JP4230830B2 - Supercritical processing equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a supercritical processing apparatus for performing predetermined processing such as development and drying on a substrate to be processed using a fluid in a supercritical state.
[0002]
[Prior art]
As is well known, in order to manufacture a large-scale and high-performance device such as an LSI, an extremely fine pattern is required. This ultrafine pattern is, for example, a resist pattern that is formed through exposure, development, and rinsing treatment and that is sensitive to light, X-rays, or electron beams. Further, the etching pattern is made of an inorganic material such as an oxide formed through etching, water washing and rinsing by selective etching using the resist pattern as a mask.
[0003]
The resist pattern described above can be formed by processing a photosensitive resist film, which is an organic material, using a lithography technique. When the photosensitive resist film is exposed, the molecular weight and molecular structure of the exposed area changes, and a difference in solubility in the developer occurs between the unexposed area and development using this difference. By the processing, a finer pattern than the photosensitive resist film can be formed.
[0004]
In the development processing described above, if the development is continued, the unexposed areas start to dissolve in the developer and the pattern disappears, so the development is stopped by rinsing with the rinse solution. Finally, by drying and removing the rinsing liquid, a resist pattern as a processing mask can be formed on the resist film.
A major problem during drying in the formation of such a fine pattern is the collapse of the pattern.
[0005]
A fine resist pattern having a large aspect ratio is formed by rinsing and drying after development. A fine pattern having a large aspect ratio can be formed even if it is not a resist. For example, when a high aspect ratio pattern is formed by etching the substrate using the resist pattern as a mask, the substrate is cleaned after the etching, and the pattern is immersed in water and rinsed with the substrate. Thereafter, drying is performed.
[0006]
However, at the time of drying, a bending force (capillary force) works due to a pressure difference between water remaining between the patterns and external air. As a result, the pattern collapses on the substrate. This falling phenomenon becomes more prominent as the pattern has a higher aspect ratio. It has been reported that the capillary force depends on the surface tension generated at the liquid / gas interface between a rinse liquid such as water and the pattern.
[0007]
The surface tension of water is about 72 x 10 ^-3 The capillary force described above is large as N / m and has the power to distort not only a resist pattern made of an organic material but also a stronger pattern such as silicon which is an inorganic material. For this reason, the problem of surface tension due to the above-described rinse liquid and cleaning liquid is important.
Here, after liquid treatment such as rinsing and washing, a supercritical fluid is used and drying is performed after the surface tension is not applied, so that problems such as pattern collapse can be solved.
[0008]
A fluid in a supercritical state (supercritical fluid) is a substance at a temperature and pressure exceeding the critical temperature and pressure, and has a dissolving power close to that of a liquid, but tension and viscosity exhibit properties close to a gas. It can be said that the liquid is kept in a gaseous state. Since the supercritical fluid having such characteristics does not form an interface between the liquid and the gas, the surface tension becomes zero. Therefore, if the film is dried in a supercritical state, the effect of surface tension is eliminated, and the pattern collapse is eliminated.
[0009]
A supercritical fluid has both gas diffusivity and liquid solubility (high density), and can change state from liquid to gas without an equilibrium line. For this reason, if this supercritical fluid is gradually released from the state filled with the supercritical fluid, the interface between the liquid and gas will not be formed, so the surface is dried without applying surface tension to the ultrafine pattern to be dried. be able to.
[0010]
In many cases, carbon dioxide, which has a low critical point and is easy to handle, is used as the supercritical fluid. Supercritical drying using a supercritical fluid is started by replacing the cleaning liquid adhering to the substrate surface with liquefied carbon dioxide in a sealed container after performing a cleaning process with a cleaning liquid. Since carbon dioxide liquefies at room temperature when pressurized to about 6 MPa, the above replacement is performed in a state where the pressure in the container is increased to about 6 MPa. After the cleaning liquid adhering to the substrate is replaced with liquefied carbon dioxide, the temperature and pressure (critical point of carbon dioxide; 31 ° C., 7.3 MPa) above the critical point of carbon dioxide is set in the container to liquefy carbon dioxide. Convert to supercritical carbon dioxide.
[0011]
Finally, while maintaining the above temperature, a part of the container is opened to release supercritical carbon dioxide to the outside, the inside of the container is reduced to atmospheric pressure, and the supercritical carbon dioxide in the container is vaporized. Finish drying. At the time of this pressure reduction, carbon dioxide is vaporized without being liquefied, so that the interface between the liquid and the gas on which the surface tension acts is not formed on the substrate. For this reason, these can be dried, without producing a fall in the ultra fine pattern currently formed on the board | substrate.
[0012]
In order to perform supercritical processing such as the above supercritical drying, for example, a single wafer processing apparatus as shown in FIG. 8 has been proposed (see Patent Document 1). This apparatus includes an apparatus in which liquefied carbon dioxide sealed in a cylinder 803 is pumped into a reaction chamber 802 in a sealable container 801 by a pump pump 804. In this apparatus, by opening the valve 805 on the liquefied carbon dioxide introduction side, liquefied carbon dioxide is introduced into the container 801, and the liquefied carbon dioxide is discharged from the front end of the introduction port 806 communicating with the valve 805. The liquefied carbon dioxide is injected onto the substrate 811 placed on the inner stage 812.
[0013]
At this time, for example, the liquefied carbon dioxide in the cylinder 803 is pumped into the reaction chamber 802 by the pressure pump 804, and the opening of the valve 807 on the discharge side is adjusted in this state, and the liquefied carbon dioxide discharged from the discharge port 809 The pressure in the reaction chamber 802 is controlled by limiting the amount of. If, for example, an automatic pressure valve is used as the discharge side valve 807, the above pressure control is possible.
[0014]
As described above, in a state where liquefied carbon dioxide is injected onto the substrate through the introduction port 806, the container 801 is heated to, for example, about 31 ° C. by the heater 813, and the pressure in the reaction chamber 802 is 7.5 MPa or more. Then, the liquefied carbon dioxide injected onto the substrate 811 in the reaction chamber 802 becomes a supercritical state.
[0015]
An apparatus as shown in FIG. 9 has also been proposed (see Patent Document 2). This apparatus includes an apparatus in which liquefied carbon dioxide sealed in a cylinder 903 is pumped by a pump pump 904 into a reaction chamber 902 in a sealable container 901. In this apparatus, by opening the valve 905 on the liquefied carbon dioxide introduction side, liquefied carbon dioxide is introduced into the container 901, and the liquefied carbon dioxide is discharged from the front end of the introduction port 906 communicating with the valve 905. The liquefied carbon dioxide is injected onto the substrate 911 placed on the inner stage 912.
[0016]
At this time, for example, liquefied carbon dioxide in the cylinder 903 is pumped into the reaction chamber 902 by the pump pump 904, and the opening degree of the valve 907 on the discharge side is adjusted in this state, and liquefied carbon dioxide discharged from the discharge port 909 The pressure in the reaction chamber 902 is controlled by limiting the amount of. If, for example, an automatic pressure valve is used for the valve 907 on the discharge side, the pressure control can be performed.
[0017]
In the case of the apparatus shown in FIG. 9, as described above, the substrate 911 is heated by the heater 913 such as a resistance heating body incorporated in the stage 912 in a state where liquefied carbon dioxide is being injected onto the substrate through the introduction port 906. Is directly heated, and the liquefied carbon dioxide in the vicinity of the substrate 911 is heated to about 31 ° C., for example. At this time, if the pressure in the reaction chamber 902 is 7.5 MPa or more, the liquefied carbon dioxide around the substrate 911 enters a supercritical state.
[0018]
In such a supercritical processing apparatus, in order to obtain a high pressure, the inside of the reaction chamber needs to be made as small as possible, and is generally a single wafer processing apparatus.
Here, in these apparatuses, it is desirable that the liquid treatment before the supercritical treatment is also performed inside the container. This is because when the liquid processing such as development and the supercritical processing such as supercritical drying are continuously performed, the supercritical processing is easily performed without drying the substrate after the liquid processing.
[0019]
By the way, liquid processing such as development is always required to be performed at a constant temperature in order to ensure the reproducibility of processing, and is performed at a temperature close to room temperature (around 23 ° C.) because of easy temperature adjustment. It is common.
On the other hand, in supercritical processing such as supercritical drying, in most cases, it is performed at a temperature higher than room temperature in order to obtain a supercritical state.
Therefore, in the supercritical processing apparatus for single wafer processing as described above, when the liquid processing and the supercritical processing are performed continuously, after the supercritical processing, in order to perform the next liquid processing, In addition, the temperature of the stage on which the substrate is placed needs to be lowered to about room temperature.
[0020]
[Patent Document 1]
JP 2000-091180 A
[Patent Document 2]
JP 2002-313773 A
[0021]
[Problems to be solved by the invention]
However, in the conventional supercritical processing apparatus described above, the temperature of the container or stage in which the heater is arranged and the temperature in the reaction chamber are set to room temperature in a state where the next liquid processing can be performed after the supercritical processing is performed. It took at least 10 minutes or more to lower the temperature. For this reason, when processing a plurality of substrates in succession, a lot of time is required in addition to the supercritical processing, which hinders shortening of the process time.
[0022]
The present invention has been made to solve the above-described problems, and an object of the present invention is to enable liquid treatment and supercritical processing to be performed continuously in the same processing apparatus in a shorter time than conventional. And
[0023]
[Means for Solving the Problems]
A supercritical processing apparatus according to the present invention includes a container having a reaction chamber that can be sealed inside, a stage that is provided inside the reaction chamber and on which a substrate to be processed is placed, and an atmospheric atmosphere inside the reaction chamber. , Supply means for supplying supercritical material that is gas and becomes supercritical under specified conditions, and pressurization control of the internal pressure of the reaction chamber to the pressure at which the supercritical material becomes supercritical After the substrate is processed in a supercritical state, the inside of the reaction chamber is depressurized to atmospheric pressure. Pressure control means for heating, heating means for heating the supercritical material introduced above the stage, and holding the stage at a temperature lower than the heating temperature by the heating means Temperature control mechanism And a discharge port for discharging the fluid inside the reaction chamber provided in the reaction chamber.
In this apparatus, the heating means does not directly heat the stage or the container. For example, heat is conducted to the stage through a fluid existing around the heater.
[0024]
In the above supercritical processing apparatus, the temperature of the container may be maintained at a temperature lower than the heating temperature by the heater by a temperature control mechanism.
In the supercritical processing apparatus, the heating means may be a heater provided facing the stage. Further, the heating means is a heater part that includes a plurality of pins that penetrate the container from the outside of the container and project from the stage surface through the stage through-hole, and move so that the through-hole can be inserted and removed. The substrate may be separated from the stage by being inserted into the hole and projecting the tip of the pin from the surface of the stage, and the substrate may be heated in this state.
[0025]
Another supercritical processing apparatus according to the present invention includes a container having a reaction chamber that can be sealed therein, a stage that is provided inside the reaction chamber and on which a substrate to be processed is placed, and a reaction chamber. Supply means for supplying a supercritical substance that is a gas in the atmosphere and becomes supercritical under specified conditions, and pressurization control of the internal pressure of the reaction chamber to a pressure at which the supercritical substance becomes supercritical After the substrate is processed in a supercritical state, the inside of the reaction chamber is depressurized to atmospheric pressure. Pressure control means to perform, a heater provided opposite the stage, and hold the stage at a temperature lower than the heating temperature by the heater Temperature control mechanism And a discharge port for discharging the fluid inside the reaction chamber provided in the reaction chamber.
In this apparatus, the stage and the container are not directly heated by the heating operation of the heater. For example, heat is conducted to the stage through a fluid existing around the heater.
[0026]
In the above supercritical processing apparatus, the temperature of the container may be maintained at a temperature lower than the heating temperature by the heater by a temperature control mechanism.
In the supercritical processing apparatus, the substrate to be processed can be brought close to the heater by providing a substrate up-and-down mechanism that moves the substrate up and down in the direction of the heater on the stage.
[0027]
Another supercritical processing apparatus according to the present invention includes a container having a reaction chamber that can be sealed inside, and a substrate to be processed that is provided inside the reaction chamber and in which the substrate is placed. A stage having a plurality of through-holes, supply means for supplying a supercritical substance that is a gas in the atmosphere and becomes supercritical under a predetermined condition, and the internal pressure of the reaction chamber Pressurization control up to the pressure that becomes supercritical state After the substrate is processed in a supercritical state, the inside of the reaction chamber is depressurized to atmospheric pressure. A pressure control means, a heater part that penetrates the container from the outside of the container and protrudes from the stage surface through the stage through-hole, and moves so that the through-hole can be inserted and removed, and a heating temperature of the stage by the heater part Keep at lower temperature Temperature control mechanism And at least a discharge port for discharging the fluid inside the reaction chamber provided in the reaction chamber, and the heater part is configured such that the tip of the pin protrudes from the surface of the stage by inserting the pin into the through hole, The substrate is separated from the stage, and the substrate is heated in this state.
In this apparatus, when the pins of the heater unit are removed from the stage, the heating of the stage by the heater unit is quickly stopped. In the supercritical processing apparatus, the temperature of the container may be maintained at a temperature lower than the heating temperature by the heater unit by a temperature control mechanism.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[Embodiment 1]
FIG. 1 is a schematic cross-sectional view (a) showing a configuration example of a supercritical processing apparatus in an embodiment of the present invention, and plan views (b) and (c) showing a part thereof. This apparatus includes a high-pressure vessel 101 that can be sealed, and a reaction chamber 102 provided inside the high-pressure vessel 101. A stage 112 on which a substrate to be processed is placed is disposed on the bottom surface of the reaction chamber 102. The high-pressure vessel 101 is made of, for example, stainless steel, and has a wall thickness of about 20 mm.
[0029]
The high-pressure vessel 101 is composed of a vessel upper portion 101a and a vessel lower portion 101b having a stage 112 fixed to the bottom. For example, the reaction chamber 102 is opened by moving the vessel upper portion 101a upward. Is possible. The high-pressure vessel 101 includes a temperature control mechanism 113 between the outer wall and the inner wall, and can be controlled to keep the temperature of the high-pressure vessel 101 constant by the control of the temperature control unit 122.
[0030]
The temperature control mechanism 113 is for holding the high-pressure vessel 101 and the stage 112 at a temperature lower than the heating temperature by the heater 114 described below. The temperature control mechanism 113 is, for example, a pipe in which water whose temperature is adjusted (temperature-controlled) to about 23 ° C. by the temperature control unit 122 in which water is circulated as a heat medium is circulated. A similar temperature control mechanism is also provided in the stage 112, and the stage 112 can be maintained at a predetermined temperature.
[0031]
Further, the supercritical processing apparatus of FIG. 1 includes a heater (heating means) 114 disposed above the stage 112 with a space of 10 mm, for example, in a state where the high-pressure vessel 101 is sealed, and a heater control unit. The area around the heater 114 can be heated by the control of 121. The heater 114 is, for example, a resistance heating body configured as shown in the plan view of FIG.
In addition, the apparatus includes a cylinder 103 in which, for example, carbon dioxide is pressurized and stored. Carbon dioxide is an example of a supercritical substance that is a gas in the air atmosphere and becomes a supercritical state under predetermined conditions. Carbon dioxide accommodated in the cylinder 103 is introduced into the reaction chamber 102 through the pipe 104 and the introduction port 105.
[0032]
A pressure feed pump 106 and an introduction valve 107 are provided in the middle of the pipe 104, and a pressure gauge 108 for measuring the pressure here is provided on the discharge side of the pressure feed pump 106. The carbon dioxide in the cylinder 103 can be pumped into the reaction chamber 102 by the pressure pump 106. Further, the opening degree of the introduction valve 107 can be controlled by the pressure measurement result of the pressure gauge 108.
[0033]
Therefore, a supply means for carbon dioxide, which is a substance that becomes a supercritical fluid, is configured by the cylinder 103, the pressure pump 106, and the like. For example, if carbon dioxide is accommodated in the cylinder 103 at a pressure as high as 20 MPa or more, this alone can serve as a supply means. Needless to say, the supply of carbon dioxide into the reaction chamber 102 is not limited to the above-described configuration, and other mechanisms may be used.
[0034]
The apparatus also includes a pressure gauge 109 that measures the internal pressure of the reaction chamber 102, a discharge port 110 that discharges the fluid inside the reaction chamber 102, and a pressure control valve 111 that is provided in the middle of the discharge port 110. ing. The pressure control valve 111 controls the opening degree according to the pressure measurement result of the pressure gauge 109 and controls the amount of fluid discharged from the discharge port 110. By controlling the pressure by these, it is possible to control the pressure inside the reaction chamber 102 up to a pressure at which the supercritical substance is in a supercritical state.
[0035]
Note that the cylinder 103 may contain a supercritical substance that is a gas in another atmospheric atmosphere and is in a supercritical state under a predetermined condition instead of carbon dioxide. For example, the cylinder 103 is SF ₆ And CHF _Three Fluorine compounds such as N ₂ It may contain a nitrogen compound such as O. Furthermore, carbonyl fluoride and CF _Three Carbonyl fluoride compounds such as COF, CF _Three OF, CHF ₂ OCHF ₂ A compound containing a carbonyl group and a halogen such as fluorine or chlorine and containing a compound that is a gas in the air atmosphere, such as a hypofluorite compound such as, may be used. The cylinder 103 can be FNO or F _Three It may contain a halogenated nitrogen compound such as NO.
[0036]
In addition, the apparatus includes a chemical solution supply unit 123 and a chemical solution nozzle 124. The chemical liquid supply unit 123 is, for example, a mechanism that supplies a predetermined developer and a rinse liquid, and can discharge the developer and the rinse liquid from a liquid discharge unit provided at the tip of the chemical liquid nozzle 124. As shown in FIG. 1B, the chemical nozzle 124 is movable above the stage 112 in a state where the container upper part 101 a is moved above the container lower part 101 b and the high-pressure container 101 is opened. By moving the tip of the chemical solution nozzle 124 above the stage 112, a chemical solution such as a developing solution is supplied onto the substrate to be processed disposed on the stage 112. The chemical nozzle 124 may be moved by rotational movement, or may be moved above the stage 112 by linear movement.
[0037]
In this supercritical processing apparatus, carbon dioxide supplied from the cylinder 103 is pumped to the pressure pump 106, passes through the piping, and is transported to the reaction chamber 102 from the inlet 105. For example, if the pressure control valve 111 is closed after the inside of the reaction chamber 102 is filled with the transported carbon dioxide in a state where carbon dioxide is being pumped at high pressure, the inside of the reaction chamber 102 is For example, a pressure state in which carbon dioxide becomes a supercritical state can be set. Further, the heater 114 is operated under the control of the heater control unit 121 so that the temperature above the stage 112 in the reaction chamber 102 can be brought to a temperature at the critical point of carbon dioxide or higher.
[0038]
In addition, the opening of the pressure control valve 111 is adjusted so that the pressure value measured by the pressure gauge 109 maintains the pressure at the critical point of carbon dioxide, and the pressure value measured by the pressure gauge 108 is the critical point of carbon dioxide. It is also possible to adjust the pressure of the pumping by the pumping pump 106 within a range in which the pressure is maintained. By doing so, a state in which carbon dioxide is always supplied into the reaction chamber 102 is obtained.
[0039]
Next, supercritical processing using the supercritical processing apparatus shown in FIG. 1 will be described.
First, as shown to Fig.2 (a), the container upper part 101a is moved above the container lower part 101b, and the high voltage | pressure container 101 is made into an open state. Further, the temperature control unit 122 is operated so that the high-pressure vessel 101 (the vessel upper portion 101a and the vessel lower portion 101b) and the stage 112 are controlled to 23 ° C., for example.
[0040]
Next, as shown in FIG. 2B, the substrate 201 to be processed is fixed on the stage 112. The substrate 201 includes, for example, a resist film on which a latent image is formed by exposing a predetermined pattern image.
When the substrate 201 is fixed on the stage 112, as shown in FIG. 2C, the chemical nozzle 124 is moved to dispose a liquid discharge unit (not shown) above the substrate 201. In this state, the chemical solution supply unit 123 is operated to supply a predetermined chemical solution such as a developer and a rinse solution onto the substrate 201. Thereby, for example, the resist film on the substrate 201 is developed and a resist pattern is formed on the substrate 201.
[0041]
Next, after retracting the chemical solution nozzle 124, as shown in FIG. 3D, the container upper part 101a is lowered and brought into close contact with the container lower part 101b, and the reaction chamber 102 inside the high-pressure container 101 is sealed. And In this state, the introduction valve 107 is opened, and the liquefied carbon dioxide supplied from the cylinder 103 is brought into a state of being pumped into the reaction chamber 102 by the pumping pump 106.
[0042]
Here, first, the opening degree of the pressure control valve 111 is adjusted in a range in which the pressure value measured by the pressure gauge 109 maintains the pressure at the critical point of carbon dioxide. In addition, the pressure of the pumping pump 106 is adjusted so that the pressure value measured by the pressure gauge 108 maintains the pressure at the critical point of carbon dioxide (for example, 7.5 MPa). As a result, a state in which liquefied carbon dioxide is always supplied into the reaction chamber 102 is obtained.
[0043]
Next, the heater control unit 121 is operated, and the liquefied carbon dioxide around the heater 114 is heated to about 31 ° C. by the heater 114. As a result, as shown in FIG. 3 (e), a supercritical carbon dioxide region 301 is formed around the heater 114 and is heated to the critical pressure carbon dioxide to be in a supercritical state. For example, by setting the temperature of the heater 114 to about 42 ° C., it is possible to form a supercritical carbon dioxide region 301 that extends in a region about 15 mm above and below the heater 114.
[0044]
Since the heater 114 is disposed at a position 10 mm above the stage 112, the substrate 201 fixed on the stage 112 is in contact with the supercritical carbon dioxide region 301. As a result, on the substrate 201, the chemical liquid (liquid) that has wetted the pattern is replaced with the supercritical fluid (supercritical carbon dioxide), and the pattern comes into contact with the supercritical fluid. This supercritical state may be a subcritical state whose temperature is slightly lower than the critical point, and the same effect as the supercritical state can be obtained even in the subcritical state.
[0045]
After maintaining the state in which the supercritical carbon dioxide region 301 is formed for a predetermined time, the operation of the pressure pump 106 is stopped, the introduction valve 107 is closed, and carbon dioxide is gradually discharged from the discharge port 110. To do. As a result, the pressure inside the reaction chamber 102 is gradually reduced, and the carbon dioxide in the reaction chamber 102 is vaporized. At this time, on the substrate 201, the carbon dioxide heated to the supercritical state by the heater 114 is vaporized without being liquefied. As a result, in the substrate 201, the resist pattern formed thereon is dried without pattern collapse.
[0046]
Here, the stage 112 that is temperature-controlled by the temperature control mechanism 113 has a temperature higher than 23 ° C. due to heat conduction from the heater 114 through the supercritical carbon dioxide region 301. However, when the internal pressure of the reaction chamber 102 decreases and the carbon dioxide in the reaction chamber 102 vaporizes, the heat conduction from the heater 114 decreases. As a result, the temperature of the stage 112 decreases to the control temperature (23 ° C.) by the temperature control mechanism 113 without taking much time. For example, the temperature of the stage 112 decreases to 23 ° C. within the time until the internal pressure of the reaction chamber 102 reaches about atmospheric pressure due to the discharge.
[0047]
Further, the temperature of the heater 114 is decreased by stopping the operation of the heater control unit 121 from the time when the supercritical carbon dioxide region 301 is vaporized by the reduced pressure in the reaction chamber 102.
When the internal pressure of the reaction chamber 102 reaches about atmospheric pressure, as shown in FIG. 3 (f), the container upper part 101a is moved above the container lower part 101b, the high pressure container 101 is opened, and the process is completed. The prepared substrate 201 is brought into a state where it can be carried out.
[0048]
After unloading the substrate 201, a new substrate to be processed is fixed on the stage 112, and chemical treatment and supercritical processing are performed in the same manner as described above (FIGS. 2B to 3F). Thus, continuous sheet processing can be performed. Further, the temperature of the heater 114 is lowered to about room temperature by the time when the high-pressure vessel 101 is next sealed and liquefied carbon dioxide is introduced. For example, the temperature of the heater 114 may be lowered more quickly by providing a cooling mechanism using a Peltier element or the like.
[0049]
Further, for example, a substrate vertical mechanism may be provided in the container lower part 101b around the stage 112 so that the substrate to be processed can be moved in the vertical direction. For example, in the state shown in FIG. 3E, the temperature of the heater 114 is set to about 35 ° C., thereby forming a supercritical carbon dioxide region 301 that extends in a region about 5 mm above and below the heater 114. In this state, if the substrate 201 is raised by a substrate up-and-down mechanism not shown in FIG. 3 so that the distance between the surface of the substrate 201 and the heater 114 is about 3 mm, the resist pattern of the substrate 201 is formed. The surface is in contact with the supercritical carbon dioxide region 301.
[0050]
If the substrate up-and-down mechanism is lowered so that the substrate 201 is placed on the stage 201, the surface of the substrate 201 is separated from the supercritical carbon dioxide region 301 and exists in the liquefied carbon dioxide. It becomes a state to do. As described above, by using the substrate up-and-down mechanism, the substrate 201 can be placed in both the supercritical carbon dioxide and the liquefied carbon dioxide even when the temperature of the heater 114 is kept constant.
[0051]
In this case, when the carbon dioxide is vaporized by lowering the internal pressure of the reaction chamber 102 from the state of FIG. 3 (e), the substrate 201 is raised by the substrate up-and-down mechanism and arranged in the vicinity of the heater 114. On the surface of the substrate 201, the supercritical carbon dioxide can be vaporized without being liquefied. Further, in this case, the above-described continuous processing can be performed even if the temperature of the heater 114 is always kept constant at 35 ° C., for example.
[0052]
FIG. 7 is a characteristic diagram showing the temperature change of the stage in the series of processes as described above. 7A shows the temperature change of the stage 812 of the apparatus shown in FIG. 8, FIG. 7B shows the temperature change of the stage 912 of the apparatus shown in FIG. 9, and FIG. 2 shows a temperature change of the stage 112 of the apparatus shown in FIG. In FIG. 7C, the temperature change of the heater 114 is indicated by a dotted line.
[0053]
As is apparent from FIG. 7, first, in the apparatus of FIG. 8 that heats the container 801, it takes time to raise and lower the temperature, and it takes much time to lower the temperature and stabilize it at room temperature. It is said. Further, in the apparatus of FIG. 9 that directly heats the stage 912, the temperature can be raised and lowered in a short time, but it takes much time for the temperature to drop and stabilize at room temperature. Therefore, it takes a lot of time before the next processing can be performed.
[0054]
On the other hand, according to the apparatus of FIG. 1 in the present embodiment, the temperature of the stage 112 shown by the solid line is immediately lowered to room temperature from the time when the processing is completed. In addition, the heater 114 exposed and used in the internal space of the reaction chamber 102 is also lowered to room temperature without taking much time after the heating is stopped, so that the next processing can be performed. It becomes.
[0055]
[Embodiment 2]
Next, another embodiment of the present invention will be described.
FIG. 4 is a schematic cross-sectional view (a) showing another configuration example of the supercritical processing apparatus in the embodiment of the present invention and a plan view (b) showing a part thereof. This apparatus includes a high-pressure vessel 401 that can be sealed, and a reaction chamber 402 provided inside the high-pressure vessel 401. A stage 412 on which a substrate 401 to be processed is placed is disposed on the bottom surface of the reaction chamber 402. The high-pressure vessel 401 is made of stainless steel, for example, and has a wall thickness of about 20 mm.
[0056]
The high-pressure vessel 401 includes a vessel upper portion 401a and a vessel lower portion 401b having a stage 412 fixed to the bottom. For example, the reaction chamber 402 is opened by moving the vessel upper portion 401a upward. Is possible.
Further, the high-pressure vessel 401 includes a temperature control mechanism 413 between the outer wall and the inner wall, and can be controlled to keep the temperature of the high-pressure vessel 401 constant by the control of the temperature control unit 422.
[0057]
The temperature control mechanism 413 holds the high-pressure vessel 401 and the stage 412 at a temperature lower than the heating temperature by the heater unit 414 described below. The temperature control mechanism 413 is, for example, a pipe in which water whose temperature is adjusted to about 23 ° C. by the temperature control unit 422 in which water is circulated as a heat medium is circulated. A similar temperature control mechanism is also provided in the stage 412 to enable the stage 412 to be maintained at a predetermined temperature.
[0058]
In the supercritical processing apparatus of FIG. 4, a heater unit (heating unit) configured by a plurality of pins that penetrates the bottom of the container lower part 401 b and partially protrudes to the upper part of the stage 412 through a through hole provided in the stage 412. Means) 414. The heater portion 414 is shielded so as to keep secret in the reaction chamber 402 in the penetrating portion of the container lower portion 401b, and can move up and down. By this vertical movement, the tip of the heater portion 414 can be inserted into and removed from the through hole provided in the stage 412. In addition, the heater unit 414 and the stage 412 are thermally blocked.
[0059]
Further, the heater unit 414 can heat at least the upper part of the pin of the heater unit 414 under the control of the heater control unit 421. For example, as shown in the plan view of FIG. 4B, the heater unit 414 includes 12 pins that are discharged from the through holes of the stage 412. The number of pins is not limited to 12, but may be more than 12. As will be described later, the substrate to be processed is separated from the stage 412 and heated by the pin tip of the heater unit 414 inserted and protruded into the through hole of the stage 412. The substrate to be processed can be heated more quickly.
[0060]
In addition, the apparatus includes, for example, a cylinder 403 in which carbon dioxide is pressurized and accommodated. Carbon dioxide is an example of a supercritical substance that is a gas in the air atmosphere and becomes a supercritical state under predetermined conditions. Carbon dioxide accommodated in the cylinder 403 is introduced into the reaction chamber 402 through the piping 404 through the inlet 405. A pressure feed pump 406 and an introduction valve 407 are provided in the middle of the pipe 404, and a pressure gauge 408 for measuring the pressure here is provided on the discharge side of the pressure feed pump 406. The pressure pump 406 can pump carbon dioxide in the cylinder 403 into the reaction chamber 402. Further, the opening degree of the introduction valve 407 can be controlled by the pressure measurement result of the pressure gauge 408.
[0061]
Therefore, the cylinder 403, the pressure pump 406, etc. constitute a means for supplying carbon dioxide, which is a substance that becomes a supercritical fluid. Moreover, if carbon dioxide is accommodated in the cylinder 403 at a high pressure of 20 MPa or more, this alone can serve as a supply means. Needless to say, the supply of carbon dioxide into the reaction chamber 402 is not limited to the above-described configuration, and other mechanisms may be used.
[0062]
The apparatus further includes a pressure gauge 409 that measures the internal pressure of the reaction chamber 402, a discharge port 410 that discharges the fluid inside the reaction chamber 402, and a pressure control valve 411 that is provided in the middle of the discharge port 410. ing. The pressure control valve 411 controls the opening degree according to the pressure measurement result of the pressure gauge 409, and controls the amount of fluid discharged from the discharge port 410. By controlling the pressure with these, it is possible to control the internal pressure of the reaction chamber 402 to a pressure at which the supercritical substance is in a supercritical state.
[0063]
The cylinder 403 may contain a supercritical substance that is a gas in another atmospheric atmosphere and becomes a supercritical state under a predetermined condition instead of carbon dioxide. For example, the cylinder 403 is SF ₆ And CHF _Three Fluorine compounds such as N ₂ It may contain a nitrogen compound such as O. Furthermore, carbonyl fluoride and CF _Three Carbonyl fluoride compounds such as COF, CF _Three OF, CHF ₂ OCHF ₂ A compound containing a carbonyl group and a halogen such as fluorine or chlorine and containing a compound that is a gas in the air atmosphere, such as a hypofluorite compound such as, may be used. In addition, the cylinder 403 is FNO or F _Three It may contain a halogenated nitrogen compound such as NO.
[0064]
In addition, the apparatus includes a chemical solution supply unit 423 and a chemical solution nozzle 424. The chemical liquid supply unit 423 is, for example, a mechanism that supplies a predetermined developer and a rinse liquid, and can discharge the developer and the rinse liquid from a liquid discharge unit provided at the tip of the chemical liquid nozzle 424. As shown in FIG. 4B, the chemical nozzle 424 is movable above the stage 412 in a state where the upper container 401 a is moved above the lower container 401 b and the high-pressure container 401 is opened. By moving the tip of the chemical solution nozzle 424 above the stage 412, a chemical solution such as a developing solution is supplied onto the substrate to be processed disposed on the stage 412. The chemical nozzle 424 may be moved by a rotational movement, or may be moved above the stage 412 by a linear movement.
[0065]
In this supercritical processing apparatus, carbon dioxide supplied from the cylinder 403 is pumped to the pump 406, passes through the piping, and is transported to the reaction chamber 402 from the inlet 405. For example, when the pressure control valve 411 is closed after the inside of the reaction chamber 402 is filled with the transported carbon dioxide in a state where carbon dioxide is being pumped at a high pressure, the inside of the reaction chamber 402 is For example, a pressure state in which carbon dioxide becomes a supercritical state can be set.
[0066]
Further, the opening of the pressure control valve 411 is adjusted within a range in which the pressure value measured by the pressure gauge 409 maintains the pressure at the critical point of carbon dioxide, and the pressure value measured by the pressure gauge 408 is the critical point of carbon dioxide. It is also possible to adjust the pressure of the pumping by the pumping pump 406 within a range where the pressure is maintained. By doing so, a state in which carbon dioxide is always supplied into the reaction chamber 402 is obtained.
[0067]
Next, supercritical processing using the supercritical processing apparatus shown in FIG. 4 will be described.
First, as shown to Fig.5 (a), the container upper part 401a is moved above the container lower part 401b, and the high voltage | pressure container 401 is made into an open state. Further, the temperature control unit 422 is operated so that the high-pressure vessel 401 (the vessel upper portion 401a and the vessel lower portion 401b) and the stage 412 are controlled to 23 ° C., for example.
[0068]
Next, as shown in FIG. 5B, the substrate 201 to be processed is fixed on the stage 412. The substrate 201 includes, for example, a resist film on which a latent image is formed by exposing a predetermined pattern image.
When the substrate 201 is fixed on the stage 412, as shown in FIG. 5C, the chemical nozzle 424 is moved to dispose a liquid discharge unit (not shown) above the substrate 201. In this state, the chemical solution supply unit 423 is operated to supply a predetermined chemical solution such as a developer and a rinse solution onto the substrate 201. Thereby, for example, the resist film on the substrate 201 is developed and a resist pattern is formed on the substrate 201.
[0069]
Next, after retracting the chemical nozzle 424, as shown in FIG. 6D, the container upper portion 401a is lowered and brought into close contact with the container lower portion 401b, and the reaction chamber 402 inside the high pressure vessel 401 is sealed. And In this state, the introduction valve 407 is opened, and the liquefied carbon dioxide supplied from the cylinder 403 is pumped into the reaction chamber 402 by the pump pump 406.
[0070]
Here, first, the opening degree of the pressure control valve 411 is adjusted in a range in which the pressure value measured by the pressure gauge 409 maintains the pressure at the critical point of carbon dioxide. In addition, the pressure of the pressure pump 406 is adjusted so that the pressure value measured by the pressure gauge 408 maintains the pressure at the critical point of carbon dioxide (for example, 7.5 MPa). As a result, a state in which liquefied carbon dioxide is always supplied into the reaction chamber 402 is obtained.
[0071]
Next, the heater unit 414 is first raised, and a pin is passed through the through hole of the stage 412 so that the tip of the pin of the heater unit 414 protrudes from the surface of the stage 412. The substrate 201 is moved above the stage 412 and separated from the stage 412 by the plurality of pin tip portions constituting the heater unit 414. After this state, the heater control unit 421 is operated to heat the tip of the heater unit 414 to about 40 ° C., for example, so that the substrate 201 becomes 31 ° C. or higher.
[0072]
As a result, as shown in FIG. 6E, a supercritical carbon dioxide region 601 is formed around the surface of the substrate 201. The supercritical carbon dioxide region 601 is heated to a critical pressure and becomes a supercritical state. . As a result, on the substrate 201, the chemical liquid (liquid) that has wetted the pattern is replaced with the supercritical fluid (supercritical carbon dioxide), and the pattern comes into contact with the supercritical fluid. This supercritical state may be a subcritical state whose temperature is slightly lower than the critical point, and the same effect as the supercritical state can be obtained even in the subcritical state.
[0073]
After maintaining the state in which the supercritical carbon dioxide region 601 is formed for a predetermined time, the operation of the pressure pump 406 is stopped, the introduction valve 407 is closed, and carbon dioxide is gradually discharged from the discharge port 410. To do. As a result, the pressure inside the reaction chamber 402 is gradually reduced, and the carbon dioxide in the reaction chamber 402 is vaporized. At this time, on the substrate 201 heated by the heater unit 414, the carbon dioxide heated to the supercritical state by the substrate 201 is vaporized without being liquefied. As a result, in the substrate 201, the resist pattern formed thereon is dried without pattern collapse.
[0074]
As described above, after the supercritical carbon dioxide on the substrate 201 is vaporized, the heater unit 414 is lowered, the pin is removed from the through hole of the stage 412, and the operation of the heater control unit 421 is stopped. The heating state of the unit 414 is terminated.
As a result, the substrate 201 is placed on the stage 412 and the temperature decreases.
[0075]
Here, the stage 412 whose temperature is controlled by the temperature control mechanism 413 is heated to a temperature higher than 23 ° C. by the heating by the heater unit 414. However, since the heat source for heating the stage 412 is eliminated by lowering the heater unit 414, the temperature of the stage 412 decreases to the control temperature (23 ° C.) by the temperature control mechanism 413 in a short time. For example, the temperature of the stage 412 decreases to 23 ° C. within the time until the internal pressure of the reaction chamber 402 becomes about atmospheric pressure due to the discharge.
[0076]
When the internal pressure of the reaction chamber 402 reaches about atmospheric pressure, as shown in FIG. 6 (f), the container upper part 401a is moved above the container lower part 401b, the high-pressure container 401 is opened, and the process is completed. The prepared substrate 201 is brought into a state where it can be carried out.
After unloading the substrate 201, a new substrate to be processed is fixed on the stage 412, and chemical treatment and supercritical processing are performed in the same manner as described above (FIGS. 5B to 6F). Thus, continuous sheet processing can be performed. Further, by the time when the high pressure vessel 401 is next sealed and liquefied carbon dioxide is introduced, the temperature of the heater unit 414 has decreased to about room temperature. For example, the temperature of the heater unit 414 may be decreased more quickly by providing a cooling mechanism using a Peltier element or the like.
[0077]
With the supercritical processing apparatus according to the present invention described above, the following processing examples are possible.
First, an electron beam resist (ZEP-520: manufactured by Nippon Zeon) is spin-coated on a silicon substrate to form a resist film having a thickness of about 500 nm. Next, a latent image having a predetermined shape is formed on the formed resist film by electron beam exposure. The formed latent image is, for example, a stripe pattern having a width of 50 nm.
[0078]
After the latent image is formed, the silicon substrate is fixed on a stage whose temperature is controlled by a temperature control unit that controls the temperature to be maintained at 23 ° C. Next, the liquid discharge portion of the chemical nozzle is moved onto the silicon substrate, the developer and the obtained rinse liquid are discharged, the resist film is developed, and a resist pattern is formed on the silicon substrate. Subsequently, the upper part of the container is lowered, the container is closed and the reaction chamber is sealed, and liquefied carbon dioxide is introduced therein, and the pressure in the reaction chamber is set to 7.5 MPa.
[0079]
In the state where the internal pressure of the reaction chamber is in the range of 7.5 MPa, liquefied carbon dioxide is continuously introduced while being discharged from the discharge port. This state is continued for 5 minutes, and the rinsing liquid adhering to the silicon substrate and the resist pattern thereon is replaced with liquefied carbon dioxide. Thereafter, the heating temperature of the heater is raised to 50 ° C., the liquefied carbon dioxide around the heater is brought into a supercritical state, and the silicon substrate is accommodated in this region. As a result, the liquefied carbon dioxide that has been in contact with the silicon substrate and the resist pattern is in a supercritical state.
[0080]
Thereafter, the supply of liquefied carbon dioxide to the inside of the reaction chamber is stopped, and the internal pressure of the reaction chamber is lowered by setting the state of being discharged from the discharge port. As a result, the carbon dioxide in the supercritical state around the heater is vaporized. That is, the supercritical carbon dioxide in contact with the silicon substrate and the resist pattern is vaporized, and supercritical drying is performed. By this drying process, the resist pattern formed on the silicon substrate is dried without causing problems such as pattern collapse.
[0081]
Next, when the internal pressure of the reaction chamber reaches about atmospheric pressure, the upper portion of the container is raised to open the reaction chamber, and heating of the heater is stopped. After opening the reaction chamber, the silicon substrate on the stage is unloaded by using a predetermined transfer mechanism, and the silicon substrate to be processed next is loaded on the stage.
[0082]
Here, in the state where the supercritical fluid exists around the heater, the heat from the heater is conducted to the stage to some extent to increase the temperature of the stage. However, when the reaction chamber is depressurized and the supercritical fluid around the heater is vaporized, a gas is interposed between the heater and the silicon substrate (stage), and the heat from the heater is conducted to the stage. It becomes difficult. As a result, the temperature of the stage whose temperature is controlled by the temperature controller immediately decreases to about 23 ° C.
[0083]
That is, as described above, the stage temperature is stable at 23 ° C. when the silicon substrate that has been processed is unloaded and the next silicon substrate to be processed is loaded. Therefore, the silicon substrate to be processed next is also processed in the same temperature environment as the silicon substrate that has been processed before.
[0084]
Moreover, the following process is also possible by the supercritical processing apparatus according to the present invention described above.
First, an electron beam resist (ZEP-520: manufactured by Nippon Zeon) is spin-coated on a silicon substrate to form a resist film having a thickness of about 500 nm. Next, a latent image having a predetermined shape is formed on the formed resist film by electron beam exposure. The formed latent image is, for example, a stripe pattern having a width of 50 nm.
[0085]
After the latent image is formed, the silicon substrate is fixed on a stage whose temperature is controlled by a temperature control unit that controls the temperature to be maintained at 23 ° C. Next, the liquid discharge portion of the chemical nozzle is moved onto the silicon substrate, the developer and the obtained rinse liquid are discharged, the resist film is developed, and a resist pattern is formed on the silicon substrate. Subsequently, the upper part of the container is lowered, the container is closed and the reaction chamber is sealed, and liquefied carbon dioxide is introduced therein, and the pressure in the reaction chamber is set to 7.5 MPa.
[0086]
In the state where the internal pressure of the reaction chamber is in the range of 7.5 MPa, liquefied carbon dioxide is continuously introduced while being discharged from the discharge port. This state is continued for 5 minutes, and the rinsing liquid adhering to the silicon substrate and the resist pattern thereon is replaced with liquefied carbon dioxide.
Thereafter, the heater part is first raised and fitted into the through hole of the stage so that the pin upper part of the heater part protrudes from the surface of the stage, and the silicon substrate is separated from the stage. The heating temperature by the pin of the heater part is raised to 50 ° C. to heat the silicon substrate, and the liquefied carbon dioxide in contact with the silicon substrate is brought into a supercritical state.
[0087]
Thereafter, the supply of liquefied carbon dioxide to the inside of the reaction chamber is stopped, and the internal pressure of the reaction chamber is lowered by setting the state of being discharged from the discharge port. As a result, the carbon dioxide brought into the supercritical state by the heating from the silicon substrate heated by the heater portion is vaporized. That is, the supercritical carbon dioxide in contact with the silicon substrate and the resist pattern is vaporized, and supercritical drying is performed. By this drying process, the resist pattern formed on the silicon substrate is dried without causing problems such as pattern collapse.
[0088]
Next, when the internal pressure of the reaction chamber reaches about atmospheric pressure, the heater unit is lowered so that the pin is removed from the through hole of the stage, and heating of the heater unit is stopped. Further, the upper part of the container is raised to open the reaction chamber. After opening the reaction chamber, the silicon substrate on the stage is unloaded by using a predetermined transfer mechanism, and the silicon substrate to be processed next is loaded on the stage.
[0089]
Here, when the pin of the heater part is extracted from the through-hole of the stage, the heating of the stage by the heater part is stopped, and the temperature of the stage that is controlled by the temperature control part immediately decreases to about 23 ° C. To do.
That is, as described above, the stage temperature is stable at 23 ° C. when the silicon substrate that has been processed is unloaded and the next silicon substrate to be processed is loaded. Accordingly, the silicon substrate that is to be dealt with in the next process is also processed in the same temperature environment as the silicon substrate that has been processed before.
[0090]
【The invention's effect】
As described above, in the present invention, the heater provided opposite to the stage is used as a heating means, and the supercritical material introduced above the stage is heated so that the supercritical material is in a supercritical state. . In addition, the stage is held at a temperature lower than the heating temperature by the heating means by the temperature control mechanism. As described above, since the temperature-maintained stage is not directly heated by the heating means, according to the present invention, the temperature of the stage is quickly set to a predetermined value after the series of supercritical processing is completed. Therefore, it is possible to obtain an excellent effect that the liquid processing and the supercritical processing can be continuously performed by the same processing apparatus in a shorter time than the conventional method.
[0091]
Further, in the present invention, a heater unit that includes a plurality of pins that penetrate the container from the outside of the container and protrude from the stage surface through the through-hole of the stage, and that moves so that the through-hole can be inserted and removed is used as a heating means. And the tip of the pin protrudes from the surface of the stage to separate the silicon substrate from the stage. In this state, the silicon substrate is heated to heat the supercritical material introduced above the stage, The critical material is in a supercritical state. Further, the stage is held at a temperature lower than the heating temperature by the heating means by the temperature control mechanism. Therefore, according to the present invention, since the temperature-maintained stage can quickly set the temperature of the stage to a predetermined value after a series of supercritical processing is completed, the liquid processing can be performed in a shorter time than conventional. An excellent effect is obtained that supercritical processing can be continuously performed by the same processing apparatus.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view (a) showing a configuration example of a supercritical processing apparatus in an embodiment of the present invention, and plan views (b) and (c) showing a part thereof.
FIG. 2 is a process diagram showing a process of supercritical processing using the supercritical processing apparatus shown in FIG. 1;
3 is a process diagram showing a process of supercritical processing using the supercritical processing apparatus shown in FIG. 1. FIG.
FIG. 4 is a schematic cross-sectional view (a) showing another configuration example of the supercritical processing apparatus in the embodiment of the present invention and a plan view (b) showing a part thereof.
FIG. 5 is a process diagram showing a process of supercritical processing using the supercritical processing apparatus shown in FIG. 4;
6 is a process diagram showing a process of supercritical processing using the supercritical processing apparatus shown in FIG. 4; FIG.
FIG. 7 is a characteristic diagram showing a temperature change of the stage.
FIG. 8 is a configuration diagram showing a configuration of a conventional supercritical processing apparatus.
FIG. 9 is a configuration diagram showing a configuration of a conventional supercritical processing apparatus.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 101 ... High pressure vessel, 101a ... Upper part of vessel, 101b ... Lower part of vessel, 102 ... Reaction chamber, 103 ... Cylinder, 104 ... Pipe, 105 ... Inlet, 106 ... Pressure feed pump, 107 ... Introducing valve, 108 ... Pressure gauge, 109 ... Pressure gauge, 110 ... Discharge port, 111 ... Pressure control valve, 112 ... Stage, 113 ... Temperature control mechanism, 114 ... Heater (heating means), 121 ... Heater control unit, 122 ... Temperature control unit, 123 ... Chemical solution supply unit, 124 ... Chemical nozzle, 401 ... High pressure vessel, 401a ... Upper portion of vessel, 401b ... Lower portion of vessel, 402 ... Reaction chamber, 403 ... Cylinder, 404 ... Pipe, 405 ... Inlet, 406 ... Pressure feed pump, 407 ... Inlet valve, 408 ... Pressure gauge, 409 ... Pressure gauge, 410 ... Discharge port, 411 ... Pressure control valve, 412 ... Stage, 413 ... Temperature control mechanism, 414 ... Heat Part (heating means), 421 ... heater control unit, 422 ... temperature control unit, 423 ... chemical supply unit, 424 ... chemical nozzle.

Claims (9)

A container with a reaction chamber that can be sealed inside;
A stage provided inside the reaction chamber on which a substrate to be processed is placed;
A supply means for supplying a supercritical substance that is a gas in an air atmosphere and is in a supercritical state under a predetermined condition into the reaction chamber;
Wherein the internal pressure of the reaction chamber supercritical substance is pressurization control to a pressure reaches a supercritical state, after treatment with a supercritical state of the substrate, and pressure control means for reducing the pressure inside of the reaction chamber to atmospheric pressure,
Heating means for heating the supercritical material introduced above the stage;
A temperature control mechanism for holding the stage at a temperature lower than the heating temperature by the heating means;
A supercritical processing apparatus comprising at least a discharge port for discharging a fluid inside the reaction chamber provided in the reaction chamber. The supercritical processing apparatus according to claim 1,
The supercritical processing apparatus, wherein the temperature control mechanism maintains the temperature of the container at a temperature lower than the heating temperature by the heating means. The supercritical processing apparatus according to claim 1,
The supercritical processing apparatus, wherein the heating means is a heater provided to face the stage. The supercritical processing apparatus according to claim 1,
The heating means includes
A heater part that penetrates the container from the outside of the container and includes a plurality of pins protruding from the stage surface from the through-hole of the stage, and moves so that the through-hole can be inserted and removed;
The substrate is separated from the stage by inserting the pin of the heater portion into the through hole and the tip of the pin protrudes from the surface of the stage, and the substrate is heated in this state. Supercritical processing equipment. A container with a reaction chamber that can be sealed inside;
A stage provided inside the reaction chamber on which a substrate to be processed is placed;
A supply means for supplying a supercritical substance that is a gas in an air atmosphere and is in a supercritical state under a predetermined condition into the reaction chamber;
Wherein the internal pressure of the reaction chamber supercritical substance is pressurization control to a pressure reaches a supercritical state, after treatment with a supercritical state of the substrate, and pressure control means for reducing the pressure inside of the reaction chamber to atmospheric pressure,
A heater provided facing the stage;
A temperature control mechanism for holding the stage at a temperature lower than the heating temperature by the heater;
A supercritical processing apparatus comprising at least a discharge port for discharging a fluid inside the reaction chamber provided in the reaction chamber. In the supercritical processing apparatus according to claim 5,
The supercritical processing apparatus, wherein the temperature control mechanism maintains the temperature of the container at a temperature lower than a heating temperature by the heater. In the supercritical processing apparatus according to claim 5,
A supercritical processing apparatus comprising a substrate up-and-down mechanism for moving the substrate up and down on the stage in the direction of the heater. A container with a reaction chamber that can be sealed inside;
A stage provided in the reaction chamber on which a substrate to be processed is placed, and a stage having a plurality of through holes in a region where the substrate is placed;
A supply means for supplying a supercritical substance that is a gas in an air atmosphere and is in a supercritical state under a predetermined condition into the reaction chamber;
Wherein the internal pressure of the reaction chamber supercritical substance is pressurization control to a pressure reaches a supercritical state, after treatment with a supercritical state of the substrate, and pressure control means for reducing the pressure inside of the reaction chamber to atmospheric pressure,
A heater section that includes a plurality of pins that penetrate the container from the outside of the container and protrude from the surface of the stage from the through hole of the stage;
A temperature control mechanism for holding the stage at a temperature lower than the heating temperature by the heater unit;
And at least a discharge port for discharging the fluid inside the reaction chamber provided in the reaction chamber,
The heater portion inserts the pin into the through hole and causes the tip of the pin to protrude from the surface of the stage, thereby separating the substrate from the stage and heating the substrate in this state. Supercritical processing equipment characterized by The supercritical processing apparatus according to claim 8,
The supercritical processing apparatus, wherein the temperature control mechanism maintains the temperature of the container at a temperature lower than a heating temperature by the heater unit.

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