JP2006303316A - Supercritical processing method and device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a sufficient supercritical processing state in a short period of time. <P>SOLUTION: Sticking a lid 103 closely togeher with a vessel-lower part 102 and closing a valve 107 hermetically seal an inside of the vessel-lower part 102 to form the high-pressure vessel. A cleaning liquid 120 contained in the inside of the vessel-lower part 102 is heated to, for instance, 200 to 250°C by a heating means (not shown in the figure). In addition, the adjustment by a back-pressure regulating valve 109 makes the inside of the hermetically sealed vessel-lower part 102 in an approximate 3 MPa. This fills the inside of the hermetically sealed vessel-lower part 102 with a supercritical fluid 121 comprising a supercritical HCF<SB>2</SB>CF<SB>2</SB>OCH<SB>2</SB>CF<SB>3</SB>and an ethyl lactate to dip the substrate 101 in the supercritical fluid 121. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a supercritical processing method and apparatus for performing processing such as removing organic substances such as a resist pattern from a substrate having a fine structure on the order of nm, for example.

  As an elemental technology for manufacturing a semiconductor device such as an LSI, there is a pattern forming technology by lithography. Today, very fine patterns of the order of nm are used, and patterns of a size of 10 nm or less have been formed at the level of research and development. In the pattern forming technique, a resist pattern formed through resist film formation by coating or the like, exposure, and development is used as a mask, and a substrate and a thin film under the mask are processed by etching. A resist used for such a mask is an organic material that is sensitive to ultraviolet rays, X-rays, electron beams, and the like, and a powdery or highly viscous liquid dissolved in a solvent is used.

  The resist pattern made of such a material and processed is removed after the pattern is formed on the substrate or thin film. For cleaning to remove the resist (resist pattern), an acid solution mainly composed of sulfuric acid has been used as a cleaning solution in the past. Nothing has become a problem. For example, when a resist pattern is formed on a pattern that has already been formed, the portion of the pattern is a region where the resist material remains even after development and etching. For this reason, the resist has entered the gap between the patterns below the resist pattern. In removing the resist, it is also necessary to remove the portion that has entered between the fine patterns as described above. However, when the pattern interval is as fine as the nm order, the cleaning liquid hardly impregnates into the gap, and thus organic matter (resist) residues may remain in the pattern gap.

  On the other hand, the ashing method using oxygen gas plasma has been used as a general method for resist removal in recent years because the gas diffuses into the fine structure without the problem of waste liquid. However, when the pattern to be formed is an organic material, it is difficult to use an ashing method for resist removal. For example, in LSI, a low dielectric constant material such as porous methylpolysiloxane or hydrogenated polysiloxane is used as a material for an interlayer insulating layer between multilayer wirings due to a decrease in wiring capacity accompanying an increase in the speed of semiconductor devices. Being started. However, when such an interlayer insulating layer is etched using a resist pattern as a mask and then ashing is performed for removing the resist pattern, methyl groups and hydrogen constituting the interlayer insulating layer are also ashed, resulting in There was a problem that the dielectric constant increased.

  As a method for solving the above-described problem, a cleaning (removal) method using a supercritical fluid has been proposed (see Non-Patent Document 1). In this technique, cleaning is performed using a supercritical fluid having both gas diffusibility and liquid solubility (high density) as a cleaning solution. In such a process using a supercritical fluid, carbon dioxide is often used as the supercritical fluid. In the processing using the supercritical fluid described above, the substrate in which the resist or the like remains is placed in a high pressure resistant container, and supercritical carbon dioxide is introduced into the high pressure resistant container so that the supercritical carbon dioxide is generated. It acts on the substrate. However, carbon dioxide does not have a dipole moment and resists, which are organic materials composed of polar molecules, hardly dissolve.

  Further, in supercritical processing using carbon dioxide, it is necessary to use a high pressure resistant container regulated by the High Pressure Gas Safety Law in order to bring carbon dioxide, which is a gas, into a high pressure state of 1 MPa or more. In such high pressure resistant containers, it is mandatory to use expensive certified high pressure valves, and it is not easy to replace valves or modify containers, and periodic inspections that are required to be done once a year. Cost for is required. For this reason, supercritical processing using carbon dioxide, which is a gas at room temperature (about 25 ° C.) and normal pressure (about atmospheric pressure), is not an easy-to-use method.

  On the other hand, a method of performing supercritical processing using a liquid at room temperature and normal pressure not regulated by the High Pressure Gas Safety Law has recently been proposed (see Patent Document 1). In the technique of Patent Document 1, for example, an organic substance such as a resist pattern formed on a substrate under a lower critical condition by using a supercritical fluid of a polar organic substance (polar solvent) such as alcohol or fluorocarbons. Has been removed. Further, conventionally, as shown in FIG. 8A, the temperature in the reaction chamber 803 on which the substrate 802 to be processed is placed by a heater 810 provided between the outer wall and the inner wall of the container 801, The polar solvent is raised to about 200 ° C. at which it becomes a supercritical state. Further, as shown in FIG. 8B, a technique has been proposed in which a substrate 802 is placed on a substrate table 811 that incorporates a heating mechanism in a container 801, and the vicinity of the substrate 802 is heated (Patent Document 2). reference).

JP 2004-335988 A Japanese Patent No. 3494939 Koichiro Tsuji et al., “Silicon wafer surface particle removal in supercritical CO 2”, Proceedings of the 65th Annual Conference of the Japan Society of Applied Physics, 3p-B-7, p. 670, September 2004.

  However, the conventional technique disclosed in Patent Document 1 has a problem that, depending on the type of resist, sufficient dissolution characteristics are not yet obtained, and it is not easy to obtain a sufficient cleaning state in a short time. . In addition, in order to make a liquid substance in a supercritical state at room temperature and normal pressure, a higher temperature is required than in the case of carbon dioxide or the like. Loss is large, and it is not easy to quickly control the temperature in the vicinity of the substrate to be processed to a predetermined temperature, resulting in a delay in processing time.

  The present invention has been made to solve the above problems, and an object thereof is to obtain a sufficient supercritical processing state in a short time.

  In the supercritical processing method according to the present invention, the first step of disposing the substrate inside the high-pressure vessel and the mixed solution consisting of the solvent that dissolves the fluorine compound and the organic substance inside the high-pressure vessel is accommodated and heated. A second step in which the inside of the high-pressure vessel is filled with a supercritical fluid containing a fluorine compound and a solvent, and a state in which the supercritical fluid is vaporized by lowering the internal pressure of the high-pressure vessel; And at least a third step. In this method, the substrate is treated with a supercritical fluid composed of a fluorine compound and a solvent in a supercritical state.

In the above supercritical processing method, the fluorine compound may be composed of at least one of hydrofluoroether and hydrofluoroester. The hydrofluoroether may be at least one of HCF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₃ , and CF ₃ CHFCF ₂ OCH ₂ CF ₂ CF ₃ . Moreover, the solvent should just have polarity. The solvent may be at least one of a polyhydric alcohol ether compound and a polycarboxylic acid ester compound.

  In the supercritical processing method, the solvent may be at least one of hydroxy acid, ester of hydroxy acid, and ether compound of hydroxy acid. The solvent may be ethyl lactate. Further, the fluorine compound and the solvent may be in an azeotropic composition ratio.

  Further, another supercritical processing method according to the present invention includes a first step of placing a substrate inside a high-pressure vessel, and heating a mixed solution made of a fluorine compound inside the high-pressure vessel, A second step of filling the inside with a supercritical fluid of a fluorine compound in a supercritical state, and a third step of lowering the internal pressure of the high-pressure vessel to vaporize the supercritical fluid The fluorine compound is composed of at least one of a fluorinated hydroxy acid, an ester compound of fluorinated hydroxy acid, and an ether compound of fluorinated hydroxy acid.

  Further, the supercritical processing apparatus according to the present invention includes a high-pressure container in which a substrate lower part provided with an open part on one side and a lid for sealing the open part of the lower part of the container are placed, and a substrate to be processed is placed inside, Supply means for supplying a mixed solution composed of a fluorine compound and a solvent that dissolves organic matter inside the high-pressure vessel, a heating plate that is disposed inside the high-pressure vessel and is made of a paramagnetic metal, and a high-frequency alternating current electric field on the heating plate At least a induction heating means for heating the heating plate by induction heating and a discharge means for discharging the fluid inside the high-pressure vessel to the outside, and the mixing supplied to the inside of the high-pressure vessel The solution is heated by a heating plate so that the inside of the high-pressure vessel is filled with a supercritical fluid composed of a fluorine compound and a solvent in a supercritical state. The heating plate can be moved from the lid toward the bottom of the lower part of the container facing the lid by a moving mechanism. A substrate to be processed is placed on the heating plate.

  Further, another supercritical processing apparatus according to the present invention comprises a lower part of a container provided with an open part on one side and a lid for sealing the open part of the lower part of the container, and a high-pressure container in which a substrate to be processed is placed. A supply means for supplying a mixed solution composed of a fluorine compound and a solvent for dissolving organic substances into the high-pressure vessel, a heating unit for heating the high-pressure vessel, and a discharge for discharging the fluid inside the high-pressure vessel to the outside And the heating part is provided with a recess into which the heating part can be fitted, and the heating part is fitted into the recess to heat the high pressure container and is supplied to the inside of the high pressure container. The mixed solution is heated so that the inside of the high-pressure vessel is filled with a supercritical fluid containing a fluorine compound and a solvent in a supercritical state. In these devices, a cooling mechanism for cooling the high-pressure vessel may be provided.

  As described above, in the present invention, a substrate is treated with a supercritical fluid in which a mixed solution of a fluorine compound such as hydrofluoroether and hydrofluoroester and a solvent that dissolves an organic substance is in a supercritical state. . In the present invention, the substrate is treated with a supercritical fluid in which a fluorine compound such as fluorinated hydroxy acid, an ester compound of fluorinated hydroxy acid, and an ether compound of fluorinated hydroxy acid is brought into a supercritical state. . As a result, according to the present invention, an excellent effect that a sufficient supercritical processing state can be obtained in a short time, for example, an organic substance such as a resist adhering to the substrate is dissolved more rapidly. Is obtained.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a process diagram for explaining a supercritical processing method according to an embodiment of the present invention. First, a low dielectric constant film made of a low dielectric constant material HSQ (hydrogen silsesquioxane) is formed on a substrate 101 made of, for example, single crystal silicon, and an ArF resist film, for example, is formed thereon. And a resist pattern having a width of about 90 nm is formed by known photolithography. Next, using the formed resist pattern as a mask, the low dielectric constant film is processed by dry etching using a plasma of a mixed gas of CHF ₃ and argon to form a pattern made of a low dielectric constant material on the silicon substrate 101. It is assumed that

When the pattern is formed as described above, the substrate 101 is held by the substrate holding portion 104 provided on the lid 103 for sealing the container lower portion 102 as shown in FIG. In addition, the container lower part 102 is provided with one open part, and this open part can be sealed with the lid | cover 103, and the sealed high pressure container can be comprised with the container lower part 102 and the lid | cover 103. FIG. Next, a fluorine compound mixed liquid in which HCF ₂ CF ₂ OCH ₂ CF ₃ (fluorine compound) and ethyl lactate (solvent) contained in the chemical solution introduction tank 105 is mixed is supplied into the container lower part 102 through the pipe 106. Then, the cleaning liquid 120 is accommodated in the container lower part 102. A valve 107 is provided in the middle of the pipe 106. The container lower part 102 is provided with a discharge pipe 108, and the discharge pipe 108 is provided with a back pressure valve 109. In addition, the container lower part 102 is disposed inside a liquid discharge container 110 that stores the liquid overflowing from the container lower part 102. The liquid discharge container 110 discharges the waste liquid stored from the discharge unit 111.

  Next, as shown in FIG. 1B, the substrate 101 held by the substrate holding unit 104 with the lid 103 approaching the container lower part 102 side is immersed in the cleaning liquid 120 accommodated in the container lower part 102. State. At this time, the supply of the fluorine compound mixed liquid from the chemical solution introduction tank 105 may be added so that the cleaning liquid 120 overflows in the container lower part 102 and the substrate 101 may be cleaned. By this cleaning, components dissolved in the cleaning liquid 120 can be removed (cleaned) from the substrate 101 at a normal temperature (about 25 ° C.) and a normal pressure (about atmospheric pressure). For example, a part of the resist pattern formed on the substrate 101 is dissolved in the cleaning liquid 120 and a part remains on the substrate 101. On the other hand, a pattern made of a low dielectric constant material is not dissolved in the cleaning liquid 120.

Next, the lid 103 is brought into close contact with the container lower part 102 and the valve 107 is closed, whereby the inside of the container lower part 102 is sealed and a high-pressure container is formed. The cleaning liquid 120 accommodated in the inside is heated to about 200 to 250 ° C., for example. In addition, the back pressure valve 109 is adjusted so that the inside of the sealed container lower part 102 is about 3 MPa. As a result, as shown in FIG. 1C, the inside of the sealed container lower part 102 is filled with a supercritical fluid 121 made of HCF ₂ CF ₂ OCH ₂ CF ₃ and ethyl lactate in a supercritical state. The substrate 101 is immersed in the supercritical fluid 121. At this stage, as shown in FIG. 2, the circulation pump 201 is connected to the container lower part 102 (high pressure container) by the pipe 202 and the pipe 203, and the supercritical fluid 121 filled in the container lower part 102 is connected to the pipe. It may be made to circulate by the route of 202-circulation pump 201-pipe 203.

  As described above, the supercritical fluid 121 acts, so that the resist pattern that remains on the substrate 101 without being dissolved in the normal temperature and normal pressure state is dissolved in the supercritical fluid 121, and the resist pattern is formed from the surface of the substrate 101. Is removed. In addition, since the supercritical fluid 121 easily penetrates into the fine pattern gaps made of the low dielectric constant material, the resist pattern portion that has entered the gaps of the pattern is also dissolved in the supercritical fluid 121. In addition, since the resist dissolution rate is improved by heating to about 200 ° C., effective cleaning can be performed. On the other hand, a pattern made of a low dielectric constant material does not dissolve in the supercritical fluid 121. Furthermore, when these materials are used in a supercritical state, the cleaning surface can be fluorinated. Since the cleaning surface is fluorinated, not only cleaning in the micropores but also removal of water by high-temperature treatment and further water re-adsorption by fluorination can be prevented. These are suitable for device characteristic stability.

Thereafter, the back pressure valve 109 is gradually opened to discharge the supercritical fluid 121 inside the container lower part 102 (high pressure container) to the outside, and the pressure inside the container lower part 102 is lowered, as shown in FIG. Thus, the inside of the container lower part 102 which is sealed and heated to about 200 to 250 ° C. is filled with the gas 122. As a result, the resist pattern is removed and dried in the region of the substrate 101 where the pattern made of the low dielectric constant material is formed. According to this supercritical processing method, a supercritical fluid in which a fluorine compound mixed liquid in which HCF ₂ CF ₂ OCH ₂ CF ₃ (fluorine compound) and ethyl lactate (solvent) are mixed is brought into a supercritical state is used. Therefore, the resist which is an organic substance can be dissolved more rapidly, and the processing can be performed in a shorter time than in the past. In this drying process, a gas-liquid interface is not formed in a pattern portion made of a low dielectric constant material, and occurrence of pattern abnormality due to the surface tension of the liquid is suppressed.

  Next, the fluorine compound mixed liquid used for the supercritical processing described above will be described. First, the fluorine compound constituting the fluorine compound mixed liquid will be described. First, a fluorine compound suitable for supercritical cleaning is required to be liquid at room temperature and pressure. The critical point should be 250 ° C. or lower. When a temperature exceeding 250 ° C. is required, there may be a case where a material for applying the hermetic seal material constituting the high-pressure vessel is reduced. Furthermore, it is better that the material is hard to burn, and it is preferable that the resist and the like are easily dissolved, and the environmental impact is low. As materials that satisfy these requirements, there are hydrofluoroethers and hydrofluoroesters.

Among these, hydrofluoroether is more suitable from the viewpoint of safety. Examples of the hydrofluoroether include CF ₃ CF ₂ CH ₂ OCHF ₂ , CF ₃ CF ₂ OCH ₂ CF ₃ , C ₃ F ₇ OCH ₃ , CHF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₃ , CF ₃ CHFOCHF ₂ , CF ₃ CHFCF ₂ CH ₂ OCHF ₂ , CF ₃ CHFCF ₂ OCH ₂ CF ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₂ CHF _2, etc. C _x F _y H _m O or C _{(x- 1)} Those having a structure of F _y H _m C ₁ O (x, y, m are natural numbers) are applicable. Furthermore, among these, the case where the most terminal group is not —CH ₃ is superior from the viewpoint of flame retardancy.

Considering availability, etc., the following fluorine compounds are particularly preferable. First, there is HCF ₂ CF ₂ OCH ₂ CF ₃ . This becomes a supercritical state at 180 ° C. and 3.7 MPa. There is also CF ₃ CHFCF ₂ OCH ₂ CF ₃ . This becomes a supercritical state at 200 ° C. and 2.4 MPa. There is also CF ₃ CHFCF ₂ OCH ₂ CF ₂ CF ₃ . This becomes a supercritical state at 210 ° C. and 2.5 MPa. As the hydrofluoroether _{ester, CHF 2 COOCH 2 CH 3,} (CF 3) 2 CHCOOCH 3 C x F y H m O 2 or C _(x-1), such as _{F y H m C 1 O 2} (x, Any structure having a structure of y and m being natural numbers) can be applied.

Next, the solvent constituting the fluorine compound mixed liquid will be described. First, the solvent dissolves organic substances such as a resist. In addition, the solvent is preferably mixed with the fluorine compound at a ratio that makes an azeotrope (lowest boiling azeotrope). If it becomes an azeotropic mixture, it will evaporate with a fixed boiling point, maintaining this ratio, and it will be very easy to collect and reuse (recycle) by distillation. For example, HCF ₂ CF ₂ OCH ₂ CF ₃ becomes an azeotrope with a mixing ratio of ethanol of 5.5%. Furthermore, in order to obtain a high effect by removing the resist and washing it by mixing, it is preferable to use a solvent for dissolving the resist, in which the resist is more easily dissolved. These are polar solvents.

  Currently, resists used in many semiconductor manufacturing processes are organic substances based on acrylate or polyhydroxystyrene, and the solvent is composed of hydroxy acids that easily dissolve these organic substances (having hydroxyl and carboxyl groups in the molecule). What is done is suitable. In addition, an esterified carboxylic acid is also suitable as the solvent. Moreover, what used the hydroxyl group as ether may be used. For example, ethyl lactate is a typical example as a solvent constituting the fluorine compound mixed liquid. Or the ether compound of a polyhydric alcohol is also applicable. For example, ethylene glycol monoethyl ether or an acetate thereof, propylene glycol monomethyl ether or an acetate thereof are examples of polyhydric alcohol ether compounds. Polyesters of polyvalent carboxylic acids can also be used as the solvent.

  By mixing these solvents and the fluorine compound in an arbitrary amount, a state in which the resist is more dissolved can be obtained. The mixing ratio is preferably an amount that forms an azeotrope as described above, and varies depending on the substance, but the mixing ratio may be in the range of about 5-10%.

Next, another embodiment using a fluorine compound mixed liquid will be described. First, for example, a low dielectric constant film made of low dielectric constant material HSQ (hydrogen silsesquioxane) is formed on a substrate made of single crystal silicon, and an ArF resist film is formed thereon, for example. The resist pattern having a width of about 90 nm is formed by known photolithography. Next, using the formed resist pattern as a mask, the low dielectric constant film is processed by dry etching using plasma of a mixed gas of CHF ₃ and argon, and a pattern made of a low dielectric constant material is formed on the silicon substrate. State.

Once the pattern is formed as described above, the substrate is immersed in the cleaning liquid stored in the high-pressure vessel. Here, the cleaning liquid is composed of a fluorine compound mixed liquid in which CF ₃ CHFCF ₂ OCH ₂ CF ₃ (fluorine compound) and propylene glycol monomethyl ether acetate (solvent) are mixed. At this time, the supply of the fluorine compound mixed liquid may be added so that the cleaning liquid overflows in the high-pressure vessel and the substrate is cleaned. By this cleaning, components dissolved in the cleaning liquid can be removed (cleaned) from the substrate at normal temperature (about 25 ° C.) and normal pressure (about atmospheric pressure). For example, a part of the resist pattern formed on the substrate is dissolved in the cleaning liquid, and a part remains on the substrate. On the other hand, a pattern made of a low dielectric constant material does not dissolve in the cleaning liquid. Furthermore, when these materials are used in a supercritical state, the cleaning surface can be fluorinated. Since the cleaning surface is fluorinated, not only cleaning in the micropores but also removal of water by high-temperature treatment and further water re-adsorption by fluorination can be prevented. These are suitable for device characteristic stability.

Next, the inside of the high-pressure vessel is sealed, and the cleaning liquid accommodated in the high-pressure vessel is heated to, for example, about 220 ° C. by a heating unit (not shown). In addition, by adjusting the back pressure valve of the high-pressure vessel, the inside of the sealed high-pressure vessel is set to about 3 MPa. As a result, the inside of the sealed high-pressure vessel is filled with a supercritical fluid composed of CF ₃ CHFCF ₂ OCH ₂ CF ₃ and propylene glycol monomethyl ether acetate in a supercritical state, and the substrate is immersed in the supercritical fluid. It will be in the state.

  In this way, the supercritical fluid acts, so that the resist pattern that remains on the substrate without being completely dissolved at room temperature and normal pressure is dissolved in the supercritical fluid, and the resist pattern is removed from the surface of the substrate. . In addition, since the supercritical fluid easily penetrates into the fine pattern gaps made of the low dielectric constant material, the resist pattern portion that has entered the gaps of the pattern is also dissolved in the supercritical fluid. In addition, since the resist dissolution rate is improved by heating to about 200 ° C., effective cleaning can be performed. On the other hand, a pattern made of a low dielectric constant material does not dissolve in the supercritical fluid. Furthermore, when these materials are used in a supercritical state, the cleaning surface can be fluorinated. Since the cleaning surface is fluorinated, not only cleaning in the micropores but also removal of water by high-temperature treatment and further water re-adsorption by fluorination can be prevented. These are suitable for device characteristic stability.

  Thereafter, the back pressure valve is gradually opened to discharge the supercritical fluid inside the high-pressure vessel to the outside, and the pressure inside the high-pressure vessel is reduced, so that the inside of the high-pressure vessel that is sealed and heated to about 220 ° C. Is filled with gas. As a result, the resist pattern is removed and dried in the region of the substrate where the pattern is formed. In this drying process, a gas-liquid interface is not formed in the pattern portion, and occurrence of pattern abnormality due to the surface tension of the liquid is suppressed.

  Further, as described below, supercritical processing may be performed efficiently by using a fluorine compound mixed liquid. First, for example, after an oxide film made of silicon oxide having a thickness of 300 nm is formed on a substrate made of single crystal silicon, a silicon layer made of polycrystalline silicon having a thickness of 600 nm is formed thereon. State. Next, the silicon layer is finely processed by a known photolithography technique and etching technique to form a silicon pattern made of polycrystalline silicon. Next, after removing the resist pattern used for forming the silicon pattern, the silicon pattern is used as a mask, and the oxide film is etched using a hydrofluoric acid aqueous solution so that the beam structure is formed by the silicon oxide pattern and the silicon pattern. .

When the beam structure is formed as described above, the substrate is washed with water and subsequently immersed in a cleaning liquid contained in a high-pressure vessel. Here, the cleaning liquid is composed of a fluorine compound mixed liquid in which HCF ₂ CF ₂ OCH ₂ CF ₃ and ethyl lactate are mixed. At this time, by setting the substrate to vibrate, the water adhering to the surface of the substrate is replaced with the fluorine compound mixed liquid. At this time, if the supply of the fluorine compound mixed liquid is added and the cleaning liquid overflows in the high-pressure vessel, the water separated from the substrate can be discharged from the upper part of the vessel.

Next, the inside of the high-pressure vessel is sealed, and the cleaning liquid accommodated in the inside of the high-pressure vessel by the heating means is heated to about 220 ° C., for example. In addition, by adjusting the back pressure valve of the high-pressure vessel, the inside of the sealed high-pressure vessel is set to about 3 MPa. As a result, the inside of the sealed high-pressure vessel is filled with a supercritical fluid consisting of HCF ₂ CF ₂ OCH ₂ CF ₃ and ethyl lactate in a supercritical state, and the substrate is immersed in the supercritical fluid. It becomes.

  Immediately after this, the back pressure valve is gradually opened to discharge the supercritical fluid inside the high-pressure vessel to the outside, and the pressure inside the high-pressure vessel is reduced, so that the high-pressure vessel that is sealed and heated to about 220 ° C. The inside is filled with gas. As a result, the fine beam structure is dried in the region of the substrate on which the pattern is formed. Further, in this drying process, a gas-liquid interface is not formed in a portion of the fine beam structure, and the occurrence of abnormality in the beam structure due to the surface tension of the liquid is suppressed.

Next, another embodiment of the present invention will be described with reference to FIG. Below, the supercritical processing method using the fluorine compound which shows the higher solubility with respect to a resist is demonstrated. First, a low dielectric constant film made of a low dielectric constant material HSQ (hydrogen silsesquioxane) is formed on a substrate 101 made of, for example, single crystal silicon, and an ArF resist film, for example, is formed thereon. And a resist pattern having a width of about 90 nm is formed by known photolithography. Next, using the formed resist pattern as a mask, the low dielectric constant film is processed by dry etching using a plasma of a mixed gas of CHF ₃ and argon to form a pattern made of a low dielectric constant material on the silicon substrate 101. It is assumed that

When the pattern is formed as described above, the substrate 101 is held by the substrate holding portion 104 provided on the lid 103 of the container lower portion 102 as shown in FIG. Next, a fluorine compound liquid made of CF ₃ CF ₂ CH (OH) OCHF ₂ accommodated in the chemical solution introduction tank 105 is supplied into the container lower part 102 through the pipe 106, and the cleaning liquid 120 is placed inside the container lower part 102. It is assumed that it is contained. A valve 107 is provided in the middle of the pipe 106. The container lower part 102 is provided with a discharge pipe 108, and the discharge pipe 108 is provided with a back pressure valve 109. In addition, the container lower part 102 is disposed inside a liquid discharge container 110 that stores the liquid overflowing from the container lower part 102. The liquid discharge container 110 discharges the waste liquid stored from the discharge unit 111.

  Next, as shown in FIG. 1B, the substrate 101 held by the substrate holding unit 104 with the lid 103 approaching the container lower part 102 side is immersed in the cleaning liquid 120 accommodated in the container lower part 102. State. At this time, the supply of the fluorine compound liquid from the chemical solution introduction tank 105 may be added so that the cleaning liquid 120 overflows in the container lower part 102 and the substrate 101 may be cleaned. By this cleaning, components dissolved in the cleaning liquid 120 can be removed (cleaned) from the substrate 101 at a normal temperature (about 25 ° C.) and a normal pressure (about atmospheric pressure). For example, a part of the resist pattern formed on the substrate 101 is dissolved in the cleaning liquid 120 and a part remains on the substrate 101. On the other hand, a pattern made of a low dielectric constant material is not dissolved in the cleaning liquid 120.

Next, the lid 103 is brought into close contact with the container lower part 102 and the valve 107 is closed, whereby the inside of the container lower part 102 is sealed to form a high-pressure container. The cleaning liquid 120 accommodated in the inside is heated to about 200 to 250 ° C., for example. In addition, the back pressure valve 109 is adjusted so that the inside of the sealed container lower part 102 is about 3 MPa. As a result, as shown in FIG. 1C, the inside of the sealed container lower part 102 is filled with a supercritical fluid 121 made of CF ₃ CF ₂ CH (OH) OCHF _{2 in} a supercritical state, The substrate 101 is immersed in the supercritical fluid 121.

  As described above, the supercritical fluid 121 acts, so that the resist pattern that remains on the substrate 101 without being dissolved in the normal temperature and normal pressure state is dissolved in the supercritical fluid 121, and the resist pattern is formed from the surface of the substrate 101. Is removed. In addition, since the supercritical fluid 121 easily penetrates into the fine pattern gaps made of the low dielectric constant material, the resist pattern portion that has entered the gaps of the pattern is also dissolved in the supercritical fluid 121. In addition, since the resist dissolution rate is improved by heating to about 200 ° C., effective cleaning can be performed. On the other hand, a pattern made of a low dielectric constant material does not dissolve in the supercritical fluid 121. Furthermore, when these materials are used in a supercritical state, the cleaning surface can be fluorinated. Since the cleaning surface is fluorinated, not only cleaning in the micropores but also removal of water by high-temperature treatment and further water re-adsorption by fluorination can be prevented. These are suitable for device characteristic stability.

Thereafter, the back pressure valve 109 is gradually opened to discharge the supercritical fluid 121 inside the container lower part 102 (high pressure container) to the outside, and the pressure inside the container lower part 102 is lowered, as shown in FIG. Thus, the inside of the container lower part 102 which is sealed and heated to about 200 to 250 ° C. is filled with the gas 122. As a result, the resist pattern is removed and dried in the region of the substrate 101 where the pattern made of the low dielectric constant material is formed. According to this supercritical processing method, a supercritical fluid is used in which a fluorine compound liquid composed of CF ₃ CF ₂ CH (OH) OCHF ₂ that exhibits high solubility in organic substances such as resist is in a supercritical state. Therefore, the resist which is an organic substance can be dissolved more rapidly, and the processing can be performed in a shorter time than in the past. In this drying process, a gas-liquid interface is not formed in a pattern portion made of a low dielectric constant material, and occurrence of pattern abnormality due to the surface tension of the liquid is suppressed.

Next, the fluorine compound liquid used for the supercritical processing described above will be described. The fluorine compound suitable for the supercritical cleaning described above is first required to be liquid at normal temperature and normal pressure. The critical point should be 250 ° C. or lower. When a temperature exceeding 250 ° C. is required, there may be a case where a material for applying the hermetic seal material constituting the high-pressure vessel is reduced. Furthermore, it is better to use a material that does not easily burn, and like the fluorine compound mixed liquid described above, it is a material in which a resist or the like is easily dissolved, and preferably has a low environmental impact. As a material satisfying these _{requirements, C (x-1) F} y H m C 1 O (OR), C (x-1) F y H m C 1 OO (OR), or C _x F _y H _m fluorine compounds of the structure of O _n (OR) is. Note that x, y, m, and n are natural numbers.

For example, CF ₃ CF ₂ CH (OR) OCHF ₂ , CF ₃ CF ₂ OCH (OR) CF ₃ , CHF ₂ CF ₂ OCH (OR) CF ₃ , CF ₃ CHFCF ₂ OCH (OR) CF ₃ , CF ₃ C ( OR) FOCHCF ₂ , CF ₃ CHFCF ₂ OCH (OR) CF ₂ CF ₃ , CHF ₂ COOCH (OR) CF ₃ , and (CF ₃ ) ₂ CHCOOCF (OR) ₂ can be used as the above-mentioned fluorine compound. . R is H, CHF ₂ , CF ₃ or the like. These can be said to be fluorinated hydroxy acids or their ester compounds, or ether compounds of fluorinated hydroxy acids. Since these fluorine compounds are more polar than the fluorine compounds described above, a good cleaning effect can be obtained even when used alone.

  In any of the above-described supercritical processing methods, not only cleaning such as resist removal, but also supercritical drying such as drying in a state in which the fine pattern after the water cleaning processing is suppressed is suppressed. Is possible. When a substrate on which a fine pattern is formed is dried after a liquid treatment such as water, pattern abnormalities such as the pattern sticking to other parts occur due to the surface tension generated by the gas-liquid interface formed in the pattern part. To do. According to the drying using a supercritical fluid having no surface tension, the above-described pattern abnormality can be suppressed. In particular, since a fluorine compound is easily miscible with water, it is suitable for replacing water adhering to the pattern after treatment with water.

  Next, a heating mechanism for bringing the fluorine compound inside the high-pressure vessel into a supercritical state will be described. First, in order to quickly increase the temperature inside the high-pressure vessel, for example, induction heating known as “IH heater” may be used. In induction heating, a phenomenon in which a heating plate is heated by applying a high-frequency AC electric field of several MHz to several tens of MHz to the heating plate and causing an induction current to flow through the heating plate is used. If the heating plate contains a paramagnetic metal, a state in which the heating plate is instantaneously heated to about 200 ° C. can be obtained by the induction heating.

  Therefore, for example, as shown in FIG. 3, the heating plate 301 made of paramagnetic metal that can move in the direction of the substrate 101 placed from the lid 103 and the bottom of the container lower part 102 can move in the direction of the lid 103. The inside of the container lower part 102 is heated by a heating plate 302 made of a paramagnetic metal, an induction heating part 303 built in the lid 103, and an induction heating part 304 built in the bottom of the container lower part 102. Also good. The heating plate 301 is moved by the moving mechanism 305, and the heating plate 302 is moved by the moving mechanism 306. At the time of heating, for example, as shown in FIG. 3B, the heating plate 301 is moved in the direction of the bottom of the container lower part 102, and the heating plate 302 is moved in the direction of the lid 103. A state is obtained in which the heating plate 301 is arranged close to the placed substrate 101.

  In such a state, the induction heating unit 303 and the induction heating unit 204 are operated so that the heating plate 301 and the heating plate 302 are heated, so that the fluorine compound liquid or the fluorine compound mixed liquid in the vicinity of the substrate 101 is removed. It becomes possible to heat efficiently. Further, since the heating plate 301 and the heating plate 302 are separated from the lid 103 and the container lower part 102, there is almost no loss due to heat conduction to the container side, and a high temperature state of about 200 ° C. is in a stable state. Can be maintained.

On the other hand, at the stage where the processing is finished and heating is not necessary, as shown in FIG. 3A, the thin heating plate 301 and the heating plate 302 are in contact with the lid 103 and the container lower part 102, and the Peltier element or the like. The temperature of the heating plate 301 and the heating plate 302 can be quickly lowered by cooling the lid 103 and the container lower portion 102 by the cooling mechanism 307 using the. The lid 103 and the container lower part 102 may be cooled by circulating a refrigerant.
Although it may be in this state, it may be slightly separated from the container wall during heating (FIG. 2 (b)), and one may be brought into close contact with the cooled container wall during cooling.

  Further, as shown in FIG. 4, a box-shaped heating container 401 made of a paramagnetic metal and having an open upper part is used, and the heating container 401 is heated by the induction heating unit 402, whereby the container lower part 102 (high-pressure container). You may make it heat the inside. For example, a fluorine compound liquid or a fluorine compound mixed liquid is accommodated in the heating container 401, and the substrate 101 is immersed therein. In this state, as shown in FIG. 4B, the heating plate 301 is moved toward the bottom of the container lower part 102, the heating plate 301 is heated by the induction heating unit 303, and the heating vessel 401 is heated by the induction heating unit 402. If it is in a heated state, the contained fluorine compound liquid or fluorine compound mixed liquid can be heated more quickly. In addition, the heated state can be held more stably. Also in this case, as shown in FIG. 4A, the heating plate 301 is in contact with the lid 103 so that the cooling is easy. In the case of the configuration shown in FIG. 4, if the lid 103 is opened and the heating container 401 is carried out, the substrate 101 placed on the heating container 401 can be cooled more quickly.

  Further, as shown in FIG. 5, a recess 103 a is provided on the outer surface of the lid 103, and the inside of the container lower part 102 is heated by heating the lid 103 using a resistance heating unit 501 fitted into the recess 103 a. It may be. In this case, when heating the inside of the container lower part 102, the resistance heating part 501 is moved using the moving mechanism 502, and the resistance heating part 501 is fitted in the recess 103a as shown in FIG. 6B. And it is sufficient. In addition, the resistance heating unit 501 is moved using the moving mechanism 502 and the resistance heating unit 501 is separated from the lid 103 as shown in FIG. If the cooling mechanism 307 is operated in this state, the inside of the container lower part 102 can be rapidly cooled.

  Moreover, as shown in FIG. 6, you may make it provide the resistance heating part 601 which provides the recessed part 102a in the outer bottom face of the container lower part 102, and fits into the recessed part 102a. The resistance heating unit 601 can be controlled to be in a state of being fitted into the recess 102 a and a state of being separated from the container lower part 102 by being moved by the moving mechanism 602. Even in this case, heating and cooling of the inside of the container lower part 102 can be performed quickly by performing the same as described above.

Hereinafter, a supercritical processing method using the supercritical processing apparatus shown in FIG. 4 will be described with reference to the process diagram of FIG. In this method, unlike the method described with reference to FIG. 1, the substrate is transported together with the holder. First, as shown in FIG. 7A ′, the substrate 101 to be processed is placed inside the heating container 401 while the heating container 401 is placed on the cooling table 701 and cooled. State. The cooling table 701 is cooled to, for example, a room temperature (for example, 20 ° C.) by being cooled by a circulating refrigerant (water) or the like.
Next, as shown in FIG. 7A, the heating container 401 on which the substrate 101 is placed is placed inside the container lower part 102, and the heating container 401 is mixed with a fluorine compound liquid or a fluorine compound mixture. The liquid 711 is introduced, and the substrate 101 is immersed in these. At this time, the lid 103 is cooled to about room temperature by the cooling mechanism 307.

  Thereafter, as shown in FIG. 7B, the inside of the container lower part 102 is sealed with the lid 103, and the moving mechanism 305 is operated to move the heating plate 301 in the direction of the substrate 101. Note that the moving mechanism 305 is composed of, for example, a drive motor. Further, the pressure adjustment valve 703 of the discharge pipe 702 is closed. In this state, the operation of the cooling mechanism 307 is stopped, and the induction heating unit 303 and the induction heating unit 402 are operated, and the heating plate 301 and the heating container 401 are heated. When the heating plate 301 and the heating container 401 rise to a predetermined temperature, the fluorine compound liquid or fluorine compound mixed liquid accommodated therein is vaporized, and the internal pressure rises. As a result, the internal pressure exceeds the critical point. Then, the contained fluorine compound liquid or fluorine compound mixed liquid becomes a supercritical state.

  Accordingly, the inside of the container lower part 102 is filled with the supercritical fluid 712. At this time, if necessary, the internal pressure of the container lower part 102 may be controlled by opening / closing control of the pressure regulating valve 703. Further, depending on the amount of liquid to be introduced, a predetermined pressure may be obtained only by heating control. By doing so, the substrate 101 can be treated with the supercritical fluid 712 of the fluorine compound liquid or the fluorine compound mixed liquid.

  Next, when the pressure adjustment valve 703 is opened to discharge the fluid inside the container lower part 102 to the outside, and the internal pressure is lowered, as shown in FIG. 713 is filled. Thereafter, after the inside of the container lower part 102 is brought to about atmospheric pressure, the heating plate 301 is raised in the direction of the lid 103, the operation of the induction heating unit 303 is stopped, and the lid 103 is cooled to about room temperature by the cooling mechanism 307. In addition, the heating plate 301 is cooled and the lid 103 is opened. Next, the heating container 401 is unloaded from the container lower part 102 and is placed on the cooling table 701 as shown in FIG. 7A ′, and the substrate 101 is cooled together with the heating container 401. And Thereafter, if the substrate 101 placed on the heating container 401 is replaced with a new processing target and the above-described steps are repeated, continuous processing can be performed.

It is process drawing for demonstrating the supercritical processing method in embodiment of this invention. It is a block diagram which shows the example of a partial structure of the apparatus which performs the supercritical process shown in FIG. It is a block diagram which shows schematically a part of structural example of the supercritical processing apparatus which performs the supercritical processing shown in FIG. It is a block diagram which shows schematically a part of structural example of the supercritical processing apparatus which performs the supercritical processing shown in FIG. It is a block diagram which shows schematically a part of structural example of the supercritical processing apparatus which performs the supercritical processing shown in FIG. It is a block diagram which shows schematically a part of structural example of the supercritical processing apparatus which performs the supercritical processing shown in FIG. It is process drawing for demonstrating an example of the supercritical processing method using the supercritical processing apparatus shown in FIG. It is a block diagram which shows a partial structure of the conventional supercritical processing apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 ... Board | substrate, 102 ... Container lower part, 102a ... Recessed part, 103 ... Cover, 103a ... Recessed part, 104 ... Substrate holding part, 105 ... Chemical solution introduction tank, 106 ... Pipe, 107 ... Valve, 108 ... Drain pipe, 109 ... Back Pressure valve, 110 ... Liquid discharge container, 111 ... Discharge part, 120 ... Cleaning liquid, 121 ... Supercritical fluid, 122 ... Gas, 201 ... Circulation pump, 202, 203 ... Piping, 301, 302 ... Heating plate, 303, 304 ... Induction Heating unit, 305, 306 ... moving mechanism, 307 ... cooling mechanism, 401 ... heating container, 402 ... induction heating unit, 501 ... resistance heating unit, 502 ... moving mechanism, 601 ... resistance heating unit, 602 ... moving mechanism.

Claims (14)

A first step of placing the substrate inside the high-pressure vessel;
A mixed solution composed of a fluorine compound and a solvent that dissolves an organic substance is accommodated in the inside of the high-pressure vessel and heated, and the inside of the high-pressure vessel is filled with the supercritical fluid by the fluorine compound and the solvent in a supercritical state. A second step to achieve the state,
And a third step of reducing the internal pressure of the high-pressure vessel to bring the supercritical fluid into a vaporized state. The supercritical processing method according to claim 1,
The supercritical processing method, wherein the fluorine compound is composed of at least one of hydrofluoroether and hydrofluoroester. The supercritical processing method according to claim 2,
The hydrofluoroether is at least one of HCF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₃ , and CF ₃ CHFCF ₂ OCH ₂ CF ₂ CF _3. Processing method. In the supercritical processing method according to any one of claims 1 to 3,
The supercritical processing method, wherein the solvent has polarity. In the supercritical processing method according to claim 4,
The solvent is at least one of an ether compound of a polyhydric alcohol and an ester compound of a polyvalent carboxylic acid. In the supercritical processing method according to claim 4,
The solvent is at least one of hydroxy acid, ester of hydroxy acid, and ether compound of hydroxy acid. The supercritical processing method according to claim 6, wherein
The supercritical processing method, wherein the solvent is ethyl lactate. In the supercritical processing method of any one of Claims 1-7,
The supercritical processing method, wherein the fluorine compound and the solvent have an azeotropic composition ratio. A first step of placing the substrate inside the high-pressure vessel;
A second step in which a mixed solution composed of a fluorine compound is accommodated in the inside of the high-pressure vessel and heated so that the inside of the high-pressure vessel is filled with a supercritical fluid of the fluorine compound in a supercritical state; ,
And at least a third step of reducing the internal pressure of the high-pressure vessel to bring the supercritical fluid into a vaporized state.
The supercritical processing method, wherein the fluorine compound is composed of at least one of a fluorinated hydroxy acid, an ester compound of fluorinated hydroxy acid, and an ether compound of fluorinated hydroxy acid. A high-pressure container comprising a lower part of a container provided with an open part on one side and a lid for sealing the open part of the lower part of the container, on which a substrate to be processed is placed;
A supply means for supplying a mixed solution comprising a fluorine compound and a solvent for dissolving the organic substance into the high-pressure vessel;
A heating plate arranged inside the high-pressure vessel and made of paramagnetic metal;
Induction heating means for applying a high-frequency alternating electric field to the heating plate to heat the heating plate by induction heating;
And at least discharge means for discharging the fluid inside the high-pressure vessel to the outside,
The mixed solution supplied to the inside of the high-pressure vessel is heated by the heating plate, and the inside of the high-pressure vessel is filled with the supercritical fluid of the fluorine compound and the solvent that are in a supercritical state. Supercritical processing equipment characterized by The supercritical processing apparatus according to claim 10, wherein
A supercritical processing apparatus comprising: a moving mechanism that moves the heating plate from the lid toward a bottom portion of the lower part of the container facing the lid. In the supercritical processing apparatus according to claim 10 or 11,
The supercritical processing apparatus, wherein the substrate is placed on the heating plate. A high-pressure container comprising a lower part of a container provided with an open part on one side and a lid for sealing the open part of the lower part of the container, on which a substrate to be processed is placed;
A supply means for supplying a mixed solution comprising a fluorine compound and a solvent for dissolving the organic substance into the high-pressure vessel;
A heating section for heating the high-pressure vessel;
And at least discharge means for discharging the fluid inside the high-pressure vessel to the outside,
The heating unit is provided with a concave portion in which the high-pressure vessel can fit the heating unit,
The fluorine compound in which the high pressure vessel is heated by fitting the heating portion into the recess, the mixed solution supplied to the inside of the high pressure vessel is heated, and the inside of the high pressure vessel is in a supercritical state. And a supercritical processing apparatus filled with a supercritical fluid of the solvent. In the supercritical processing apparatus according to any one of claims 10 to 13,
A supercritical processing apparatus comprising a cooling mechanism for cooling the high-pressure vessel.

Images