TWI774198B - Substrate treatment method - Google Patents

Abstract

The subject of the present invention is to supply the processing liquid to the upper surface of the substrate while suppressing exposure of the gas after the plasma processing to the atmosphere. The substrate processing method of the present invention includes: the step of holding the substrate; the step of forming a liquid film of the processing liquid on the upper surface of the substrate by supplying the processing liquid to the upper surface of the substrate; bringing the end of the nozzle into contact with the liquid film, and The step of supplying gas from the nozzle toward the liquid film; the step of applying plasma treatment for generating plasma from the gas; and the step of supplying the gas subjected to the plasma treatment to the liquid film.

Description

Substrate processing method

The techniques disclosed in this specification relate to substrate processing methods.

Conventionally, there has been a technique for improving the efficiency of substrate processing by performing plasma processing on a processing liquid that can be used for the substrate processing to improve the oxidative power of the processing liquid, etc., during substrate processing. (For example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-345797

(The problem that the invention intends to solve)

According to the structure shown in patent document 1 etc., it becomes a plasma state in a gas, and can generate|occur|produce active species, such as an ion and a radical. However, in the configuration shown in Patent Document 1 and the like, before supplying the above-mentioned gas containing the active species or the liquid containing the gas to the substrate, many active species diffuse into the atmosphere, or the active species come into contact with each other. The problem is that the active species react with the molecules in the atmosphere to be destroyed when they reach the outside air.

The technique disclosed in this specification was completed in view of the above-described problems, and is a technique for supplying a processing liquid to the upper surface of a substrate while suppressing exposure of the gas after plasma processing to the atmosphere. (Technical means to solve problems)

The first aspect of the substrate processing method and technology disclosed in this specification includes the step of holding the substrate; and forming a portion of the processing liquid on the upper surface of the substrate by supplying the processing liquid to the upper surface of the substrate. the step of bringing the end of the nozzle into contact with the liquid film, and the step of supplying gas from the nozzle toward the liquid film; the step of applying plasma treatment to generate plasma from the gas; and the step of applying the plasma treatment The step of supplying the above-mentioned gas to the above-mentioned liquid film.

A second aspect of the technology disclosed in this specification is related to the first aspect, wherein the nozzle is a nozzle for supplying the processing liquid, and the step of performing the plasma treatment is performed by causing the gas supplied to the processing liquid to be The above step of generating plasma inside the nozzle.

The third aspect of the technology disclosed in this specification is related to the first or second aspect, wherein the step of performing the plasma treatment is a step of generating plasma from the gas before being supplied to the treatment liquid.

A fourth aspect of the technology disclosed in this specification is related to the first or second aspect, wherein the step of performing the plasma treatment is to generate the gas supplied to the treatment liquid to become bubbles inside the nozzle Plasma steps.

A fifth aspect of the technology disclosed in this specification is related to any one of aspects 1 to 4, wherein the step of supplying the gas after the plasma treatment is performed to the liquid film is performed by placing the nozzle in the The step of supplying the above-mentioned gas after the above-mentioned plasma treatment to the above-mentioned liquid film while moving along the upper surface of the above-mentioned substrate while being in contact with the above-mentioned liquid film.

The sixth aspect of the technology disclosed in this specification is related to any one of the first to fifth aspects, wherein the treatment liquid is deionized water.

A seventh aspect of the technology disclosed in this specification is related to any one of the first to sixth aspects, wherein the step of performing the plasma treatment is a step of generating plasma from the gas in the vicinity of the end of the nozzle .

An eighth aspect of the technology disclosed in this specification is related to any one of aspects 1 to 7, wherein the step of supplying the gas after the plasma treatment to the liquid film is performed from the nozzle while the nozzle is The step of supplying the above-mentioned gas after the above-mentioned plasma treatment to the above-mentioned liquid film while discharging the inert gas in the direction along the upper surface of the above-mentioned substrate through the opening of the side surface of the nozzle. (Compared to the efficacy of the prior art)

According to the first to eighth aspects of the technology disclosed in this specification, it is possible to suppress the exposure of the gas after the plasma treatment to the atmosphere. Therefore, it is possible to supply the processing liquid to the upper surface of the substrate while suppressing a decrease in the oxidative power of the processing liquid, which is increased by the plasma treatment, and the like.

In addition, the objects, features, aspects, and advantages related to the technology disclosed in this specification will become more apparent from the detailed description and the accompanying drawings shown below.

Hereinafter, embodiments will be described with reference to the drawings. In the following embodiments, the detailed features and the like of the technology are described, but these are merely examples, and not all of them are features that are absolutely necessary for a feasible embodiment.

In the following embodiments, "substrate" refers to semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FED (Field Emission Display), and optical discs. Various substrates such as substrates, substrates for magnetic disks, and substrates for optical and magnetic disks. Hereinafter, a substrate processing apparatus that can be used for processing a disc-shaped semiconductor wafer will be mainly described as an example, but it can be similarly applied to the processing of the above-mentioned various substrates. In addition, various shapes can be applied to the shape of the substrate.

It should be noted that the drawings are schematically shown, and for the convenience of description, the configuration is omitted or the configuration is simplified in the drawings as appropriate. In addition, the mutual relationship of the size and the position of the structure etc. which are shown separately in a different drawing is not necessarily described correctly, and it may be obtained by making an appropriate change.

In addition, in the description shown below, the same component code|symbol is attached|subjected to the same component, and these names and functions are handled similarly. Therefore, there are cases where the detailed description is omitted in order to avoid repetition.

In addition, in the description described below, when it is described that "has", "includes" or "has" a certain component, unless otherwise specified, it is not a closure for excluding the existence of other components formula expression.

In addition, in the description described below, even when the ordinal numbers such as "1st" or "2nd" are used, these terms are only used to facilitate the user's understanding of the content of the embodiment, but the present invention is not intended to is limited to the order produced by the ordinal numbers, etc.

In addition, in the descriptions described below, expressions indicating the state of equality, such as "same", "equal", "uniform" or "homogeneous", etc., unless otherwise specified, refer to the situation of the same state strictly speaking, and There are differences in the functional range with tolerances or the same degree.

In addition, in the following description, expressions such as "moving the object in a specific direction" refer to the case of moving the object in parallel with the specific direction, as well as moving the object in the specific direction unless otherwise specified. A situation in which the direction of the component moves.

In addition, in the description described below, even if the use of "top", "bottom", "left", "right", "side", "bottom", "front" or "back" means a specific position or In the case of the terms of the direction, these terms are only used to easily understand the content of the embodiment, which is convenient for the user, and has nothing to do with the actual position or direction in the implementation.

In addition, in the description described below, when it is described as "the upper surface of ..." or "the lower surface of ...", it means that in addition to the upper surface itself or the lower surface itself of the constituent element of the object, it also includes A state in which other constituent elements are formed on the upper surface or the lower surface of the constituent element of the object. That is, for example, in the case where it is described as "B provided on the upper surface of A", it does not prevent that another component "C" is interposed between A and B.

<First Embodiment> Hereinafter, the substrate processing apparatus and the substrate processing method in the substrate processing system of the present embodiment will be described.

<About the configuration of the substrate processing system> FIG. 1 is a plan view schematically showing a configuration example of a substrate processing system 1 according to the present embodiment. The substrate processing system 1 includes a load port LP, an indexing robot IR, a central robot CR, a control unit 90 , and at least one processing unit UT (four processing units in FIG. 1 ).

Each processing unit UT is used for processing the substrate W (wafer), and at least one of them corresponds to the substrate processing apparatus 100 . The substrate processing apparatus 100 is a so-called single-wafer type apparatus that processes each of the substrates W one at a time, and performs cleaning, etching, and the like of the substrates W. As shown in FIG.

In the substrate processing apparatus 100 , by setting various conditions such as the type of the processing liquid to be supplied to the substrate W, various processing can be performed. The monolithic substrate processing apparatus 100 can perform a process of removing the used photoresist film attached to the substrate W, for example. The photoresist film is used, for example, as an implant mask for the ion implantation step.

Furthermore, the substrate processing apparatus 100 may have the chamber 80 . In this case, by using the control unit 90 to control the ambient gas in the chamber 80, the substrate processing apparatus 100 can perform substrate processing in a desired ambient gas.

The control unit 90 can control each of the components in the substrate processing system 1 (the rotation motor 10D of the rotation jig 10, the actuator 22C of the nozzle arm 22, the actuator 32C of the nozzle arm 32, the processing liquid supply source 29, the valve 25, The operation of the gas supply source 39, the AC power source 40, etc.) is controlled. The carrier C is a container in which the substrates W are accommodated. In addition, the load port LP is a container holding mechanism for holding a plurality of carriers C. As shown in FIG. The index robot IR can transfer the substrate W between the load port LP and the substrate placement portion PS. The central robot CR can transfer the substrate W between the substrate placement portion PS and the processing unit UT.

The operations of the indexing robot IR, the substrate placement unit PS, and the center robot CR will be described below.

The unprocessed substrate W is taken out from the carrier C by the indexing robot IR. Then, the unprocessed substrate W is transferred to the central robot CR via the substrate placement portion PS.

The central robot CR carries the unprocessed substrate W into the processing unit UT. Then, the processing unit UT processes the substrate W.

In the processing unit UT, the processed substrate W is taken out from the processing unit UT by the central robot CR. Then, the processed substrate W is transferred to the indexing robot IR via the substrate placement portion PS after passing through another processing unit UT as necessary. The indexing robot IR carries the processed substrate W into the carrier C. As shown in FIG. Thereby, the processing of the substrate W is performed.

FIG. 2 is a diagram schematically showing a configuration example of the control unit 90 shown in FIG. 1 . The control unit 90 may also be constituted by a general computer having an electric circuit. Specifically, the control unit 90 includes a central processing unit (CPU) 91 , a read only memory (ROM) 92 , and a random access memory (RAM) ) 93 , a storage device 94 , an input unit 96 , a display unit 97 , a communication unit 98 , and a bus wire 95 connecting these to each other.

The ROM 92 stores basic programs. The RAM 93 is used as a work area when the CPU 91 performs predetermined processing. The storage device 94 is composed of a non-volatile storage device such as a flash memory or a hard disk device. The input unit 96 is composed of various switches, a touch panel, and the like, and accepts input setting instructions such as processing recipes from an operator. The display unit 97 is composed of, for example, a liquid crystal display device and lamps, and displays various information under the control of the CPU 91 . The communication unit 98 has a data communication function via a local area network (LAN) or the like.

The storage device 94 is preset with a plurality of modes related to the control of each configuration of the substrate processing system 1 of FIG. 1 . When the CPU 91 executes the processing program 94P, one of the above-mentioned plural modes is selected, and each configuration is controlled by this mode. Furthermore, the processing program 94P can also be stored in a recording medium. When this recording medium is used, the processing program 94P can be installed in the control unit 90 . In addition, a part or all of the functions performed by the control unit 90 are not necessarily realized by software, and may be realized by hardware such as a dedicated logic circuit.

FIG. 3 is a side view schematically showing a configuration example of the substrate processing apparatus 100 according to the present embodiment.

Furthermore, the configuration shown in FIG. 3 may be surrounded by the chamber 80 of FIG. 1 . In addition, the pressure in the chamber 80 may be substantially atmospheric pressure (for example, 0.5 atmospheric pressure or more and 2 atmospheric pressure or less). In other words, the plasma treatment described later may be atmospheric pressure plasma treatment performed under atmospheric pressure.

The substrate processing apparatus 100 includes a rotating jig 10, a processing liquid nozzle 20, a processing liquid supply source 29, a valve 25, a nozzle arm 22, a plasma processing nozzle 30, a gas supply source 39, an AC power supply 40, a nozzle arm 32, and a cylindrical shape. the processing cup 12; the rotating jig 10 rotates the substrate W around the vertical rotation axis Z1 passing through the center of the substrate W while holding one substrate W in a substantially horizontal posture; the processing liquid nozzle 20 discharges the processing liquid toward the substrate W; the The processing liquid supply source 29 supplies the processing liquid to the processing liquid nozzle 20; the valve 25 switches the supply and stop of the processing liquid from the processing liquid supply source 29 to the processing liquid nozzle 20; the nozzle arm 22 is provided with the processing liquid nozzle 20 at the end The plasma processing nozzle 30 generates plasma from the gas flowing inside; the gas supply source 39 supplies gas to the plasma processing nozzle 30; the AC power source 40 applies AC voltage to the plasma processing nozzle 30; the nozzle arm 32 is in the A plasma processing nozzle 30 is installed at the end; the cylindrical processing cup 12 surrounds the rotating jig 10 around the rotation axis Z1 of the substrate W.

As the processing liquid, various solutions can be used according to the application of the substrate processing apparatus 100 for processing the substrate. For example, a solution containing hydrochloric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, sulfuric acid, sulfate, peroxysulfuric acid, peroxysulfate, aqueous hydrogen peroxide, or tetramethylammonium hydroxide can be used as the etching solution. In addition, the cleaning solution can be a mixture containing SC1 (standard cleaning solution 1: a mixture of deionized water, ammonium hydroxide, and hydrogen peroxide), SC2 (standard cleaning solution 2: deionized water, salted hydrogen, and hydrogen peroxide) mixture) solution. Also, deionized water (DIW) can be used as the cleaning/rinsing solution.

In this embodiment, the process of removing the photoresist film on the substrate W will be described as an example. In this case, the treatment liquid can be assumed to be a solution containing at least one of sulfuric acid, sulfate, sulfuric acid peroxide, and peroxosulfate, or a solution containing hydrogen peroxide, or the like.

When it is assumed that there are plural kinds of treatment liquids, the treatment liquid nozzles 20 may be provided in plural for each treatment liquid. The processing liquid nozzle 20 supplies the processing liquid to the substrate W so as to form a liquid film of the processing liquid on the upper surface of the substrate W. As shown in FIG.

The gas supply source 39 supplies, for example, O ₂ (ozone gas), Ne, CO ₂ , air, an inert gas, or a combination thereof toward the plasma processing nozzle 30 . The inert gas is, for example, N ₂ or a noble gas. The rare gas is, for example, He, Ar, or the like. For example, when the gas to be supplied to the plasma processing nozzle 30 contains O ₂ , oxygen radicals as active species may be generated in the plasma processing nozzle 30 .

The rotating jig 10 is provided with a disk-shaped rotating base 10A, a rotating shaft 10C, and a rotating motor 10D; the disk-shaped rotating base 10A vacuum suctions the lower surface of the substrate W in a substantially horizontal posture; the rotating shaft 10C rotates from The central portion of the base 10A extends downward, and the rotary motor 10D rotates the substrate W attracted to the rotary base 10A by rotating the rotary shaft 10C. Furthermore, instead of the rotating jig 10, a clamping pin provided with a plurality of clamping pins protruding upward from the outer peripheral portion of the upper surface of the rotating base, and the peripheral edge portion of the substrate W may be clamped by the clamping pins. type fixture.

The nozzle arm 22 includes an arm portion 22A, a shaft body 22B, and an actuator 22C. The actuator 22C adjusts the angle around the axis of the shaft body 22B. One end of the arm portion 22A is fixed to the shaft body 22B, and the other end portion of the arm portion 22A is disposed away from the axis of the shaft body 22B. Moreover, the processing liquid nozzle 20 is attached to the other end part of 22A of arm parts. Thereby, the processing liquid nozzle 20 is configured to be swingable in the radial direction of the substrate W. As shown in FIG. Furthermore, the moving direction of the processing liquid nozzle 20 by swinging only needs to have a component in the radial direction of the substrate W, and does not need to be strictly parallel to the radial direction of the substrate W. FIG. Here, the nozzle arm 22 may be moved up and down in the vertical direction by a motor or the like not shown. In this case, the distance between the processing liquid nozzle 20 mounted on the end of the nozzle arm 22 and the upper surface of the substrate W can be adjusted by raising and lowering the nozzle arm 22 .

The nozzle arm 32 includes an arm portion 32A, a shaft body 32B, and an actuator 32C. The actuator 32C adjusts the angle around the axis of the shaft body 32B. One end portion of the arm portion 32A is fixed to the shaft body 32B, and the other end portion of the arm portion 32A is disposed away from the axis of the shaft body 32B. Moreover, the plasma processing nozzle 30 is attached to the other end part of 32A of arm parts. Thereby, the plasma processing nozzle 30 is configured to be swingable in the radial direction of the substrate W. As shown in FIG. Furthermore, the moving direction of the plasma processing nozzle 30 by swinging only needs to have a component in the radial direction of the substrate W, and does not need to be strictly parallel to the radial direction of the substrate W. FIG. Here, the nozzle arm 32 may be moved up and down in the vertical direction P by a motor or the like not shown. In this case, by raising and lowering the nozzle arm 32, the distance between the plasma processing nozzle 30 mounted on the end of the nozzle arm 32 and the upper surface of the substrate W can be adjusted.

3, although the processing liquid nozzle 20 and the plasma processing nozzle 30 are attached to each nozzle arm, the processing liquid nozzle 20 and the plasma processing nozzle 30 may be attached to a common nozzle arm.

<About the operation of the substrate processing apparatus> Next, the operation of the substrate processing apparatus will be described. The substrate processing method of the substrate processing apparatus according to the present embodiment includes a step of performing chemical treatment on the substrate W that has been transferred to the processing unit UT, and a step of performing cleaning treatment on the substrate W that has been subjected to the chemical treatment. ; a step of performing a drying process on the substrate W that has been subjected to the cleaning process; and a step of carrying out the substrate W that has been subjected to the drying process from the processing unit UT.

Hereinafter, the operation of the substrate processing apparatus includes the step of removing the organic matter (eg, used photoresist film) adhering to the substrate W during or after the chemical solution treatment (the above-mentioned steps belong to the application of the chemical solution). The steps of the treatment or the steps of performing the cleaning treatment) will be described with reference to FIGS. 4 and 5 . Here, FIG. 4 is a cross-sectional view showing a configuration example of the processing liquid nozzle 20 and the plasma processing nozzle 30 arranged to face the upper surface of the substrate W. As shown in FIG. 5 is a flowchart showing an example of the operation of the substrate processing apparatus.

As shown in FIG. 4 , the processing liquid 101 flows to the processing liquid nozzle 20 made of resin or the like, and a liquid film 101A of the processing liquid 101 is formed on the upper surface of the substrate W held by the rotary jig 10 . Here, the distance between the liquid level of the liquid film 101A and the upper surface of the substrate W (that is, the film thickness of the liquid film 101A) is set as the distance D1.

On the other hand, the plasma processing nozzle 30 includes a pipe 30A made of an insulator or the like, and a pair of electrodes 30B. A pair of electrodes 30B are attached to the outer surface of the piping 30A, and are arranged to face each other with the piping 30A interposed therebetween.

The AC power supply 40 applies an AC voltage between the two electrodes 30B. Furthermore, as a modification example, a DC pulse power supply may be used instead of the AC power supply 40 . In this case, for example, one electrode 30B is set as the anode, and the other electrode 30B is set as the cathode.

Next, the step of removing the organic matter adhering to the substrate W will be described. First, the rotary jig 10 holds the substrate W (step ST01 in FIG. 5 ). Then, the substrate W is rotated by the rotation of the rotating jig 10 .

Next, the processing liquid 101 is supplied from the processing liquid supply source 29 toward the processing liquid nozzle 20, and the processing liquid 101 is discharged from the processing liquid nozzle 20 toward the upper surface of the substrate W while the substrate W is rotating (step ST02 in FIG. 5 ). ). At this time, the position of the processing liquid nozzle 20 attached to the end of the nozzle arm 22 on the upper surface of the substrate W can be adjusted by moving the nozzle arm 22 in the horizontal direction and the vertical direction. Furthermore, in this embodiment, although the case where the processing liquid 101 is discharged while the substrate W is rotating is shown, the substrate W may not be rotated, or may be in a paddling state in which the substrate W rotates at a low speed.

When the processing liquid 101 is discharged from the processing liquid nozzle 20, a liquid film 101A of the processing liquid 101 is formed on the upper surface of the substrate W (step ST03 in FIG. 5). When the liquid film is too thick, the amount of the processing liquid on the substrate W increases. Therefore, when the gas is introduced in the subsequent step ST04, the activation effect of the treatment liquid on the substrate W is suppressed. Therefore, the thickness of the liquid film is preferably the minimum thickness required to cover the processing object on the substrate W (in this embodiment, the used photoresist film on the substrate W). The film thickness of the liquid film 101A (that is, the distance D1 ) is, for example, 0.3 mm or more and 2.0 mm or less, preferably about 1 mm.

On the other hand, the gas is supplied from the gas supply source 39 toward the plasma processing nozzle 30 (step ST04 in FIG. 5 ). Then, by applying a predetermined alternating voltage to the pair of electrodes 30B, plasma PL is generated in the vicinity of the space in the pipe 30A sandwiched by the pair of electrodes 30B (step ST05 in FIG. 5 ). Active species are generated from the gas passing through the plasma PL by the action of the plasma PL. As the active species, there are charged ions, electrically neutral radicals, and the like. For example, in the case where the gas contains O ₂ , an oxygen radical of an active species is generated by the action of the plasma PL in the plasma treatment nozzle 30 .

The active species generated in the plasma processing nozzle 30 move from the piping 30A toward the liquid film 101A along the flow of the gas supplied from the gas supply source 39 . In this way, the active species generated by the plasma PL are supplied to the liquid film 101A together with the gas in the piping 30A (step ST06 in FIG. 5 ).

At this time, the position of the plasma processing nozzle 30 attached to the end of the nozzle arm 32 on the upper surface of the substrate W can be adjusted by moving the nozzle arm 32 in the horizontal and vertical directions. In particular, the position in the vertical direction of the plasma processing nozzle 30 may be such that the distance D2 between the lower end of the plasma processing nozzle 30 and the upper surface of the substrate W is smaller than the distance D1 (that is, in such a way that the plasma processing nozzle 30 has a smaller distance D1 than the distance D1). The lower end is positioned below the liquid level of the liquid film 101A, and the manner in which the lower end of the plasma processing nozzle 30 contacts the liquid film 101A) is adjusted. By adjusting the position in the vertical direction of the plasma processing nozzle 30 in this way, it is possible to prevent the gas after the plasma processing from being exposed to the atmosphere.

When the active species are supplied to the liquid film 101A, the active species activate the treatment liquid in the liquid film 101A. For example, when the active species contains oxygen radicals, the removal of the photoresist film on the substrate W is promoted by the oxidative power of the oxygen radicals.

In addition, by arranging the pair of electrodes 30B at the end of the pipe 30A, the position where the plasma PL is generated is set near the end of the pipe 30A (for example, about 1 mm away from the end of the pipe 30A facing the substrate W) ), the plasma PL can be supplied to the liquid film 101A before the active species in the plasma PL are largely deactivated. The same applies to other configurations shown in the following embodiments. For example, considering the case of active species OH radicals, the lifetime coefficient of OH radicals is about 100 μs, and when the droplet velocity is several tens of m/s, the OH radical activity is presumed to be sufficiently maintained. Those around 10mm.

In this embodiment, although the treatment liquid may be a solution containing at least one of sulfuric acid, sulfate, sulfuric acid peroxide, and sulfuric acid peroxide, deionized water (DIW), or a solution containing hydrogen peroxide, if it is used Deionized water (DIW) can be used as a treatment liquid to improve the oxidative power by plasma treatment, while reducing the difficulty of drainage (improving safety) and performing low temperature treatment (for example, below 100°C).

Furthermore, in the above description, although the operation of the plasma processing nozzle 30 is performed after the operation of the processing liquid nozzle 20, the operation sequence is not limited to this, and for example, the processing liquid nozzle 20 may be operated almost simultaneously. The operation corresponds to the operation of the plasma processing nozzle 30 .

In addition, the position of the plasma processing nozzle 30 supplying the plasma PL on the upper surface of the substrate W can be moved in the rotation direction of the substrate W along the upper surface of the substrate W as the substrate W rotates. In addition, by driving the nozzle arm 32 to swing the plasma processing nozzle 30, the position of the plasma processing nozzle 30 supplying the plasma PL on the upper surface of the substrate W may be directed toward the substrate W along the upper surface of the substrate W radial movement. By moving the position of the plasma processing nozzle 30 on the upper surface of the substrate W in at least one of the rotational direction and the radial direction, the active species generated by the plasma PL can be uniformly diffused with respect to the liquid film 101A. The same applies to other configurations shown in the following embodiments.

In addition, the formation of the liquid film 101A is started by starting the supply of the processing liquid 101 to the upper surface of the substrate W and stopped by stopping the supply of the processing liquid 101 to the upper surface of the substrate W. However, when the processing liquid 101 is stopped After the supply from the processing liquid nozzle 20 , the liquid film 101A can be maintained without the substrate W rotating at a high speed (eg, the substrate W is slowly rotating at a low speed, or the substrate W is not rotating). The supply of the active species generated by the plasma PL to the liquid film 101A is performed after the supply of the treatment liquid 101 is started and before the supply of the treatment liquid 101 is stopped. After the supply of the liquid 101 is stopped, the active species generated by the plasma PL are supplied to the liquid film 101A.

In addition, after the above-mentioned removal process, the rinsing process (cleaning process) and the drying process of the board|substrate W are normally performed. For example, the rinsing step is performed by spitting deionized water (DIW) onto the substrate W, and the drying step is performed by drying with isopropyl alcohol (IPA).

<Second Embodiment> Hereinafter, the substrate processing apparatus and the substrate processing method of the substrate processing system of the present embodiment will be described. In addition, in the following description, the same components as those described in the above-described embodiment are denoted by the same reference numerals and shown in the drawings, and detailed descriptions thereof are appropriately omitted.

<About the configuration of the substrate processing apparatus> FIG. 6 is a cross-sectional view showing a configuration example of a processing liquid nozzle 200 arranged on the upper surface of the substrate W facing the substrate processing apparatus in the substrate processing system according to the present embodiment.

As shown in FIG. 6 , in the processing liquid nozzle 200 , a liquid film of the processing liquid 101 is formed on the upper surface of the substrate W held by the rotary jig 10 by flowing the processing liquid 101 in the nozzle portion 20A made of resin or the like. 101A. Furthermore, the processing liquid nozzle 200 is attached to the end of the nozzle arm 22 .

Moreover, the processing liquid nozzle 200 is provided with the plasma processing part 300 connected to the side surface of the nozzle part 20A. The plasma processing unit 300 includes a pipe 30C made of an insulator or the like, and a pair of electrodes 30B. A pair of electrodes 30B are attached to the outer surface of the piping 30C, and are arranged to face each other with the piping 30C interposed therebetween.

One end of the piping 30C is connected to the side surface of the nozzle portion 20A, where the nozzle portion 20A communicates with the piping 30C. Moreover, the processing liquid nozzle 200 is provided with the porous material 20B in the nozzle part 20A where the nozzle part 20A communicates the nozzle part 20A and the piping 30C. In addition, the porous material 20B may not be provided.

<About the operation of the substrate processing apparatus> Next, the step of removing the organic matter adhering to the substrate W included in the operation of the substrate processing apparatus will be described with reference to FIG. 7 . Here, FIG. 7 is a flowchart showing an operation example of the substrate processing apparatus.

First, the rotary jig 10 holds the substrate W (step ST01 in FIG. 7 ). Then, by the rotation of the rotating jig 10, the substrate W also rotates.

Next, the processing liquid 101 is supplied from the processing liquid supply source 29 toward the nozzle portion 20A, and the processing liquid 101 is discharged from the nozzle portion 20A toward the upper surface of the substrate W while the substrate W is rotating (step ST02 in FIG. 7 ). . At this time, the position of the processing liquid nozzle 200 attached to the end of the nozzle arm 22 on the upper surface of the substrate W can be adjusted by moving the nozzle arm 22 in the horizontal direction and the vertical direction. In particular, the vertical position of the nozzle portion 20A may be such that the distance D2 between the lower end of the nozzle portion 20A and the upper surface of the substrate W is smaller than the distance D1 corresponding to the film thickness of the liquid film 101A (that is, by The lower end of the nozzle portion 20A is positioned below the liquid surface of the liquid film 101A, and the manner in which the lower end of the nozzle portion 20A is brought into contact with the liquid film 101A) is adjusted. In this way, by adjusting the position of the processing liquid nozzle 200 in the vertical direction, it is possible to prevent the gas after the plasma treatment from being exposed to the atmosphere.

Then, the processing liquid 101 is discharged from the nozzle portion 20A, and a liquid film 101A of the processing liquid 101 is formed on the upper surface of the substrate W (step ST03 in FIG. 7 ).

On the other hand, the gas is supplied from the gas supply source 39 toward the plasma processing unit 300 (step ST04 in FIG. 7 ). Then, by applying a predetermined alternating voltage to the pair of electrodes 30B, plasma PL is generated in the vicinity of the space in the pipe 30C sandwiched by the pair of electrodes 30B (step ST05 in FIG. 7 ). The active species generated by the plasma PL generated in the plasma processing section 300 move from the piping 30C toward the porous material 20B in the nozzle section 20A along the flow of the gas supplied from the gas supply source 39 . In this way, the active species generated by the plasma PL are supplied to the porous material 20B together with the gas in the piping 30C (step ST07 in FIG. 7 ).

Then, the active species in the bubbles 20C are supplied to the treatment liquid 101 passing through the porous material 20B, and the active species in the state of the bubbles 20C contained in the treatment liquid 101 are also supplied toward the liquid film 101A (step ST06 in FIG. 7 ). ). The active species encapsulated by the air bubbles 20C are supplied to the liquid film 101A together with the treatment liquid so as not to contact the outside air.

The treatment liquid in the liquid film 101A is activated by the supply of the active species to the liquid film 101A. Thereby, the processing of the substrate W is accelerated. For example, removal of the photoresist film from the substrate W is facilitated (not shown).

<About the shape of the processing liquid nozzle> Hereinafter, a modification example of the shape of the processing liquid nozzle is shown.

8 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle 200A arranged to face the upper surface of the substrate W. As shown in FIG.

As shown in FIG. 8 , in the processing liquid nozzle 200A, the processing liquid 101 flows through the nozzle portion 20D formed of an insulator or the like, and a liquid film of the processing liquid 101 is formed on the upper surface of the substrate W held by the rotary jig 10 . 101A. In addition, 200 A of process liquid nozzles are attached to the edge part of the nozzle arm 22. As shown in FIG.

Furthermore, the processing liquid nozzle 200A includes a pipe 30D connected to a corner portion of the nozzle portion 20D and a side surface made of an insulator or the like, and a pair of electrodes 30B provided at the end portion of the nozzle portion 20D facing the substrate W. The pair of electrodes 30B are attached to the outer surface of the nozzle portion 20D, and are arranged to face each other with the nozzle portion 20D interposed therebetween.

One end of the piping 30D is connected to the side surface of the corner portion of the nozzle portion 20D, where the nozzle portion 20D communicates with the piping 30D.

In the step of removing the organic matter adhering to the substrate W, the processing liquid 101 is supplied from the processing liquid supply source 29 toward the nozzle portion 20D, and the processing liquid 101 is discharged toward the upper surface of the substrate W from the nozzle portion 20D. At this time, the position of the processing liquid nozzle 200A attached to the end of the nozzle arm 22 on the upper surface of the substrate W is adjusted by the movement of the nozzle arm 22 in the horizontal direction and the vertical direction. In particular, the position of the nozzle portion 20D in the vertical direction can be achieved by such that the distance D2 between the lower end of the nozzle portion 20D and the upper surface of the substrate W is smaller than the distance D1 corresponding to the film thickness of the liquid film 101A (ie, The lower end of the nozzle portion 20D is adjusted so that the lower end of the nozzle portion 20D contacts the liquid film 101A by being positioned below the liquid level of the liquid film 101A.

When the processing liquid 101 is discharged from the nozzle portion 20D, a liquid film 101A of the processing liquid 101 is formed on the upper surface of the substrate W. As shown in FIG.

On the other hand, the gas is supplied from the gas supply source 39 toward the piping 30D, becomes the bubbles 20E, and is supplied to the processing liquid 101 in the nozzle portion 20D. In addition, when the bubble 20E reaches the region in the nozzle portion 20D sandwiched by the pair of electrodes 30B, a predetermined alternating voltage is applied to the pair of electrodes 30B, and the gas in the bubble 20E generates plasma PL, which is The role of plasma PL to generate active species. The active species in the bubbles 20E are supplied to the processing liquid 101, and are supplied to the liquid film 101A together with the processing liquid. In this way, the active species in the bubbles 20E are supplied to the liquid film 101A together with the treatment liquid without contacting the outside air.

9 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle 20 and the plasma processing nozzle 300A arranged to face the upper surface of the substrate W. As shown in FIG.

As shown in FIG. 9 , the processing liquid 101 flows to the processing liquid nozzle 20 to form a liquid film 101A of the processing liquid 101 on the upper surface of the substrate W held by the rotary jig 10 .

On the other hand, the plasma processing nozzle 300A includes a pipe 30A made of an insulator or the like, a pair of electrodes 30B, and a gas discharge mechanism provided at an end of the pipe 30A that is closer to the substrate W than the pair of electrodes 30B 30E.

The gas discharge mechanism 30E is provided at the end of the piping 30A facing the substrate W, and the opening 30F for discharging gas from the side surface of the piping 30A is formed in a ring shape when the substrate W is viewed in plan. The gas discharged from the opening 30F of the gas discharge mechanism 30E is radially formed from the piping 30A in plan view, and is discharged substantially parallel to the liquid surface of the liquid film 101A in the cross-sectional view of FIG. 9 .

The gas is supplied from the gas supply source 38 toward the gas discharge mechanism 30E. The gas supplied from the gas supply source 38 can be assumed to be an inert gas (eg, nitrogen gas or argon gas). In addition, the gas supplied from the gas supply source 38 to the gas discharge mechanism 30E may be the same gas as the gas supplied from the gas supply source 39 into the piping 30A, or may be a different gas.

In addition, in the present embodiment, although the gas discharge mechanism 30E is arranged on the side facing the end portion of the substrate W rather than the electrode 30B, the electrode 30B may be arranged on the side opposite to the gas discharge mechanism 30E. The end side of the substrate W. In addition, the gas discharge mechanism 30E may be attached to the nozzle part 20A shown in FIG. 6 or the nozzle part 20D shown in FIG. 8 .

In the step of removing organic matter adhering to the substrate W, the processing liquid 101 is supplied from the processing liquid supply source 29 toward the processing liquid nozzle 20 , and the processing liquid 101 is supplied from the processing liquid nozzle 20 toward the upper surface of the substrate W. Then, the liquid film 101A of the processing liquid 101 is formed on the upper surface of the substrate W when the processing liquid 101 is discharged from the processing liquid nozzle 20 .

On the other hand, the gas is supplied from the gas supply source 39 toward the piping 30A of the plasma processing nozzle 300A. Then, by applying a predetermined alternating voltage to the pair of electrodes 30B, plasma PL is generated in the vicinity of the space in the pipe 30A sandwiched by the pair of electrodes 30B. Active species are generated from the gas passing through the plasma PL by the action of the plasma PL. Then, the generated active species are supplied to the liquid membrane 101A together with the gas in the piping 30A.

At this time, the lower end of the pipe 30A is moved in the horizontal direction and the vertical direction by the nozzle arm 32, and the lower end of the pipe 30A can be used for adjustment by being positioned below the liquid level of the liquid film 101A and in contact with the liquid film 101A. The position in the vertical direction of the plasma processing nozzle 300A.

Moreover, the gas is supplied from the gas supply source 38 to the gas discharge mechanism 30E provided in the end part of the piping 30A. Then, the supplied gas is discharged from the opening 30F of the gas discharge mechanism 30E toward the liquid surface of the liquid film 101A in a substantially parallel manner.

Therefore, the inert gas discharged along the upper surface of the substrate W covers the liquid surface of the liquid film 101A. Therefore, it is possible to suppress the dissolution of unexpected substances in the atmosphere into the liquid film 101A. In addition, it can also suppress the unexpected reaction of the substance in the treatment liquid 101 and the liquid film 101A.

10 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle 200B and the plasma processing unit 300B arranged to face the upper surface of the substrate W. As shown in FIG.

As shown in FIG. 10 , the processing liquid 101 flows through the nozzle portion 20G of the processing liquid nozzle 200B to form a liquid film 101A of the processing liquid 101 on the upper surface of the substrate W held by the rotary jig 10 .

On the other hand, the plasma processing unit 300B includes a plasma chamber 50 that performs plasma processing on a gas supplied from the outside, and a pipe 51 that connects the plasma chamber 50 and the processing liquid nozzle 200B.

The plasma chamber 50 includes a pair of electrodes 30B, and an AC power source 40 that applies a voltage to the pair of electrodes 30B. The plasma chamber 50 is a chamber that is separated from the outside air, and is a chamber that generates atmospheric pressure plasma.

The plasma chamber 50 generates active species in the gas supplied from the outside by subjecting the gas to plasma processing. The active species generated in the plasma chamber 50 move into the nozzle portion 20G through the piping 51 . Then, the active species supplied into the nozzle portion 20G are supplied to the liquid film 101A together with the processing liquid 101 in a state of being surrounded by the bubbles 20F.

Here, the position of the plasma chamber 50 may be movable or fixed. When the position of the plasma chamber 50 is to be fixed, the piping 51 is made of a bendable member.

In addition, in order to maintain the activity of the active species until it is supplied to the liquid film 101A as much as possible, the path from the plasma chamber 50 to the liquid film 101A is preferably set as short as possible. The length of this path is, for example, several tens of cm or less.

<About the effects of the above-described embodiment> Next, the example of the effect by the embodiment described above is shown. Furthermore, in the following description, although the effect is described based on the specific configuration exemplified in the above-described embodiment, it can be replaced by other specific configurations other than those exemplified in this specification within the scope of producing the same effect. constitute.

In addition, this replacement may span over a plurality of embodiments. That is, it is also possible to combine the respective configurations illustrated in different embodiments to produce the same effect.

According to the above-described embodiment, the substrate processing method includes the step of holding the substrate W; The step of film 101A; the step of bringing the end of the nozzle into contact with the liquid film 101A, and the step of supplying gas from the nozzle toward the liquid film 101A; the step of applying plasma treatment for generating plasma from the gas; and supplying the gas after the plasma treatment Steps up to the liquid film 101A. Here, the nozzle may be, for example, one corresponding to the plasma processing nozzle 30 , the plasma processing nozzle 300A, the processing liquid nozzle 200 , or the processing liquid nozzle 200A, or the like.

According to this configuration, it is possible to suppress the exposure of the gas after the plasma treatment to the atmosphere. Therefore, it is possible to supply the processing liquid 101 to the upper surface of the substrate W while suppressing a decrease in the oxidative power of the processing liquid 101 due to the plasma treatment.

In addition, in the case where there is no particular limitation, the order of the processing performed in each case may be changed.

In addition, even when other structures other than those illustrated in this specification are appropriately added to the above-mentioned structures, that is, when other structures not mentioned in the present specification are appropriately added to the above-mentioned structures, the same effects can still be produced.

Moreover, according to the embodiment described above, the nozzle is the one of the processing liquid nozzle 200 or the processing liquid nozzle 200A that supplies the processing liquid 101 . Furthermore, the step of performing the plasma treatment is a step of generating plasma in the gas supplied to the treatment liquid 101 inside the nozzle. With this configuration, since the plasma PL is supplied to the processing liquid 101 in the nozzle portion 20A (or in the nozzle portion 20D), one nozzle can be used to supply the processing liquid 101 to the liquid film 101A. In this way, the device configuration can be simplified.

Moreover, according to the embodiment described above, the step of performing the plasma treatment is a step of generating plasma in the gas before being supplied to the treatment liquid 101 . According to such a configuration, the treatment liquid 101 can be supplied to the upper surface of the substrate W while the oxidizing power of the treatment liquid 101 is increased by the plasma treatment.

Moreover, according to the embodiment described above, the step of performing the plasma treatment is a step of generating plasma in the gas supplied to the processing liquid 101 to become the bubbles 20E inside the processing liquid nozzle 200A. According to this configuration, the treatment liquid 101 can be supplied to the upper surface of the substrate W in a state where the oxidative power of the treatment liquid 101 is increased by the plasma treatment.

Further, according to the above-described embodiment, in the step of supplying the gas after the plasma treatment to the liquid film 101A, the nozzle is in contact with the liquid film 101A along the upper surface of the substrate W (the rotation direction of the substrate W). A step of supplying the gas subjected to the plasma treatment to the liquid film 101A while moving in at least one of the radial direction. According to this configuration, by moving the position of the plasma processing nozzle 30 on the upper surface of the substrate W in at least one of the rotational direction and the radial direction, the plasma PL can be uniformly diffused with respect to the liquid film 101A.

Moreover, according to the embodiment described above, the treatment liquid 101 is deionized water. According to such a structure, it becomes possible to reduce the difficulty of draining and low-temperature processing, improving oxidizing power etc. by plasma processing.

Moreover, according to the embodiment described above, the step of performing the plasma treatment is a step of generating plasma in the gas near the end of the nozzle. With such a configuration, the active species can be supplied to the liquid film 101A before the active species generated by the plasma PL are largely deactivated.

In addition, according to the above-described embodiment, the step of supplying the gas after the plasma treatment to the liquid film 101A is carried out from the opening 30F provided on the side surface of the plasma treatment nozzle 300A toward the plasma treatment nozzle 300A. A step of supplying the plasma-treated gas to the liquid film 101A while discharging an inert gas in the direction of the upper surface of the substrate W. According to such a configuration, since the inert gas discharged along the upper surface of the substrate W covers the liquid surface of the liquid film 101A, it is possible to suppress the dissolution of unexpected substances in the air into the liquid film 101A, and also to suppress the liquid Unexpected reaction with the substance in film 101A.

<About the modified example of the above-mentioned embodiment> The shape of the plasma processing nozzle or the nozzle portion of the above-described embodiment is, for example, a circular hollow, a square hollow, a fan-shaped hollow, or a full-scale hollow covering the entire surface of the substrate W in plan view.

In the above-described embodiment, although the material, material, size, shape, relative arrangement relationship, and implementation conditions of each constituent element are also described, these are only one example of all the aspects, and the present invention It is not limited to what is described in this specification.

Therefore, innumerable modification examples and equivalents (equivalent) which are not illustrated can be regarded as being within the technical scope disclosed in this specification. For example, it includes the case where at least one constituent element is modified, the case where it is added or omitted, and the case where at least one constituent element of at least one embodiment is extracted and combined with constituent elements of other embodiments. situation.

In addition, in the above-described embodiment, when the material name is not specified, other additives, such as alloys, may be included in the material as long as there is no conflict.

1: Substrate processing system 10: Rotary fixture 10A: Swivel base 10C: Rotary axis 10D: Rotary Motor 12: Processing Cups 20, 200, 200A, 200B: Treatment fluid nozzle 20B: Porous Materials 20A, 20D, 20G: Nozzle part 20C, 20E, 20F: bubbles 22, 32: Nozzle Arm 22A, 32A: Arm 22B, 32B: Shaft body 22C, 32C: Actuator 25: Valve 29: Treatment liquid supply source 30, 300A: plasma treatment nozzle 30B: Electrodes 30A, 30C, 30D, 51: Piping 30E: Gas discharge mechanism 30F: Opening 38, 39: Gas supply source 40: AC power 50: Plasma chamber 80: Chamber 90: Control Department 91:CPU 92:ROM 93: RAM 94: Storage Device 94P: Handler 95: bus wire 96: Input section 97: Display part 98: Ministry of Communications 100: Substrate processing device 101: Treatment liquid 101A: Liquid film 300, 300B: Plasma Treatment Department C: vehicle CR: Central Robot IR: Indexing Robot LP: Load port PS: Substrate mounting part PL: Plasma UT: processing unit W: substrate Z1: Rotation axis

FIG. 1 is a plan view schematically showing a configuration example of a substrate processing system according to the embodiment. FIG. 2 is a diagram schematically showing a configuration example of the control unit shown in FIG. 1 . FIG. 3 is a side view schematically showing a configuration example of the substrate processing apparatus according to the embodiment. 4 is a cross-sectional view showing a configuration example of a processing liquid nozzle and a plasma processing nozzle arranged to face the upper surface of the substrate. FIG. 5 is a flowchart showing an example of the operation of the substrate processing apparatus. 6 is a cross-sectional view showing an example of the configuration of a processing liquid nozzle disposed facing the upper surface of the substrate in the substrate processing apparatus in the substrate processing system according to the embodiment. FIG. 7 is a flowchart showing an example of the operation of the substrate processing apparatus. FIG. 8 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle arranged to face the upper surface of the substrate. 9 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle and the plasma processing nozzle arranged to face the upper surface of the substrate. 10 is a cross-sectional view showing a modified example of the configuration of the processing liquid nozzle and the plasma processing nozzle arranged to face the upper surface of the substrate.

10A: Swivel base

20: Treatment fluid nozzle

30: Plasma treatment nozzle

30A: Piping

30B: Electrodes

40: AC power

101: Treatment liquid

101A: Liquid film

PL: Plasma

W: substrate

Claims (11)

A substrate processing method, comprising: a step of holding a substrate; a step of forming a liquid film of the above-mentioned processing liquid on the upper surface of the above-mentioned substrate by supplying a processing liquid to the upper surface of the above-mentioned substrate from a first nozzle; a step of arranging the front end of the nozzle so as to be in contact with the liquid film; a step of supplying a gas to the second nozzle; a step of subjecting the gas supplied to the second nozzle to plasma treatment; The gas supply step in which the gas for the slurry treatment is supplied to the liquid film from the front end of the second nozzle. A substrate processing method comprising: the steps of holding a substrate; the step of forming a liquid film of the processing liquid on the upper surface of the substrate by supplying a processing liquid to the upper surface of the substrate from a processing liquid nozzle; The step of arranging the front end of the liquid nozzle so as to be in contact with the liquid film; supplying the gas subjected to plasma treatment to the processing liquid nozzle for supplying the processing liquid, and making the gas mixed in the processing liquid nozzle to flow and a mixed gas supply step of supplying the gas mixed in the processing liquid to the liquid film together with the processing liquid from the front end of the processing liquid nozzle. A substrate processing method, comprising: a step of holding a substrate; by supplying a processing liquid to the upper surface of the substrate from a processing liquid nozzle, and placing a processing liquid on the upper surface of the substrate. The step of forming a liquid film of the above-mentioned treatment liquid on the upper surface; the step of arranging the front end of the above-mentioned treatment liquid nozzle in a state where it is in contact with the above-mentioned liquid film; the step of supplying gas to the above-mentioned treatment liquid nozzle, so that the above-mentioned gas is mixed in the above-mentioned treatment liquid. The step of applying the above-mentioned treatment liquid flowing in the liquid nozzle; the step of applying plasma treatment to the above-mentioned gas mixed in the above-mentioned treatment liquid; The gas is supplied to the mixed gas supply step in the above-mentioned liquid film. The substrate processing method according to claim 1, wherein, in the gas supply step, the second nozzle moves the gas to be subjected to the plasma treatment while moving along the upper surface of the substrate in a state where the second nozzle is in contact with the liquid film. The step of supplying to the above-mentioned liquid film. The substrate processing method according to claim 2 or 3, wherein in the step of supplying the mixed gas, the processing liquid nozzle is moved along the upper surface of the substrate while being in contact with the liquid film while the plasma processing is performed. The step of supplying the above-mentioned gas to the above-mentioned liquid film. The substrate processing method according to any one of claims 1 to 3, wherein the processing liquid is deionized water. The substrate processing method according to claim 1, wherein the plasma treatment to which the gas is applied is performed in the vicinity of the end portion of the second nozzle. The substrate processing method according to claim 2 or 3, wherein the plasma processing to which the gas is applied is performed in the vicinity of the end portion of the processing liquid nozzle. The substrate processing method according to claim 1, wherein, in the gas supply step, The second nozzle supplies the gas subjected to the plasma treatment to the liquid film while discharging an inert gas from an opening provided on a side surface of the second nozzle in a direction along the upper surface of the substrate. step. The substrate processing method according to claim 2 or 3, wherein in the step of supplying the mixed gas, the processing liquid nozzle discharges an inert gas from an opening provided on a side surface of the processing liquid nozzle in a direction along the upper surface of the substrate , while supplying the gas subjected to the plasma treatment to the liquid film. The substrate processing method according to any one of claims 1 to 3, wherein the thickness of the liquid film is 0.3 mm or more and 2.0 mm or less.

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