JP2003188137A - Substrate processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate processing apparatus which can realize a uniform cleaning process of the substrate surface. <P>SOLUTION: A substrate W is moved downward with a lifter 20 and is then transferred to a couple of rollers 30. The roller 30 is rotated while it is holding the substrate W. When the substrate W is rotated, the substrate W is heated by the radiation of the light from a halogen lamp 80 and moreover vapor and ozone gas are respectively supplied to the substrate W from a vapor nozzle 50 and an ozone gas nozzle 60. At the surface of substrate W, the resist peeling process is performed with radical of hydroxyl group generated by decomposition of the ozone gas. In this case, since vapor and ozone gas are supplied while the substrate W is rotating, the ozone gas is supplied uniformly to the surface of substrate W and thereby uniform cleaning of the substrate surface can be realized. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment of a semiconductor substrate, a glass substrate for a liquid crystal display device, a glass substrate for a photomask, a substrate for an optical disk, etc. (hereinafter referred to as "substrate"), and particularly ozone (O ₃ The present invention relates to a substrate processing apparatus for performing a cleaning process using a) and a removal process of organic substances such as resist.

[0002]

2. Description of the Related Art In general, a part of a process for manufacturing a semiconductor, a liquid crystal display or the like includes a photolithography process for the above substrate. In the photolithography process, a photoresist (hereinafter simply referred to as a resist) is applied to a substrate, a resist film formed on the substrate is exposed with a pattern, and then a development process is performed. After the development process is completed, the unnecessary resist is removed.

Conventionally, the resist removing process is performed by using sulfuric acid (H ₂ S
Although it has been performed by using a solution containing O ₄ ), in recent years, a resist removing process using ozone water, which is easy to drain and has a low environmental load, has been attracting attention. In order to effectively remove the resist using ozone water, it is necessary to immerse the substrate in high-temperature and high-concentration ozone water, but in the case of ozone as well as other gases, the temperature of the solution becomes high. Since the solubility decreases, it is difficult to generate high-temperature and high-concentration ozone water, and even if ozone water is used, a high resist removal treatment rate cannot be obtained.

For this reason, recently, a method of supplying water vapor and ozone gas to the substrate to generate a large amount of highly reactive hydroxyl radicals and the like to oxidize and remove the resist is attracting attention. According to this method, even if the temperature of the substrate is high, a highly reactive hydroxyl radical or the like can be efficiently supplied to the substrate surface, and a higher processing speed than that using ozone water can be obtained.

[0005]

However, the method of supplying water vapor and ozone gas to the substrate has a problem that it is difficult to obtain the uniformity of processing, as compared with the case of immersing in ozone water. That is, it is difficult to supply water vapor and ozone gas under uniform conditions to the entire surface of the substrate, and as a result, the resist removal process becomes non-uniform.

The present invention has been made in view of the above problems, and an object thereof is to provide a substrate processing apparatus capable of uniformly processing the surface of a substrate.

[0007]

In order to solve the above problems, the invention of claim 1 is a substrate processing apparatus for processing a substrate surface, wherein a chamber for housing the substrate and a substrate for holding the substrate in the chamber are provided. Rotation holding means for rotating the substrate held by the rotation holding means, ozone gas supply means for supplying ozone gas to the substrate held by the rotation holding means, and water vapor is supplied to the substrate held by the rotation holding means to generate water vapor on the surface of the substrate. Steam supply means for condensing.

The invention according to claim 2 is the substrate processing apparatus according to claim 1, further comprising pure water supply means for supplying pure water to the substrate held by the rotation holding means.

According to a third aspect of the present invention, in the substrate processing apparatus according to the second aspect of the invention, the pure water supply means supplies pure water to the substrate after the ozone gas has been supplied from the ozone gas supply means. ing.

According to a fourth aspect of the invention, in the substrate processing apparatus according to any one of the first to third aspects,
The ozone gas supply means further comprises a decomposition promoter supply means for supplying a decomposition promoter for an organic substance attached to the substrate when the ozone gas supply means supplies ozone gas.

According to a fifth aspect of the invention, in the substrate processing apparatus according to the fourth aspect of the invention, the decomposition accelerator is acetic acid.

The invention according to claim 6 is the substrate processing apparatus according to any one of claims 1 to 5,
It further comprises heating means for heating the substrate held by the rotation holding means.

According to a seventh aspect of the present invention, in the substrate processing apparatus according to the sixth aspect of the invention, the rotation holding means holds the heating means at least until the steam is supplied from the steam supply means. The substrate is being heated.

Further, the invention of claim 8 is the substrate processing apparatus according to any one of claims 1 to 7,
The chamber further comprises a pressure reducing means for reducing the pressure in the chamber to less than atmospheric pressure.

According to a ninth aspect of the invention, in the substrate processing apparatus according to the eighth aspect of the invention, the inside of the chamber is decompressed before the ozone gas supply means supplies the ozone gas to the decompression means.

According to a tenth aspect of the invention, in the substrate processing apparatus according to the eighth or ninth aspect of the invention, there is provided organic solvent vapor supply means for supplying organic solvent vapor to the substrate held by the rotation holding means. Further prepare.

According to the invention of claim 11, in the substrate processing apparatus according to any one of claims 1 to 10, hydrofluoric acid vapor for supplying hydrofluoric acid vapor to the substrate held by the rotation holding means. A supply means is further provided.

According to a twelfth aspect of the present invention, in the substrate processing apparatus according to any one of the first to eleventh aspects of the present invention, the rotation holding means is parallel to the ozone gas supply direction from the ozone gas supply means. The substrate is rotated in the plane.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to the drawings.

<1. Configuration of Substrate Processing Apparatus> FIG. 1 is a diagram showing the overall configuration of a substrate processing apparatus 1 according to the present invention. 2 is a side view of the substrate processing apparatus of FIG. In addition, in FIG. 1 and the following drawings, in order to clarify the directional relationship between them, the Z-axis direction is set as a vertical direction and XY is set as necessary.
An XYZ orthogonal coordinate system in which the plane is the horizontal plane is attached.

The substrate processing apparatus 1 has a basic function of supplying water vapor and ozone gas to the substrate to perform resist removal processing. In addition to the basic function, the function of removing the silicon oxide film and the substrate are also provided. It has the function of performing the drying process of. The substrate processing apparatus 1 is provided in the chamber 10.
A lifter 20 that raises and lowers the substrate W, a rotating roller 30 that holds and rotates the substrate W during processing, a pure water nozzle 40 that discharges a shower of pure water into the chamber 10, and a water vapor nozzle 50 that discharges water vapor. An ozone gas nozzle 60 for ejecting ozone gas, a treatment liquid nozzle 70 for ejecting vapor of a treatment liquid such as hydrofluoric acid, and a halogen lamp 80 for heating the substrate W by light irradiation are provided. In addition, the substrate processing apparatus 1 is provided outside the chamber 10 with a mechanism for supplying a processing liquid or gas to each nozzle, a mechanism for reducing the pressure inside the chamber 10, and the like.

The chamber 10 is a housing for accommodating the substrate W for processing. A lid 11 is provided above the chamber 10.
Is provided, and the lid 11 can be opened and closed by a slide opening / closing mechanism (not shown). When the lid 11 is opened, the lifter 2 is opened through the opened portion.
0 and the transfer robot outside the apparatus can transfer the substrate W to and from the chamber 10. On the other hand, in the state where the lid 11 is closed, the space between the lid 11 and the chamber 10 is sealed by the O-ring, so that the inside of the chamber 10 can be a closed space. In this state, the gas in the chamber 10 does not leak to the outside, and the inside of the chamber 10 can be brought into a depressurized state lower than atmospheric pressure.

The lifter 20 includes lifter arms 23 and 3
Book holding bars 21a, 21b, 21c and lifting drive unit 2
Equipped with 2. The lift drive unit 22 includes the lifter arm 2
3 has a function of moving up and down along the vertical direction (Z-axis direction). The lifter arm 23 has three holding bars 21.
a, 21b, and 21c are fixed so that the longitudinal direction thereof is substantially horizontal (parallel to the Y-axis direction), and the three holding rods 2 are provided.
Each of 1a, 21b, 21c is provided with a plurality of holding grooves arranged at a predetermined pitch so that the outer edge portion of the substrate W fits therein and holds the substrate W in a standing posture.

With such a configuration, the lifter 20 has three
The plurality of substrates W, which are stacked and held in parallel with each other at a predetermined pitch by the book holding bars 21a, 21b, and 21c, can be moved up and down along the vertical direction. When the lifter 20 is lifted, the plurality of substrates W are held at the transfer position (the position indicated by the chain double-dashed line in FIG. 1) with the transfer robot outside the apparatus. Also, as shown by the solid line in FIG.
When the lifter 20 descends below the rotation roller 30, a plurality of substrates W are attached to the three holding bars 21a, 21b,
21c is passed to the rotary roller 30. It should be noted that various mechanisms such as a feed screw mechanism using a ball screw and a belt mechanism using a pulley and a belt can be adopted as the mechanism for raising and lowering the lifter arm 23 in the lift drive unit 22 of the lifter 20.

FIG. 3 is a perspective view of the rotary roller 30.
The rotating roller 30 is a cylindrical rod-shaped member, and a plurality of holding grooves 31 for holding the substrate W in an upright posture by arranging the outer edge portion of the substrate W on the outer peripheral surface thereof are arranged at a predetermined pitch. It is engraved. Then, such two rotary rollers 30 are connected to and held by the rotary drive unit 32 in parallel with each other such that their longitudinal directions are along the Y-axis direction. The pitch at which the holding grooves 31 are engraved is the same as the pitch of the holding grooves provided on the holding rods 21a, 21b, and 21c. Therefore, when the lifter 20 descends, the plurality of substrates W are attached to the three holding bars 21a, 21b, 21.
It is passed from the holding groove of c to the holding groove 31 of the rotating roller 30. On the contrary, when the lifter 20 moves up, the plurality of substrates W move from the holding groove 31 of the rotating roller 30 to the holding rod 21a,
It is passed to the holding grooves 21b and 21c.

The rotary drive unit 32 rotates the two rotary rollers 30 in the same direction and at the same rotational speed with an axis parallel to the Y-axis direction as the center of rotation. By rotating the two rotation rollers 30 while holding the plurality of substrates W, the plurality of substrates W are moved in the Y direction as indicated by an arrow AR1 in FIG.
It is possible to rotate all at once in the XZ plane with an axis parallel to the axial direction as the center of rotation. That is, the rotating roller 30 holds the plurality of substrates W in the chamber 10 and rotates the held substrates W.

The pure water nozzle 40 is a cylindrical member having a plurality of discharge holes 41 on its outer peripheral surface. Two such pure water nozzles 40 are provided in the chamber 10. The two deionized water nozzles 40 are installed parallel to each other in the upper part of the chamber 10 so that their longitudinal directions are along the Y-axis direction. The plurality of discharge holes 41 are formed in a row along the longitudinal direction of the pure water nozzle 40 at the same pitch as the pitch of the holding grooves 31 of the rotary roller 30. Further, the plurality of ejection holes 41 are provided such that the ejection direction thereof is parallel to the XZ plane and faces the substrate W held by the rotating roller 30. The number of ejection holes 41 provided in one pure water nozzle 40 is 1 than the number of holding grooves 31 of the rotary roller 30.
In many cases, the discharge holes 41 are provided at least at positions corresponding to the intermediate points of the adjacent holding grooves 31 (positions where the XZ plane including the intermediate points intersects the pure water nozzle 40) (see FIG. 2). Therefore, the deionized water nozzle 40 can eject deionized water between the adjacent substrates W held by the rotating roller 30.

The two pure water nozzles 40 are connected to a pure water supply source 44 by a pipe 42. A pure water valve 43 is provided in the middle of the pipe 42. By opening the deionized water valve 43, deionized water is supplied from the deionized water supply source 44 to the two deionized water nozzles 40, and the deionized water is showered onto the substrate W held by the rotating roller 30 from the ejection holes 41. Can be discharged. On the other hand, when the pure water valve 43 is closed, the pure water discharge from the pure water nozzle 40 is stopped.

Like the pure water nozzle 40, the water vapor nozzle 50 is a cylindrical member having a plurality of discharge holes 51 on the outer peripheral surface. Two such water vapor nozzles 50 are provided in the chamber 10. The two water vapor nozzles 50 are installed in the upper part of the chamber 10 and below the pure water nozzle 40 in parallel with each other with their longitudinal directions along the Y-axis direction. The plurality of ejection holes 51 are formed in a row along the longitudinal direction of the water vapor nozzle 50 at the same pitch as the pitch of the holding grooves 31 of the rotary roller 30. Further, the plurality of ejection holes 51 are provided such that their ejection directions are parallel to the XZ plane and toward the substrate W held by the rotating roller 30. The number of the discharge holes 51 provided in one steam nozzle 50 is one more than the number of the holding grooves 31 of the rotating roller 30, and at least the position corresponding to the middle point of the adjacent holding grooves 31 (including the middle point). A discharge hole 51 is provided at a position where the XZ plane intersects with the water vapor nozzle 50 (see FIG. 2). Therefore, similar to the pure water nozzle 40, the water vapor nozzle 50 can also eject water vapor between the adjacent substrates W held by the rotating roller 30.

The two steam nozzles 50 are connected by a pipe 52 to a steam supply source 54. The steam supply source 54 has a function of generating steam from pure water. A steam valve 53 is arranged in the middle of the pipe 52. By opening the water vapor valve 53, the water vapor is supplied from the water vapor supply source 54 to the two water vapor nozzles 50, and the substrate W held by the rotating roller 30 through the discharge holes 51.
Water vapor can be discharged to. On the other hand, when the water vapor valve 53 is closed, the water vapor discharge from the water vapor nozzle 50 is stopped. Regarding water vapor, hydrogen (H ₂ )
It may be generated by burning gas and oxygen (O ₂ ) gas.

The ozone gas nozzle 60 is also the pure water nozzle 40.
Similarly to the above, it is a cylindrical member having a plurality of discharge holes 61 on the outer peripheral surface. Two such ozone gas nozzles 60 are provided in the chamber 10. Two ozone gas nozzles 6
0s are installed below the water vapor nozzle 50 in the chamber 10 in parallel to each other with their longitudinal directions along the Y-axis direction. The plurality of ejection holes 61 are formed in a row along the longitudinal direction of the ozone gas nozzle 60 at the same pitch as the pitch of the holding grooves 31 of the rotary roller 30. In addition, the plurality of discharge holes 61 have the discharge direction X.
It is provided so as to be parallel to the Z plane and face the substrate W held by the rotating roller 30. The number of the ejection holes 61 provided in one ozone gas nozzle 60 is one more than the number of the holding grooves 31 of the rotating roller 30, and at least the position corresponding to the middle point of the adjacent holding grooves 31 (including the middle point). A discharge hole 61 is provided at a position where the XZ plane intersects with the ozone gas nozzle 60 (see FIG. 2). Therefore, like the pure water nozzle 40, the ozone gas nozzle 60 can also discharge ozone gas between the adjacent substrates W held by the rotating roller 30.

The two ozone gas nozzles 60 have a pipe 6
One end of 2 is connected for communication. The pipe 62 is branched into two, one of which is connected in communication with an ozone gas supply source 64 as an ozone pipe 62a, and the other is a nitrogen pipe 6
2b is connected to the nitrogen gas supply source 65 so as to communicate therewith.
An ozone gas valve 63 is arranged in the middle of the ozone pipe 62a, and a nitrogen gas valve 66 is arranged in the middle of the nitrogen pipe 62b.
Is provided.

By opening the ozone gas valve 63, the ozone gas is supplied from the ozone gas supply source 64 to the two ozone gas nozzles 60, and the ozone gas is discharged from the discharge holes 61 to the substrate W held by the rotating roller 30. it can. On the other hand, if the ozone gas valve 63 is closed,
The discharge of ozone gas from the ozone gas nozzle 60 is stopped. Further, by opening the nitrogen gas valve 66, the two ozone gas nozzles 6 from the nitrogen gas supply source 65 are
Nitrogen gas (N ₂ ) can be fed to 0 to discharge the nitrogen gas from the discharge holes 61 to the substrate W held by the rotating roller 30. On the other hand, when the nitrogen gas valve 66 is closed, the discharge of nitrogen gas from the ozone gas nozzle 60 is stopped.

Like the pure water nozzle 40, the treatment liquid nozzle 70 is also a cylindrical member having a plurality of ejection holes 71 on its outer peripheral surface. Two such processing liquid nozzles 70 are provided in the chamber 10. The two processing liquid nozzles 70 are installed below the halogen lamp 80 in the chamber 10 in parallel with each other with their longitudinal directions along the Y-axis direction. The plurality of discharge holes 71 are formed by the rotary roller 3
They are formed in a row along the longitudinal direction of the treatment liquid nozzle 70 at the same pitch as the holding grooves 31 of 0. Also,
The plurality of ejection holes 71 are provided so that their ejection directions are parallel to the XZ plane and toward the substrate W held by the rotating roller 30. The number of the ejection holes 71 provided in one processing liquid nozzle 70 is one more than the number of the holding grooves 31 of the rotating roller 30, and at least the position corresponding to the midpoint of the adjacent holding grooves 31 (the midpoint). A discharge hole 71 is provided at a position where the containing XZ plane intersects with the processing liquid nozzle 70) (see FIG. 2). Therefore, like the pure water nozzle 40, the treatment liquid nozzle 70 can also discharge hydrofluoric acid vapor or the like between the adjacent substrates W held by the rotating roller 30.

One end of a pipe 72 is connected to the two processing liquid nozzles 70 so as to communicate with each other. The pipe 72 is branched into three, one of which is an IPA pipe 72a.
It is connected to the steam supply source 74, another one is connected to the hydrofluoric acid steam supply source 76 as the hydrofluoric acid pipe 72b, and the other one is connected to the acetic acid supply source 78 as the acetic acid pipe 72c.
It is connected with. I in the middle of the IPA pipe 72a
A PA valve 73 is provided, a hydrofluoric acid vapor valve 75 is provided in the middle of the hydrofluoric acid pipe 72b, and an acetic acid valve 77 is provided in the middle of the acetic acid pipe 72c.

By opening the IPA valve 73, the two processing liquid nozzles 70 are supplied from the IPA vapor supply source 74.
The vapor of IPA (isopropyl alcohol) is fed to the substrate W held on the rotating roller 30 from the discharge hole 71 by the vapor.
PA vapor can be discharged. On the other hand, when the IPA valve 73 is closed, the IPA vapor discharge from the processing liquid nozzle 70 is stopped. Further, by opening the hydrofluoric acid vapor valve 75, hydrofluoric acid (HF) vapor is fed from the hydrofluoric acid vapor supply source 76 to the two processing liquid nozzles 70, and the hydrofluoric acid vapor is held on the rotary roller 30 through the discharge holes 71. Hydrofluoric acid vapor can be discharged onto the substrate W. When the hydrofluoric acid vapor valve 75 is closed, the discharge of hydrofluoric acid vapor from the treatment liquid nozzle 70 is stopped. Further, by opening the acetic acid valve 77, acetic acid (CH ₃ COOH) is supplied from the acetic acid supply source 78 to the two processing liquid nozzles 70, and the acetic acid is applied to the substrate W held by the rotating roller 30 from the discharge hole 71. The mist of can be discharged. When the acetic acid valve 77 is closed, the discharge of acetic acid mist from the treatment liquid nozzle 70 is stopped.

In this embodiment, IPA and hydrofluoric acid are discharged in the form of vapor, and acetic acid is discharged in the form of mist in the form of mist, but the supply form of these is limited. Alternatively, for example, IPA and hydrofluoric acid may be discharged in the form of mist, and acetic acid may be discharged in the form of shower.

The halogen lamps 80 are arranged inside the chamber 10 on both sides of the substrate W held by the rotating roller 30. A plurality of halogen lamps 80 are arranged in a line along the Y-axis direction on each side of the plurality of substrates W held by the rotating roller 30, and each halogen lamp 80 corresponds to the holding groove 31 of the rotating roller 30. It is installed in the position (in the same XZ plane as the holding groove 31).

The halogen lamp 80 is electrically connected to a power source 81, is a heater that is turned on by receiving power from the power source 81, and heats the substrate W held by the rotating roller 30 by light irradiation. The shape of the halogen lamp 80 may be a cylindrical shape, a rod shape, or the like, as long as the substrate W held by the rotating roller 30 can be irradiated with light to be heated. good.

An exhaust pipe 91 is communicatively connected to the chamber 10. A vacuum pump 90 is arranged in the middle of the exhaust pipe 91. By operating the vacuum pump 90, the pressure inside the chamber 10 can be reduced to below atmospheric pressure.

A drain pipe 92 is provided at the bottom of the chamber 10.
Are connected in communication. The drainage pipe 92 is connected to a drainage drain 94 outside the apparatus, and a drainage valve 93 is provided in the middle thereof. By opening the drainage valve 93, the drainage generated by processing the substrate W is drained from the bottom of the chamber 10 through the drainage pipe 92 to the drainage drain 94.
Is discharged to.

Further, the substrate processing apparatus 1 is provided with a controller 99 for managing the entire apparatus. The controller 99 is configured by using a computer, and includes a lifting drive unit 22, a rotation drive unit 32, a power supply 81, and a vacuum pump 9.
0 and each valve electrically connected to control their operation.

<2. Operation of Substrate Processing Apparatus> Next, the operation of the substrate processing apparatus 1 having the above configuration will be described. FIG. 4 is a flowchart showing an outline of the processing procedure in the substrate processing apparatus 1. Further, FIG. 5 is a timing chart of the operation in the substrate processing apparatus 1. As shown in FIG. 4, the outline of the processing procedure in the substrate processing apparatus 1 is that after the surface treatment of the substrate W with hydrofluoric acid, the surface treatment with ozone is performed, and then the drying treatment of the substrate W is continuously performed. That is. It should be noted that all of these processes are executed by the controller 99 controlling each unit.

A plurality of substrates W, which have undergone the resist coating, exposure, and development processing steps prior to the processing of FIG. 4, are carried into the substrate processing apparatus 1 at time t0. At this time, the lid 11 is opened and the lifter 20 is raised to the delivery position (the position indicated by the chain double-dashed line in FIG. 1). Then, a transfer robot outside the apparatus transfers a plurality of substrates W, which are targets of the resist removal processing and are stacked in advance at a predetermined pitch, and collectively transfer them to the lifter 20. The holding rods 21a, 21b, 21c of the lifter 20 hold a plurality of substrates W stacked in a predetermined pitch in a standing posture. After that, the lifter 20 descends below the rotating roller 30 to pass the plurality of substrates W to the two rotating rollers 30, and
The lid 11 is closed to make the inside of the chamber 10 a closed space. The two rotating rollers 30 also hold the plurality of substrates W stacked and arranged at a predetermined pitch in an upright posture.

Next, the surface treatment with hydrofluoric acid is performed from time t1 to time t4 (step S1). First, at time t1, the two rotation rollers 3 are rotated by the rotation driving unit 32.
When 0 starts rotating, the halogen lamp 80 lights up by receiving power from the power supply 81. When the two rotating rollers 30 rotate, the plurality of substrates W held by the two rotating rollers 30 also rotate simultaneously with the axis parallel to the Y-axis direction as the rotation axis. That is, the plurality of substrates W rotate in a plane parallel to the ejection direction from each nozzle. Also, the halogen lamp 8
By lighting 0, the plurality of substrates W are heated.
In the present embodiment, the rotation of the substrate W by the rotating roller 30 and the heating of the substrate W by the halogen lamp 80 are continued through all the treatment steps of hydrofluoric acid, ozone, and subsequent drying.

Next, at time t2, the hydrofluoric acid vapor valve 75 is opened to supply hydrofluoric acid vapor (HF vapor) from the processing liquid nozzle 70 to the substrate W held by the rotating roller 30.
A part of the supplied hydrofluoric acid vapor acts on silicon oxide (SiO ₂ ) formed on the surface of the substrate W to decompose and remove it. Further, the hydrofluoric acid vapor also has a so-called lift-off effect that acts on the unnecessary resist on the substrate W to release it.

Next, at time t3, the hydrofluoric acid vapor valve 75 is closed, and the pure water valve 43 and the nitrogen gas valve 66 are opened. As a result, the pure water shower is supplied from the pure water nozzle 40 to the substrate W, and the nitrogen gas is supplied from the ozone gas nozzle 60 into the chamber 10. That is, the substrate W is rinsed with pure water in an atmosphere of nitrogen gas, and the hydrofluoric acid attached to the substrate W is washed away. Substrate W in an inert nitrogen gas atmosphere
Therefore, the surface of the substrate W is prevented from being oxidized. At this time, the drain valve 93 is also opened, and the generated drainage is drained from the drainage pipe 92 to the drainage drain 94.

Then, at time t4, the pure water valve 43 and the nitrogen gas valve 66 are closed to complete the rinse treatment with pure water. This completes a series of hydrofluoric acid surface treatments (step S1) in which the surface of the substrate W is washed with hydrofluoric acid and then rinsed with pure water. Next, from time t4 to time t11, surface treatment with ozone (step S
2) is performed.

At time t4, the vacuum pump 90 is operated and all the other valves are closed. This allows
The atmospheric gas in the chamber 10 is exhausted through the exhaust pipe 91, and the pressure in the chamber 10 is reduced to below atmospheric pressure.

Next, at time t5, the operation of the vacuum pump 90 is stopped and the water vapor valve 53 is opened. As a result, water vapor is supplied to the substrate W from the water vapor nozzle 50. The supplied water vapor is condensed on the surface of the substrate W, and as a result, a thin water film is formed on the surface of the substrate W. At this time, since the pressure inside the chamber 10 is lower than atmospheric pressure, the water vapor discharged from the water vapor nozzle 50 diffuses into the chamber 10 quickly and uniformly, and is condensed on the surface of the substrate W uniformly. In order to effectively condense the water vapor, it is preferable that the heating temperature of the substrate W by the halogen lamp 80 be equal to or lower than the temperature of the water vapor supplied.

Next, at time t6, the ozone gas valve 63 and the acetic acid valve 77 are opened while continuing to supply the steam from the steam nozzle 50. As a result, ozone gas is supplied from the ozone gas nozzle 60 to the substrate W, and acetic acid mist is supplied from the processing liquid nozzle 70. Therefore, ozone gas and acetic acid mist are supplied from the outside of the thin water film formed on the surface of the substrate W.

At this time, pure water and ozone gas react with each other to generate hydroxyl radicals, which move through the water film to reach the surface of the substrate W and act on the resist on the surface of the substrate W. Disassemble this. Since the water film formed by condensation of water vapor is thin, there are few hydroxyl radicals that move in the water film and undergo self-decomposition before reaching the surface of the substrate W, and the resist film can be effectively decomposed. it can.

Further, the acetic acid mist acts as a decomposition accelerator of the resist which is an organic substance. That is, when ozone gas and acetic acid are mixed, the self-decomposition action of ozone is suppressed and a larger amount of hydroxyl radicals are generated. A large amount of generated hydroxyl radicals contribute to the decomposition of the resist, so that the resist film can be decomposed more quickly.

After the ozone treatment for a predetermined time, the time t
When it reaches 7, the ozone gas valve 63 and the acetic acid valve 77 are closed to stop the supply of ozone gas and acetic acid. At the same time (time t7), the pure water valve 43 is opened to supply the pure water shower to the substrate W from the pure water nozzle 40. By this pure water shower, the resist decomposed on the surface of the substrate W and attached in the state of a residue is washed away, and the resist peeling is completed.

Next, at time t8, the steam valve 53 and the pure water valve 43 are closed to stop the supply of steam and pure water shower. At the same time, the nitrogen gas valve 66
Is opened and the vacuum pump 90 is operated. Chamber 10
By supplying nitrogen gas from the ozone gas nozzle 60 while forcibly exhausting the inside, the inside of the chamber 10 can be quickly replaced with the nitrogen gas atmosphere.

Thereafter, at time t9, the operation of the vacuum pump 90 is stopped while continuing the supply of nitrogen gas. As a result, the inside of the chamber 10 is filled with the nitrogen gas atmosphere. Then, at time t10, the nitrogen gas valve 66 is closed to stop the supply of nitrogen gas. As a result, a series of ozone surface treatments in which the resist on the surface of the substrate W is decomposed by a combination of a water film of water vapor, ozone gas, and acetic acid, and the decomposed residue is flushed with a pure water shower (step S
2) is completed. Next, from time t11 to time t14, the substrate W is dried (step S3).

First, at time t11, the IPA valve 73 is opened to supply the IPA vapor to the substrate W from the processing liquid nozzle 70. The supplied IPA vapor condenses on the surface of the substrate W,
The water attached to the surface of the substrate W is replaced.

Thereafter, at time t12, the IPA valve 73 is closed to stop the supply of IPA vapor, the nitrogen gas valve 66 is opened, and the vacuum pump 90 is operated. While exhausting the inside of the chamber 10, an ozone gas nozzle 60
By supplying nitrogen gas from the inside, the inside of the chamber 10 is replaced with the nitrogen gas atmosphere from the IPA atmosphere. At this time, the supply flow rate of nitrogen gas from the ozone gas nozzle 60 is set to be smaller than the exhaust flow rate of the vacuum pump 90. By doing so, the pressure inside the chamber 10 can be reduced while being replaced with the nitrogen gas atmosphere, and the boiling point of the IPA adhering to the substrate W is lowered, so that the IPA
Evaporates rapidly. Therefore, the reduced-pressure drying by so-called IPA is performed, and the IPA attached to the substrate W is quickly dried.

At time t13, the operation of the vacuum pump 90 is stopped while continuing the supply of nitrogen gas. This allows
The inside of the chamber 10 is filled with a nitrogen gas atmosphere, and the pressure is restored to atmospheric pressure. Then, at time t14, the nitrogen gas valve 66 is closed to stop the supply of nitrogen gas.
At time t14, the rotation of the plurality of substrates W held by them is stopped by stopping the two rotating rollers 30, and the heating of the substrate W is stopped by turning off the halogen lamp 80. As a result, a series of drying processes (step S3) of drying the water adhering to the substrate W by vacuum drying IPA is completed.

After that, the lifter 20 rises to receive the plurality of substrates W from the two rotating rollers 30, further holds the plurality of substrates W, and rises to the delivery position. At the same time, the lid 11 is opened. Then, the transfer robot outside the apparatus receives the processed substrate W from the lifter 20 and carries it out from the chamber 10, and all the processes are completed.

By doing so, since the substrate W is rotated by the rotating roller 30 through all the steps of the surface treatment with hydrofluoric acid, the surface treatment with ozone, and the drying treatment, uniform treatment can be performed. For example, if the substrate W is not rotated during the surface treatment with ozone, the treatment conditions will be different between the position close to the water vapor nozzle 50 and the position far from the ozone gas nozzle 60 on the surface of the substrate W, and the position will be uniform. The resist stripping process may be hindered. Therefore, as in the present embodiment, if the water vapor is supplied from the water vapor nozzle 50 while rotating the substrate W by the rotating roller 30, the water vapor is supplied to the entire surface of the substrate W under a uniform condition to form a uniform water film. Can be formed. Further, the substrate W is rotated by the rotating roller 30.
If ozone gas is supplied from the ozone gas nozzle 60 while rotating, the ozone gas can be uniformly supplied to the entire surface of the substrate W and uniform resist stripping processing can be performed. Similarly, for the surface treatment with hydrofluoric acid and the drying treatment, uniform treatment can be performed by rotating the substrate W.

The substrate W can be uniformly heated by heating the halogen lamp 80 while rotating the substrate W by the rotating roller 30. By heating the substrate W, the rate of resist decomposition by ozone increases, but by uniformly heating the substrate W at this time, the temperature factor for resist stripping can be made uniform, and a uniform resist can be obtained. A peeling treatment can be performed.

Further, since the discharge holes of the respective nozzles are provided at the positions corresponding to the intermediate points of at least the holding grooves 31 adjacent to each other, water vapor, ozone gas, etc. are surely provided on all of the plurality of substrates W held by the rotating roller 30. Can be supplied.

<3. Modifications> Although the embodiments of the present invention have been described above, the present invention is not limited to the above examples. For example, in the above-described embodiment, the substrate W is rotated by the rotating roller 30 through all the processing steps of the surface treatment with hydrofluoric acid, the surface treatment with ozone, and the subsequent drying treatment, but at least during the surface treatment with ozone. The substrate W may be rotated. Thereby, the uniform resist stripping process can be performed.

In the above embodiment, the rotary roller 30 is used.
Although the plurality of substrates W are directly held and rotated in the holding groove, the substrates W may be fixed and held in a casing having a predetermined shape, and the casing may be rotated by the rotating roller 30. By doing so, it is possible to prevent dust generation due to sliding between the rotating roller 30 and the edge portion of the substrate W.

Further, in the above embodiment, the substrate W is heated by the halogen lamp 80 through all the processing steps of the surface treatment with hydrofluoric acid, the surface treatment with ozone, and the drying treatment, but the present invention is not limited to this. However, the substrate W held by the rotating roller 30 may be heated at least until the steam is supplied from the steam nozzle 50 (before time t5 in FIG. 5). The heating of the substrate W by the halogen lamp 80 is performed to increase the resist decomposition rate by ozone, and the substrate W is not supplied when ozone gas is supplied (between time t6 and time t7 in FIG. 5).
The purpose is achieved if the temperature is increased. Then, if the substrate W is heated by the halogen lamp 80 until the water vapor is supplied from the water vapor nozzle 50, then the heating state of the substrate W is maintained by the heat of the water vapor supplied from the water vapor nozzle 50. . Therefore, at least before the time t5 in FIG.
The substrate W may be heated to 0.

In the above embodiment, the IPA vapor is supplied to the substrate W during the drying process, but the present invention is not limited to this, and vapor of another organic solvent may be supplied. The organic solvent here is a hydrophilic organic solvent,
It is a water-soluble organic solvent. More specifically, it is a liquid that is mixed with water to lower the boiling point of the mixture. As such an organic solvent, ketones, ethers, and polyhydric alcohols can be used. For example, ketones such as acetone and diethyl ketone can be used, ethers such as methyl ether and ethyl ether can be used, and polyhydric alcohols such as ethylene glycol can be used. In view of the fact that many products containing a small amount of impurities such as metals are provided on the market, it is most preferable to use isopropyl alcohol (IPA) as in the present embodiment.

In the above embodiment, acetic acid is used as a resist decomposition accelerator. However, the invention is not limited to this. For example, carboxylic acid or phosphorus may be used as long as it suppresses the self-decomposition action of ozone. Acids and their salts can also be used.

In the above embodiment, the time t5 in FIG.
From the time to the time t8, the water vapor was supplied to the substrate W, but since the purpose of supplying the water vapor is to form a thin water film on the surface of the substrate W, such a water film can be formed. If so, the steam may be supplied at least until the time when the supply of ozone gas is started (time t6).

Further, from time t7 to time t8 in FIG. 5, the resist which was decomposed on the surface of the substrate W by the pure water shower and adhered in a residue state was washed away.
The resist may be washed away by discharging water vapor from the water vapor nozzle 50 without supplying the pure water shower.

Although a plurality of discharge holes are provided in each nozzle such as the water vapor nozzle 50 and the ozone gas nozzle 60, the shape of each nozzle may be as shown in FIG.
In the nozzle shown in FIG. 6, slits SL are provided along the longitudinal direction of the cylindrical member. The water vapor, ozone gas, etc. sent to each nozzle are discharged toward the substrate W from this slit SL. Even in this way, the rotating roller 3
It is possible to reliably supply water vapor, ozone gas, etc. to all of the plurality of substrates W held at zero.

Further, instead of each nozzle such as the water vapor nozzle 50 and the ozone gas nozzle 60, a punching plate or the like having a large number of small holes for discharging a fluid may be used.

The structure of the substrate processing apparatus according to the present invention may be as shown in FIG. The substrate processing apparatus 2 is different from the substrate processing apparatus 1 of the above-described embodiment in that the pure water nozzle 40 is removed from the chamber 10 and the processing bath 100 is provided. The rest is the same as that of the substrate processing apparatus 1, and the same members are designated by the same reference numerals as those in the above-described embodiment and the description thereof is omitted.

The processing bath 100 is provided at the bottom of the chamber 10. Further, two pure water nozzles 110 are provided at the bottom of the processing tank 100. Pure water nozzle 11
The configuration of 0 may be the same as that of the pure water nozzle 40 described above.
The pure water nozzle 110 is connected to a pure water supply source 44 by a pipe 42 similar to that shown in FIG. 1, and a pure water valve 43 is arranged in the middle of the pipe 42. Pure water valve 43
Is opened and pure water is discharged from the pure water nozzle 110, whereby pure water is stored in the processing bath 100.

Further, in the substrate processing apparatus 2, the rotation driving section 32 has an opening / closing function for opening / closing the rotation roller 30. As indicated by an arrow AR7 in FIG. 7, the rotation drive unit 32 slides the rotation roller 30 in the horizontal direction to increase the distance between the two rotation rollers 30.
The substrate W can pass between them. The lifter 20 holding the substrate W is lowered in a state where the distance between the two rotating rollers 30 is expanded, and thus the substrate W is lowered to the immersion position in the processing bath 100 (the position indicated by a chain double-dashed line in FIG. 7). Can be made. On the other hand, in the state where the distance between the two rotating rollers 30 is narrowed, the substrate W can be held and rotated as in the above embodiment.

The mechanism for communicating with other nozzles such as the water vapor nozzle 50 and the ozone gas nozzle 60 is the same as in the above embodiment.

The processing procedure in the substrate processing apparatus 2 is almost the same as that shown in FIGS. 4 and 5, but instead of the pure water shower from the pure water nozzle 40, the pure water is stored in the processing bath 100. The substrate W will be immersed. Even in this case, the same uniform resist stripping process as in the above-described embodiment can be performed.

Further, in the substrate processing apparatus 2 of FIG. 7, hydrofluoric acid can be supplied to the processing bath 100, and the surface treatment with hydrofluoric acid can be performed in the processing bath 100.

Further, in the above embodiment, the halogen lamp 80 is used to heat the substrate W, but instead of this, the substrate W held by the rotating roller 30 is heated by a UV lamp or the like. May be. If a UV lamp is used as a heating source, not only can the substrate W be heated, but also the decomposition of ozone gas can be promoted by ultraviolet rays to further improve the processing speed.

Further, in the above embodiment, the steam is supplied from the steam supply source 54 to the two steam nozzles 50, but the invention is not limited to this, and the resistance heating type inside the chamber 10 is used. A heater may be provided to heat pure water to generate water vapor.

[0081]

As described above, according to the first aspect of the invention, the chamber for containing the substrate, the rotation holding means for holding and rotating the substrate in the chamber, and the rotation holding means are held. The substrate to be rotated is provided with ozone gas supply means for supplying ozone gas to the substrate, and water vapor supply means for supplying water vapor to the substrate held by the rotation holding means to condense the water vapor on the surface of the substrate. Since the water vapor and the ozone gas are uniformly supplied to the surface, the substrate surface can be uniformly processed.

Further, according to the invention of claim 2, since the pure water supply means for supplying the pure water to the substrate held by the rotation holding means is further provided, the processing of the substrate can be made more reliable. .

According to the third aspect of the invention, since pure water is supplied to the substrate after the ozone gas has been supplied, the substrate after the surface treatment with ozone can be reliably cleaned.

According to the fourth aspect of the present invention, since the ozone decomposition accelerator is supplied to the substrate when the ozone gas is supplied, the surface treatment efficiency of the substrate with ozone can be further improved.

According to the invention of claim 5, the decomposition accelerator is acetic acid, and the surface treatment efficiency of the substrate with ozone is further improved.

Further, according to the invention of claim 6, since the heating means for heating the substrate held by the rotation holding means is further provided, the surface treatment efficiency of the substrate with ozone can be further improved.

Further, according to the invention of claim 7, since the substrate held by the rotation holding means is heated at least until the water vapor is supplied from the water vapor supplying means, the temperature of the substrate is raised to a high temperature during the surface treatment with ozone. It can be maintained, and the surface treatment efficiency of the substrate with ozone can be improved.

Further, according to the invention of claim 8, further comprising a decompression means for decompressing the inside of the chamber to less than atmospheric pressure, the water vapor and the ozone gas can be uniformly diffused in the chamber, and the surface of the substrate can be made more uniform. Various cleaning processes can be performed.

According to the ninth aspect of the present invention, since the pressure inside the chamber is reduced before the ozone gas is supplied, the ozone gas can be uniformly and surely diffused into the chamber, and the substrate surface can be uniformly cleaned. Can be done.

According to the tenth aspect of the invention, since the organic solvent vapor supply means for supplying the organic solvent vapor to the substrate held by the rotation holding means is further provided, the substrate after the cleaning treatment is dried by the organic solvent. be able to.

According to the eleventh aspect of the invention, since the apparatus further comprises hydrofluoric acid vapor supply means for supplying hydrofluoric acid vapor to the substrate held by the rotation holding means, the silicon oxide formed on the substrate surface is removed. can do.

According to the twelfth aspect of the invention, since the substrate is rotated in a plane parallel to the ozone gas supply direction from the ozone gas supply means, the ozone gas is uniformly supplied to the surface of the rotated substrate. This means that the substrate surface can be uniformly cleaned.

[Brief description of drawings]

FIG. 1 is a diagram showing an overall configuration of a substrate processing apparatus according to the present invention.

FIG. 2 is a side view of the substrate processing apparatus of FIG.

3 is a perspective view of a rotating roller of the substrate processing apparatus of FIG.

4 is a flowchart showing an outline of a processing procedure in the substrate processing apparatus of FIG.

5 is a timing chart of an operation in the substrate processing apparatus of FIG.

FIG. 6 is a diagram showing another example of a nozzle.

FIG. 7 is a diagram showing another configuration example of the substrate processing apparatus according to the present invention.

[Explanation of symbols]

1, 2 substrate processing equipment 10 chambers 20 lifters 30 rotating rollers 40 Pure water nozzle 50 steam nozzle 60 ozone gas nozzle 70 Treatment liquid nozzle 80 halogen lamp 90 vacuum pump 99 controller 100 processing tanks W board

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazumi Kanemoto             4-chome Tenjin, which runs up to Teranouchi, Horikawa-dori, Kamigyo-ku, Kyoto             1 Kitamachi No. 1 Dai Nippon Screen Manufacturing Co., Ltd.             Inside the company F term (reference) 2H090 HC18 JA13 JB02 JC08 JC19                 3B116 AA01 AB02 AB33 AB47 BB02                       BB22 BB82 BB89 CD11 CD35                 3B201 AA01 AB02 AB33 AB47 BB02                       BB22 BB89 BB92 BB98 CD11                       CD35 CD36

Claims (12)

[Claims] 1. A substrate processing apparatus for processing a surface of a substrate, the chamber containing the substrate, a rotation holding unit for holding and rotating the substrate in the chamber, and a rotation holding unit. Substrate processing comprising: an ozone gas supply means for supplying ozone gas to the substrate; and a steam supply means for supplying water vapor to the substrate held by the rotation holding means to condense the water vapor on the surface of the substrate. apparatus. 2. The substrate processing apparatus according to claim 1, further comprising pure water supply means for supplying pure water to the substrate held by the rotation holding means. 3. The substrate processing apparatus according to claim 2, wherein the pure water supply means supplies pure water to the substrate after the ozone gas is supplied from the ozone gas supply means. 4. The substrate processing apparatus according to claim 1, wherein when the ozone gas supply means supplies ozone gas, a decomposition promoter supply that supplies a decomposition promoter for an organic substance attached to the substrate. A substrate processing apparatus further comprising means. 5. The substrate processing apparatus according to claim 4, wherein the decomposition accelerator is acetic acid. 6. The substrate processing apparatus according to claim 1, further comprising a heating unit that heats the substrate held by the rotation holding unit. 7. The substrate processing apparatus according to claim 6, wherein the heating means heats the substrate held by the rotation holding means at least until the water vapor is supplied from the water vapor supply means. Substrate processing equipment. 8. The substrate processing apparatus according to claim 1, further comprising a decompression unit that decompresses the inside of the chamber to less than atmospheric pressure. 9. The substrate processing apparatus according to claim 8, wherein the decompression unit decompresses the inside of the chamber before the ozone gas supply unit supplies ozone gas. 10. The substrate processing apparatus according to claim 8, further comprising an organic solvent vapor supply means for supplying an organic solvent vapor to the substrate held by the rotation holding means. Processing equipment. 11. The substrate processing apparatus according to claim 1, further comprising hydrofluoric acid vapor supply means for supplying hydrofluoric acid vapor to the substrate held by the rotation holding means. Substrate processing equipment. 12. The substrate processing apparatus according to claim 1, wherein the rotation holding unit rotates the substrate in a plane parallel to a supply direction of ozone gas from the ozone gas supply unit. A substrate processing apparatus characterized by the above.