Patent Grant
11342162
The present application is a 35 U.S.C. §§ 371 national phase conversion of PCT International Application No. PCT/JP2018/022981, filed Jun. 15, 2018, which claims priority to Japanese Patent Application No. 2017-177975, filed Sep. 15, 2017, the contents of both of which are incorporated herein by reference. The PCT International Application was published in the Japanese language.
The present invention relates to a resist removing method and a resist removing apparatus.
In a process of manufacturing a semiconductor substrate (hereinafter, referred to simply as a “substrate”), conventionally, performed is an ion implantation in which ions are implanted into a material of a substrate surface, to thereby change the properties of the material. In the ion implantation, for preventing the ions from being implanted into some portions that do not require the ion implantation, a pattern of a photoresist (hereinafter, referred to simply as a “resist”) which is a photosensitive material is formed as a mask on the substrate surface. After the ion implantation, the pattern of the resist is removed in a resist removal process using a resist stripper.
In recent years, the dose amount of ions in the ion implantation has been increasing. In a case where a high dose amount of ions (for example, 1015 ions/cm2 or more) is implanted, an altered layer (hardened layer) which requires time to be removed by the resist stripper is formed on a surface of the resist. Japanese Patent Application Laid-Open No. 2006-286830 proposes a method of quickly removing a resist, in which emission of ultraviolet rays is performed on a surface of a substrate, to thereby cut the bond of carbon and hydrogen in the resist and then a resist stripper is supplied onto the surface of the substrate.
Further, Japanese Patent Application Laid-Open No. 1-186619 (Document 2) discloses an apparatus for removing a resist on a substrate by using ozone under a heating condition. In the apparatus, a support mount is provided in a sealable reaction chamber and a substrate is placed on the support mount. Further, a CO2 concentration meter is provided between the reaction chamber and an ozone decomposer on the downstream side. For removing the resist, the support mount is heated and ozone is carried into the reaction chamber. Further, the CO2 concentration is measured by the CO2 concentration meter, and when the CO2 concentration becomes lower than a predetermined value, it is determined that the resist is completely decomposed and removed.
In a case where removal of a resist is performed by supplying ozone gas onto a substrate and heating the substrate which has been implanted with a high dose amount of ions, like in the method disclosed in Document 2, in the resist on which an altered layer is formed, a phenomenon sometimes occurs, in which the altered layer is ruptured due to an expansion of the inside thereof (a portion inner than the altered layer). This phenomenon is termed “popping”, and due to the popping, a pattern on the substrate is collapsed and/or scattered fragments of the altered layer are deposited on a surface of the substrate and the inside of the apparatus. Though there is a possible case where the popping is prevented by lowering the heating temperature of the substrate, it takes a longer time to remove the resist.
The present invention is intended for a resist removing method for removing a resist from a substrate having, on a main surface thereof, a pattern of the resist having a surface on which an altered layer is formed, and it is an object of the present invention to efficiently remove the resist from the substrate while preventing popping.
The resist removing method according to the present invention, which is to remove a resist from a substrate having, on a main surface thereof, a pattern of the resist having a surface on which an altered layer is formed, includes a) removing the altered layer by supplying the main surface with ozone gas while disposing the substrate at a first processing position with a clearance from a hot plate heated to a predetermined temperature in a processing space shut off from the outside and b) removing the resist by supplying the main surface with the ozone gas while disposing the substrate at a second processing position with a clearance smaller than that between the first processing position and the hot plate, after the operation a).
According to the present invention, it is possible to efficiently remove the resist from the substrate while preventing popping.
In one preferred embodiment of the present invention, the resist removing method further includes c) detecting an endpoint of removal of the altered layer by measuring a concentration of a predetermined component in a gas exhausted from the processing space, concurrently with the operation a).
In this case, preferably, the endpoint of removal of the altered layer is detected on the basis of a rate of change in the concentration of the predetermined component in the operation c).
Further, the resist removing method may include detecting an endpoint of removal of the resist by measuring a concentration of the predetermined component in a gas exhausted from the processing space, concurrently with the operation b).
In another preferred embodiment of the present invention, the processing space is openable and closable, and when the processing space is opened, the substrate is passed from a holding part for holding the substrate to an external transfer mechanism in a state where the substrate is disposed at a position farther away from the hot plate than the first processing position.
In still another preferred embodiment of the present invention, a heating part is provided around a supply port for the ozone gas in a processing space forming part for forming the processing space.
In one aspect of the present invention, the predetermined temperature of the hot plate is not lower than a temperature at which a rupture of the altered layer occurs due to an expansion of the inside thereof in the resist on which the altered layer is formed.
The present invention is also intended for a resist removing apparatus. The resist removing apparatus according to the present invention includes a processing space forming part for forming a processing space which is shut off from the outside, a hot plate which is disposed in the processing space and heated to a predetermined temperature, a holding part for holding a substrate in the processing space, the substrate having, on a main surface thereof, a pattern of a resist having a surface on which an altered layer is formed, a moving mechanism for moving the holding part relative to the hot plate, an ozone gas supply part for supplying the main surface with ozone gas, and a control part for disposing the substrate at a first processing position with a clearance from the hot plate and removing the altered layer by using the ozone gas and for subsequently controlling the moving mechanism to dispose the substrate at a second processing position with a clearance smaller than that between the first processing position and the hot plate and removing the resist by using the ozone gas.
These and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
The chamber 2 includes a chamber body 21 and a chamber cover 22. The chamber body 21 includes a bottom plate 211 having a disk-like shape and a main-body side portion 212 having a cylindrical shape. The bottom plate 211 extends in a horizontal direction and the main-body side portion 212 extends upward from an outer edge portion of the bottom plate 211. The chamber cover 22 includes a top plate 221 having a disk-like shape and a cover side portion 222 having a cylindrical shape. The top plate 221 extends in the horizontal direction and the cover side portion 222 extends downward from an outer edge portion of the top plate 221. On a lower surface of the top plate 221, a shower plate 223 extending in the horizontal direction is fixed with a plate support part 224 interposed therebetween. The shower plate 223 is disposed between the top plate 221 and the hot plate 4. In the shower plate 223, formed are a large number of through holes. A lower end surface of the cover side portion 222 faces an upper end surface of the main-body side portion 212 along the entire circumference in an up-and-down direction. In the upper end surface of the main-body side portion 212, provided is an annular recessed portion, and an O-ring 23 is provided in the annular recessed portion. The chamber body 21 and the chamber cover 22 (including the shower plate 223) are formed of, for example, stainless steel.
The cover up-and-down moving mechanism 31 moves the chamber cover 22 up and down in the up-and-down direction, to thereby selectively dispose the chamber cover 22 at a lower position shown in
The hot plate 4 is arranged in the processing space 20. The hot plate 4 has a thick disk-like shape and has a diameter larger than that of the disk-like substrate 9. In the hot plate 4, provided is a heater 40 including an electrically heated wire. The hot plate 4 is heated to a predetermined set temperature by a current supplied from an external power supply to the heater 40. The set temperature is, for example, 200° C. or higher and is not lower than an after-mentioned popping temperature at which popping occurs. An upper limit of the set temperature for the hot plate 4 shown in
In the hot plate 4, a plurality of through holes 41 are arranged at a certain angular interval in the circumferential direction. In the bottom plate 211, through holes 213 are provided at positions which coincide with the through holes 41, respectively, in the up-and-down direction. Each of the plurality of lift pins 51 is inserted into a corresponding one of the pairs of the through holes 41 and the through holes 213. The number of lift pins 51 is typically three, and in this case, the lift pins 51 are arranged at an angular interval of 120 degrees in the circumferential direction. The number of lift pins 51 may be four or more. Respective lower ends of the plurality of lift pins 51 are fixed onto a pin support plate 52. Below the bottom plate 211, the circumference of each lift pin 51 is surrounded by a bellows 53. An upper end of the bellows 53 is fixed to a lower surface of the bottom plate 211 and a lower end of the bellows 53 is fixed to an upper surface of the pin support plate 52. The bellows 53 and the pin support plate 52 serve to prevent passage of gas or liquid between the inside and the outside of the chamber 2 through the through holes 213 in the bottom plate 211.
The pin up-and-down moving mechanism 32 includes a stepping motor and moves the pin support plate 52 up and down in the up-and-down direction. The plurality of lift pins 51 are thereby moved in the up-and-down direction. By the drive of the stepping motor, the pin support plate 52 and the plurality of lift pins 51 can be arranged at any position, for example, between the position shown in
In the resist removing apparatus 1, when the tip of each of the plurality of lift pins 51 is disposed inside the through hole 41, the substrate 9 is placed on the upper surface of the hot plate 4 and held in a horizontal position. Further, when the tip of each of the plurality of lift pins 51 is disposed upper than the upper surface of the hot plate 4, the substrate 9 is supported by the plurality of lift pins 51 from below and held in the horizontal position. Thus, in the resist removing apparatus 1, a holding part for holding the substrate 9 in the processing space 20 is switched between the hot plate 4 and the plurality of lift pins 51. When the plurality of lift pins 51 serve as the holding part, the pin up-and-down moving mechanism 32 serves as a moving mechanism for moving the holding part relative to the hot plate 4. Further, a plurality of projections may be provided on the upper surface of the hot plate 4. In this case, when the respective tips of the plurality of lift pins 51 are positioned lower than respective upper surfaces of the plurality of projections, the substrate 9 is supported by the plurality of projections from below.
The ozone gas supply part 6 of
As described earlier, between the top plate 221 and the hot plate 4, disposed is the shower plate 223. The ozone gas passes through a large number of through holes of the shower plate 223 and is supplied uniformly onto an upper main surface 91 (hereinafter, referred to simply as an “upper surface 91”) of the substrate 9. In the top plate 221, a plurality of gas nozzles 64 may be dispersedly provided. In this case, the shower plate 223 may be omitted. In the present preferred embodiment, the ozone gas is ozone diluted with a predetermined gas. Another type of oxidizing gas or the like may be mixed into the ozone gas.
The gas exhaust part 71 includes a gas exhaust port 711 and a gas exhaust pipe 712. The gas exhaust port 711 is provided at the center of the bottom plate 211 and connected to one end of the gas exhaust pipe 712. The other end of the gas exhaust pipe 712 is connected to an ozone decomposition part (not shown) such as a filter or the like. The gas inside the processing space 20 is exhausted outside through the gas exhaust port 711 and the gas exhaust pipe 712. In the resist removing apparatus 1, a plurality of gas exhaust ports 711 may be provided, and the gas exhaust port(s) 711 may be provided in the outer edge portion of the bottom plate 211, on the main-body side portion 212, or the like. To the gas exhaust pipe 712, a concentration measurement part 72 is connected. The concentration measurement part 72 measures a concentration of a predetermined component in the gas (hereinafter, referred to as an “exhaust gas”) exhausted from the processing space 20. In the present preferred embodiment, the concentration measurement part 72 measures a concentration of ozone and a concentration of carbon dioxide (CO2) in the exhaust gas.
Next, a resist formed on the substrate 9 will be described.
Herein, when the substrate 9 having the resist 95 on which the altered layer 96 is formed is heated, popping in which the altered layer 96 is ruptured sometimes occurs due to an expansion of the inside thereof (for example, fullness of gas generated from the unaltered portion 97). The popping does not occur when the heating temperature of the substrate 9 is low. The temperature of the substrate 9 at which the popping occurs with a high frequency (for example, with a frequency of 50% or more) can be specified as a popping temperature by an experiment or the like. Hereinafter, description will be made on a process for efficiently removing the resist 95 on which the altered layer 96 is formed while preventing the popping.
When the support part of the transfer mechanism moves outside the chamber body 21 and the chamber cover 22, the plurality of lift pins 51 move down, to thereby move the substrate 9 down from the transfer position to a position (hereinafter, referred to as a “first processing position”) shown in
The hot plate 4 has been heated to a constant set temperature, and in a state of
Subsequently, the gas supply valve 63 is opened in the ozone gas supply part 6 and the ozone gas is ejected from the gas supply port 641 into the processing space 20 at a predetermined supply flow rate. In other words, the supply of the ozone gas onto the upper surface 91 of the substrate 9 is started (Step S14). The supply of the ozone gas is continuously performed concurrently with the heating of the substrate 9 by the hot plate 4. In an actual case, a not-shown exhaust valve which is provided on the gas exhaust pipe 712 shown in
The air in the processing space 20 is replaced with the ozone gas little by little. As indicated by the solid line L1 in
When the decomposition of the altered layer 96 proceeds by supplying the ozone gas, part of the unaltered portion 97 is exposed in the resist 95. Since the unaltered portion 97 is easier to be decomposed than the altered layer 96, a larger amount of ozone gas is consumed than that in the altered layer removal period and a rate of change in the ozone concentration decreases. The control part 10 always obtains the rate of change in the ozone concentration during the resist removal. When the rate of change in the ozone concentration becomes not higher than a predetermined threshold value, it is determined that the removal of most part of the altered layer 96 is finished (Step S15). Thus, an endpoint of the removal of the altered layer 96 is detected on the basis of the rate of change in the ozone concentration. In
When the endpoint of the removal of the altered layer 96 is detected, or when a predetermined time has elapsed from the detection of the endpoint, the plurality of lift pins 51 move down, to thereby move the substrate 9 down from the first processing position to the position (hereinafter, referred to as a “second processing position”) shown in
As the amount of resist 95 remaining on the substrate 9 decreases, the carbon dioxide concentration in the exhaust gas becomes lower. After that, the ozone concentration is saturated at a certain value and the carbon dioxide concentration becomes almost zero. When the carbon dioxide concentration becomes not higher than a predetermined threshold value, the control part 10 determines that the removal of the unaltered portion 97 is finished (Step S17). Thus, an endpoint of the removal of the resist 95 is detected by measuring the carbon dioxide concentration. In the resist removing apparatus 1, by disposing the substrate 9 at the second processing position after the removal of the altered layer 96, it is possible to complete the removal of the resist 95 in a shorter time as compared with a case where the processing continues while the substrate 9 is still disposed at the first processing position.
At time T3, when the endpoint of the removal of the resist 95 is detected, the gas supply valve 63 is closed, to thereby stop the supply of the ozone gas at time T4 when a predetermined time has elapsed from the time T3 (Step S18). The processing performed on the substrate 9 by using the ozone gas is thereby completed. The time period from the time T3 to the time T4 is a time period (overetching time) set for more reliably removing the resist 95 on the substrate 9. In an actual case, the not-shown exhaust valve which is provided on the gas exhaust pipe 712 is closed, and the exhaust operation of the gas from the processing space 20 is also stopped. Further, after the stop of the supply of the ozone gas, there may be a case where nitrogen gas or the like is supplied into the processing space 20 and the ozone gas is replaced with the nitrogen gas in the processing space 20.
Subsequently, the chamber cover 22 is moved up by the cover up-and-down moving mechanism 31 and disposed at the upper position shown in
Herein, a resist removing apparatus in a comparative example will be described. In the resist removing apparatus of the comparative example, after loading of the substrate 9, the substrate 9 is disposed at the second processing position shown in
When the popping occurs, the pattern on the substrate 9 is collapsed and/or scattered fragments of the altered layer 96 are deposited on the upper surface 91 of the substrate 9 and the inside of the chamber 2. There is a possible case where the popping is prevented by making the set temperature of the hot plate 4 lower than the popping temperature. Since a removal rate of the resist 95 is affected by the temperature of the substrate 9, however, it takes a longer time to remove the resist 95. Further, there is a possibility that the substrate 9 may be excessively oxidized. Furthermore, though there is a possible case where the set temperature of the hot plate 4 is changed during the resist removal, it is difficult to sharply change the temperature of the hot plate 4.
In contrast to this, in the resist removing apparatus 1, the substrate 9 is disposed at the first processing position with a clearance from the hot plate 4 and the removal of the altered layer 96 is performed by using the ozone gas. Subsequently, by controlling the pin up-and-down moving mechanism 32, the substrate 9 is disposed at the second processing position with a clearance from the hot plate 4, which is smaller than that between the first processing position and the hot plate 4, and the removal of the resist 95 is performed by using the ozone gas. It is thereby possible to remove the resist 95 on the substrate 9 efficiently (in a short time) while preventing the popping, by using the hot plate 4 which is difficult to sharply change the temperature thereof. As a result, it is also possible to suppress excessive oxidation of the substrate 9. Further, since the second processing position is a position at which the substrate 9 comes into contact with the upper surface of the hot plate 4, it is possible to efficiently heat the substrate 9 to a high temperature.
By measuring a concentration of a predetermined component in the gas exhausted from the processing space 20 concurrently with the removal of the altered layer 96 by using the ozone gas, the endpoint of the removal of the altered layer 96 can be appropriately detected for each substrate 9. It is thereby possible to prevent the time period while the substrate 9 is heated at a relatively low temperature (while the substrate 9 is disposed at the first processing position) from becoming unnecessarily longer and reduce the time required to remove the resist 95 on the substrate 9. Further, it is possible to more reliably prevent the popping.
By measuring a concentration of a predetermined component in the gas exhausted from the processing space 20 concurrently with the removal of the resist 95 (mainly the unaltered portion 97) by using the ozone gas, the endpoint of the removal of the resist 95 can be also appropriately detected for each substrate 9. As a result, it is thereby possible to prevent the time period while the substrate 9 is heated from becoming unnecessarily longer and more reliably suppress excessive oxidation of the substrate 9. Further, it is possible to more reliably remove the resist 95.
In the pin up-and-down moving mechanism 32 having the stepping motor, the clearance between the substrate 9 and the hot plate 4 can be freely changed. As a result, it is possible to easily adjust the temperature of the substrate 9 in the altered layer removal period and more reliably prevent the popping.
The heating part 24 provided in the chamber cover 22 surrounds the circumference of the gas supply port 641 which ejects the ozone gas. Therefore, when the ozone gas is supplied onto the upper surface 91 of the substrate 9, the top plate 221 is heated by the heating part 24 and the ozone gas to be ejected from the gas supply port 641 is also heated. The temperature of the ozone gas thereby becomes higher and the generation of the oxygen radical or the like is accelerated. As a result, it is possible to perform the removal of the altered layer 96 from the substrate 9 disposed at the first processing position and the removal of the unaltered portion 97 from the substrate 9 disposed at the second processing position in a short time without excessively increasing the temperature of the substrate 9. Thus, in the resist removing apparatus 1 of
In the resist removing apparatus 1 and the resist removing method described above, various modifications can be made.
The holding part for holding the substrate 9 at the first processing position may be other than the plurality of lift pins 51. For example, a holding part having a mechanism for gripping the outer edge portion of the substrate 9 may be adopted in the resist removing apparatus 1. In this case, depending on the design of the resist removing apparatus 1, the removal of the resist 95 may be performed with the main surface on which the resist 95 is formed facing downward or sideward. Further, the holding part has only to move relative to the hot plate 4, and a moving mechanism for moving the hot plate 4 in the up-and-down direction may be adopted.
The gas supply port 641 of the ozone gas supply part 6 may be provided in a portion other than the top plate 221 of the chamber cover 22 and may be provided in, for example, the cover side portion 222.
There may be a case where the concentration measurement part 72 measures only one of the ozone concentration and the carbon dioxide concentration and the endpoint of the removal of the altered layer 96 and the endpoint of the removal of the resist 95 are detected on the basis of a measured value of the one concentration. Further, a concentration of the ions implanted in the ion implantation performed by using the pattern of the resist 95 may be detected by the concentration measurement part 72.
If the concentration of the predetermined component in the gas exhausted from the processing space 20 can be practically measured, the concentration measurement part 72 may be provided on other than the gas exhaust pipe 712. For example, the concentration measurement part 72 may be provided in the vicinity of the gas exhaust port 711 in the bottom plate 211.
The control part 10 may detect the endpoint of the removal of the altered layer 96 by using any one of various methods on the basis of the measured value of the concentration measurement part 72. There may be a case, for example, where a reference profile indicating a typical change in the ozone concentration or the carbon dioxide concentration from the start of the removal of the altered layer 96 to the end thereof is prepared and the endpoint of the removal of the altered layer 96 is detected by fitting between a profile of an actually-obtained concentration change and the reference profile. Similarly, the control part 10 may detect the endpoint of the removal of the resist 95 (the unaltered portion 97) by using any one of various methods on the basis of the measured value of the concentration measurement part 72.
The configurations in the above-discussed preferred embodiment and variations may be combined as appropriate only if those do not conflict with one another.
While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore understood that numerous modifications and variations can be devised without departing from the scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP2017-177975 | Sep 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/022981 | 6/15/2018 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/053981 | 3/21/2019 | WO | A |
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| Number | Date | Country |
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| Entry |
|---|
| International Preliminary Report on Patentability and Written Opinion dated Mar. 17, 2020 in corresponding International Patent Application No. PCT/JP2018/022981 with English translation. |
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| Written Opinion dated Aug. 28, 2018 in corresponding PCT International Application No. PCT/JP2018/022981. |
| Korean Office Action dated May 1, 2021 in connection with Korean Application No. 10-20207007239. |
| Office Action dated Oct. 25, 2021 for the corresponding Japanese Application No. 2017-177975, machine translation attached. |
| Decision to Grant dated Nov. 3, 2021 for the corresponding Korean Patent Application No. 10-2020-7007239, machine translation attached. |
| Number | Date | Country | |
|---|---|---|---|
| 20200272057 A1 | Aug 2020 | US |
