TW201409188A - Resist removing device and resist removing method - Google Patents

Abstract

This resist removing apparatus is provided with: a substrate holding section that holds a substrate having a resist, which has predetermined ions implanted therein, and which has a cured layer formed on the surface thereof; a sulfuric acid supplying section, which has a heater that heats sulfuric acid, and which supplies the sulfuric acid to the substrate being held by means of the substrate holding section, said sulfuric acid being at 200 DEG C or higher by having been heated by means of the heater, and not containing hydrogen peroxide water; and an ozone water supplying section, which supplies ozone water having a concentration of 150 ppm or more to the substrate having been supplied with the sulfuric acid by means of the sulfuric acid supplying section.

Description

Photoresist removal device and photoresist removal method Technical field

The present invention relates to a photoresist removal apparatus and method for removing photoresist on a substrate.

Background technique

In the process of the semiconductor device, various processes such as an insulating film formed on the surface of the substrate and the substrate are implanted with predetermined ions by ion implantation technology, and the surface characteristics are changed. For example, by implanting a predetermined ion toward the surface of the substrate, a conductive portion of the transistor can be formed on the surface of the substrate.

The ion implantation process is usually performed after the photoresist is formed on the substrate, and the photoresist is removed after the ion implantation process. However, the photoresist after high-dose ion implantation forms a hardened layer on the surface, so that it is difficult to peel off from the substrate. Therefore, the surface is provided with the removal of the photoresist of the hardened layer, and a method of applying a plasma ashing treatment to the photoresist and then wet-cleaning the substrate is generally used (see, for example, Patent Document 1).

The method of wet washing can be exemplified by a treatment liquid mixed with sulfuric acid and hydrogen peroxide water. The above cleaning process is called SPM (Sulfuric acid/hydrogen peroxide mixture) cleaning.

[First technical literature]

[Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. Hei 7-37780

Summary of invention

However, according to the method disclosed in Patent Document 1, since the plasma ashing treatment is performed, the substrate may be damaged by the destruction of the plasma.

Further, in consideration of the wet cleaning after the plasma ashing, the processing form of the substrate is often a batch type in which a plurality of substrates are stacked and immersed in a treatment tank in which the treatment liquid is placed for treatment. The batch type can reduce the amount of treatment liquid used for each substrate. The single-chip type processing for each substrate is more expensive than the batch type, and is hardly used.

In addition, the conventional photoresist removal method combined with batch plasma ashing and SPM cleaning is performed only once for each individual process, and the photoresist cannot be sufficiently removed, so it may be necessary to carry out separate processes for individual processes. Times. Further, the batch type SPM cleaning cannot sufficiently remove impurities such as metals contained in the photoresist, so metal contamination may occur. Therefore, after the SPM cleaning, it is necessary to carry out HPM (hydrochloric acid/hydrogen peroxide mixture) cleaning or the like by mixing a treatment liquid containing hydrochloric acid and hydrogen peroxide water to remove the metal residue.

As described above, the conventional photoresist removal method adopts a batch type, and the amount of the treatment liquid used can be reduced more than the single sheet type, but the predetermined amount of light is removed. The process required for the resistance is more and the time is longer. In other words, it is not possible to fully balance the reduction in the amount of the treatment liquid used and the efficiency of removing the photoresist.

Accordingly, an object of the present invention is to solve the above problems, and to provide a photoresist removing apparatus and a method thereof which can reduce damage to a substrate, reduce the amount of processing liquid used, and efficiently remove the photoresist.

In order to achieve the above object, the present invention is constituted as follows.

According to a first aspect of the present invention, there is provided a photoresist removing apparatus for removing a photoresist from a substrate, comprising: a substrate holding portion for holding a predetermined implanted ion on the surface a substrate having a photoresist having a hardened layer; a sulfuric acid supply portion provided with a heater for heating sulfuric acid, and a substrate for holding the substrate held by the substrate holding portion to be heated to 200 ° C or higher without peroxidation And the ozone water supply unit is capable of supplying ozone water having a concentration of 150 ppm or more to a substrate to which sulfuric acid is supplied from a sulfuric acid supply unit.

According to a second aspect of the present invention, there is provided a photoresist removal apparatus as disclosed in the first aspect, which is monolithic.

According to a third aspect of the present invention, there is provided a photoresist removal apparatus as disclosed in the first aspect or the second aspect, wherein the sulfuric acid supply unit supplies the partially thermally decomposed sulfuric acid.

According to a fourth aspect of the present invention, there is provided a photoresist removal apparatus as disclosed in the third aspect, which supplies 1 to 20% of the thermally decomposed sulfuric acid in the whole.

According to a fifth aspect of the present invention, there is provided a photoresist removal apparatus as disclosed in any of the first aspect to the fourth aspect, wherein the sulfuric acid supply unit Sulfuric acid supplied at 200 ° C or higher can cause thermal stress to the photoresist to cause damage to the photoresist.

According to a sixth aspect of the present invention, there is provided a photoresist removing apparatus as disclosed in the fifth aspect, wherein the damage is a crack.

According to a seventh aspect of the present invention, there is provided a photoresist removal apparatus according to any one of the first aspect to the sixth aspect, wherein the ozone water supply unit supplies ozone water of 50 ° C or more.

According to an eighth aspect of the present invention, there is provided a photoresist removal apparatus according to any one of the first aspect to the seventh aspect, wherein the substrate is subjected to sulfuric acid in a state in which the substrate is rotated by the substrate holding portion. And the supply of ozone water.

According to a ninth aspect of the present invention, a photoresist removal method for removing photoresist from a substrate includes the following steps: a sulfuric acid supply step, which is performed on a photoresist formed on a substrate, and implanted with ions On the surface of the photoresist on which the hardened layer is formed, sulfuric acid containing 200 ° C or more containing no hydrogen peroxide water is supplied; and the ozone water supply step is supplied to the surface of the photoresist of sulfuric acid by a sulfuric acid supply step, and the supply concentration is 150 ppm or more. Ozone water.

According to a tenth aspect of the present invention, there is provided a photoresist removal method as disclosed in the ninth aspect, wherein the substrate is processed in a single chip.

According to an eleventh aspect of the present invention, there is provided a photoresist removal method as disclosed in the ninth aspect or the tenth aspect, which supplies the partially thermally decomposed sulfuric acid in the sulfuric acid supply step.

According to a twelfth aspect of the present invention, there is provided a photoresist removal method as disclosed in the eleventh aspect, which supplies 1 to 20% of the thermally decomposed sulfuric acid in the whole in the sulfuric acid supply step.

According to a thirteenth aspect of the present invention, there is provided a photoresist removal method as disclosed in any one of the ninth aspect to the twelfth aspect, wherein the sulfuric acid to the photoresist which is supplied at a temperature of 200 ° C or higher supplied in the sulfuric acid supply step Applying heating stress causes damage to the photoresist.

According to a fourteenth aspect of the present invention, there is provided a photoresist removal method as disclosed in the thirteenth aspect, wherein the damage is a crack.

According to a fifteenth aspect of the present invention, there is provided a photoresist removal method as disclosed in any one of the ninth aspect to the fourteenth aspect, which supplies ozone water of 50 ° C or more in the ozone water supply step.

According to a sixteenth aspect of the present invention, there is provided a photoresist removal method as disclosed in any one of the ninth aspect to the fifteenth aspect, wherein the substrate is rotated in the sulfuric acid supply step and the ozone water supply step.

The photoresist removing device and method thereof can reduce damage to the substrate, reduce the amount of processing liquid used, and efficiently remove the photoresist.

1‧‧‧Light removal device

2‧‧‧Substrate

3‧‧‧Substrate holder

4‧‧‧Sulphuric Acid Supply Department

5‧‧‧Ozone Water Supply Department

6‧‧‧ stage

7‧‧‧Rotary axis

8‧‧‧Rotating table

9‧‧‧Light resistance

10‧‧‧Connected section

11‧‧‧ hardened layer

12‧‧‧heater

13‧‧‧ supply port

14‧‧‧ supply port

15‧‧‧ crack

C-G‧‧‧ measuring point

S1-S4‧‧‧ Process Steps

The above-described aspects and features of the present invention are apparent from the following description of the preferred embodiments.

Fig. 1 is a cross-sectional view showing a photoresist removal apparatus 1 according to an embodiment of the present invention.

2(a) to 2(b) are cross-sectional views of the substrate 2 used in the present embodiment.

Fig. 3 is a cross-sectional view showing the sulfuric acid supply unit 4 used in the present embodiment.

Figure 4 is a flow chart showing the steps of photoresist removal.

5(a) to 5(c) are cross-sectional views showing the operation of the photoresist removing device 1 corresponding to the flowchart of Fig. 4.

6(a) to 6(d) are explanatory views for explaining the principle of photoresist removal by the photoresist removing device 1.

Fig. 7 is a plan view of the substrate 2 used in the embodiment.

8(a) to (b) show the results of measurement of the amount of metal residue in Example 1.

9(a) to (b) show the results of measurement of the amount of metal residue in Example 2.

Form for implementing the invention

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Fig. 1 is a cross-sectional view showing a photoresist removal apparatus 1 according to an embodiment of the present invention. The photoresist removal device 1 includes a substrate holding device 3 that can hold the substrate 2, a sulfuric acid supply unit 4, and an ozone water supply unit 5.

The substrate holding device 3 includes a stage 6 and a rotary table 8. The stage 6 can hold and hold the substrate 2 to which the transport mechanism (not shown) is transported. The turntable 8 supports the stage 6, and integrally rotates the stage 6 and the substrate 2 placed on the stage 6 around the rotating shaft 7 extending in the vertical direction. FIG. 1 shows a state in which the substrate 2 has been held by the substrate holding device 3.

The sulfuric acid supply unit 4 is provided above the stage 6 of the substrate holding device 3, and is connected to a sulfuric acid supply source (not shown), and contains sulfuric acid (without hydrogen peroxide water) inside. The sulfuric acid supply unit 4 constitutes the sulfuric acid stored inside the substrate 2 which can be placed on the lower stage 6 below. In the present embodiment, the temperature of the sulfuric acid supplied from the sulfuric acid supply unit 4 is set to 200 ° C or higher.

The ozone water supply unit 5 is disposed above the stage 6 at a position different from the position at which the sulfuric acid supply unit 4 is disposed, and is connected to an ozone water supply source (not shown), and contains ozone water therein. The ozone water supply unit 5 is the same as the sulfuric acid supply unit 4. The internally stored ozone water is dripped on the surface of the substrate 2 which is positioned below. In the present embodiment, the concentration of the ozone water supplied from the ozone water supply unit 5 is 150 ppm or more, and the temperature is 50 ° C or higher.

Each of the sulfuric acid supply unit 4 and the ozone water supply unit 5 described above is configured to be movable in the direction along the surface of the row substrate 2 (the horizontal direction in the drawing in the present embodiment).

The operation of the substrate holding device 3, the sulfuric acid supply unit 4, and the ozone water supply unit 5 of the photoresist removal device 1 is controlled by a control device (not shown) similarly provided in the photoresist removal device 1.

Hereinafter, the substrate 2 to be processed in the present embodiment will be described with reference to Fig. 2 .

Fig. 2 is a cross-sectional view showing a method of manufacturing the substrate 2 used in the embodiment. In the present embodiment, the substrate 2 implantable with a high dose of ions such as arsenic or the like is particularly used. Fig. 2(a) shows the substrate 2 before ion implantation, and Fig. 2(b) shows the substrate 2 after ion implantation (substrate 2 used in the present embodiment).

As shown in FIG. 2(a), the patterned photoresist 1 is placed on the substrate 2 before ion implantation. Once the high dose ion is implanted into the substrate 2, a surface such as the conductive portion 10 will be formed on the surface of the substrate 2 exposed between the adjacent photoresists 9.

Further, it is directly exposed to the surface of the high-dose ion photoresist 9, and a hardened layer 11 which is difficult to peel off is formed by the reaction with ions. As shown in FIG. 2(b), the substrate 2 used in the present embodiment is provided with a photoresist 9 having a hardened layer 11 formed on its surface.

Hereinafter, the photoresist removal apparatus 1 of the present embodiment will be described with reference to FIG. Sulfuric acid supply unit 4.

Fig. 3 is a cross-sectional view showing the sulfuric acid supply unit 4 used in the present embodiment. As shown in FIG. 3, in the sulfuric acid supply unit 4 in which sulfuric acid is stored, a heater 12 for heating is disposed in the center portion. By heating the sulfuric acid in the sulfuric acid supply unit 4 by the heater 12, the sulfuric acid adjusted to 200 ° C or higher can be supplied from the supply port 13 at the downstream end of the sulfuric acid supply unit 4 .

Further, the inside of the sulfuric acid supply unit 4 will be described in detail, and the temperature of the sulfuric acid in the sulfuric acid supply unit 4 will differ depending on the distance from the heater 12. That is, the sulfuric acid located in the vicinity of the heater 12 is easily heated and the temperature is high. On the other hand, the sulfuric acid which is located away from the heater 12 is not easily heated and the temperature is relatively low. In the sulfuric acid supply unit 4, sulfuric acid heated to 200 ° C or lower and sulfuric acid heated to 200 ° C or higher are present, but by supplying sulfuric acid at different temperatures and supplying them, sulfuric acid which is finally at 200 ° C or higher can be supplied from the supply port 13 .

Further, the thermal decomposition temperature of sulfuric acid is about 292 °C. Therefore, in the sulfuric acid supply unit 4 configured as described above, sulfuric acid which has been thermally decomposed at a temperature of 292 ° C or higher and sulfuric acid which has not been thermally decomposed at a temperature of 292 ° C or lower are present. Finally, it is supplied in a state in which the thermally decomposed sulfuric acid and the non-thermally decomposed sulfuric acid are mixed, and the sulfuric acid in a partially thermally decomposed state can be supplied from the supply port 13.

According to the sulfuric acid supply unit 4 configured as described above, sulfuric acid of 200 ° C or higher in a partially thermally decomposed state can be supplied from the supply port 13 .

Hereinafter, specific steps of photo-resistance removal using the photoresist removal apparatus 1 of the present invention will be described. For the description, a flow chart showing the steps of photoresist removal is shown in FIG. 4, and FIG. 5 is used to illustrate the flowchart of FIG. The operation of the photoresist removal device 1 shown in each step.

(substrate rotation step)

As shown in FIG. 4, the substrate 2 held on the substrate holding device 3 is first rotated (step S1). Specifically, as shown in FIG. 5( a ), the stage 6 is rotated around the rotary shaft 7 by the rotary table 8 of the substrate holding device 3 so that the substrate 6 and the substrate placed on the stage 6 are placed. 2 rotates in one.

(sulfuric acid supply step)

Next, sulfuric acid is supplied from the sulfuric acid supply unit 4 to the substrate 2 that has been rotated around the rotating shaft 7 (step S2). Specifically, as shown in FIG. 5(b), the sulfuric acid supply unit 4 is controlled to move in the direction along the surface of the row substrate 2, and is dripped downward from the supply port 13 of the sulfuric acid supply unit 4 without peroxidation. Sulfuric acid in hydrogen water. Thereby, sulfuric acid is supplied to the surface of the substrate 2. By supplying sulfuric acid to the substrate 2 in a rotating state, sulfuric acid of 200 ° C or higher containing no hydrogen peroxide water can be supplied to the entire surface of the substrate 2 .

Then, after the lapse of the predetermined time, the supply of sulfuric acid in the sulfuric acid supply unit 4 and the movement of the sulfuric acid supply unit 4 are stopped.

(Ozone water supply step)

Next, ozone water is supplied from the ozone water supply unit 5 to the substrate 2 to which sulfuric acid has been supplied in step S2 (step S3). Specifically, similarly to step S2, as shown in FIG. 5(c), the ozone water supply unit 5 is controlled to move in the direction along the surface of the row substrate 2, and from the supply port 14 of the ozone water supply unit 5. Drain the ozone water downwards. Thereby, ozone water having a concentration of 150 ppm or more and a temperature of 50 ° C or higher can be supplied to the entire surface of the substrate 2.

Then, after the predetermined time elapses, the ozone water supply unit 5 is stopped. The ozone water supply and the movement of the ozone water supply unit 5.

(substrate rotation stop step)

Finally, the rotation of the substrate 2 is stopped (step S4). Specifically, the rotation of the stage 6 caused by the rotary table 8 is stopped, and the rotation of the substrate 2 is stopped.

As described above, by performing steps S1 to S4, it is possible to supply ozone water having a concentration of 150 ppm or more after supplying sulfuric acid of 200 ° C or higher containing no hydrogen peroxide water to the surface of the substrate 2 .

Hereinafter, the principle of photoresist removal performed in the above steps S1 - S4 will be described with reference to a cross-sectional view of the substrate 2 shown in FIG.

Fig. 6(a) shows the substrate 2 before the supply of sulfuric acid and ozone water. As shown in Fig. 6(a), the substrate 2 provided with the photoresist 9 having the hardened layer 11 formed on its surface is supplied with sulfuric acid as described in the step S2, and the hardened layer 11 formed on the surface of the photoresist 9 is damaged. Specifically, the sulfuric acid supplied to the hardened layer 11 is supplied at a high temperature of 200 ° C or higher, and thermal stress is applied to the hardened layer 11 . As shown in Fig. 6(b), a crack 15 which is one example of damage due to thermal stress is formed on the hardened layer 11. The crack 15 is formed, whereby the solvent or the like is allowed to penetrate into the uncured photoresist 9 under the hardened layer 11 via the crack 15 .

As described above, in a state where the crack 15 is formed on the hardened layer 11, sulfuric acid is continuously supplied from the sulfuric acid supply unit 4, and sulfuric acid penetrates into the crack 15. The sulfuric acid that has penetrated into the crack 15 will in turn penetrate downward and penetrate into the uncured photoresist 9 .

Here, the sulfuric acid supplied from the sulfuric acid supply unit 4 is partially thermally decomposed as described above. Therefore, it contains SO ₃ ions generated by thermal decomposition. As described above, the SO ₃ ion and the sulfuric acid are supplied to the uncured photoresist 9 in a mixed state, and an oxidation reaction by SO ₃ ions and a reduction reaction by sulfuric acid are caused in the photoresist 9 . Thereby, as shown in FIG. 6(c), the adhesion of the photoresist 9 to the substrate 2 under it is greatly reduced (a part of the photoresist 9 is peeled off from the substrate 2). Further, even if the hardened layer 11 is subjected to the redox reaction by the combination of the above SO ₃ ions and sulfuric acid, it is almost impossible to peel off from the photoresist 9 .

Next, the substrate 2 having the photoresist 9 having the reduced adhesion as described above is supplied with ozone water as described in the step S3, and as shown in Fig. 6(d), the photoresist 9 is stripped by the ozone water. The photoresist 9 and the hardened layer 11 can be removed from the substrate 2. Thus, the photoresist 9 can be removed from the substrate 2. Further, by setting the concentration of the ozone water to 150 ppm or more and increasing the reactivity of the ozone water, the photoresist 9 can be removed stably and quickly. Further, by setting the temperature of the ozone water to 50 degrees or more and increasing the reactivity of the ozone water, the photoresist 9 can be removed stably and quickly.

As described above, according to the photoresist removal apparatus 1 of the present embodiment, the photoresist 9 formed on the substrate 2 can be supplied to the surface of the photoresist 9 on which the hardened layer 11 is formed by implantation of ions, and the supply is free of peroxidation. Sulfuric acid having a temperature of 200 ° C or higher in hydrogen water is supplied with ozone water having a concentration of 150 ppm or more on the surface of the photoresist 9 to which sulfuric acid is supplied. Thus, the removal of the photoresist 9 can be performed by the so-called wet processing, so that damage to the substrate 2 caused by the plasma generated when plasma ashing or the like is caused can be avoided. Further, after the adhesion between the photoresist 9 and the substrate 2 is lowered by sulfuric acid, the photoresist 9 is stripped by ozone water, and the temperature of the sulfuric acid is set to 200 ° C or higher, and the concentration of the ozone water is 150 ppm or more. The reactivity of the treatment liquid is maintained above a predetermined level. Thereby, the removal of the photoresist can be efficiently performed, and the amount of the treatment liquid used can be reduced. Moreover, by removing the photoresist 9 by using ozone water having a concentration of 150 ppm or more, the gold contained in the photoresist 9 can be removed at the same time. Affiliate. That is, the so-called rinsing treatment can be replaced with the photoresist removal treatment of ozone water, so that the cleaning treatment such as HPM can be omitted.

Moreover, in the present embodiment, the processing of the substrate 2 is performed in a single piece instead of a batch type, and the heat distribution on the substrate 2 can be further enlarged than the batch type, so that the reactivity of sulfuric acid and ozone water can be improved, and Increase the removal force of the photoresist 9. In this way, the removal of the photoresist can be performed efficiently.

Further, in the present embodiment, since the sulfuric acid in a partially thermally decomposed state is supplied, in addition to the reduction reaction of sulfuric acid, the oxidation reaction by the SO ₃ ions generated by the thermal decomposition of sulfuric acid can be utilized. Thereby, the removal force of the photoresist 9 can be improved, and the photoresist removal can be performed efficiently. In addition, it is preferred to thermally decompose more than 1 to 20% of the entire sulfuric acid. By supplying sulfuric acid at the above ratio, the redox reaction can be utilized more efficiently.

Further, in the present embodiment, the temperature of the sulfuric acid supplied to the substrate 2 is set to 200 ° C or higher, and thermal stress can be applied to the photoresist 9 to be damaged. Thereby, sulfuric acid can be stably infiltrated into the photoresist 9 and the photoresist can be removed efficiently.

Further, in the present embodiment, ozone water of 50 ° C or more is supplied, and the photoresist removal power of ozone water can be enhanced. In this way, the removal of the photoresist can be performed efficiently.

Further, in the present embodiment, the supply of sulfuric acid and ozone water is performed while the substrate 2 is rotated, and sulfuric acid and ozone water can be uniformly supplied onto the substrate 2, and the photoresist 9 can be uniformly removed from the substrate 2.

(Example)

Hereinafter, the use of the photoresist removing device 1 configured as above will be described with reference to FIGS. 7-9. An embodiment. In the present embodiment, after a plurality of measurement points are set in advance on the substrate 2, the same processes as the above steps S1 to S4 are performed on the substrate 2, and the amount of metal residue on the substrate 2 before and after the above-described implementation is measured.

Fig. 7 is a plan view showing the substrate 2 used in the present embodiment. This embodiment uses a substrate 2 having a diameter of about 300 mm. As shown in FIG. 7, the measurement point C-G of 5 points is set on the board|substrate 2. The measurement point C is disposed at the center of the substantially circular substrate 2 in plan view, and the remaining measurement points D-G are disposed at approximately 70 mm from the center measurement point C at substantially equal intervals. The type of the substrate 2 is prepared by a substrate which has been forcibly contaminated before the processing of the photoresist removing device 1 and a substrate which is not subjected to forced contamination.

After the measurement point C-G was set as described above, the experiment was performed using the photoresist removal device 1 for each of the two types of substrates 2 (Examples 1 and 2). In the first and second embodiments, only the types of the substrates 2 to be used are different, and other experimental conditions and the like are common.

The main processing conditions common to the first and second embodiments are as follows.

Rotation speed of the substrate: 150 rpm

Supply temperature of sulfuric acid: 200 ° C

Sulfuric acid supply time: 120 seconds

Total supply of sulfuric acid: 400mL

Ozone water supply concentration: 150ppm

Ozone water supply temperature: 70 ° C

Ozone water supply time: 60 seconds

Total supply of ozone water: 2000mL

Fig. 8 shows the measurement results of Example 1 (non-mandatory contamination), and Fig. 9 shows the measurement results of Example 2 (forced contamination). In Figs. 8 and 9, (a) shows that the photoresist is removed, and (b) shows the data after the photoresist is removed. As shown in Figs. 8 and 9, the metal species measured are 8 kinds of Ti, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and the amount of metal residue is shown in various types of metals (unit: atoms/cm). ² ).

As shown in FIGS. 8 and 9, the amount of metal before removing the photoresist is removed, and after the photoresist is removed by the photoresist removing device 1, the amount of metal residue of the five measurement points CG can be made except for a part of Fe and Mn. It is roughly 0. Moreover, a part of the residual Fe and Mn can also be controlled within the range allowed by the semiconductor process. As described above, according to the photoresist removal method using the photoresist removing device 1, it is known that the amount of metal residue can be minimized. Therefore, it can be inferred that the photoresist removal device 1 has a large photoresist removal force, and can remove the photoresist 9 and a large amount of metal.

Further, according to the photoresist removing apparatus 1 of the present embodiment described above, the photoresist 9 can be removed in about 54 seconds on the substrate 2 after implanting a high dose of arsenic ions at 1 × 10 ¹⁵ atoms/cm ² . Further, the amount of metal residue other than a part of Fe can be reduced to a predetermined amount or less within 10 seconds.

Further, the present invention is not limited to the above embodiment, and can be implemented in other various aspects. For example, in the present embodiment, the sulfuric acid and the ozone water are supplied from different devices (sulfuric acid supply unit 4 and ozone water supply unit 5), but the present invention is not limited thereto. For example, sulfuric acid may be supplied from the same device. And both sides of ozone water.

Further, in the present embodiment, the photoresist removing device 1 is described as a single Slice type, but not limited to this, it can also be batch type.

In the present embodiment, the heater 12 is disposed in the center portion of the sulfuric acid supply unit 4, but the heater 12 is not limited thereto, and the heater 12 may be disposed at another portion.

In the present embodiment, the supply temperature of the ozone water is 50° C. or more. However, the present invention is not limited thereto. For example, ozone water at normal temperature may be supplied.

Further, if any of the above-described various embodiments is appropriately combined, the individual effects such as these can be obtained.

The present invention can be applied to a photoresist removal apparatus and a method thereof for removing a photoresist from a substrate provided with a photoresist having a hardened layer formed on the surface by implantation of ions.

The present invention has been fully described in detail with reference to the accompanying drawings, and those skilled in the art can make various modifications and modifications. Such variations and modifications are intended to be included within the scope of the present invention as defined by the appended claims.

The disclosure of the specification, the drawings and the claims of the Japanese Patent Application No. 2012-188899, the entire disclosure of which is incorporated herein in

2‧‧‧Substrate

9‧‧‧Light resistance

10‧‧‧Connected section

11‧‧‧ hardened layer

15‧‧‧ crack

Claims (16)

A photoresist removal device for removing photoresist from a substrate, comprising: a substrate holding portion for holding a substrate provided with a photoresist having a predetermined layer of ions implanted with a hardened layer on the surface a sulfuric acid supply unit provided with a heater for heating sulfuric acid, and a substrate containing the hydrogen peroxide-free water heated by the heater to 200° C. or higher can be supplied to the substrate held by the substrate holding portion; and the ozone water supply In the part, it is possible to supply ozone water having a concentration of 150 ppm or more to a substrate to which sulfuric acid is supplied from a sulfuric acid supply unit. The photoresist removal device of claim 1, which is monolithic. A photoresist removal apparatus according to claim 1, wherein the sulfuric acid supply unit supplies the sulfuric acid which has been partially thermally decomposed. The photoresist removal apparatus of claim 3, wherein the sulfuric acid supply unit supplies 1 to 20% of the thermally decomposed sulfuric acid in the whole. The photoresist removal apparatus according to claim 1, wherein the sulfuric acid of 200 ° C or more supplied by the sulfuric acid supply portion applies thermal stress to the photoresist to cause damage to the photoresist. The photoresist removal device of claim 5, wherein the damage is a crack. The photoresist removal apparatus of claim 1, wherein the ozone water supply unit supplies ozone water of 50 ° C or more. The photoresist removal device according to any one of claims 1 to 7, wherein the substrate is subjected to sulfuric acid and ozone water in a state in which the substrate is rotated by the substrate holding portion. Supply. A photoresist removal method for removing photoresist from a substrate, comprising the steps of: a sulfuric acid supply step on a photoresist formed on a substrate, on a photoresist surface formed with a hardened layer by implantation of ions The sulfuric acid is supplied at a temperature of 200 ° C or higher containing no hydrogen peroxide water; and the ozone water supply step is supplied to the surface of the photoresist of sulfuric acid via a sulfuric acid supply step, and ozone water having a concentration of 150 ppm or more is supplied. According to the photoresist removal method of claim 9, the substrate is processed in a single chip. The photoresist removal method of claim 9, wherein the partially decomposed sulfuric acid is supplied in the sulfuric acid supply step. The photoresist removal method of claim 11 is to supply 1 to 20% of the thermally decomposed sulfuric acid in the whole in the sulfuric acid supply step. The photoresist removal method according to claim 9, wherein the sulfuric acid of 200 ° C or more supplied in the sulfuric acid supply step applies thermal stress to the photoresist to cause damage to the photoresist. The method of removing photoresist from claim 13, wherein the damage is a crack. The photoresist removal method according to claim 9 is characterized in that ozone water of 50 ° C or more is supplied in the ozone water supply step. The photoresist removal method according to any one of claims 9 to 15, wherein the substrate is rotated in the sulfuric acid supply step and the ozone water supply step.