KR20190112093A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

A substrate processing method for removing resist from a surface of a substrate includes a support step of allowing the support member to horizontally support the substrate, and a mixed gas supply step of supplying a mixed gas of water vapor and ozone gas to the vicinity of the surface of the substrate. (T4) and the ultraviolet irradiation process (T6) which irradiates an ultraviolet-ray to the mixed gas supplied near the surface of the said board | substrate.

Description

Substrate processing method and substrate processing apparatus

TECHNICAL FIELD This invention relates to the substrate processing method and substrate processing apparatus which process a board | substrate. Examples of the substrate to be processed include a semiconductor wafer, a substrate for a liquid crystal display, a substrate for a flat panel display (FPD) such as an organic EL (Electroluminescence) display device, a substrate for an optical disk, a substrate for a magnetic disk, a magneto-optical disk. Substrates such as a substrate for use, a substrate for photomask, a ceramic substrate, and a substrate for solar cell are included.

In manufacturing processes, such as a semiconductor device, the resist coating process which apply | coats a resist liquid on a board | substrate and forms a resist, the exposure process which exposes a predetermined pattern to the said resist, and the developing process which develops the exposed resist are sequentially performed, for example. A photolithography process is performed. As a result, a predetermined resist pattern is formed on the substrate. And the etching process of the to-be-processed film on a board | substrate is performed using this resist pattern as a mask. Thereafter, by removing the resist, a predetermined pattern is formed on the surface of the substrate.

The following patent document 1 discloses the method of peeling the resist formed in the surface of a board | substrate by the action of an ultraviolet-ray and ozone. In detail, in this method, the inside of a chamber becomes an ozone atmosphere by supplying ozone containing gas (mixed gas of ozone and oxygen) in the chamber which accommodates a board | substrate. And ozone is decomposed by irradiating an ultraviolet-ray to a board | substrate in ozone atmosphere. Accordingly, hydroxy radicals (OH radicals) and the like, which are active oxygen having a relatively high oxidizing power, are generated. By this hydroxy radical, peeling of the resist by ozone is promoted.

Japanese Patent Publication No. 2000-286251 US Patent Application Publication No. 2017/252781

Hydroxy radicals are likely to be generated when ozone and hydrogen radicals react. However, in the method of patent document 1, sufficient hydrogen radicals cannot be supplied in a chamber. Therefore, since hydroxy radicals cannot be produced | generated enough, there exists a possibility that delamination of a resist cannot fully be accelerated | stimulated.

On the other hand, patent document 2 discloses the method of irradiating an ultraviolet-ray to the surface of a board | substrate in the state in which the film (liquid film) of liquids, such as ozone water, was formed in the surface of a board | substrate. In this method, hydrogen radicals can be generated from water by ultraviolet rays. However, since ultraviolet rays are absorbed by the liquid film, there is a fear that sufficient hydrogen radicals cannot be generated near the surface of the substrate, and sufficient hydrogen radicals cannot be generated near the surface of the substrate. In this way, sufficient hydroxy radicals cannot be generated near the surface of the substrate. Therefore, there exists a possibility that peeling of a resist cannot fully be accelerated | stimulated.

Therefore, it is required to solve these problems and to facilitate the peeling of the resist formed on the surface of the substrate.

One object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of satisfactorily removing a resist formed on a surface of a substrate.

One embodiment of the present invention is a substrate processing method for removing a resist from a surface of a substrate, comprising: a support step for causing the support member to horizontally support the substrate; and a mixed gas of water vapor and ozone gas on the surface of the substrate. A substrate processing method is provided, including a mixed gas supplying step for supplying in the vicinity and an ultraviolet irradiation step for irradiating ultraviolet rays to the mixed gas supplied near the surface of the substrate.

According to this method, the mixed gas which mixed water vapor and ozone gas is supplied in the vicinity of the surface of the board | substrate supported horizontally. When the mixed gas is irradiated with ultraviolet rays, water vapor in the mixed gas is decomposed. As a result, hydrogen radicals are produced. Thus, by reacting hydrogen radicals and ozone, a sufficient amount of hydroxy radicals can be generated near the surface of the substrate.

Further, since water vapor, that is, water of gas, is supplied to the surface of the substrate, it is possible to suppress the attachment of liquid water to the surface of the substrate. Therefore, ozone can be decomposed in the vicinity of the surface of the substrate without being impeded by the absorption of ultraviolet rays by the liquid water.

As a result, the resist formed on the surface of the substrate can be satisfactorily removed (peeled out).

In one embodiment of the present invention, the ultraviolet irradiation step includes a step of generating hydroxy radicals near the surface of the substrate by irradiation of ultraviolet rays, and a step of decomposing the resist by the hydroxy radicals. Therefore, the resist can be reliably decomposed by the hydroxy radicals generated by the irradiation of ultraviolet rays.

In one embodiment of this invention, the said substrate processing method is performed in parallel with the said mixed gas supply process, and also includes the 1st heating process which heats the said board | substrate. Thereby, the mixed gas near the surface of a board | substrate can be heated. Therefore, liquefaction of the water vapor in the surface vicinity of a board | substrate can be suppressed.

In one embodiment of this invention, the said substrate processing method is performed in parallel with the said ultraviolet irradiation process, and also includes the 2nd heating process which heats the said board | substrate. As a result, the decomposition product of the resist generated near the surface of the substrate is heated. Therefore, the decomposition products of the resist can be sublimed into a gaseous state. Therefore, the decomposition products of the resist can be suppressed from solidifying on the surface of the substrate. Therefore, the resist formed on the surface of the substrate can be satisfactorily removed.

In one embodiment of this invention, the said mixed gas supply process includes the mixed gas discharge process which discharges the said mixed gas toward the surface of the said board | substrate from a discharge port. According to this method, compared with the structure where water vapor and ozone gas are discharged toward the surface of a board | substrate from different discharge ports, the ratio of water vapor and ozone gas in the vicinity of the surface of a board | substrate is maintained uniformly over the whole surface of a board | substrate. Can be.

In one embodiment of the present invention, the substrate processing method includes, at least before the start of the ultraviolet irradiation step, a space forming step of accommodating the substrate and forming a space cut off from the outside, and during the execution of the ultraviolet irradiation step, It further includes an exhaust process for exhausting the space.

Accordingly, the substrate is accommodated in a space cut off from the outside before ultraviolet rays are irradiated to the mixed gas near the surface of the substrate. Therefore, ultraviolet rays can be irradiated in a state in which the mixed gas is filled in the space (in the space near the surface of the substrate). Thus, it is possible to generate a sufficient amount of hydroxy radicals. On the other hand, the space which accommodates a board | substrate is exhausted during irradiation of an ultraviolet-ray. Accordingly, the decomposition products of the resist can be discharged to the outside of the space before solidifying at the surface of the substrate.

In one embodiment of the present invention, the substrate processing method further includes a mixed gas forming step of forming the mixed gas by supplying the ozone gas to the liquid water stored in the tank. Therefore, when preparing a mixed gas, it is not necessary to mix ozone gas and water vapor after preparing steam separately from ozone gas. That is, mixed gas can be prepared simply.

In one embodiment of the present invention, there is provided a substrate processing apparatus for removing a resist from a surface of a substrate, comprising: a supporting member for horizontally supporting the substrate, a mixed gas supply unit for supplying a mixed gas toward the surface of the substrate, An ultraviolet irradiation unit for irradiating ultraviolet rays toward the surface of the substrate, a mixed gas supply step of supplying the mixed gas from the mixed gas supply unit near the surface of the substrate, and the mixed gas supplied near the surface of the substrate And a controller programmed to execute an ultraviolet irradiation process for causing the ultraviolet irradiation unit to irradiate ultraviolet rays in a closed state.

According to this structure, the mixed gas which mixed water vapor and ozone gas is supplied to the surface vicinity of the board | substrate supported horizontally by the support member. By irradiating the mixed gas with ultraviolet rays from the ultraviolet irradiation unit, water vapor in the mixed gas is decomposed. As a result, hydrogen radicals are produced. Thus, by reacting hydrogen radicals and ozone, a sufficient amount of hydroxy radicals can be generated near the surface of the substrate.

Further, since water vapor, that is, water of gas, is supplied to the surface of the substrate, it is possible to suppress the attachment of liquid water to the surface of the substrate. Therefore, ozone can be decomposed in the vicinity of the surface of the substrate without being impeded by the absorption of ultraviolet rays by the liquid water.

As a result, the resist formed on the surface of the substrate can be satisfactorily removed.

In one embodiment of the present invention, in the ultraviolet irradiation step, the controller generates hydroxy radicals near the surface of the substrate by irradiation of ultraviolet rays and decomposes the resist by the hydroxy radicals. Is programmed to run. Therefore, the resist can be reliably decomposed by the hydroxy radicals generated by the irradiation of ultraviolet rays.

In one embodiment of the present invention, the substrate processing apparatus further includes a first substrate heating unit that heats the substrate. And the said controller is programmed to perform the 1st heating process which makes the said 1st board | substrate heating unit heat the said board | substrate in parallel with the said mixed gas supply process. Therefore, the mixed gas of the surface vicinity of a board | substrate can be heated using a 1st board | substrate heating unit. Therefore, liquefaction of the water vapor in the vicinity of the surface of a board | substrate can be suppressed.

In one embodiment of the present invention, the substrate processing apparatus further includes a second substrate heating unit that heats the substrate. The controller is programmed to execute a second heating step for causing the second substrate heating unit to heat the substrate in parallel with the ultraviolet irradiation step. Therefore, the decomposition product of the resist which generate | occur | produces in the vicinity of the surface of a board | substrate can be heated using a 2nd board | substrate heating unit. Thereby, the decomposition product of the resist can be sublimed into a gaseous state. Therefore, the decomposition products of the resist can be suppressed from solidifying on the surface of the substrate. Thus, the resist formed on the surface of the substrate can be satisfactorily removed.

In one embodiment of this invention, the said substrate processing apparatus further contains the space formation unit which accommodates the said board | substrate, and forms the space interrupted | blocked from the exterior, and the exhaust unit which exhausts the said space. The controller further controls the space forming unit to form a space at least before the ultraviolet irradiation process starts, and exhausts the space by controlling the exhaust unit during the execution of the ultraviolet irradiation process. It is programmed to run the process further.

As a result, the space-blocking unit forms a space blocked from the outside before the mixed gas near the surface of the substrate is irradiated with ultraviolet rays, and the substrate is accommodated in the space. Therefore, ultraviolet-ray can be irradiated from an ultraviolet irradiation unit in the state in which the mixed gas was filled in the space (in the space near the surface of a board | substrate). Thus, it is possible to generate a sufficient amount of hydroxy radicals. On the other hand, the space which accommodates a board | substrate is exhausted by the exhaust unit during irradiation of an ultraviolet-ray. Accordingly, the decomposition products of the resist can be discharged to the outside of the space before solidifying at the surface of the substrate.

In one embodiment of the present invention, the substrate processing apparatus further includes a tank for storing liquid water and an ozone gas supply unit for supplying ozone gas to the water of the liquid stored in the tank. The controller is programmed to execute the mixed gas forming step of forming the mixed gas by supplying the ozone gas from the ozone gas supply unit to the liquid water stored in the tank. According to this structure, a mixed gas is formed by supplying ozone gas from the ozone gas supply unit to the liquid water stored in the tank. Therefore, when preparing a mixed gas, it is not necessary to mix ozone gas and water vapor after preparing steam separately from ozone gas. That is, mixed gas can be prepared simply.

The above-mentioned or another object, a characteristic, and an effect in this invention are confirmed by description of embodiment described below with reference to an accompanying drawing.

BRIEF DESCRIPTION OF THE DRAWINGS It is a typical top view for demonstrating the layout of the inside of the substrate processing apparatus which concerns on 1st Embodiment of this invention.
2 is a schematic view of a gas processing unit included in the substrate processing apparatus.
FIG. 3 is a schematic diagram of a cross section taken along the line III-III of FIG. 2.
4 is a schematic view for explaining the configurations of the mixed gas supply unit and the discharge unit included in the gas processing unit.
5 is a block diagram for explaining the electrical configuration of the main part of the substrate processing apparatus.
6 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus.
FIG. 7 is a schematic diagram showing a cross-sectional state of the substrate before and after the substrate processing shown in FIG. 6 is executed.
FIG. 8 is a flowchart showing an example of the dry processing step (step S2 of FIG. 6) shown in FIG. 6.
It is a schematic diagram for demonstrating the said dry processing process.
It is a schematic diagram for demonstrating the said dry processing process.
It is a schematic diagram for demonstrating the said dry processing process.
It is a schematic diagram for demonstrating the said dry processing process.
10 is a graph for comparing the binding potential of the oxidizing agent with the covalent bond.
11 is a schematic view of the gas processing unit according to the first modification of the present embodiment.
12 is a schematic view of the gas processing unit according to the second modification of the present embodiment.
FIG. 13: is a schematic diagram which looked at the hood of the gas processing unit which concerns on the 3rd modified example of this embodiment from the bottom.

1 is a schematic plan view for explaining the layout of the interior of the substrate processing apparatus 1 according to one embodiment of the present invention.

The substrate processing apparatus 1 is a sheet | leaf type apparatus which processes each board | substrate W, such as a silicon wafer, one by one. The substrate processing apparatus 1 uses the load port LP which hold | maintains the some carrier C which accommodates the board | substrate W, respectively, and the board | substrate W conveyed by the some load port LP as processing fluid. A plurality of processing units 2 for processing are included. The processing fluid includes a processing gas that is a gas that processes the substrate W and a processing liquid that is a liquid that processes the substrate W.

The substrate processing apparatus 1 includes an indexer robot IR, a shuttle SH, and a main transport robot CR disposed on a transport path extending from the plurality of load ports LP to the plurality of processing units 2. And a controller 3 for controlling the substrate processing apparatus 1.

The indexer robot IR conveys the substrate W between the plurality of load ports LP and the shuttles SH. The shuttle SH conveys the substrate W between the indexer robot IR and the main transport robot CR. The main transport robot CR transports the substrate W between the shuttle SH and the plurality of processing units 2. The thick arrow shown in FIG. 1 has shown the movement direction of the indexer robot IR, and the movement direction of the shuttle SH.

The plurality of processing units 2 form four towers each disposed at four horizontally spaced positions. Each tower includes a plurality of processing units 2 stacked in the vertical direction. The tower is arrange | positioned two by the both sides of a conveyance path | route. The plurality of processing units 2 include a plurality of dry processing units 2D for processing the substrate W while the substrate W is dried, and a plurality of wet processing units for processing the substrate W with a processing liquid. (2W). Two towers on the load port LP side are configured by a plurality of dry processing units 2D. The remaining two towers are constituted by a plurality of wet processing units 2W.

The wet processing unit 2W includes a wet chamber 9 provided with a carry-in / out port through which the substrate W passes, a shutter 10 for opening and closing the carry-in / out port of the wet chamber 9, and a wet chamber 9. The spin chuck 11 which rotates the board | substrate W around the rotation axis A1 which passes the center part of the board | substrate W, maintaining the board | substrate W horizontally in the inside, and the board | substrate held by the spin chuck 11 A plurality of nozzles 12 and 13 for discharging the processing liquid toward (W) are included. The plurality of nozzles 12 and 13 include a chemical liquid nozzle 12 for discharging a chemical liquid and a rinse liquid nozzle 13 for discharging a rinse liquid.

The dry processing unit 2D includes a dry chamber 4 provided with a carry-in / out port through which the substrate W passes, a shutter 5 that opens and closes the carry-in / out port of the dry chamber 4, water vapor and ozone gas ( And a gas processing unit 8 for treating the substrate W with a mixed gas of O ₃ gas).

2 is a schematic diagram for describing a configuration example of the gas processing unit 8.

The gas processing unit 8 is supported by the support member 23 by heating the support member 23 and the support member 23 that support the substrate W from below so that the substrate W is in a horizontal posture. The heater 22 which heats the board | substrate W, the hood 30 which opposes the support member 23 from upper direction, and the hood which raises and lowers the hood 30 with respect to the support member 23 and the base ring 27 A lifting unit 29. The gas processing unit 8 includes a base ring 27 that supports the hood 30 from below, an O ring 28 that seals between the hood 30 and the base ring 27, and a support member 23. ) And a plurality of lift pins 24 for horizontally supporting the substrate W between the hood 30 and the hood 30, and a lift elevating unit 26 for elevating the plurality of lift pins 24.

The heater 22 is connected to the heater electricity supply unit 31 which supplies electric power to the heater 22. The heater 22 is adjacent to the support member 23 from the bottom in this embodiment, but unlike the present embodiment, the heater 22 may be disposed inside the support member 23.

The support member 23 includes a disc-shaped base portion 23b disposed below the substrate W, a plurality of hemispherical protrusions 23a projecting upward from an upper surface of the base portion 23b, and a base portion. And an annular flange portion 23c protruding outward from the outer circumferential surface of 23b. The upper surface of the base part 23b is parallel to the lower surface of the board | substrate W, and has an outer diameter more than the outer diameter of the board | substrate W. As shown in FIG. The plurality of protrusions 23a contact the bottom surface of the substrate W at a position away from the top surface of the base portion 23b. The plurality of protrusions 23a are disposed at a plurality of positions in the upper surface of the base portion 23b so that the substrate W is horizontally supported. The substrate W is horizontally supported with the lower surface of the substrate W separated upward from the upper surface of the base portion 23b. The base ring 27 is connected to the flange part 23c.

The dry processing unit 2D includes a cooling unit 7 (see FIG. 1) that cools the substrate W heated by the heater 22 in the dry chamber 4, and the gas processing unit 8. The heated substrate W may include the indoor conveyance mechanism 6 (refer FIG. 1) which conveys the board | substrate W in the dry chamber 4.

The plurality of lift pins 24 are respectively inserted into the plurality of through holes penetrating the support member 23. Entry of fluid into the through hole from the outside of the gas processing unit 8 is prevented by the bellows 25 surrounding the lift pins 24. The gas processing unit 8 may be provided with an O-ring sealing the gap between the outer circumferential surface of the lift pin 24 and the inner circumferential surface of the through hole in place of or in addition to the bellows 25. . The lift pin 24 includes a hemispherical upper end portion in contact with the lower surface of the substrate W. As shown in FIG. Upper ends of the plurality of lift pins 24 are arranged at the same height.

The lift elevating unit 26 includes an upper position (position shown in FIGS. 9A and 9B) at which upper ends of the plurality of lift pins 24 are located above the support member 23, and a plurality of lift pins 24. The plurality of lift pins 24 are moved in the vertical direction between the lower positions (positions shown in FIG. 2) in which the upper end portion is retracted into the support member 23. An electric motor or an air cylinder may be sufficient as the lift elevating unit 26, and actuators other than these may be sufficient as it.

The hood lifting unit 29 moves the hood 30 vertically between the upper position (position shown in FIG. 9A) and the lower position (position shown in FIG. 2). The upper position is a position where the lower surface of the hood 30 is separated upward from the upper surface of the base ring 27 so that the substrate W can pass between the lower surface of the hood 30 and the upper surface of the base ring 27. The lower position is a position at which a gap between the lower surface of the hood 30 and the upper surface of the base ring 27 is sealed to form a space S for accommodating the substrate W supported by the support member 23. The hood lifting unit 29 may be an electric motor or an air cylinder, or may be an actuator other than these.

The gas processing unit 8 includes a mixed gas supply unit 14 for supplying a mixed gas toward the upper surface of the substrate W, an exhaust unit 15 for exhausting the space S, and an upper surface of the substrate W. It further includes an ultraviolet irradiation unit 16 for irradiating ultraviolet rays toward.

The mixed gas supply unit 14 includes a plurality of mixed gas nozzles 40 for discharging the mixed gas toward the upper surface of the substrate W, and a plurality of mixed gas nozzles 40 for the mixed gas from the mixed gas supply source 41. ), And a mixed gas valve 43 interposed between the mixed gas supply pipes 42. The plurality of mixed gas nozzles 40 have a discharge port 40a that is opened at a position facing the substrate W on the bottom surface of the hood 30. The mixed gas valve 43 switches the presence or absence of supply of the mixed gas to the plurality of mixed gas nozzles 40.

The exhaust unit 15 has a plurality of discharge ports 50a opened at the upper surface of the support member 23 and is provided to the exhaust pipe 52 which guides the gas in the space S to the outside of the space S, and the exhaust pipe 52. And an exhaust valve 53 interposed to open and close the flow path.

The ultraviolet irradiation unit 16 includes the plurality of ultraviolet lamps 60 and the lamp energizing unit 61 connected to the plurality of ultraviolet lamps 60. The ultraviolet lamp 60 emits ultraviolet rays by being fed from the lamp energizing unit 61. In this embodiment, although one lamp electricity supply unit 61 is provided in each ultraviolet ray lamp 60, the common lamp electricity supply unit may be provided with respect to the some ultraviolet lamp 60. As shown in FIG. The plurality of ultraviolet lamps 60 are attached to the lower surface of the hood 30, and at least some of them face the substrate W. As shown in FIG. The ultraviolet lamp 60 is comprised by the low pressure mercury lamp which irradiates an ultraviolet-ray of 185 nm, for example.

FIG. 3 is a schematic diagram of a cross section taken along the line III-III of FIG. 2.

The plurality of mixed gas nozzles 40 include a center nozzle 40A having an ejection opening 40a opened at a position facing the center of the substrate W, and an ejection opening opened at a position facing the outer peripheral portion of the substrate W. As shown in FIG. A plurality of outer peripheral nozzles 40B having 40a are included. The center part of the board | substrate W means the part located in the center of the board | substrate W in planar view. The outer peripheral part of the board | substrate W means the part between the center part of the board | substrate W, and the periphery of the board | substrate W in planar view. The plurality of outer circumferential nozzles 40B are disposed at equal intervals around the vertical line A2 passing through the center portion of the substrate W. As shown in FIG. Four outer nozzles 40B are provided in total at intervals of 90 degrees, for example.

The ultraviolet lamp 60 includes a center lamp 60A facing the central portion of the substrate W and a plurality of outer lamps 60B facing the outer peripheral portion of the substrate W. As shown in FIG. The center lamp 60A surrounds the center nozzle 40A in plan view, and is located on the vertical line A2 side than the plurality of outer circumferential nozzles 40B. The plurality of outer circumferential lamps 60B are arranged at equal intervals around the vertical line A2. The plurality of outer lamps 60B are provided in total, for example, at intervals of 90 degrees. The plurality of outer circumferential lamps 60B is located on the side opposite to the vertical line A2 side than the plurality of outer circumferential nozzles 40B. The plurality of outer circumferential lamps 60B also faces the periphery of the substrate W. As shown in FIG.

FIG. 4: is a schematic diagram for demonstrating the structure of the mixed gas supply unit 14 and the exhaust unit 15 with which the gas processing unit 8 was equipped.

The mixed gas supply source 41 includes a tank 41A in which liquid water is stored, and an ozone gas supply unit 41B for supplying ozone gas to the liquid water stored in the tank 41A. The ozone gas supply unit 41B includes an ozone gas nozzle 44 for supplying ozone gas to water in the tank 41A, and an ozone supply pipe 45 for supplying ozone gas from the ozone gas supply source to the ozone gas nozzle 44. ) And an ozone gas valve 46 interposed in the ozone supply pipe 45. The ozone gas nozzle 44 has a discharge port 44a disposed in the water in the tank 41A. The ozone gas valve 46 switches the presence / absence of ozone gas to the ozone gas nozzle 44.

The mixed gas supply pipe 42 of the mixed gas supply unit 14 includes a main pipe 42A with a mixed gas valve 43 interposed therebetween, and a plurality of branch pipes 42B branched from the other end of the main pipe 42A. . The main pipe 42A has an intake port 42a provided at a position above the water surface in the tank 41A. The branch piping 42B is provided in the same number as the mixed gas nozzle 40, and each branch pipe 42B is connected to the corresponding mixed gas nozzle 40. As shown in FIG.

The exhaust pipe 52 of the exhaust unit 15 includes a main pipe 52A with an exhaust valve 53 and a filter 54 interposed therebetween, and a plurality of branch pipes 52B branched from the main pipe 52A. Each branch pipe 52B has one discharge port 50a (see also FIG. 2). The filter 54 is for filtering the gas discharged from the space S.

The mixed gas valve 43, the ozone gas valve 46, the tank 41A, the exhaust valve 53, and the filter 54 are disposed in the fluid box 17 adjacent to the dry chamber 4.

5 is a block diagram for explaining the electrical configuration of the main part of the substrate processing apparatus 1. The controller 3 is equipped with a microcomputer, and controls the control object with which the substrate processing apparatus 1 was equipped in accordance with a predetermined program. More specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B in which a program is stored, and the processor 3A executes a program to execute various controls for substrate processing. It is configured to. In particular, the controller 3 includes the indexer robot IR, the main transport robot CR, the shuttle SH, the lifting units 26 and 29, the energizing units 31 and 61, the valves 43, 46 and 53. ) And the wet processing unit 2W.

FIG. 6 is a process chart showing an example of a substrate W processing performed by the substrate processing apparatus 1, and mainly shows a process realized by the controller 3 executing a program. FIG. 7: is a schematic diagram which shows the cross section of the board | substrate W before and after an example of the process of processing the board | substrate W shown in FIG.

As shown in the left side of FIG. 7, the substrate W processed by the substrate processing apparatus 1 has the etching process process of etching the thin film covered with the pattern PR of resist, and forming the pattern PF of thin film. It is a board | substrate performed. That is, the carrier C on which the substrate W is accommodated is placed on the load port LP. As will be described below, in the substrate processing by the substrate processing apparatus 1, the pattern PR of the resist located on the pattern PF of the thin film is removed (resist removal step). The right side of FIG. 7 has shown the cross section of the board | substrate W in which the resist removal process was performed.

When the substrate W is processed by the substrate processing apparatus 1, the indexer robot IR, the shuttle SH, and the main transport robot CR are arranged in the substrate C in the carrier C placed on the load port LP. W is conveyed to the dry processing unit 2D (step S1 in FIG. 6). In the dry processing unit 2D, a dry processing step of treating the substrate W with a mixed gas is performed (step S2 in FIG. 6). Thereafter, the main transport robot CR carries the substrate W in the dry processing unit 2D into the wet processing unit 2W (step S3 in FIG. 6).

In the wet processing unit 2W, a wet processing step of supplying a processing liquid to the upper surface of the substrate W while rotating the substrate W is performed (step S4 in FIG. 6). Specifically, the chemical liquid supply step of discharging the chemical liquid to the chemical liquid nozzle 12 toward the upper surface of the substrate W while rotating the substrate W is performed. Then, the rinse liquid supplying process which discharges a rinse liquid to the rinse liquid nozzle 13 toward the upper surface of the board | substrate W, rotating the board | substrate W is performed. Thereafter, a drying step of drying the substrate W is performed by rotating the substrate W at a high speed. Next, the indexer robot IR, the shuttle SH, and the main transport robot CR carry the substrate W in the wet processing unit 2W to the carrier C placed in the load port LP (FIG. Step S5).

8 is a flowchart illustrating an example of a dry processing process (step S2 of FIG. 6). 9A to 9D are schematic diagrams for explaining the dry processing step (step S2 of FIG. 6).

As shown in FIG. 9A, when bringing the substrate W into the dry processing unit 2D, the hood lifting unit 29 positions the hood in an upper position, and the lift lifting unit 26 includes a plurality of lift pins ( 24) in the upper position. In this state, the main transport robot CR enters the hand H into the dry chamber 4 while supporting the substrate W with the hand H. As shown in FIG. Subsequently, the substrate W having its surface, which is the device formation surface, is placed on the plurality of lift pins 24. The main transport robot CR transfers the substrate W on the hand H to the dry processing unit 2D, and then moves the hand H out of the dry chamber 4. Thereafter, the carry-in / out port of the dry chamber 4 is closed. Thus, carrying in of the board | substrate W to the dry chamber 4 is completed (step T1). The substrate W may be placed on the plurality of lift pins 24 by the hand H of the main transport robot CR, and the plurality of lift pins (by the indoor transport mechanism 6 (see FIG. 1)). 24) may be placed on.

As shown in FIG. 9B, the hood lifting unit 29 moves the hood 30 to the lower position (step T2). Thereby, the space S which accommodates the board | substrate W is formed between the hood 30 and the support member 23 (space formation process). The hood 30 and the support member 23 function as a space forming unit that accommodates the substrate W. As shown in FIG. And the lift elevating unit 26 moves the some lift pin 24 to a lower position. In the process of moving the some lift pin 24 to a lower position, the board | substrate W is received by the support member 23, and the water supply is carried out from the some lift pin 24 to the support member 23. FIG. do. Thereby, the board | substrate W is supported by the support member 23 (support process).

The heater energization unit 31 energizes the heater 22 before the substrate W is supported by the support member 23. Therefore, the support member 23 is heated by the heater 22 before the substrate W is supported by the support member 23. The support member 23 is maintained at a temperature higher than room temperature (for example, 100 ° C. or higher). When the substrate W is supported by the support member 23, heating of the substrate W is started (step T3).

Next, as shown in FIG. 9C, the ozone gas valve 46 is opened to transfer the ozone gas into the water in the tank 41A. Specifically, bubbling causes bubbles of ozone gas to pass through the water in the tank 41A. Thereby, water vapor | steam generate | occur | produces in a bubble, this water vapor mixes with ozone gas, and mixed gas is formed (mixed gas formation process). Then, the mixed gas valve 43 is opened, and the mixed gas is discharged from the discharge ports 40a of the plurality of mixed gas nozzles 40 through the tank 41A and the mixed gas supply pipe 42 (step T4). That is, the mixed gas discharge process is performed. As a result, the mixed gas is supplied into the space S. FIG.

Then, the exhaust valve 53 is opened (step T5). As a result, the air in the space S is pushed out of the space S by the mixed gas. By continuing to supply the mixed gas to the space S, the mixed gas is filled in the space S. When the mixed gas is filled in the space S, the mixed gas is sufficiently supplied to the vicinity of the upper surface of the substrate W (mixed gas supply process).

In addition, the substrate W is heated by the heater 22 even while being supplied to the mixed gas near the upper surface of the substrate W (first heating step). That is, a 1st heating process is performed in parallel with a mixed gas supply process. The heater 22 functions as a 1st heating unit which heats the board | substrate W. As shown in FIG.

As shown in FIG. 9D, ultraviolet light is irradiated from the ultraviolet lamp 60 by energizing the ultraviolet lamp 60 while the mixed gas is supplied near the upper surface of the substrate W (step T6). Thereby, an ultraviolet-ray is irradiated to the mixed gas of the upper surface vicinity of the board | substrate W (ultraviolet irradiation process).

Before the ultraviolet rays are irradiated to the mixed gas near the upper surface of the substrate W (before the ultraviolet ray irradiation step), the space S is already formed. In addition, the exhaust valve 53 is kept open even while ultraviolet rays are irradiated to the mixed gas near the upper surface of the substrate W. As shown in FIG. Therefore, the exhaust process which exhausts space S is performed during execution of an ultraviolet irradiation process.

The substrate W is also heated by the heater 22 while the ultraviolet rays are being irradiated to the mixed gas near the upper surface of the substrate W (second heating step). That is, a 2nd heating process is performed in parallel with an ultraviolet irradiation process. The heater 22 functions as a 2nd heating unit which heats the board | substrate W. As shown in FIG. In this embodiment, the heater 22 heats the substrate W so that the first heating step and the second heating step are performed in parallel.

Although mentioned later in detail, by irradiating an ultraviolet-ray to the mixed gas of the upper surface vicinity of the board | substrate W, the resist formed in the upper surface of the board | substrate W is oxidized and decompose | disassembles. As a result, the pattern PR of the resist is removed from the upper surface of the substrate W. As shown in FIG.

After the ultraviolet irradiation is performed for a predetermined time, the lamp energizing unit 61 stops energizing the ultraviolet lamp 60 from the upper surface of the substrate W (step T7). Then, the mixed gas valve 43 is closed to stop the supply of the mixed gas to the space S (step T8). Then, the exhaust valve 53 is closed to exhaust the space S (step T9). Subsequently, the substrate W on the supporting member 23 is lifted up by the plurality of lift pins 24 (step T10), and the hood lifting unit 29 raises the hood 30 to the upper position ( Step T11).

The main transport robot CR receives the board | substrate W with the hand H after the board | substrate W is cooled by the cooling unit 7 (refer FIG. 1). Thereafter, the main transport robot CR carries the substrate W on the hand H into the wet processing unit 2W.

According to this embodiment, the mixed gas which mixed water vapor and ozone gas is supplied in the vicinity of the upper surface of the board | substrate W supported horizontally by the support member 23. Hydroxy radicals (.OH) are generated by irradiating the mixed gas with ultraviolet rays from the ultraviolet irradiation unit 16. Specifically, first, by irradiation with ultraviolet rays, water vapor (H ₂ O) is decomposed to generate hydroxy radicals (.OH) and hydrogen radicals (.H) as in the following formula (1).

And, as shown in the following formula (2), the hydrogen radical (· H) and ozone (O ₃ ) reacts, generating hydroxy radical (· OH) and oxygen (O ₂ ).

Therefore, a sufficient amount of hydroxy radical (.OH) can be generated by decomposition of water vapor (H ₂ O) and reaction of hydrogen radical (.H) and ozone (O ₃ ).

Moreover, since water vapor (water of gas) is supplied to the upper surface of the board | substrate W, attachment of a droplet (water of liquid) to the upper surface of the board | substrate W can be suppressed. Therefore, ozone can be decomposed in the vicinity of the upper surface of the substrate W without being impeded by the absorption of ultraviolet rays by the liquid water.

The hydroxy radicals and ozone generated in this way oxidize the phenol resin constituting the resist. As a result, the phenol resin is decomposed into lower carboxylic acids such as acetic acid and oxalic acid. These lower carboxylic acids are further oxidized by hydroxy radicals and ozone to decompose into carbon dioxide and water. In this way, the resist is decomposed by hydroxy radicals and ozone.

As described above, since the resist formed on the upper surface of the substrate W is decomposed by a sufficient amount of hydroxy radicals, the resist can be satisfactorily removed from the surface of the substrate W. As shown in FIG.

Further, the life of the hydroxy radical hydroxy is, 1.0 × 10 ^{- 6} sec, according to the bar, the configuration (method) of the present embodiment, it is possible to generate the hydroxyl radical in the vicinity of the upper surface of the substrate (W). Therefore, it is possible to increase the amount of hydroxy radicals that decompose the resist before the hydroxy radicals disappear.

In other words, in the present embodiment, the ultraviolet irradiation step includes a step of generating hydroxy radicals near the upper surface of the substrate W by irradiation of ultraviolet rays, and a step of decomposing a resist by hydroxy radicals. Therefore, the resist can be reliably decomposed by the hydroxy radicals generated by the irradiation of the ultraviolet rays from the ultraviolet irradiation unit 16.

Here, the decomposition mechanism of the resist will be described. In the molecules constituting the resist formed on the surface of the substrate W, double bonds (C = C) of carbons are contained, and the double bonds are cleaved by oxidation to decompose the resist.

10 is a graph for comparing the binding potential of the oxidizing agent with the covalent bond. In the right half of the graph shown in FIG. 10, the binding energy required for cleaving the representative covalent bond contained in an organic compound is shown. In the left half of the graph shown in FIG. 10, the oxidation potential is shown as an index of the oxidation capability of a typical oxidizing agent. If the oxidation potential of the oxidant is higher than the binding energy of the covalent bond, the covalent bond is cleaved by oxidation. As shown in FIG. 10, the bond energy of the double bond (C = C) of carbon is 1.5V. On the other hand, the oxidation potential of ozone (O ₃ ) is 2.07V, and the oxidation potential of hydroxy radical (.OH) is 2.81V. Thus, the double bond between the carbon (C = C) is, or is oxidized by any of ozone (O ₃₎ and hydroxy radicals (· OH). Since the oxidation potential of hydroxy radicals (.OH) is higher than that of ozone (O ₃ ), by generating more hydroxy radicals, double bonds (C = C) between carbons can be efficiently oxidized. . That is, the resist can be decomposed efficiently.

Moreover, according to this embodiment, the 1st heating process which heats the board | substrate W is performed in parallel with a mixed gas supply process. Therefore, the mixed gas in the vicinity of the upper surface of the substrate W is heated by the heater 22. Therefore, liquefaction of the water vapor in the vicinity of the upper surface of the substrate W can be suppressed.

Moreover, according to this embodiment, the 2nd heating process which heats the board | substrate W is performed in parallel with an ultraviolet irradiation process. Therefore, the decomposition products of the resist generated near the upper surface of the substrate W are heated by the heater 22. Thereby, the decomposition product of the resist can be sublimed into a gaseous state. Therefore, the decomposition product of the resist can be suppressed from solidifying on the upper surface of the substrate W. FIG. Therefore, the resist formed on the surface of the substrate W can be satisfactorily removed. By carrying out a 2nd heating process which heats the board | substrate W in parallel with an ultraviolet irradiation process, liquefaction of the water vapor in the vicinity of the upper surface of the board | substrate W also in an ultraviolet irradiation process can be suppressed.

According to the present embodiment, the mixed gas is discharged from the discharge port 40a toward the upper surface of the substrate W (mixed gas discharge step). As a result, the mixed gas is discharged from the discharge port 40a toward the upper surface of the substrate W. As shown in FIG. Therefore, water vapor and ozone in the vicinity of the upper surface of the substrate W in the entire upper surface of the substrate W, as compared with the configuration in which water vapor and ozone gas are discharged toward the upper surface of the substrate W from different discharge ports. The proportion of gas can be kept even.

Moreover, according to this embodiment, the space S is formed before the start of an ultraviolet irradiation process (space formation process), and the inside of space S is exhausted during execution of an ultraviolet irradiation process (exhaust process).

As a result, the substrate W is accommodated in the space S blocked from the outside before the mixed gas near the upper surface of the substrate W is irradiated with ultraviolet rays. Therefore, ultraviolet-ray can be irradiated in the state which filled the mixed gas in space S (space near the upper surface of the board | substrate W). Thus, it is possible to generate a sufficient amount of hydroxy radicals. On the other hand, the space S is exhausted during the irradiation of ultraviolet rays. Accordingly, before the decomposition product of the resist is solidified on the upper surface of the substrate W, the decomposition product of the resist can be discharged to the outside of the space S. FIG.

In addition, according to the present embodiment, a mixed gas is formed by supplying ozone gas from the ozone gas supply unit 41B to the liquid water stored in the tank 41A (mixed gas forming step). Therefore, when preparing a mixed gas, it is not necessary to mix ozone gas and water vapor after preparing steam separately from ozone gas. That is, compared with the case where steam is prepared separately from ozone gas, a mixed gas can be prepared simply.

11 is a schematic diagram of the gas processing unit 8 according to the first modification of the present embodiment. In the gas processing unit 8 which concerns on a 1st modification, the mixed gas supply pipe 42 is connected to each mixed gas nozzle 40 one by one. The mixed gas supply pipe 42 is supplied from a confluence pipe 42C connected to the mixed gas nozzle 40, a steam pipe 42D for supplying steam supplied from a steam supply source to the confluence pipe 42C, and an ozone gas supply source. An ozone gas pipe 42E for supplying the ozone gas to be supplied to the confluence pipe 42C is included. Water vapor in the steam pipe 42D and ozone gas in the ozone gas pipe 42E are mixed in the confluence pipe 42C. The mixed gas mixed in the joining pipe 42C is supplied from the mixed gas nozzle 40. The steam pipe 42D is provided with a steam valve 43D for opening and closing the flow path. The ozone gas pipe 42E is interposed with an ozone gas valve 43E for opening and closing the flow path.

Also in the substrate processing apparatus 1 which concerns on a 1st modification, the same substrate processing as the substrate processing apparatus 1 which concerns on this embodiment can be performed. Moreover, also in a 1st modification, it exhibits the same effect as this embodiment. Moreover, in the 1st modification, the component ratio of the water vapor and ozone gas in mixed gas can be adjusted by adjusting the opening degree of the steam valve 43D and the ozone gas valve 43E. For example, when there is too much water vapor contained in a mixed gas, water droplets will adhere to the upper surface of the board | substrate W easily. On the other hand, if the water vapor contained in the mixed gas is too small, hydroxy radicals cannot be generated sufficiently. By adjusting the ratio of water vapor in the mixed gas, adhesion of water droplets to the upper surface of the substrate W can be suppressed while generating hydroxy radicals sufficiently.

12 is a schematic view of the gas processing unit 8 according to the second modification of the present embodiment. In the gas processing unit 8 according to the second modification, water vapor and ozone gas are discharged from different discharge ports 80a and 81a. The mixed gas supply unit 14 includes, instead of the mixed gas nozzle 40, a steam nozzle 80 for discharging water vapor and an ozone gas nozzle 81 for discharging ozone gas. The steam nozzle 80 has a discharge port 80a. The ozone gas nozzle 81 has a discharge port 81a. The mixed gas supply unit 14 includes a steam supply pipe 82 for supplying steam from a steam supply source to the steam nozzle 80, a steam valve 83 interposed in the steam supply pipe 82 to open and close the flow path; An ozone gas supply pipe 84 for supplying ozone gas from an ozone gas supply source to the ozone gas nozzle 81 and an ozone gas valve 85 interposed in the ozone gas supply pipe 84 to open and close the flow path. The mixed gas is formed by mixing the water vapor discharged from the water vapor nozzle 80 and the ozone gas discharged from the ozone gas nozzle 81 in the space S. FIG. By forming the mixed gas in the space S, the mixed gas is supplied near the upper surface of the substrate W. As shown in FIG.

Also in the substrate processing apparatus 1 which concerns on a 2nd modification, the same substrate processing as the substrate processing apparatus 1 which concerns on this embodiment can be performed. Moreover, also in a 2nd modification, the same effect as this embodiment is exhibited.

This invention is not limited to embodiment described above, It can implement in another form.

For example, in embodiment mentioned above, the mixed gas supply process and the ultraviolet irradiation process were performed in parallel. However, unlike embodiment mentioned above, you may start irradiation of an ultraviolet-ray after stopping supply of a mixed gas. That is, in FIG. 8, before the ultraviolet irradiation start (step T6), the mixed gas supply stop (step T8) may be performed.

In such a case, the second heating step is started after the completion of the first heating step. Therefore, changing the temperature of the heater 22 in the first heating step of heating the substrate W in the mixed gas supply process and the second heating step of heating the substrate W in the ultraviolet irradiation step. It is possible. For example, when the sublimation temperature of the decomposition product of the resist is different from the temperature required to prevent water droplets from adhering to the surface of the substrate W, the temperature of the substrate W in the first heating step is different from each other. It is possible to change the temperature of the substrate W in the second heating step. Moreover, when a 2nd heating process is started after completion | finish of a 1st heating process, instead of the heater 22, the board | substrate W in the 1st heater which heats the board | substrate W in a 1st heating process, and a 2nd heating process. The 2nd heater which heats the heat may be provided.

Moreover, in embodiment mentioned above, the hood 30 was lowered and the space S was formed before starting supply of a mixed gas. However, unlike embodiment mentioned above, you may form space S after starting supply of a mixed gas. That is, in FIG. 8, mixed gas supply start (step T4) may be performed before hood lowering (step T2).

In addition, unlike the above-described embodiment, the exhaust unit 15 includes an exhaust pump (not shown) such as a vacuum pump connected to the exhaust pipe 52 to exhaust the space S through the discharge port 50a. You may do it.

In addition, unlike the above-mentioned embodiment, as shown in FIG. 13, the ultraviolet-ray lamp 60 is a rod-type extended linearly instead of the center lamp 60A and the outer lamp 60B (refer FIG. 3). The lamp 60C may be included. The ultraviolet lamp 60 is not limited to these forms, and in order to generate | occur | produce hydroxy radicals all over the surface of the board | substrate W, it is preferable to be provided so that it may oppose all the board | substrates without missing.

3, the plurality of outer circumferential nozzles 40B of the mixed gas nozzle 40 are arranged along the radial direction orthogonal to the vertical line A2 passing through the center portion of the substrate W. As shown in FIG. You may be. In addition, the rows of the plurality of outer circumferential nozzles 40B arranged in the radial direction may be arranged at regular intervals around the vertical line A2.

Although embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical details of the present invention, and the present invention should not be construed as being limited to these embodiments, but the scope of the present invention is It is limited only by the appended claims.

This application corresponds to Japanese Patent Application No. 2017-060073, filed with the Japan Patent Office on March 24, 2017, and all disclosures of this application are incorporated herein by reference.

1: substrate processing apparatus 3: controller
14: mixed gas supply unit 15: exhaust unit
16: ultraviolet irradiation unit
22: heater (first substrate heating unit, second substrate heating unit)
23: support member (space forming unit) 30: hood (space forming unit)
40a: discharge port 41A: tank
41B: Ozone Gas Supply Unit S: Space
W: Substrate

Claims (13)

A substrate processing method for removing a resist from a surface of a substrate,
A support step of causing the support member to horizontally support the substrate;
A mixed gas supply step of supplying a mixed gas of water vapor and ozone gas to the vicinity of the surface of the substrate;
And a UV irradiation step of irradiating ultraviolet rays to the mixed gas supplied near the surface of the substrate. The method according to claim 1,
The ultraviolet irradiation step includes a step of generating hydroxy radicals near the surface of the substrate by irradiation of ultraviolet rays, and a step of decomposing the resist by the hydroxy radicals. The method according to claim 1 or 2,
And a first heating step that is performed in parallel with the mixed gas supply step and heats the substrate. The method according to any one of claims 1 to 3,
And a second heating step that is performed in parallel with the ultraviolet irradiation step and heats the substrate. The method according to any one of claims 1 to 4,
And the mixed gas supplying step includes a mixed gas discharging step of discharging the mixed gas from a discharge port toward the surface of the substrate. The method according to any one of claims 1 to 5,
A space forming step of receiving the substrate and forming a space cut off from the outside at least before the start of the ultraviolet irradiation step;
And an exhausting step of exhausting the inside of the space during the execution of the ultraviolet irradiation step. The method according to any one of claims 1 to 6,
And a mixed gas forming step of forming the mixed gas by supplying the ozone gas to the liquid water stored in the tank. A substrate processing apparatus for removing a resist from a surface of a substrate,
A support member for horizontally supporting the substrate;
A mixed gas supply unit supplying a mixed gas toward a surface of the substrate;
An ultraviolet irradiation unit for irradiating ultraviolet rays toward the surface of the substrate;
A mixed gas supply step of supplying the mixed gas from the mixed gas supply unit near the surface of the substrate, and an ultraviolet ray which causes the ultraviolet irradiation unit to irradiate ultraviolet rays with the mixed gas supplied near the surface of the substrate; A substrate processing apparatus comprising a controller programmed to execute an irradiation process. The method according to claim 8,
Wherein the controller is programmed to perform a step of generating hydroxy radicals near the surface of the substrate by irradiation of ultraviolet rays and a step of decomposing a resist by the hydroxy radicals in the ultraviolet irradiation step. Processing unit. The method according to claim 8 or 9,
Further comprising a first substrate heating unit for heating the substrate,
And the controller is programmed to execute a first heating step of causing the first substrate heating unit to heat the substrate in parallel with the mixed gas supplying step. The method according to any one of claims 8 to 10,
Further comprising a second substrate heating unit for heating the substrate,
And the controller is programmed to execute a second heating step of causing the second substrate heating unit to heat the substrate in parallel with the ultraviolet irradiation step. The method according to any one of claims 8 to 11,
A space forming unit configured to receive the substrate and form a space blocked from the outside, and an exhaust unit configured to exhaust the space;
A space forming step of controlling the space forming unit to form a space at least before the start of the ultraviolet irradiation step; and an exhausting step of controlling the exhaust unit to exhaust the space during execution of the ultraviolet irradiation step. A substrate processing apparatus, programmed to further execute. The method according to any one of claims 8 to 12,
Tanks for storing liquid water,
It further comprises an ozone gas supply unit for supplying ozone gas to the water of the liquid stored in the tank,
And the controller is programmed to execute a mixed gas forming step of forming the mixed gas by supplying the ozone gas from the ozone gas supply unit to the liquid water stored in the tank.

Images