate W horizontally. The rotating shaft A1 is a vertical shaft passing through the central portion of the substrate W.

The spin chuck 10 includes a plurality of chuck pins 11, a spin base 12, a spin motor 13, a cup 14, and a cup elevating unit 15.

The spin base 12 is a disk-shaped member. The plurality of chuck pins 11 hold the substrate W in a horizontal posture on the spin base 12. The spin motor 13 rotates the substrate W around the rotation axis A1 by rotating the plurality of chuck pins 11.

The spin chuck 10 of the present embodiment is a holding type chuck that brings a plurality of chuck pins 11 into contact with the outer peripheral surface of the substrate W. However, the present invention is not limited to this. The spin chuck 10 may be a vacuum type chuck. The vacuum type chuck holds the substrate W horizontally by adsorbing the back surface (lower surface) of the substrate W, which is a non-device forming surface, to the upper surface of the spin base 12.

The cup 14 receives the liquid discharged from the substrate W. The cup 14 includes an inclined portion 14a, a guide portion 14b, and a liquid receiving portion 14c. The inclined portion 14a is a tubular member extending diagonally upward toward the rotation axis A1. The inclined portion 14a includes an annular upper end having an inner diameter larger than that of the substrate W and the spin base 12. The upper end of the inclined portion 14a corresponds to the upper end of the cup 14. The upper end of the cup 14 surrounds the substrate W and the spin base 12 in a plan view. The guide portion 14b is a cylindrical member extending downward from the lower end portion (outer end portion) of the inclined portion 14a. The liquid receiving portion 14c is located below the guide portion 14b and forms an annular groove that opens upward.

The cup elevating unit 15 raises and lowers the cup 14 between the ascending position and the descending position. When the cup 14 is in the ascending position, the upper end of the cup 14 is located above the spin chuck 10. When the cup 14 is in the lowered position, the upper end of the cup 14 is located below the spin chuck 10.

When the liquid is supplied to the substrate W, the cup 14 is located in the ascending position. The liquid scattered outward from the substrate W is received by the inclined portion 14a and then collected in the liquid receiving portion 14c via the guide portion 14b.

The processing unit 1 further includes a rinse liquid nozzle 16, a rinse liquid pipe 17, and a rinse liquid valve 18. The rinse liquid nozzle 16 discharges the rinse liquid toward the substrate W held by the spin chuck 10. The rinse liquid nozzle 16 is connected to the rinse liquid pipe 17. The rinse liquid pipe 17 is connected to the rinse liquid supply source. A rinse liquid valve 18 is interposed in the rinse liquid pipe 17.

When the rinse liquid valve 18 is opened, the rinse liquid is supplied from the rinse liquid pipe 17 to the rinse liquid nozzle 16. Then, the rinse liquid is discharged from the rinse liquid nozzle 16. The rinsing solution is, for example, pure water (deionized water). The rinsing solution is not limited to pure water, and may be carbonated water, electrolytic ionized water, hydrogen water, ozone water, and / or hydrochloric acid water having a diluted concentration. The dilution concentration is, for example, a concentration of 10 ppm or more and 100 ppm or less.

The processing unit 1 further includes a first chemical solution nozzle 21, a first chemical solution pipe 22, and a first chemical solution valve 23. The first chemical solution nozzle 21 discharges the alkaline chemical solution toward the substrate W held by the spin chuck 10. In this embodiment, the alkaline chemical solution is SC1. SC1 is a mixed solution of aqueous ammonia, hydrogen peroxide and water. The first chemical solution nozzle 21 is connected to the first chemical solution pipe 22. The first chemical solution pipe 22 is connected to the supply source of SC1. A first chemical solution valve 23 is interposed in the first chemical solution pipe 22.

The processing unit 1 further includes a second chemical solution nozzle 24, a second chemical solution pipe 25, and a second chemical solution valve 26. The second chemical solution nozzle 24 discharges the chemical solution DHF (dilute hydrofluoric acid) toward the substrate W held by the spin chuck 10. The second chemical solution nozzle 24 is connected to the second chemical solution pipe 25. The second chemical solution pipe 25 is connected to the source of the chemical solution DHF. A second chemical solution valve 26 is interposed in the second chemical solution pipe 25.

The processing unit 1 further includes a generation device 30. The generator 30 produces Caro's acid from sulfuric acid. The generation device 30 includes a third chemical solution nozzle 31 and a nozzle moving unit 32. The third chemical solution nozzle 31 discharges caroic acid toward the substrate W held by the spin chuck 10. The nozzle moving unit 32 moves the third chemical solution nozzle 31 between the processing position and the retracted position. The processing position indicates a position where the third chemical solution nozzle 31 discharges caroic acid toward the substrate W. In the present embodiment, the treatment position is such that the substrate W is located on the extension line of the sulfuric acid movement path R (see FIG. 7) used by the third chemical solution nozzle 31, and the third chemical solution nozzle 31 is closest to the substrate W. It is a position. That is, when the third chemical solution nozzle 31 is located at the processing position, the generation region E (see FIG. 7) is located in the immediate vicinity of the substrate W. The retracted position indicates a position where the third chemical solution nozzle 31 is separated from the substrate W. The nozzle moving unit 32 moves the third chemical solution nozzle 31 by, for example, turning the third chemical solution nozzle 31 around the swing axis A2. The swing axis A2 is a vertical axis located around the cup 14.

Caroic acid is the first example of the processing fluid of the present invention.

Next, the generator 30 will be described with reference to FIG. FIG. 3 is a diagram schematically showing the configuration of the generator 30.

The structure of the third chemical solution nozzle 31 will be described. As shown in FIG. 3, the third chemical solution nozzle 31 has a discharge unit 311.

The discharge unit 311 discharges the sulfuric acid droplets. The discharge unit 311 includes a main body 31a, a first supply port 31b, a second supply port 31c, a third supply port 31d, a discharge port 31e, a first passage 31f, a second passage 31g, and a third. It has a passage 31h.

The main body portion 31a is a structure forming the discharge portion 311.

The first supply port 31b, the second supply port 31c, the third supply port 31d, and the discharge port 31e are openings formed on the outer surface of the main body 31a. The first passage 31f, the second passage 31g, and the third passage 31h are vacant spaces formed in the main body portion 31a.

The first passage 31f communicates with the first supply port 31b and also communicates with the discharge port 31e. The first passage 31f has a first outer passage 311f, a second outer passage 312f, and a first continuous passage 313f. The first outer passage 311f communicates with the second outer passage 312f via the first communication passage 313f.

The first passage 31f may be formed in a ring shape around the third passage 31h.

The second passage 31g is arranged inside the first passage 31f. The second passage 31g communicates with the second supply port 31c and also communicates with the first passage 31f. The second passage 31g has a first inner passage 311g, a second inner passage 312g, and a second continuous passage 313g. The first inner passage 311g communicates with the second inner passage 312g via the second communication passage 313g.

The second passage 31g may be formed in a ring shape around the third passage 31h.

The third passage 31h is arranged inside the second passage 31g. The third passage 31h communicates with the third supply port 31d and also communicates with the discharge port 31e. As a result, the discharge port 31e communicates with the third supply port 31d via the third passage 31h.

The first passage 31f has a communication portion G. The communication portion G is a portion of the first passage 31f that communicates with the second passage 31g. The communication portion G is located in the middle of the first passage 31f.

The third chemical solution nozzle 31 further includes a pipe portion 312. The tube portion 312 is formed in a tubular shape with both ends open. The tube portion 312 may have a hollow shape with both ends open, and is not limited to a cylindrical shape. The shape of the pipe portion 312 may be, for example, a prismatic shape in which both ends of the hollow polygonal column member are opened.

The pipe portion 312 is formed integrally with the discharge portion 311. The pipe portion 312 may be separate from the discharge portion 311. In this case, the pipe portion 312 may be fixed to the discharge portion 311 or may be separated from the discharge portion 311.

The pipe portion 312 and the discharge portion 311 are formed of, for example, quartz. When the discharge unit 311 is separate from the pipe unit 312, the discharge unit 311 may be, for example, a member coated with resin or metal.

The base end portion 31q of the pipe portion 312 is connected to the discharge port 31e of the discharge portion 311. The pipe portion 312 protrudes from the discharge port 31e.

The pipe portion 312 has an inflow port 31m and a discharge port 31n. The inflow port 31m is formed at the base end portion 31q and communicates with the discharge port 31e and also communicates with the inside 31p of the pipe portion 312. The discharge port 31n is formed at the tip portion 31r and communicates with the inside 31p of the pipe portion 312 and also communicates with the outside of the pipe portion 312. The discharge port 31n discharges caroic acid.

The generation device 30 further includes a chemical solution supply unit 33.

The chemical supply unit 33 supplies a liquid containing sulfuric acid to the discharge unit 311. The chemical solution supply unit 33 has a third chemical solution pipe 33a and a third chemical solution valve 33b.

The third chemical solution pipe 33a communicates with the sulfuric acid supply source. The third chemical liquid pipe 33a communicates with the second supply port 31c. The third chemical solution pipe 33a supplies a liquid containing sulfuric acid to the second passage 31g via the second supply port 31c. A third chemical solution valve 33b is interposed in the third chemical solution pipe 33a. The third chemical solution valve 33b opens and closes the flow path of the sulfuric acid liquid formed inside the third chemical solution pipe 33a.

The liquid containing sulfuric acid is the first example of the treatment liquid of the present invention.

The generator 30 further includes a gas supply unit 34.

The gas supply unit 34 supplies gas to the discharge unit 311. The gas contains at least one of oxygen, nitrogen, argon, and helium.

The gas supply unit 34 includes a first gas pipe 34a, a second gas pipe 34b, a first gas valve 34c, and a second gas valve 34d.

The first gas pipe 34a communicates with the gas supply source. The first gas pipe 34a communicates with the first supply port 31b. The first gas pipe 34a supplies gas to the first passage 31f via the first supply port 31b. A first gas valve 34c is interposed in the first gas pipe 34a. The first gas valve 34c opens and closes a gas flow path formed inside the first gas pipe 34a.

The second gas pipe 34b communicates with the gas supply source. The second gas pipe 34b communicates with the third supply port 31d. The second gas pipe 34b supplies gas to the third passage 31h via the third supply port 31d. A second gas valve 34d is interposed in the second gas pipe 34b. The second gas valve 34d opens and closes a gas flow path formed inside the second gas pipe 34b.

The generator 30 further includes a generator 35.

The generation unit 35 generates plasma. The plasma is generated from the gas supplied by the gas supply unit 34. The generation unit 35 employs, for example, an inductively coupled plasma (ICP) method to generate inductively coupled plasma.

In the following, the region where the generation unit 35 generates plasma may be referred to as the plasma generation region E. The generation region E is located inside 31p of the pipe portion 312.

The generation unit 35 has a coil 351 and a power supply unit 352. A pipe portion 312 is arranged inside the coil 351. The power supply unit 352 is connected to the coil 351. The power supply unit 352 causes a current to flow through the coil 351 to induce a magnetic field in the coil 351 to generate, for example, high-temperature plasma of about 200 ° C. or higher and 2000 ° C. or lower in the generation region E. As a result, oxygen gas is excited in the generation region E, and an oxygen plasma containing oxygen radicals and oxygen ions is generated. Oxygen plasma is generated at substantially normal pressure. The generation region E is, in other words, an region inside the coil 351.

The generation device 30 further includes a temperature control mechanism 36.

The temperature control mechanism 36 controls the temperature of the generation region E. The temperature control mechanism 36 includes a wall portion 361, a cooling passage portion 362, a cooling pipe 363, and a cooling valve 364. The wall portion 361 is connected to the tip portion 31r of the pipe portion 312 and is formed so as to surround the pipe portion 312. The cooling passage portion 362 is an empty space formed between the pipe portion 312 and the wall portion 361. The cooling pipe 363 communicates with the supply source of the coolant. In this embodiment, the coolant is cold water. The cooling pipe 363 communicates with the cooling passage portion 362. The cooling pipe 363 supplies cold water to the cooling passage portion 362. As a result, the temperature rise in the generation region E is suppressed. A cooling valve 364 is interposed in the cooling pipe 363. The cooling valve 364 opens and closes a flow path of cold water formed inside the cooling pipe 363.

Next, an example of processing on the substrate W executed by the substrate processing apparatus 100 will be described with reference to FIGS. 2 and 4. FIG. 4 is a flow chart showing an example of processing on the substrate W executed by the substrate processing apparatus 100.

As shown in FIGS. 2 and 4, in step S1, the control unit 3 performs a substrate loading process for loading the substrate W into the chamber 6. The procedure for carrying in the substrate will be described below.

First, in a state where the first chemical solution nozzle 21 is retracted from above the substrate W, the center robot CR allows the hand to enter the chamber 6 while supporting the substrate W with the hand. Then, the center robot CR places the substrate W supported by the hand on the spin chuck 10. As a result, the substrate W is conveyed onto the spin chuck 10.

When the substrate W is conveyed onto the spin chuck 10, the chuck pin 11 grips the substrate W. Then, the spin motor 13 rotates the chuck pin 11. As a result, the substrate W rotates. When the substrate W rotates, the process shifts to step S2.

In step S2, the control unit 3 performs a DHF supply process of supplying the chemical solution DHF from the second chemical solution nozzle 24 to the main surface Wa of the substrate W. When the control unit 3 controls the second chemical solution valve 26 to open the second chemical solution valve 26, the chemical solution DHF is discharged from the second chemical solution nozzle 24 toward the main surface Wa of the rotating substrate W. By discharging the chemical solution DHF onto the main surface Wa of the substrate W, the natural oxide film formed on the main surface Wa of the substrate W is removed. When the DHF supply process is completed, the second chemical solution valve 26 is closed.

The main surface Wa of the substrate W is a surface of the substrate W that faces upward while the substrate W is held by the spin chuck 10.

In step S3, the control unit 3 performs a caroic acid supply process of supplying caroic acid from the third chemical solution nozzle 31 to the main surface Wa of the substrate W. When the caroic acid supply process is performed, caroic acid is discharged from the third chemical solution nozzle 31 toward the main surface Wa of the rotating substrate W. The resist film is removed from the main surface Wa of the substrate W by discharging the caroic acid onto the main surface Wa of the substrate W.

In step S4, the control unit 3 performs an SC1 supply process of supplying SC1 from the first chemical solution nozzle 21 to the main surface Wa of the substrate W. When the control unit 3 controls the first chemical solution valve 23 to open the first chemical solution valve 23, the SC1 is discharged from the first chemical solution nozzle 21 toward the main surface Wa of the rotating substrate W. When SC1 is discharged to the main surface Wa of the substrate W, the caroic acid on the main surface Wa of the substrate W is swept outward by the SC1 and discharged to the periphery of the substrate W. Then, the entire area of the main surface Wa of the substrate W is covered with the liquid film of SC1. When the SC1 supply process is completed, the first chemical solution valve 23 is closed.

In step S5, the control unit 3 performs a rinse liquid supply process of supplying the rinse liquid from the rinse liquid nozzle 16 to the main surface Wa of the substrate W. When the control unit 3 controls the rinse liquid valve 18 to open the rinse liquid valve 18, the rinse liquid is discharged from the rinse liquid nozzle 16 toward the main surface Wa of the rotating substrate W. By discharging the rinse liquid onto the main surface Wa of the substrate W, the SC1 on the main surface Wa of the substrate W is washed away by the rinse liquid. When the rinse liquid supply process is completed, the rinse liquid valve 18 is closed.

In step S6, the control unit 3 performs a drying process of drying the substrate W by rotating the substrate W. The procedure of the drying process will be described below.

First, the spin motor 13 rotates the substrate W at a high speed (for example, several thousand rpm) that is larger than the rotation speed of the substrate W during the chemical supply processing and the rotation speed of the substrate W during the rinse liquid supply processing. As a result, the liquid is removed from the substrate W, so that the substrate W dries.

When a predetermined time elapses after the high-speed rotation of the substrate W is started, the spin motor 13 stops the rotation of the substrate W. When the rotation of the substrate W is stopped, the process proceeds to step S7.

In step S7, the control unit 3 performs a carry-out process of carrying out the substrate W from the chamber 6. The procedure for carrying out processing will be described below.

First, the cup elevating unit 15 lowers the cup 14 to the lower position. Then, the center robot CR causes the hand to enter the chamber 6. Then, the plurality of chuck pins 11 release the grip of the substrate W.

After the plurality of chuck pins 11 release the grip on the substrate W, the center robot CR supports the substrate W on the spin chuck 10 by hand. Then, the center robot CR retracts the hand from the inside of the chamber 6 while supporting the substrate W with the hand. As a result, the processed substrate W is carried out from the chamber 6.

When the processed substrate W is carried out from the chamber 6, the carry-out process shown in step S7 is completed.

By repeating the processes shown in steps S1 to S7, the plurality of substrates W conveyed to the processing unit 1 are processed one by one.

Next, the caroic acid supply treatment in step S3 will be described with reference to FIGS. 3 to 7. FIG. 5 is a flow chart showing the caroic acid supply treatment. FIG. 6 is a first diagram showing the operation of the generator 30. FIG. 7 is a second diagram showing the operation of the generator 30.

As shown in FIGS. 4 and 5, when the process shown in step S2 is completed, the process shifts to step S31.

As shown in FIGS. 3, 5, and 6, in step S31, the control unit 3 performs a gas supply process for supplying gas to the discharge unit 311. The gas is supplied to the first supply port 31b and the third supply port 31d of the discharge unit 311.

The control unit 3 controls the first gas valve 34c and the second gas valve 34d to open the first gas valve 34c and the second gas valve 34d, thereby forming the first supply port 31b and the third supply port 31d. Gas is supplied.

When the gas K1 supplied to the first supply port 31b passes through the first passage 31f, it reaches the discharge port 31e. The gas K2 supplied to the third supply port 31d reaches the discharge port 31e when passing through the third passage 31h. The gas K1 and the gas K2 that have reached the discharge port 31e merge to form the gas K3. The gas K3 flows into the inside 31p of the pipe portion 312 from the inflow port 31m.

The gas K3 that has flowed into the inside 31p of the pipe portion 312 passes through the generation region E and is then discharged from the discharge port 31n to the outside of the pipe portion 312.

In step S32, the control unit 3 performs a plasma generation process of generating plasma in the generation region E by the generation unit 35. Specifically, the control unit 3 causes the power supply unit 352 to pass a current through the coil 351 to induce a magnetic field in the coil 351. As a result, plasma (oxygen plasma) is generated in the generation region E.

In step S33, the control unit 3 performs a temperature control process for controlling the temperature of the generation region E. Specifically, the control unit 3 supplies cold water to the cooling passage unit 362 by opening the cooling valve 364. As a result, the temperature rise in the generation region E is suppressed.

As shown in FIGS. 3, 5, and 6, in step S34, the control unit 3 performs a sulfuric acid supply process for supplying sulfuric acid to the discharge unit 311. Sulfuric acid is supplied to the second supply port 31c.

When the control unit 3 controls the third chemical solution valve 33b to open the third chemical solution valve 33b, sulfuric acid is supplied to the second supply port 31c.

Sulfuric acid supplied to the second supply port 31c flows into the second passage 31g and flows through the second passage 31g.

In step S35, sulfuric acid droplet α is generated. The procedure for generating the sulfuric acid droplet α will be described below.

Sulfuric acid flowing in the second passage 31 g reaches the communication portion G. The gas K1 collides with the sulfuric acid that has reached the communication portion G. As a result, sulfuric acid droplet α is generated.

The sulfuric acid droplet α generated in the communication portion G flows through the first passage 31f and then reaches the discharge port 31e. The gas K2 collides with the sulfuric acid droplet α that has reached the discharge port 31e. As a result, the sulfuric acid droplet α that has reached the discharge port 31e is guided from the discharge port 31e to the generation region E located inside 31p of the pipe portion 312 through the inflow port 31m. In other words, the sulfuric acid droplet α that has reached the discharge port 31e is guided to the generation region E by the fluid pressure of the gas K2.

In step S36, the plasma treatment is performed to generate caroic acid. The plasma treatment is that sulfuric acid is supplied to the plasma generation region E. The procedure for producing caroic acid will be described below.

The sulfuric acid droplet α that has flowed into the inner 31p of the tube portion 312 flows through the inner 31p of the tube portion 312 and reaches the generation region E. That is, the generation region E is located on the movement path R of sulfuric acid. The movement path R is located inside 31p of the pipe portion 312, and is formed in the direction from the inflow port 31m of the pipe portion 312 toward the discharge port 31n. In the present embodiment, the sulfuric acid moves along the movement path R in the state of the droplet α. Further, in the present embodiment, the movement path R is formed downward, and sulfuric acid falls along the movement path R. Since the generation region E is located inside 31p of the pipe portion 312, the sulfuric acid can be guided toward the generation region E by the pipe portion 312.

When the sulfuric acid droplet α flows through the generation region E, it is oxidized by the oxygen plasma. As a result, caroic acid is produced from sulfuric acid in the generation region E. Specifically, a liquid drop β of caroic acid is generated from a liquid drop α of sulfuric acid.

In step S37, the liquid drop β of caroic acid is discharged from the discharge port 31n of the pipe portion 312 to the outside of the pipe portion 312. Specifically, a gas containing a droplet β of caroic acid is released. The liquid drop β of caroic acid is discharged from the discharge port 31n by the pressure of the gas K3 (see FIG. 6).

The discharge port 31n of the pipe portion 312 faces the main surface Wa (see FIG. 2) of the substrate W. The liquid drop β of caroic acid discharged from the discharge port 31n of the pipe portion 312 is supplied to the main surface Wa of the substrate W. By supplying the droplet β of caroic acid to the main surface Wa of the substrate W, the resist film is removed from the main surface Wa of the substrate W by the oxidizing power of the caroic acid. As a result, the caroic acid supply process is completed. When the caroic acid supply treatment is completed, the treatment proceeds to step S4 shown in FIG.

As described above with reference to FIGS. 3 to 7, the generation region E is located on the movement path R of sulfuric acid (see FIG. 7). Therefore, plasma is supplied to the moving sulfuric acid. As a result, it is possible to suppress the irradiation of plasma only to a specific portion of sulfuric acid, so that plasma can be effectively supplied to sulfuric acid and caroic acid can be efficiently generated. Efficient production of caroic acid means that a large amount of caroic acid can be produced with respect to the amount of sulfuric acid used. Further, in the present embodiment, the substrate W (see FIG. 2) is located on the extension line of the sulfuric acid movement path R. Therefore, the sulfuric acid discharged from the discharge unit 311 goes toward the substrate W along the movement path R. In addition, the amount of sulfuric acid used for processing the substrate W is discharged from the discharge unit 311. As a result, sulfuric acid can be used without waste. Further, in the present embodiment, when the third chemical solution nozzle 31 supplies caroic acid to the substrate W, the substrate W is located at a position where the third chemical solution nozzle 31 is closest to the substrate W on the extension line of the sulfuric acid movement path R. Be placed. That is, the generation region E is located in the immediate vicinity of the substrate W. Therefore, it is possible to suppress the supply of caroic acid to a place other than the substrate W, and the caroic acid can be effectively supplied to the substrate W.

Further, as shown in FIG. 7, the discharge unit 311 generates a liquid drop α of sulfuric acid by mixing sulfuric acid and a gas. Therefore, the sulfuric acid droplet α is supplied to the generation region E. As a result, plasma can be effectively supplied to the entire area of the sulfuric acid droplet α, so that caroic acid can be generated more efficiently.

Further, since the sulfuric acid droplet α is supplied to the generation region E, plasma can be easily supplied to the entire area of the sulfuric acid droplet α, so that the dimension of the generation region E in the Z direction can be shortened. As a result, the generator 30 can be made compact. The Z direction is a direction along the movement path R. In the present embodiment, the Z direction is the vertical direction.

Further, the temperature control mechanism 36 limits the temperature of the generation region E to a temperature within a predetermined range by supplying a coolant such as cold water around the pipe portion 312. The temperature within the predetermined range is, for example, a temperature of 150 ° C. or higher and 200 ° C. or lower. Therefore, since it is possible to suppress the vaporization of the caroic acid generated in the generation region E, in step S37, the caroic acid can be discharged in the state of the droplet β from the discharge port 31n of the pipe portion 312. As a result, the caroic acid discharged from the discharge port 31n is suppressed from diffusing, so that the caroic acid can be easily supplied toward the substrate W. The generation device 30 does not have to include the temperature control mechanism 36. As a result, since the temperature control mechanism 36 is not provided, it is advantageous in that the apparatus configuration of the generator 30 can be simplified.

Further, the generation device 30 may have a temperature sensor that detects the temperature of the generation region E. In this case, the control unit 3 controls the temperature of the generation region E to a temperature within a predetermined range by adjusting the opening degree of the cooling valve 364 based on the detection value of the temperature sensor.

The embodiments of the present invention have been described above with reference to the drawings (FIGS. 1 to 10). However, the present invention is not limited to the above-described embodiment, and can be implemented in various embodiments without departing from the gist thereof (for example, (1) to (9)). In addition, various inventions can be formed by appropriately combining the plurality of components disclosed in the above embodiments. For example, some components may be removed from all the components shown in the embodiments. The drawings are schematically shown mainly for each component for easy understanding, and the number of each component shown may differ from the actual one due to the convenience of drawing. Further, each component shown in the above embodiment is an example, and is not particularly limited, and various modifications can be made without substantially deviating from the effect of the present invention.

(1) For example, the dimension of the generation region E in the Z direction (see FIG. 7) may be changed according to the amount of sulfuric acid supplied per unit time supplied to the first supply port 31b. Specifically, the larger the supply amount of sulfuric acid, the larger the dimension of the generation region E in the Z direction. The dimension of the generation region E in the Z direction is adjusted, for example, by changing the length of the coil 351.

(2) When the third chemical solution nozzle 31 (see FIG. 1) is located in the standby position, the third chemical solution nozzle 31 may be cooled. In this case, for example, the third chemical solution nozzle 31 may be cooled by injecting, for example, an air flow of nitrogen gas. Further, the third chemical solution nozzle 31 may be cooled by the temperature control mechanism 36. The third chemical solution nozzle 31 is cooled to, for example, about room temperature. As a result, when the standby state of the third chemical solution nozzle 31 is released and the third chemical solution nozzle 31 starts the caroic acid supply process shown in FIG. 5, the caroic acid supply process can be smoothly started.

(3) A modified example 300 of the generator 30 will be described with reference to FIG. FIG. 8 is a diagram showing a modification 300 of the generation device 30.

As shown in FIG. 3, in the present embodiment, the first outer passage 311f communicates with the second outer passage 312f via the first communication passage 313f. However, the present invention is not limited to this. As shown in FIG. 8, the first outer passage 311f is independent of the second outer passage 312f and does not have to be communicated with the second outer passage 312f. That is, the first passage 313f may not be provided. In this case, the first outer passage 311f communicates with the first supply port 31b. The second outer passage 312f communicates with the fourth supply port 312b, which is different from the first supply port 31b. Then, gas is supplied to each of the first supply port 31b and the fourth supply port 312b.

As shown in FIG. 3, the first inner passage 311g communicates with the second inner passage 312g via the second communication passage 313g. However, the present invention is not limited to this. As shown in FIG. 8, the first inner passage 311g is independent of the second inner passage 312g and does not have to be communicated with the second inner passage 312g. That is, the second passage 313g may not be provided. In this case, the first inner passage 311g communicates with the second supply port 31c. The second inner passage 312g communicates with a fifth supply port 312c, which is different from the second supply port 31c. Then, sulfuric acid is supplied to each of the second supply port 31c and the fifth supply port 312c.

By using the modification 300 of the generation device 30, the same effect as when the generation device 30 of the present embodiment is used can be obtained.

(4) In the present embodiment, caroic acid is produced by the generation device 30. However, the present invention is not limited to this. SC1 may be generated by the generation device 30.

In the following, with reference to FIG. 9, a first example of the device configuration of the generation device 30 for generating SC1 will be described. FIG. 9 is a diagram showing a first example of an apparatus configuration of the generator 30 for generating SC1.

As shown in FIG. 9, when SC1 is generated by the generation device 30, ammonia water is supplied to the second supply port 31c instead of sulfuric acid. For example, the same gas as the gas of the present embodiment is supplied to the first supply port 31b and the third supply port 31d. Then, when the droplet α1 of the ammonia water passes through the plasma generation region E, the plasma is supplied to the water contained in the ammonia water to generate the hydrogen peroxide solution. As a result, SC1 which is a mixed solution of aqueous ammonia, hydrogen peroxide and water is produced.

The liquid drop β1 of SC1 generated in the generation region E is discharged from the tube portion 312. As a result, SC1 can be produced without preparing a hydrogen peroxide solution.

SC1 is a second example of the processing fluid of the present invention. Ammonia water is a second example of the treatment liquid of the present invention.

(5) With reference to FIG. 10, a second example of the apparatus configuration of the generator 30 for generating SC1 will be described. FIG. 10 is a diagram showing a second example of the device configuration of the generation device 30 that generates SC1.

The second example differs from the first example in that the modified example 300 of the generator 30 shown in FIG. 8 is used.

As shown in FIG. 10, nitrogen is supplied to the first supply port 31b, ammonia water is supplied to the second supply port 31c, water is supplied to the fifth supply port 312c, and the fourth supply port is supplied. Argon is supplied to the 312b. The same gas or air as in this embodiment is supplied to the third supply port 31d. As a result, SC1 can be produced by generating hydrogen peroxide solution by water and plasma. Further, by merging nitrogen and ammonia water at the communication portion G, it is possible to suppress the decomposition of the ammonia component. Further, hydrogen peroxide can be effectively generated by using argon.

(6) With reference to FIG. 11, the discharge unit 400, which is a modified example of the discharge unit 311, will be described. FIG. 11 is a schematic view showing a discharge unit 400 which is a modified example of the discharge unit 311.

As shown in FIG. 11, the discharge unit 400 has a main body unit 401, a sixth supply port 402, a seventh supply port 403, a discharge port 404, a fourth passage 405, and a fifth passage 406.

The main body portion 401 is a structure forming the discharge portion 400.

The sixth supply port 402, the seventh supply port 403, and the discharge port 404 are openings formed on the outer surface of the main body 401. The fourth passage 405 and the fifth passage 406 are vacant spaces formed in the main body 401.

The sixth supply port 402 is connected to the supply pipe 500. The supply pipe 500 communicates with the gas supply source. The gas supply source supplies gas to the sixth supply port 402 via the supply pipe 500. The gas supplied from the gas source is the same gas as the gas of the present embodiment.

The seventh supply port 403 communicates with the sulfuric acid supply source to supply sulfuric acid.

The discharge port 404 has a first discharge port 404a and a second discharge port 404b. The second discharge port 404b is formed in an annular shape so as to surround the first discharge port 404a.

A pipe portion 312 is connected to the discharge port 404. Similar to the present embodiment, the pipe portion 312 is provided with a generating portion 35 and a temperature control mechanism 36 (see FIG. 3).

The fourth passage 405 is formed in a ring shape around the fifth passage 406. The fourth passage 405 communicates with the sixth supply port 402 and also communicates with the second discharge port 404b. As a result, the second discharge port 404b communicates with the sixth supply port 402 via the fourth passage 405.

The fifth passage 406 communicates with the seventh supply port 403 and also communicates with the first discharge port 404a. As a result, the first discharge port 404a communicates with the seventh supply port 403 via the fifth passage 406.

The operation of the discharge unit 400 will be described.

The gas supplied from the sixth supply port 402 flows through the fourth passage 405 and then is discharged from the second discharge port 404b. Sulfuric acid supplied from the seventh supply port 403 flows through the fifth passage 406 and then is discharged from the first discharge port 404a. The gas discharged from the second discharge port 404b and the sulfuric acid discharged from the first discharge port 404a collide with each other to generate sulfuric acid droplets. Sulfuric acid droplets flow through the tube section 312. Then, when the sulfuric acid droplet α flows through the tube portion 312, caroic acid is generated by passing through the generation region E existing on the movement path R (see FIG. 7). In the present embodiment, since the sulfuric acid droplet α passes through the generation region E, the caroic acid droplet β is generated. As a result, the liquid drop β of caroic acid is released from the tube portion 312.

The fourth passage 405 is formed in a ring shape around the fifth passage 406. However, like the first outer passage 311f and the second outer passage 312f shown in FIG. 8, the fourth passage 405 may be composed of a plurality of independent passages. Further, like the first outer passage 311f and the second outer passage 312f shown in FIG. 7, the fourth passage 405 may have a structure in which a plurality of independent passages communicate with each other.

Further, SC1 may be generated by using the discharge unit 400. In this case, ammonia water is supplied to the 7th supply port 403, and gas is supplied to the 6th supply port 402.

(7) As shown in FIG. 7, in the present embodiment, the sulfuric acid droplet α is discharged from the discharge unit 311. However, the present invention is not limited to this. Liquid sulfuric acid that has not been separated into the droplet α may be discharged from the discharge unit 311. That is, the liquid containing sulfuric acid may be continuously discharged from the discharge unit 311. As a result, the configuration in which the gas and sulfuric acid are mixed (collised) in the communication portion G becomes unnecessary, so that the apparatus configuration of the generation apparatus 30 can be simplified.

(8) As shown in FIG. 7, in the present embodiment, the generation region E is located inside the pipe portion 312. However, the present invention is not limited to this. The generation region E may be located on the movement path R of sulfuric acid, and may be located at a location other than the inside of the pipe portion 312. For example, the generation region E may be located outside the pipe portion 312 (outside the third chemical solution nozzle 31). In this case, the third chemical solution nozzle 31 does not have to include the pipe portion 312. As a result, the device configuration of the generation device 30 can be simplified.

(9) The substrate processing apparatus 100 is a single-wafer type apparatus that processes substrates W one by one. However, the present invention is not limited to this. The substrate processing apparatus 100 may be a batch type apparatus that simultaneously processes a plurality of substrates W.

The present invention is available in the fields of generators, substrate processing devices, and substrate processing methods.

30 Generation device 35 Generation unit 311 Discharge unit E Generation area R Movement path W Substrate α Drop model

Claims (12)

A generator that generates a processing fluid used for processing a substrate from a processing liquid.
A discharge unit that discharges the treatment liquid and
Equipped with a generator that generates plasma
A generator in which the plasma generation region is located on the movement path of the processing liquid discharged from the discharge unit. The processing fluid contains caroic acid and
The generator according to claim 1, wherein the treatment liquid contains sulfuric acid. The generator according to claim 1 or 2, wherein the discharge unit generates droplets of the treatment liquid by mixing the treatment liquid and a gas. The discharge part
The first supply port to which the gas is supplied and
The second supply port to which the treatment liquid is supplied and
The third supply port to which the gas is supplied and
An outlet that communicates with the third supply port and
A first passage that communicates with the first supply port and also communicates with the discharge port,
The generator according to claim 3, further comprising a second passage communicating with the second supply port and communicating with the first passage. The discharge part
The first supply port to which the gas is supplied and
The second supply port to which the treatment liquid is supplied and
The first discharge port communicating with the second supply port and
The generator according to claim 3, further comprising a second discharge port formed so as to surround the first discharge port and communicating with the first supply port. The generator according to any one of claims 3 to 5, wherein the gas contains at least one of oxygen, nitrogen, argon, and helium. Further provided with a pipe portion protruding from the discharge portion,
The generator according to any one of claims 1 to 6, wherein the plasma generation region is located inside the tube portion. The generator according to any one of claims 1 to 7, wherein the plasma is an inductively coupled plasma. The generator according to any one of claims 1 to 8, wherein the generating unit generates oxygen plasma at normal pressure. The generator according to any one of claims 1 to 9, further comprising a temperature control mechanism for controlling the temperature of the plasma generation region. The generator according to any one of claims 1 to 10 is provided.
A substrate processing apparatus that supplies the processing fluid generated by the generator to the substrate. A substrate processing method for processing a substrate having a resist film on its surface.
The process of producing the sulfuric acid droplets by mixing gas and sulfuric acid, and
The process of producing caroic acid by moving the sulfuric acid droplets in the plasma generation region, and
A substrate processing method comprising a step of supplying the caroic acid to a substrate.

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