JP2020170808A - Processing liquid generation device, substrate processing device, processing liquid generation method and substrate processing method - Google Patents

Abstract

To easily generate the processing liquid for liquid processing of a substrate.SOLUTION: A processing liquid generating device 7 is a device that generates the processing liquid used in a substrate processing device which performs liquid on a substrate. The processing liquid generating device 7 includes: a sublimation part 71; a processing liquid generation part 72; and a gas supply passage 73. The sublimation part 71 sublimates a solid raw material 81 containing a solid solute (e.g., camphor) to produce raw material gas. The processing liquid generating part 72 dissolves the raw material gas into a solvent (e.g., IPA) to generate the processing liquid. The gas supply passage 73 guides the raw material gas from the sublimation part 71 to the processing liquid generating part 72. As a result, the processing liquid for liquid processing of the substrate can be easily generated.SELECTED DRAWING: Figure 4

Description

The present invention relates to a technique for producing a treatment liquid and a technique for performing liquid treatment of a substrate using the treatment liquid.

Conventionally, in the manufacturing process of a semiconductor substrate (hereinafter, simply referred to as "substrate"), various treatments are applied to the substrate. For example, an etching process is performed in which an etching solution is supplied to a bevel portion of a substrate on which a film is formed on the surface to remove the film on the bevel portion. Further, Patent Document 1 discloses an apparatus for forming a film on a substrate by chemical vapor deposition (CVD). In the apparatus, the raw material gas used for CVD is generated by liquefying a raw material in a solid state at room temperature, mixing it with an organic solvent, and heating the mixed solution.

On the other hand, Patent Document 2 discloses a method for purifying an organic compound used in an electronic device. In this method, a sample containing an organic compound in a solid state at room temperature is heated and sublimated, the obtained gas is dissolved in an ionic liquid, and the organic compound is precipitated in the ionic liquid. Further, Patent Documents 3 and 4 disclose a technique for heating and sublimating a solid substance to be treated inside a sublimation purification tube and recovering a coagulated component on the inner wall surface of the sublimation purification tube as a sublimation purification substance. Has been done.

Japanese Unexamined Patent Publication No. 11-11706 JP-A-2018-150246 Japanese Unexamined Patent Publication No. 2014-61465 JP-A-2014-176839

By the way, when the treatment liquid is supplied onto the substrate to perform the liquid treatment of the substrate, the raw material may be dissolved in a solvent to generate the treatment liquid. In this case, it is necessary to treat impurities in the raw material, which may complicate the production of the treatment liquid.

The present invention has been made in view of the above problems, and an object of the present invention is to easily generate a treatment liquid for liquid treatment of a substrate.

The invention according to claim 1 is a processing liquid generating apparatus for producing a processing liquid used in a substrate processing apparatus for treating a substrate, and sublimates a solid raw material containing a solid solute to provide a raw material gas. It is provided with a sublimation unit for generating the raw material gas, a processing liquid generating unit for generating the processing liquid by dissolving the raw material gas in a solvent, and a gas supply flow path for guiding the raw material gas from the sublimation unit to the processing liquid generating unit. ..

The invention according to claim 2 is the treatment liquid generating apparatus according to claim 1, wherein the solid raw material further contains a low sublimation temperature impurity having a sublimation point lower than that of the solute, and the sublimation portion is said. Low sublimation point The first sublimation part that sublimates the solid raw material at a temperature higher than the sublimation point of the impurity and lower than the sublimation point of the solute, and the solid raw material after the sublimation treatment in the first sublimation part. It includes a second sublimation section that generates the raw material gas by sublimating at a temperature higher than the sublimation point of the solute.

The invention according to claim 3 is the treatment liquid generating apparatus according to claim 1, wherein the solid raw material further contains a low sublimation point impurity having a sublimation point lower than that of the solute, and the sublimation part is said. The solute is coagulated by setting the temperature of the first sublimation section, which sublimates the solid raw material to generate an intermediate gas, and the temperature of the intermediate gas between the sublimation point of the low sublimation point impurity and the sublimation point of the solute. It includes a coagulation part to be flowered and a second sublimation part to generate the raw material gas by sublimating the coagulant obtained in the coagulation part.

The invention according to claim 4 is the treatment liquid generating apparatus according to any one of claims 1 to 3, wherein the solid raw material further contains a high sublimation point impurity having a higher sublimation point than the solute. In the sublimation section, the solid raw material is sublimated at a temperature higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity.

The invention according to claim 5 is the treatment liquid generating apparatus according to any one of claims 1 to 4, wherein the temperature of the gas supply flow path is maintained at a temperature higher than the sublimation point of the solute. Further provided with a heat insulating part.

The invention according to claim 6 is the treatment liquid generating apparatus according to any one of claims 1 to 5, wherein the concentration of the solute in the gas flowing through the gas supply flow path or the solvent is used. A concentration sensor for measuring the concentration of the dissolved solute and a sublimation control unit for controlling the sublimation rate of the solid raw material in the sublimation unit based on the measurement result of the concentration sensor are further provided.

The invention according to claim 7 is the treatment liquid generating apparatus according to any one of claims 1 to 6, wherein the weight sensor for measuring the weight of the solid raw material in the sublimation portion and the weight sensor. Further provided is a sublimation control unit that controls the sublimation rate of the solid raw material in the sublimation unit based on the measurement result.

The invention according to claim 8 is the treatment liquid generation apparatus according to any one of claims 1 to 7, wherein the treatment liquid generation unit is in a storage unit for storing the solvent and the storage unit. A raw material gas supply unit for supplying the raw material gas in nanobubbles to the stored solvent is provided.

The invention according to claim 9 is the treatment liquid generation apparatus according to any one of claims 1 to 8, wherein the treatment liquid generation unit uses the raw material gas supplied from the gas supply flow path. It includes a raw material solution generating unit that dissolves in a solvent to generate a raw material solution, and a diluting unit that dilutes the raw material solution generated in the raw material solution generating unit with the solvent to produce the treatment liquid.

The invention according to claim 10 is a substrate processing apparatus for treating a liquid on a substrate, wherein a pattern is formed in advance on the upper surface of the treatment liquid generating apparatus according to any one of claims 1 to 9. From the substrate holding portion that holds the substrate in a horizontal state, the processing liquid discharging portion that discharges the processing liquid generated by the processing liquid generator to the upper surface of the substrate, and the processing liquid on the upper surface of the substrate. By vaporizing the solvent, a film forming portion for embedding a solute in the gap of the pattern to form a solute film is provided.

The invention according to claim 11 is the substrate processing apparatus according to claim 10, based on a film thickness measuring unit for measuring the film thickness of the solute film and a measurement result by the film thickness measuring unit. Further provided is a film thickness control unit that controls the concentration of the solute in the treatment liquid or the discharge time of the treatment liquid from the treatment liquid discharge unit.

The invention according to claim 12 is a method for producing a treatment liquid used in the liquid treatment of a substrate, wherein a) a solid raw material containing a solid solute is sublimated to generate a raw material gas. It includes a step and b) a step of dissolving the raw material gas supplied through the gas supply flow path in a solvent to generate a treatment liquid.

The invention according to claim 13 is the treatment liquid producing method according to claim 12, wherein the solid raw material further contains a low sublimation point impurity having a sublimation point lower than that of the solute, and the step a) is described. c) The step of sublimating the solid raw material at a temperature higher than the sublimation point of the low sublimation temperature impurity and lower than the sublimation point of the solute, and d) the step of sublimating the solid raw material after the step c). It includes a step of generating the raw material gas by sublimating at a temperature higher than the sublimation point of the solute.

The invention according to claim 14 is the treatment liquid producing method according to claim 12, wherein the solid raw material further contains a low sublimation point impurity having a sublimation point lower than that of the solute, and the step a) is described. e) The step of sublimating the solid raw material to generate an intermediate gas, and f) The solute by setting the temperature of the intermediate gas to a temperature between the sublimation point of the low sublimation temperature impurity and the sublimation point of the solute. It is provided with a step of coagulating the above-mentioned raw material gas and a step of producing the raw material gas by sublimating the coagulated product obtained in the g) step f).

The invention according to claim 15 is the treatment liquid producing method according to any one of claims 12 to 14, wherein the solid raw material further contains a high sublimation temperature impurity having a sublimation point higher than that of the solute. In step a), the solid raw material is sublimated at a temperature higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity.

The invention according to claim 16 is the treatment liquid generation method according to any one of claims 12 to 15, wherein the temperature of the gas supply flow path is maintained higher than the sublimation point of the solute. To.

The invention according to claim 17 is the treatment liquid generation method according to any one of claims 12 to 16, wherein the concentration of the solute in the gas flowing through the gas supply flow path or the solvent is used. The sublimation rate of the solid raw material in the step a) is controlled based on the concentration of the dissolved solute.

The invention according to claim 18 is the treatment liquid generation method according to any one of claims 12 to 17, wherein the solid raw material is sublimated in the step a) based on the weight change of the solid raw material. The speed is controlled.

The invention according to claim 19 is the treatment liquid generation method according to any one of claims 12 to 18, wherein the raw material gas is added to the solvent stored in the storage unit in the step b). Convert and supply.

The invention according to claim 20 is the treatment liquid generation method according to any one of claims 12 to 19, wherein the b) step is h) the raw material gas is dissolved in the solvent to prepare the raw material solution. A step of producing the treatment liquid, and i) a step of diluting the raw material solution with the solvent to produce the treatment liquid.

The invention according to claim 21 is a substrate processing method for liquid-treating a substrate, in which j) a step of holding a substrate having a pattern formed on the upper surface in advance in a horizontal state, and k) claims 12 to 20. The step of discharging the treatment liquid generated by the treatment liquid generation method according to any one of the above to the upper surface of the substrate, and l) vaporizing the solvent from the treatment liquid on the upper surface of the substrate. A step of embedding a solute in the gap of the pattern to form a solute film is provided.

The invention according to claim 22 is the substrate processing method according to claim 21, wherein m) a step of measuring the film thickness of the solute film after the step l) and n) the step m). Based on the measurement result in, the step of controlling the concentration of the solute in the treatment liquid or the discharge time of the treatment liquid in the step k) is further provided.

In the present invention, a treatment liquid for liquid treatment of a substrate can be easily generated.

It is a side view which shows the structure of the substrate processing apparatus which concerns on 1st Embodiment. It is a block diagram which shows the processing liquid supply part and the gas supply part. It is a figure which shows an example of the processing flow of a substrate. It is a side view which shows the structure of the processing liquid generator. It is a figure which shows an example of the flow of production of a treatment liquid. It is a figure which shows an example of the flow of production of a treatment liquid. It is a figure which shows an example of the flow of production of a treatment liquid. It is a side view which shows the structure of the substrate processing apparatus. It is a figure which shows an example of the flow of production of a treatment liquid. It is a side view which shows the structure of the substrate processing apparatus which concerns on 2nd Embodiment. It is a figure which shows an example of the flow of production of a treatment liquid.

FIG. 1 is a side view showing the configuration of the substrate processing apparatus 1 according to the first embodiment of the present invention. The substrate processing apparatus 1 is a single-wafer processing apparatus that processes semiconductor substrates 9 (hereinafter, simply referred to as “substrates 9”) one by one. The substrate processing apparatus 1 supplies a processing liquid to the substrate 9 to perform liquid treatment on the substrate 9. In FIG. 1, a part of the configuration of the substrate processing apparatus 1 is shown in cross section.

The substrate processing device 1 includes a substrate holding unit 31, a substrate rotating mechanism 33, a cup unit 4, a processing liquid supply unit 5, a gas supply unit 6, and a housing 11. The substrate holding portion 31, the substrate rotating mechanism 33, the cup portion 4, and the like are housed in the internal space of the housing 11. In FIG. 1, the housing 11 is drawn in cross section. The canopy portion of the housing 11 is provided with an airflow forming portion 12 that supplies gas to the internal space to form an airflow (so-called downflow) that flows downward. As the airflow forming unit 12, for example, an FFU (fan filter unit) is used.

The substrate holding portion 31 faces the lower main surface (that is, the lower surface) of the horizontal substrate 9 and holds the substrate 9 from the lower side. The substrate holding portion 31 is, for example, a mechanical chuck that mechanically supports the substrate 9. The substrate holding portion 31 is rotatably provided about a central axis J1 that faces in the vertical direction. A pattern is formed in advance on the upper main surface of the substrate 9 (hereinafter, referred to as “upper surface 91”). The pattern is a structure that is a collection of a large number of fine structure elements, and is, for example, a circuit pattern used in a product.

The substrate holding portion 31 includes a holding portion main body and a plurality of chuck pins. The holding portion main body is a substantially disk-shaped member facing the lower surface of the substrate 9. The plurality of chuck pins are arranged at substantially equal angular intervals in the circumferential direction (hereinafter, also simply referred to as “circumferential direction”) about the central axis J1 at the peripheral edge of the holding portion main body. Each chuck pin projects upward from the upper surface of the holding portion main body and contacts the peripheral region and the side surface of the lower surface of the substrate 9 to support the substrate 9. The substrate holding portion 31 may be a vacuum chuck or the like that attracts and holds the central portion of the lower surface of the substrate 9.

The substrate rotation mechanism 33 is arranged below the substrate holding portion 31. The substrate rotation mechanism 33 rotates the substrate 9 together with the substrate holding portion 31 about the central axis J1. The substrate rotation mechanism 33 includes, for example, an electric rotary motor in which a rotation shaft is connected to a holding portion main body of the substrate holding portion 31. The substrate rotation mechanism 33 may have another structure such as a hollow motor.

The treatment liquid supply unit 5 individually supplies a plurality of types of treatment liquids to the substrate 9. The plurality of types of treatment solutions include, for example, a chemical solution, a rinsing solution, and a film-forming solution, which will be described later. The processing liquid supply unit 5 includes a first nozzle 51 and a second nozzle 52. The first nozzle 51 and the second nozzle 52 each discharge the processing liquid from above the substrate 9 toward the central portion of the upper surface 91 of the substrate 9. The first nozzle 51 and the second nozzle 52 are formed of, for example, a resin having high chemical resistance such as Teflon (registered trademark). The first nozzle 51 and the second nozzle 52 may each be a part of one common nozzle.

The cup portion 4 is an annular member centered on the central axis J1. The cup portion 4 is arranged over the entire circumference around the substrate 9 and the substrate holding portion 31 and covers the sides of the substrate 9 and the substrate holding portion 31. The cup portion 4 is a liquid receiving container that receives a liquid such as a processing liquid that scatters from the rotating substrate 9 toward the surroundings. The inner surface of the cup portion 4 is formed of, for example, a water repellent material. The cup portion 4 is stationary in the circumferential direction regardless of the rotation and rest of the substrate 9. The bottom of the cup portion 4 is provided with a drainage port (not shown) for discharging the treatment liquid or the like received by the cup portion 4 to the outside of the housing 11. The cup portion 4 can be moved in the vertical direction between a processing position, which is a position around the substrate 9 shown in FIG. 1, and a retracting position below the processing position, by an elevating mechanism (not shown).

Unlike the single-layer structure shown in FIG. 1, the cup portion 4 has a laminated structure in which a plurality of cups are laminated in the radial direction (hereinafter, simply referred to as “diameter direction”) about the central axis J1. May be good. When the cup portion 4 has a laminated structure, the plurality of cups can move independently in the vertical direction, and the plurality of cups are switched to receive the treatment liquid according to the type of the treatment liquid scattered from the substrate 9. Used for liquids.

The gas supply unit 6 supplies gas to the substrate 9. The gas supply unit 6 includes a third nozzle 63. The third nozzle 63 delivers gas from above the substrate 9 toward the central portion of the upper surface 91 of the substrate 9.

FIG. 2 is a block diagram showing a processing liquid supply unit 5 and a gas supply unit 6 of the substrate processing apparatus 1. FIG. 2 also shows configurations other than the treatment liquid supply unit 5 and the gas supply unit 6. The treatment liquid supply unit 5 includes a chemical solution supply unit 54, a rinse solution supply unit 55, and a film forming liquid supply unit 56.

The chemical solution supply unit 54 includes a first nozzle 51 and a chemical solution supply source 541. The first nozzle 51 is connected to the chemical solution supply source 541 via the pipe 542. The chemical solution delivered from the chemical solution supply source 541 is discharged from the first nozzle 51 toward the upper surface 91 of the substrate 9. Examples of the chemical solution include a mixed solution of hydrofluoric acid (HF) and nitric acid (HNO ₃ ), concentrated hydrofluoric acid, dilute hydrofluoric acid, ammonium hydroxide (NH ₄ OH), TMAH (tetramethylammonium hydroxide), SC1 ( That is, a mixed aqueous solution of ammonia (NH ₃ ) and nitric acid (H ₂ O ₂ )), SC2 (ie, a mixed aqueous solution of hydrogen chloride (HCl) and hydrogen fluoride), or FPM (ie, fluoride). A mixed aqueous solution of hydrogen and ammonia) is used. The chemical solution supply source 541 may be provided outside the substrate processing device 1.

The rinse liquid supply unit 55 includes a first nozzle 51 and a rinse liquid supply source 551. The first nozzle 51 is shared by the chemical solution supply unit 54 and the rinse solution supply unit 55. The first nozzle 51 is connected to the rinse liquid supply source 551 via the pipe 552. The rinse liquid sent out from the rinse liquid supply source 551 is discharged from the first nozzle 51 toward the upper surface 91 of the substrate 9. As the rinsing liquid, for example, an aqueous treatment liquid such as DIW (De-ionized Water), carbonated water, ozone water or hydrogen water is used. The rinse liquid supply source 551 may be provided outside the substrate processing apparatus 1.

The film forming liquid supply unit 56 includes a second nozzle 52 and a processing liquid generating device 7. The second nozzle 52 is connected to the processing liquid generator 7 via the pipe 562. The treatment liquid generating device 7 is a film forming liquid generating device that produces a film forming liquid used for treating the substrate 9. The film-forming liquid generated by the treatment liquid generator 7 is sent to the second nozzle 52, and is discharged from the second nozzle 52 toward the upper surface 91 of the substrate 9. The second nozzle 52 is a processing liquid discharging unit that discharges the film forming liquid, which is the processing liquid generated by the processing liquid generating device 7, to the upper surface 91 of the substrate 9.

The film-forming solution is a solution obtained by sublimating a solute, which is a solid sublimating substance, into a gas at normal temperature and pressure, and then dissolving the solution in a solvent. The structure of the treatment liquid generation device 7 and the formation of the film-forming liquid in the treatment liquid generation device 7 will be described later.

Examples of the solute include alcohols such as 2-methyl-2-propanol (also known as tert-butyl alcohol and t-butyl alcohol) or cyclohexanol, fluorinated hydrocarbon compounds, and 1,3,5-trioxane (also known as trioxane). : Metaformaldehyde), camphor (also known as camphor, camphor), naphthalene, or iodine is used. The solute may be a substance other than the above.

Examples of the solvent include pure water, IPA (isopropyl alcohol), methanol, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), and PGEE (propylene glycol monoethyl ether, also known as 1-ethoxy-. 2-propanol) or ethylene glycol is used. The solvent may be a substance other than the above.

The gas supply unit 6 includes a third nozzle 63 and a gas supply source 65. The third nozzle 63 is connected to the gas supply source 65 via the pipe 64. The third nozzle 63 is a gas discharge unit that discharges the gas delivered from the gas supply source 65 toward the upper surface 91 of the substrate 9. As the gas, for example, an inert gas such as nitrogen (N ₂ ) gas is used. The gas may be a gas other than the inert gas (for example, dry air). The gas supply source 65 may be provided outside the substrate processing device 1.

Next, the processing of the substrate 9 in the substrate processing apparatus 1 will be described with reference to FIG. FIG. 3 is a diagram showing an example of a processing flow of the substrate 9 in the substrate processing apparatus 1. The treatment of the substrate 9 in the substrate processing apparatus 1 is performed in the order of, for example, a chemical solution treatment, a rinsing treatment, a film forming treatment, and a drying treatment by removing the film.

Specifically, first, the substrate 9 on which the above-mentioned pattern is formed in advance on the upper surface 91 is held in a horizontal state by the substrate holding portion 31 (step S11). Subsequently, the rotation of the substrate 9 is started, and the chemical solution is supplied from the first nozzle 51 to the rotating substrate 9. Then, when the supply of the chemical solution is continued for a predetermined time, the chemical solution treatment (for example, the cleaning treatment with the cleaning liquid) is performed on the substrate 9 (step S12). The chemical solution supplied to the substrate 9 moves radially outward due to the centrifugal force of the rotating substrate, and scatters radially outward from the outer peripheral edge of the substrate 9. The chemical solution scattered from the substrate 9 is received by the cup portion 4 and discharged to the outside of the housing 11. The same applies to the treatment liquids (that is, the rinsing liquid and the film forming liquid) scattered from the substrate 9 in steps S13 to S15 described later.

When the chemical solution treatment is completed, the supply of the chemical solution is stopped, and the rinse solution is supplied from the first nozzle 51 to the rotating substrate 9. Then, the rinsing treatment for the substrate 9 is performed by continuing the supply of the rinsing liquid for a predetermined time (step S13). In the rinsing treatment, the chemical solution on the substrate 9 is washed away by the rinsing solution (for example, DIW) supplied from the first nozzle 51.

When the rinsing treatment is completed, the supply of the rinsing liquid is stopped, and the rotation speed of the substrate 9 is reduced. Then, the film-forming liquid is discharged from the second nozzle 52 toward the upper surface 91 of the substrate 9 rotating at a relatively low speed (step S14). As described above, the film-forming liquid is a solution produced by the treatment liquid generator 7. In the following, the solute and solvent of the membrane-forming solution will be described as camphor and IPA, respectively.

The film-forming liquid supplied onto the upper surface 91 of the rotating substrate 9 spreads radially outward from the central portion of the substrate 9 by centrifugal force, and removes the rinse liquid on the substrate 9 from the outer peripheral edge of the substrate 9. To reach. As a result, a liquid film of the film forming liquid is formed on the upper surface 91 of the substrate 9. The film-forming liquid is also filled in the gaps of the pattern (that is, the spaces between adjacent structural elements in the pattern) on the upper surface 91 of the substrate 9. When a liquid film of the film-forming liquid is formed on the substrate 9, the supply of the film-forming liquid from the second nozzle 52 is stopped.

Subsequently, the solvent (that is, IPA) is vaporized from the film-forming solution on the upper surface 91 of the substrate 9, so that the solute (that is, camphor) of the film-forming solution is precipitated on the upper surface 91 of the substrate 9, and the pattern is formed. Enter the gap. As a result, the solute is embedded in the gap of the pattern, and a solute film is formed on the upper surface 91 of the substrate 9 (step S15). The ratio of the thickness of the solute film to the height of the pattern on the upper surface 91 of the substrate 9 (hereinafter referred to as “embedding rate”) is preferably 85% to 170%, more preferably 100% to 140%. Is. The height of the pattern is the vertical distance from the bottom of the pattern to the top of the structural element. The thickness of the solute film is the vertical distance from the bottom of the pattern to the top surface of the solute film.

The vaporization of the solvent in step S15 is performed, for example, by rotating the substrate 9 by the substrate rotation mechanism 33. At this time, by increasing the rotation speed of the substrate 9 as compared with the case of forming the liquid film in step S14, the film-forming liquid on the substrate 9 is moved outward in the radial direction by centrifugal force, and is peripheral from the outer peripheral edge of the substrate 9. It may be scattered to. Thereby, the vaporization of the solvent can be promoted. In the substrate processing device 1, the substrate rotation mechanism 33 is a film forming portion that vaporizes a solvent from the film forming liquid on the upper surface 91 of the substrate 9 to form a solute film.

In step S15, a solute film may be formed by a configuration other than the above. For example, when the substrate 9 is heated by the heating unit, the solvent may be vaporized from the film-forming liquid to form a solute film. In this case, the heating portion that heats the substrate 9 is the film forming portion. Alternatively, the film forming portion may include the heating portion and the substrate rotation mechanism 33 described above.

When the formation of the solute film is completed, gas (for example, nitrogen gas) is sent from the third nozzle 63 toward the central portion of the upper surface 91 of the substrate 9, and spreads radially outward along the upper surface 91 of the substrate 9. .. On the substrate 9, an air flow is formed from the central portion of the substrate 9 to the outside in the radial direction. As a result, the solute film on the upper surface 91 of the substrate 9 is sublimated and removed from the substrate 9 (step S16). In other words, the substrate 9 is sublimated and dried by sublimating the solute film by supplying gas from the third nozzle 63, which is the film sublimation section. In step S16, there is substantially no liquid between the patterns on the substrate 9, and the solid solute film embedded between the patterns sublimates, so that the pattern collapse due to the surface tension of the liquid is suppressed. Will be done.

The substrate 9 that has been sublimated and dried is carried out from the substrate processing apparatus 1. In the substrate processing apparatus 1, the processes of steps S11 to S16 described above are sequentially performed on the plurality of substrates 9.

In step S16, the third nozzle 63 may be reciprocated in the substantially radial direction above the substrate 9. In this case, the third nozzle 63 is connected to the nozzle rotation mechanism via a rod-shaped arm extending in a substantially horizontal direction. Then, the arm is rotated in the horizontal direction by the nozzle rotation mechanism, so that the reciprocating movement of the third nozzle 63 is realized. The nozzle rotation mechanism includes, for example, a rotary electric motor arranged on the radial outer side of the cup portion 4.

Further, in step S16, the solute film may be sublimated by a configuration other than the above. For example, the solute film may be sublimated by heating the substrate 9 by the heating unit. In this case, the heating portion that heats the substrate 9 is the film sublimation portion. Alternatively, the film sublimation portion may include the heating portion and the above-mentioned third nozzle 63.

Next, the details of the processing liquid generation device 7 will be described. FIG. 4 is a side view showing the configuration of the processing liquid generator 7. The treatment liquid generation device 7 includes a sublimation unit 71, a treatment liquid generation unit 72, a gas supply flow path 73, a heat retention unit 74, and a generation control unit 77.

The generation control unit 77 controls the sublimation unit 71, the processing liquid generation unit 72, and the like. The generation control unit 77 includes, for example, a normal computer including a processor, a memory, an input / output unit, and a bus. A bus is a signal circuit that connects a processor, memory, and an input / output unit. The memory stores programs and various information. The processor executes various processes (for example, numerical calculation) while using the memory or the like according to a program or the like stored in the memory. The input / output unit includes a keyboard and mouse that receive input from the operator, a display that displays output from the processor, and a transmission unit that transmits output from the processor.

The generation control unit 77 includes a storage unit 771 and a sublimation control unit 772. The storage unit 771 is mainly realized by a memory and stores various information such as a recipe for generating a processing liquid. The sublimation control unit 772 is mainly realized by a processor, and controls the sublimation unit 71, the processing liquid generation unit 72, and the like according to the processing liquid generation recipe and the like stored in the storage unit 771.

The sublimation unit 71 sublimates the solid raw material 81 used for producing the above-mentioned treatment liquid (that is, the film-forming liquid) to generate a raw material gas. The solid raw material 81 contains the solid solute (that is, camphor). The solid raw material 81 contains impurities in addition to the solute. Impurities include, for example, high sublimation point impurities having a higher sublimation point than the solute and low sublimation point impurities having a lower sublimation point than the solute. The solid raw material 81 may contain only one of a high sublimation point impurity and a low sublimation point impurity.

The sublimation section 71 includes a first sublimation section 711, a second sublimation section 712, and a solid raw material transport mechanism 713. In the first sublimation section 711 and the second sublimation section 712, the solid raw material 81 is sublimated. The solid raw material transport mechanism 713 transports the solid raw material 81 from the first sublimation section 711 to the second sublimation section 712. The solid raw material transfer mechanism 713 includes, for example, a belt conveyor.

The first sublimation unit 711 includes a chamber 714, a decompression unit 715, and a heating unit 716. Chamber 714 is a container having a closed space inside. The decompression unit 715 sucks the gas in the internal space of the chamber 714 to depressurize the internal space. The decompression unit 715 includes, for example, an electric suction pump. The heating unit 716 heats the solid raw material 81 located in the internal space of the chamber 714. The heating unit 716 includes, for example, an electric heater. In the first sublimation section 711, the internal space of the chamber 714 is heated by the heating section 716 in a state where the internal space of the chamber 714 is made into a reduced pressure atmosphere by the depressurizing section 715, and the solid raw material 81 in the chamber 714 is heated.

In the first sublimation section 711, the temperature and pressure in the internal space of the chamber 714 are continuously measured by the temperature sensor 763 and the pressure sensor 764. The measured values of the temperature sensor 763 and the pressure sensor 764 are transmitted to the generation control unit 77. The generation control unit 77 maintains the temperature and pressure in the internal space of the chamber 714 at a predetermined temperature and a predetermined pressure by controlling the heating unit 716 and the depressurizing unit 715 based on the measured values of the temperature sensor 763 and the pressure sensor 764. To do. The predetermined temperature is higher than the sublimation temperature of the low sublimation temperature impurities contained in the solid raw material 81 and lower than the sublimation temperature of the solute and the high sublimation temperature impurities under the predetermined pressure.

Therefore, in the first sublimation section 711, only the low sublimation point impurities contained in the solid raw material 81 are sublimated and removed from the solid raw material 81. The sublimated gaseous low sublimation point impurities are discharged to the outside of the chamber 714. The solid raw material 81 (that is, solute and high sublimation point impurities) remaining without sublimation is transported to the second sublimation section 712 by the solid raw material transport mechanism 713.

The second sublimation unit 712 includes a chamber 717, a decompression unit 718, and a heating unit 719. Chamber 717 is a container having a closed space inside. The decompression unit 718 sucks the gas in the internal space of the chamber 717 to depressurize the internal space. The decompression unit 718 includes, for example, an electric suction pump. The heating unit 719 heats the solid raw material 81 located in the internal space of the chamber 717. The heating unit 719 includes, for example, an electric heater. In the second sublimation section 712, the internal space of the chamber 717 is heated by the heating section 719 in a state where the internal space of the chamber 717 is made into a reduced pressure atmosphere by the depressurizing section 718, and the solid raw material 81 in the chamber 717 is heated.

In the second sublimation section 712, the temperature and pressure in the internal space of the chamber 717 are continuously measured by the temperature sensor 763 and the pressure sensor 764. The measured values of the temperature sensor 763 and the pressure sensor 764 are transmitted to the generation control unit 77. The generation control unit 77 maintains the temperature and pressure in the internal space of the chamber 717 at a predetermined temperature and a predetermined pressure by controlling the heating unit 719 and the depressurizing unit 718 based on the measured values of the temperature sensor 763 and the pressure sensor 764. To do. Under the predetermined pressure, the predetermined temperature is higher than the sublimation point of the solute contained in the solid raw material 81 and lower than the sublimation point of the high sublimation point impurity.

Therefore, in the second sublimation section 712, only the solute contained in the solid raw material 81 after the sublimation treatment in the first sublimation section 711 (that is, after the removal of the low sublimation point impurities) is sublimated to generate the raw material gas. The high sublimation point impurities contained in the solid raw material 81 remain on the solid raw material transport mechanism 713 in a solid state without being sublimated.

In the second sublimation unit 712, the weight of the solid raw material 81 mounted on the solid raw material transfer mechanism 713 is continuously measured by the weight sensor 762 in the internal space of the chamber 717. The measured value of the weight sensor 762 is transmitted to the sublimation control unit 772 of the generation control unit 77. In the sublimation control unit 772, the difference between the weight of the solid raw material 81 at the time of being carried into the chamber 717 and the measured value of the weight sensor 762 is obtained as the weight of the generated raw material gas. Further, the production rate of the raw material gas per unit time (that is, the sublimation rate of the solid raw material 81) can be obtained from the production weight of the raw material gas. Then, the sublimation control unit 772 controls the decompression unit 718 and the heating unit 719 to control the sublimation speed of the solid raw material 81 in the second sublimation unit 712.

When the generation of the raw material gas is completed in the second sublimation section 712, the shutters provided on the side walls of the chambers 714 and 717 are opened to form an opening. Then, by driving the belt conveyor of the solid material transport mechanism 713, the high sublimation point impurities remaining in the chamber 717 of the second sublimation unit 712 are carried out to the outside through the opening of the chamber 717 and discarded. Ru. Further, in parallel with carrying out the high sublimation point impurities, the solid raw material 81 from which the low sublimation point impurities have been removed in the first sublimation part 711 is carried into the chamber 717 of the second sublimation part 712 through an opening. Further, the new solid raw material 81 is carried into the chamber 714 of the first sublimation section 711 through the opening. After transporting the solid raw material 81, the shutters of the chambers 714 and 717 are closed, and the internal space of the chambers 714 and 717 is sealed. The solid raw material transport mechanism 713 may include a structure other than the belt conveyor (for example, a turret type transport mechanism in which a plurality of mounting portions on which the solid raw material 81 is mounted are provided in a circumferential shape). The same applies to the solid raw material transfer mechanisms 713a and 713b of the processing liquid generation device 7a described later.

The raw material gas generated by the second sublimation unit 712 of the sublimation unit 71 is guided to the processing liquid generation unit 72 together with the carrier gas (for example, nitrogen gas) via the gas supply flow path 73 connected to the chamber 717. .. The gas supply flow path 73 is a pipeline through which the raw material gas flows. The gas supply flow path 73 is maintained at a temperature higher than the above-mentioned sublimation point of the solute by being heated by the heat retaining unit 74. This prevents the solute from coagulating (also referred to as solidification, precipitation or deposition) from the raw material gas in the gas supply flow path 73. The heat insulating unit 74 includes, for example, an electric heater that contacts the outer surface of the gas supply flow path 73, or a jacket that contacts the outer surface and allows a heat medium to flow inside.

The treatment liquid generation unit 72 dissolves the raw material gas generated by the sublimation unit 71 in a solvent to generate the above-mentioned treatment liquid (that is, the film-forming liquid). The treatment liquid generation unit 72 includes a storage unit 721, a raw material gas supply unit 722, a solvent supply source 723, and a dilution unit 724. The storage unit 721 is a closed container that stores a predetermined amount of the solvent of the treatment liquid. The raw material gas supply unit 722 supplies the raw material gas to the solvent stored in the storage unit 721. The raw material gas supply unit 722 supplies bubbles of the raw material gas into the solvent from the vicinity of the bottom of the storage unit 721, for example. As a result, the bubbles of the raw material gas are dissolved in the solvent to generate a raw material solution. In other words, the storage unit 721 and the raw material gas supply unit 722 are raw material solution generation units that generate the raw material solution.

The upper and lower limits of the diameter of the bubbles in the bubbling of the raw material gas described above are not particularly limited, but are preferably relatively small. Preferably, the raw material gas supply unit 722 nanobubbles the raw material gas (that is, in the form of bubbles having a diameter of less than 1 μm) and supplies the raw material gas to the solvent. As a result, the contact area between the bubbles of the raw material gas and the solvent is increased, so that the dissolution rate of the raw material gas in the solvent can be increased. As the raw material gas supply unit 722, various nanobubble generators such as a venturi-type nanobubble generator or a shear-force-type nanobubble generator that forms nanobubbles by utilizing the shearing force due to the flow of liquid can be used. Is. Although the nanobubbles in the solvent are substantially invisible to the naked eye, FIG. 4 illustrates the bubbles of the raw material gas in the storage unit 721 in order to facilitate the understanding of the figure.

The raw material solution produced in the storage unit 721 is guided to the second nozzle 52 by the above-mentioned pipe 562. A concentration sensor 761a is provided on the pipe 562, and the concentration of the solute in the raw material solution flowing through the pipe 562 (that is, the concentration of the solute dissolved in the solvent) is measured. As the concentration sensor 761a, various sensors such as a sound velocity measurement type concentration sensor can be used. The measured value of the concentration sensor 761a is transmitted to the generation control unit 77. When the solute concentration in the raw material solution measured by the concentration sensor 761a is within the desired range, the raw material solution sent out from the storage unit 721 is supplied to the second nozzle 52 as the treatment liquid (that is, the film forming liquid). Then, it is discharged from the second nozzle 52 toward the substrate 9 (see FIG. 1). The storage unit 721 is replenished with substantially the same amount of solvent as the discharged raw material solution from the solvent supply source 723. As a result, the amount of liquid in the storage unit 721 is maintained substantially constant. The solvent supply source 723 may be provided outside the treatment liquid generation device 7.

On the other hand, when the solute concentration in the raw material solution measured by the concentration sensor 761a is higher than the above range, the solvent is controlled from the solvent supply source 723 to the diluting unit 724 provided on the pipe 562 under the control of the generation control unit 77. Is supplied. In the diluting unit 724, the raw material solution from the storage unit 721 and the solvent from the solvent supply source 723 are mixed. As a result, the raw material solution is diluted to generate the above-mentioned treatment liquid, which is supplied to the second nozzle 52. The dilution unit 724 includes, for example, a static mixer. The flow rate of the solvent supplied from the solvent supply source 723 to the dilution section 724 is adjusted, for example, by changing the opening degree of the valve 726 (preferably the motor needle valve).

When the solute concentration in the raw material solution measured by the concentration sensor 761a is higher than the above range, the sublimation control unit 772 controls the sublimation speed of the solid raw material 81 in the second sublimation unit 712 as described above. Sublimation speed is reduced. As a result, the flow rate of the raw material gas supplied from the raw material gas supply unit 722 to the solvent in the storage unit 721 is reduced, and the solute concentration in the raw material solution is kept within the above range. On the other hand, when the solute concentration in the raw material solution measured by the concentration sensor 761a is lower than the above range, the sublimation control unit 772 controls the sublimation speed of the solid raw material 81 in the second sublimation unit 712, and the sublimation speed is increased. To. As a result, the flow rate of the raw material gas supplied from the raw material gas supply unit 722 to the solvent in the storage unit 721 is increased, and the solute concentration in the raw material solution is kept within the above range.

In the treatment liquid generation unit 72, a concentration sensor 761b is provided on the gas supply flow path 73 between the sublimation unit 71 and the treatment liquid generation unit 72, and the second sublimation unit 712 is based on the measurement result of the concentration sensor 761b. The sublimation rate of the solid raw material 81 in the above may be controlled. Specifically, the concentration sensor 761b measures the concentration of the solute in the raw material gas and the carrier gas (hereinafter collectively referred to as “mixed gas”) flowing through the gas supply flow path 73, and the measured solute concentration is desired. If it is higher than the range of, as described above, the sublimation control unit 772 controls the sublimation speed of the solid raw material 81 in the second sublimation unit 712, and the sublimation speed is reduced. As a result, the solute concentration in the mixed gas is reduced to within the above range. On the other hand, when the solute concentration in the mixed gas measured by the concentration sensor 761b is lower than the above range, the sublimation control unit 772 controls the sublimation rate of the solid raw material 81 in the second sublimation unit 712, and the sublimation rate is increased. To. As a result, the solute concentration in the mixed gas is increased to be within the above range. In this case, as the density sensor 761b, various sensors such as an optical density sensor can be used.

When the treatment liquid generation unit 72 controls the sublimation rate based on the measured values of the concentration sensor 761a and / or the concentration sensor 761b, the dilution in the dilution unit 724 does not necessarily have to be performed. Further, the concentration of the solute in the raw material solution produced in the storage unit 721 is always higher than the predetermined concentration (that is, the concentration of the solute in the treatment liquid) without controlling the sublimation rate, and the dilution unit. Dilution of the raw material solution in 724 may always be carried out to produce a treatment solution.

In the treatment liquid generation unit 72, the raw material gas that was not completely dissolved in the solvent in the storage unit 721 is returned to the chamber 717 of the second sublimation unit 712 of the sublimation unit 71 via the circulation flow path 725. Preferably, the circulation flow path 725 is also kept warm by the heat retaining unit 74, similarly to the gas supply flow path 73. The circulation flow path 725 may be provided with a discharge port for discharging excess gas. Further, a safety device may be provided that measures the concentration of combustible substances or the like in the gas discharged from the discharge port and issues an alarm or the like when the concentration exceeds a predetermined concentration. In the treatment liquid generation device 7, the raw material gas may be circulated using the circulation flow path 725 even when the solute concentration in the treatment liquid is low at the start of generation of the treatment liquid.

Next, the production of the treatment liquid (that is, the film-forming liquid) in the treatment liquid generation device 7 will be described with reference to FIGS. 5 to 7. 5 to 7 are diagrams showing an example of the flow of generating the treatment liquid in the treatment liquid generation device 7.

In the treatment liquid generating apparatus 7, first, the sublimation unit 71 sublimates the solid raw material 81 containing the solid solute to generate the raw material gas (step S21). Specifically, first, in the first sublimation section 711, a solid is formed at a first temperature which is higher than the sublimation point of the above-mentioned low sublimation point impurities and lower than the sublimation points of the solute and the high sublimation point impurities. The raw material 81 is sublimated (step S211). As a result, only the low sublimation point impurities contained in the solid raw material 81 are sublimated and removed from the solid raw material 81. Subsequently, after step S211 in the second sublimation section 712, the solid raw material 81 is sublimated at a second temperature which is higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity. (Step S212). As a result, only the solute contained in the solid raw material 81 is sublimated, and the raw material gas is generated.

When the raw material gas is generated in step S21, the treatment liquid generation unit 72 dissolves the raw material gas in a solvent to generate the treatment liquid (step S22). Specifically, the raw material solution is generated by supplying the raw material gas by the raw material gas supply unit 722 and dissolving it in a predetermined amount of solvent stored in the storage unit 721 (step S221). At this time, the raw material gas supplied into the solvent is preferably nanobubbled as described above.

As described above, the raw material solution produced in step S221 may be used as it is as a treatment solution, or may be used as a treatment solution after being diluted with a solvent, if necessary (step S222). In other words, in step S222, the raw material solution is diluted with a solvent as needed to produce a treatment solution. The processing liquid generated in step S22 is supplied to the second nozzle 52 of the substrate processing apparatus 1.

In the method for producing the treatment liquid, the temperature of the gas supply flow path 73 through which the raw material gas flows is maintained at a temperature higher than the sublimation point of the solute between steps S21 and S22, as described above. This prevents the solute from coagulating (also referred to as solidification, precipitation or deposition) from the raw material gas in the gas supply flow path 73.

In the method for producing the treatment liquid, even if the sublimation rate of the solid raw material 81 in step S21 is controlled based on the concentration of the solute in the mixed gas or the concentration of the solute dissolved in the solvent as described above. Good. As a result, the solute concentration in the mixed gas is within the desired range, and the solute concentration in the treatment liquid is within the desired range. Further, as described above, the sublimation rate of the solid raw material 81 in step S21 may be controlled based on the weight change of the solid raw material 81 in the second sublimation section 712 of the sublimation section 71. As a result, similarly to the above, the solute concentration in the mixed gas is within the desired range, and the solute concentration in the treatment liquid is within the desired range.

As described above, the treatment liquid generation device 7 is a device that generates the treatment liquid used in the substrate processing device 1 that performs the liquid treatment of the substrate 9. The treatment liquid generation device 7 includes a sublimation unit 71, a treatment liquid generation unit 72, and a gas supply flow path 73. The sublimation unit 71 sublimates a solid raw material 81 containing a solid solute (for example, camphor) to generate a raw material gas. The treatment liquid generation unit 72 dissolves the raw material gas in a solvent (for example, IPA) to generate a treatment liquid. The gas supply flow path 73 guides the raw material gas from the sublimation unit 71 to the processing liquid generation unit 72. As a result, a treatment liquid for liquid treatment of the substrate 9 can be easily generated. As a result, the cost required for the liquid treatment of the substrate 9 can be reduced.

As described above, when the solid raw material 81 further contains low sublimation point impurities having a sublimation point lower than that of the solute, the sublimation part 71 preferably includes a first sublimation part 711 and a second sublimation part 712. The first sublimation section 711 sublimates the solid raw material 81 at a temperature higher than the sublimation point of the low sublimation point impurity and lower than the sublimation point of the solute. The second sublimation section 712 generates a raw material gas by sublimating the solid raw material 81 after the sublimation treatment in the first sublimation section 711 at a temperature higher than the sublimation point of the solute. As a result, a high-purity raw material gas from which low sublimation temperature impurities have been removed can be obtained.

As described above, when the solid raw material 81 further contains a high sublimation point impurity having a higher sublimation point than the solute, the sublimation portion 71 is higher than the sublimation point of the solute and higher than the sublimation point of the high sublimation point impurity. It is preferable that the solid raw material 81 is sublimated at a low temperature. As a result, a high-purity raw material gas from which high sublimation temperature impurities have been removed can be obtained. In the example shown in FIG. 4, the sublimation of the solid raw material 81 at the above temperature is performed in the second sublimation section 712.

As described above, it is preferable that the treatment liquid generation device 7 further includes a heat retaining unit 74 that maintains the temperature of the gas supply flow path 73 at a temperature higher than the sublimation point of the solute. This makes it possible to prevent unintentional deposition of the solute in the gas supply flow path 73.

As described above, it is preferable that the processing liquid generation device 7 further includes a concentration sensor 761a or a concentration sensor 761b and a sublimation control unit 772. The concentration sensor 761b or the concentration sensor 761a measures the concentration of the solute in the gas (that is, the raw material gas and the carrier gas) flowing through the gas supply flow path 73, or the concentration of the solute dissolved in the solvent. The sublimation control unit 772 controls the sublimation speed of the solid raw material 81 in the sublimation unit 71 based on the measurement results of the concentration sensor 761a or the concentration sensor 761b. As a result, a treatment liquid having a desired solute concentration can be produced.

As described above, it is preferable that the processing liquid generation device 7 further includes a weight sensor 762 and a sublimation control unit 772. The weight sensor 762 measures the weight of the solid raw material 81 in the sublimation section 71. The sublimation control unit 772 controls the sublimation speed of the solid raw material 81 in the sublimation unit 71 based on the measurement result of the weight sensor 762. As a result, a treatment liquid having a desired solute concentration can be produced.

As described above, the treatment liquid generation unit 72 preferably includes a storage unit 721 for storing the solvent and a raw material gas supply unit 722. The raw material gas supply unit 722 supplies the raw material gas in nanobubbles to the solvent stored in the storage unit 721. As a result, the dissolution rate of the raw material gas in the solvent can be increased, and the time required for producing the treatment liquid can be shortened.

As described above, the treatment liquid generation unit 72 preferably includes a raw material solution generation unit and a dilution unit 724. The raw material solution generation unit (that is, the storage unit 721 and the raw material gas supply unit 722) dissolves the raw material gas supplied from the gas supply flow path 73 in a solvent to generate a raw material solution. The dilution unit 724 dilutes the raw material solution generated in the raw material solution generation unit with a solvent to generate a treatment liquid. Thereby, a treatment liquid having a desired solute concentration can be easily produced.

The above-mentioned treatment liquid generation method includes a step of sublimating a solid raw material 81 containing a solid solute to generate a raw material gas (step S21) and a step of dissolving the raw material gas in a solvent to generate a treatment liquid (step S22). ) And. As a result, as described above, a treatment liquid for liquid treatment of the substrate 9 can be easily generated. As a result, the cost required for the liquid treatment of the substrate 9 can be reduced.

The substrate processing device 1 described above includes a substrate holding unit 31, a processing liquid discharge unit (that is, a second nozzle 52), a film forming unit (that is, a substrate rotation mechanism 33), and a processing liquid generating device 7. The substrate holding portion 31 holds the substrate 9 having a pattern formed on the upper surface 91 in advance in a horizontal state. The treatment liquid discharge unit discharges the treatment liquid generated by the treatment liquid generation device 7 to the upper surface 91 of the substrate 9. The film forming portion forms a solute film by embedding a solute in the gap of the pattern by vaporizing the solvent from the treatment liquid on the upper surface 91 of the substrate 9. As a result, the substrate 9 can be dried while suppressing the collapse of the pattern.

The above-mentioned substrate processing method includes a step of holding the substrate 9 having a pattern formed on the upper surface 91 in advance in a horizontal state (step S11) and a treatment liquid generated by the above-mentioned treatment liquid generation method (steps S21 to S22). Is discharged onto the upper surface 91 of the substrate 9 (step S14), and a step of embedding a solute in the gaps of the pattern to form a solute film by vaporizing the solvent from the treatment liquid on the upper surface 91 of the substrate 9 (step S15). ) And. As a result, as described above, the substrate 9 can be dried while suppressing the collapse of the pattern.

The substrate processing apparatus 1 may be provided with a configuration for controlling the film thickness of the solute film formed on the substrate 9. For example, as shown in FIG. 8, a film thickness measuring unit 35 and a film thickness control unit 15 are further provided in the substrate processing device 1. The film thickness measuring unit 35 is a sensor that measures the film thickness of the solute film formed on the upper surface 91 of the substrate 9. The film thickness measuring unit 35 includes, for example, a spectral film thickness sensor using a spectroscopic interferometry.

The film thickness control unit 15 includes, for example, a normal computer including a processor, a memory, an input / output unit, and a bus. A bus is a signal circuit that connects a processor, memory, and an input / output unit. The memory stores programs and various information. The processor executes various processes (for example, numerical calculation) while using the memory or the like according to a program or the like stored in the memory. The input / output unit includes a keyboard and mouse that receive input from the operator, a display that displays output from the processor, and a transmission unit that transmits output from the processor. The film thickness control unit 15 includes a film forming liquid supply unit 56 (see FIG. 2), a second sublimation unit 712 of the treatment liquid generation device 7 (see FIG. 4), and a treatment liquid generation unit 72 of the treatment liquid generation device 7. (See FIG. 4) and the like are controlled.

In the substrate processing apparatus 1, the film thickness measuring unit 35 performs after the solute film is formed on the substrate 9 in step S15 (see FIG. 3) described above and before the solute film is sublimated in step S16. The film thickness of the solute film is measured (FIG. 9: step S31). Then, based on the measurement result by the film thickness measuring unit 35 in step S31, the film thickness control unit 15 controls the concentration of the solute in the treatment liquid (that is, the film forming liquid) (step S32). Specifically, when the film thickness of the solute film is thinner than the desired range, the solute concentration in the treatment liquid is increased. Further, when the film thickness of the solute film is thicker than the desired range, the solute concentration in the treatment liquid is reduced. As a result, in the substrate 9 to be processed next in the substrate processing apparatus 1 (hereinafter, also simply referred to as “next substrate 9”), the film thickness of the solute film formed on the substrate 9 is in a desired range (for example, The embedding rate is 85% to 170%). Note that step S32 may be performed at any time as long as it is after step S31 and before step S15 for the next substrate 9.

The increase in the solute concentration in the treatment liquid described above is realized, for example, by controlling the second sublimation unit 712 of the treatment liquid generation device 7 by the film thickness control unit 15 and increasing the sublimation rate of the solid raw material 81. .. Alternatively, when the solute concentration in the treatment liquid is increased, the film thickness control unit 15 controls the valve 726 of the treatment liquid generation unit 72, and the flow rate of the solvent supplied from the solvent supply source 723 to the dilution unit 724 is reduced. It may be realized by. Further, the reduction of the solute concentration in the treatment liquid described above is realized, for example, by controlling the second sublimation section 712 by the film thickness control section 15 and reducing the sublimation rate of the solid raw material 81. Alternatively, the reduction of the solute concentration in the treatment liquid may be realized by controlling the valve 726 by the film thickness control unit 15 and increasing the flow rate of the solvent supplied from the solvent supply source 723 to the dilution unit 724. Good.

In step S32, based on the measurement result by the film thickness measuring unit 35 in step S31, the processing liquid (that is, the film forming liquid) from the second nozzle 52, which is the treatment liquid discharge unit, is used instead of the solute concentration in the treatment liquid. The discharge time of the above may be controlled by the film thickness control unit 15. The control of the discharge time is performed in parallel with the discharge of the processing liquid to the next substrate 9 (step S15). Specifically, when the film thickness of the solute film is thinner than the desired range, the discharge time of the treatment liquid with respect to the next substrate 9 is extended. Further, when the film thickness of the solute film is thicker than the desired range, the discharge time of the treatment liquid to the next substrate 9 is shortened. As a result, the film thickness of the solute film formed on the next substrate 9 is in a desired range (for example, the embedding rate is 85% to 170%). The extension and shortening of the discharge time is realized by controlling the film forming liquid supply unit 56 (see FIG. 2) by the film thickness control unit 15.

As described above, it is preferable that the substrate processing apparatus 1 further includes a film thickness measuring unit 35 and a film thickness control unit 15. The film thickness measuring unit 35 measures the film thickness of the solute film. The film thickness control unit 15 controls the concentration of the solute in the treatment liquid or the discharge time of the treatment liquid from the treatment liquid discharge unit (that is, the second nozzle 52) based on the measurement result by the film thickness measurement unit 35. To do. Thereby, in the substrate 9 to be processed next in the substrate processing apparatus 1, the film thickness of the solute film formed on the substrate 9 can be set within a desired range. As a result, the collapse of the pattern can be further suppressed.

In the substrate processing apparatus 1, the substrate 9 in which the film thickness of the solute film was found to be out of the desired range as a result of measurement by the film thickness measuring unit 35 did not undergo sublimation of the solute film in step S16. It may be carried out from the processing device 1. Further, after the solvent (for example, IPA) of the film-forming liquid is supplied to the upper surface 91 of the substrate 9 and the solute film on the substrate 9 is dissolved, the treatments of steps S14 to S16 are performed again on the substrate 9. It may be carried out.

Next, the treatment liquid generation device 7a according to the second embodiment of the present invention will be described. FIG. 10 is a side view showing the configuration of the processing liquid generator 7a. The treatment liquid generator 7a is substantially the same as the treatment liquid generation device 7 shown in FIG. 4, except that a coagulation portion 75 is provided between the first sublimation portion 711 and the second sublimation portion 712 in the sublimation portion 71a. Has a structure. In the following description, in the treatment liquid generation device 7a, the same reference numerals are given to the configurations corresponding to the respective configurations of the treatment liquid generation device 7.

The coagulation unit 75 includes a chamber 751 and a cooling unit 752. Chamber 751 is a container having a closed space inside. The cooling unit 752 is arranged in the internal space of the chamber 751 to lower the temperature of the surrounding atmosphere. The cooling unit 752 is, for example, a metal rod-shaped member provided with a refrigerant flow path inside.

The flow of generating the treatment liquid in the treatment liquid generation device 7a is substantially the same as that shown in FIG. 5, but the specific flow of the generation of the raw material gas (FIG. 5: step S21) is the flow of step S211 shown in FIG. ~ Different from S212. FIG. 11 is a diagram showing an example of a specific flow of raw material gas generation in the sublimation section 71a of the processing liquid generation device 7a.

In the sublimation section 71a, first, in the first sublimation section 711, the internal space of the chamber 714 is heated by the heating section 716 while the internal space of the chamber 714 is made into a depressurized atmosphere by the decompression section 715, and the solid in the chamber 714. The raw material 81 is heated. In the first sublimation unit 711, the heating unit 716 and the depressurizing unit 715 are controlled by the generation control unit 77 based on the measured values of the temperature sensor 763 and the pressure sensor 764, so that the solid raw material 81 has a low sublimation point impurity and It is heated and sublimated at a third temperature which is higher than the sublimation point of the solute of the treatment liquid (that is, the film-forming liquid) and lower than the sublimation point of the high sublimation point impurity (step S215). As a result, low sublimation point impurities and solutes contained in the solid raw material 81 are sublimated to generate an intermediate gas. The intermediate gas produced in the first sublimation section 711 contains a gaseous solute and a gaseous low sublimation point impurity.

The high sublimation point impurities contained in the solid raw material 81 are not sublimated and remain in a solid state on the solid raw material transport mechanism 713a. The solid raw material transfer mechanism 713a includes, for example, a belt conveyor like the solid raw material transfer mechanism 713 (see FIG. 4). The high sublimation point impurity on the solid material transfer mechanism 713a is generated when the next solid material 81 (that is, the solid material 81 on the left side of the chamber 714 in FIG. 10) is carried into the chamber 714 by the solid material transfer mechanism 713a. , Is carried out of the chamber 714 and discarded.

The intermediate gas generated in the first sublimation section 711 is supplied to the chamber 751 of the coagulation section 75 together with the carrier gas (for example, nitrogen gas) via the pipe 753. It is preferable that the pipe 753 is kept warm at the third temperature or higher by the heat retaining portion 74 or the like. In the internal space of the chamber 751, the intermediate gas is cooled around the cooling unit 752, and the temperature of the intermediate gas is set to the fourth temperature, which is the temperature between the sublimation point of the low sublimation impurity and the sublimation point of the solute. As a result, the solute contained in the intermediate gas is coagulated and adheres to the surface of the cooling unit 752 as the solid raw material 81 (step S216). In FIG. 10, the solid raw material 81 adhering to the surface of the cooling unit 752 is drawn in cross section. On the other hand, the low sublimation point impurities contained in the intermediate gas remain in the internal space of the chamber 751 in the form of gas without being coagulated. The gaseous low sublimation temperature impurities are discharged from the discharge port of chamber 751.

As described above, the solid raw material 81 coagulated in the coagulation section 75 contains almost no low sublimation point impurities and high sublimation point impurities, and the solid raw material 81 adhering to the cooling section 752 is substantially a treatment liquid. It is formed only by the solute of. The solid raw material 81 is peeled off from the surface of the cooling unit 752, falls, and is deposited on the solid material transport mechanism 713b located below the cooling unit 752. The solid raw material transfer mechanism 713b includes, for example, a belt conveyor like the solid raw material transfer mechanism 713a.

The solid raw material 81 may be peeled from the cooling unit 752 by various methods. For example, the cooling unit 752 may be vibrated by applying ultrasonic waves, and the debris of the solid raw material 81 may be separated from the cooling unit 752 by the vibration. Alternatively, the solid raw material 81 may be peeled off from the cooling unit 752 by scraping the solid raw material 81 adhering to the surface of the cooling unit 752 with a doctor blade or the like. Alternatively, the surface of the cooling unit 752 is temporarily heated to a temperature higher than the sublimation point of the solid material 81 by a heat medium or the like to sublimate the innermost layer of the solid material 81 adhering to the cooling unit 752. Therefore, the portion of the solid raw material 81 other than the innermost layer may be peeled off from the cooling portion 752.

The solid raw material 81 exfoliated from the cooling section 752 (that is, the coagulated product obtained in step S216) is carried into the chamber 717 of the second sublimation section 712 by the solid raw material transport mechanism 713b. In the second sublimation section 712, the internal space of the chamber 717 is heated by the heating section 719 in a state where the internal space of the chamber 717 is made into a reduced pressure atmosphere by the depressurizing section 718, and the solid raw material 81 in the chamber 717 is heated. In the second sublimation unit 712, the heating unit 719 and the depressurizing unit 718 are controlled by the generation control unit 77 based on the measured values of the temperature sensor 763 and the pressure sensor 764, so that the solid raw material 81 is moved from the sublimation point of the solute. Is heated at the fifth temperature, which is a high temperature, and sublimates. As described above, since the solid raw material 81, which is a coagulant obtained in the coagulation section 75, is substantially formed only by the solute of the treatment liquid, the solid raw material 81 is substantially sublimated. A raw material gas containing only a gaseous solute is produced (step S217).

The raw material gas generated by the second sublimation unit 712 of the sublimation unit 71a is guided to the processing liquid generation unit 72 together with the carrier gas (for example, nitrogen gas) via the gas supply flow path 73 connected to the chamber 717. ..

As described above, in the processing liquid generator 7a, the sublimation section 71a includes a first sublimation section 711, a coagulation section 75, and a second sublimation section 712. The first sublimation unit 711 sublimates the solid raw material 81 to generate an intermediate gas. The coagulation unit 75 coagulates the solute by setting the temperature of the intermediate gas to a temperature between the sublimation point of the low sublimation point impurity and the sublimation point of the solute. The second sublimation section 712 produces a raw material gas by sublimating the coagulated product obtained in the coagulation section 75. As a result, a high-purity raw material gas from which low sublimation temperature impurities have been removed can be obtained.

As described above, in the sublimation section 71a, it is preferable that the solid raw material 81 is sublimated at a temperature higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity (that is, the third temperature). As a result, a high-purity raw material gas from which high sublimation temperature impurities have been removed can be obtained. In the example shown in FIG. 10, the sublimation of the solid raw material 81 at the third temperature (that is, the removal of high sublimation point impurities) is performed in the first sublimation section 711.

In the sublimation section 71a, the removal of the high sublimation point impurities from the solid raw material 81 may be performed not in the first sublimation section 711 but in the second sublimation section 712. In this case, the third temperature may be higher than the sublimation point of the solute, while the heating temperature (that is, the fifth temperature) of the solid raw material 81 in the second sublimation portion 712 is higher than the sublimation point of the solute. Higher sublimation temperature Higher temperature than the sublimation temperature of impurities. The removal of the high sublimation point impurities may be performed by both the first sublimation section 711 and the second sublimation section 712.

Various changes can be made in the above-mentioned processing liquid generating devices 7 and 7a, the substrate processing device 1, the processing liquid generating method, and the substrate processing method.

For example, in the processing liquid generation device 7, the heat retaining unit 74 may be omitted. The same applies to the treatment liquid generator 7a.

In the treatment liquid generators 7 and 7a, impurities are removed from the solid raw material 81 by utilizing the difference in sublimation points, but impurities may be removed by various other methods. For example, impurities may be removed by sublimating the solid raw material 81 to make it gaseous and then passing it through a filter or the like.

In the treatment liquid generating apparatus 7, for example, when the solid raw material 81 does not substantially contain the low sublimation point impurities, the removal of the low sublimation point impurities in the first sublimation unit 711 may be omitted. Further, for example, when the solid raw material 81 does not substantially contain the high sublimation point impurities, the removal of the high sublimation point impurities in the second sublimation section 712 may be omitted.

Similarly, in the treatment liquid generating apparatus 7a, for example, when the solid raw material 81 does not substantially contain the low sublimation point impurities, the removal of the low sublimation point impurities in the coagulation portion 75 may be omitted. Further, for example, when the solid raw material 81 does not substantially contain the high sublimation point impurities, the removal of the high sublimation point impurities in the first sublimation part 711 (and / or the second sublimation part 712) may be omitted. ..

In the processing liquid generator 7a, a pressure adjusting unit (for example, an electric pump) for adjusting the pressure in the internal space of the chamber 751 is provided instead of the cooling unit 752 of the coagulation unit 75, and the internal space of the chamber 751 is pressurized. By doing so, coagulation of the solute in the intermediate gas may be realized. Further, the coagulation of the solute in the coagulation unit 75 may be realized by both the cooling by the cooling unit 752 and the pressurization of the internal space of the chamber 751.

In the first sublimation section 711 and the second sublimation section 712 of the processing liquid generator 7, the solid raw material 81 is sublimated by heating and depressurizing, but the solid raw material 81 is sublimated only by heating or depressurizing. May be good. Alternatively, the sublimation of the solid raw material 81 may be performed by supplying an inert gas or the like to the surrounding atmosphere of the solid raw material 81, and the supply of the inert gas or the like is combined with the above-mentioned heating and / or depressurization. It may be done by. The same applies to the treatment liquid generator 7a.

In the treatment liquid generation unit 72 of the treatment liquid generation device 7, the raw material gas may be dissolved in the solvent by various methods other than bubbling. For example, the raw material gas may be dissolved in a solvent using a hollow fiber membrane. The same applies to the treatment liquid generator 7a.

In the treatment liquid generation device 7, a treatment liquid is generated by dissolving one kind of raw material gas generated by one sublimation unit 71 in a solvent in the treatment liquid generation unit 72, but the treatment liquid is not limited to this. For example, the treatment liquid generation device 7 is provided with a plurality of sublimation units 71, and the plurality of sublimation units 71 generate a plurality of types of raw material gases (that is, a plurality of types of gaseous solutes) from a plurality of types of solid raw materials. A treatment liquid (hereinafter, referred to as "mixed treatment liquid") may be generated by dissolving the plurality of types of raw material gases in one solvent in the treatment liquid generation unit 72. In this case, the concentration of the plurality of types of solutes in the mixing treatment liquid may be controlled by controlling the mixing ratio of the plurality of types of raw material gases supplied to the solvent. Further, a part or all of the plurality of sublimation units 71 may be changed to the sublimation unit 71a. The same applies to the treatment liquid generator 7a.

The processing liquid generating devices 7 and 7a do not necessarily have to be a part of the above-mentioned substrate processing device 1, and may be incorporated and used in another substrate processing device that performs liquid processing on the substrate 9. Further, the processing liquid generating devices 7 and 7a may be used independently of the substrate processing device.

In addition to the semiconductor substrate, the above-mentioned substrate processing device 1 is used for a glass substrate used for a liquid crystal display device, a flat panel display such as an organic EL (Electro Luminescence) display device, or another display device. It may be used for processing a glass substrate to be processed. Further, the above-mentioned substrate processing device 1 may be used for processing an optical disk substrate, a magnetic disk substrate, a magneto-optical disk substrate, a photomask substrate, a ceramic substrate, a solar cell substrate, and the like.

The above-described embodiments and configurations in each modification may be appropriately combined as long as they do not conflict with each other.

1 Substrate processing device 7, 7a Treatment liquid generator 9 Sublimation 15 Thickness control unit 31 Substrate holding unit 33 Substrate rotation mechanism 35 Thickness measurement unit 52 Second nozzle 71, 71a Sublimation unit 72 Treatment liquid generation unit 73 Gas supply flow path 74 Heat insulation part 75 Coagulation part 81 Solid raw material 91 (of substrate) Top surface 711 First sublimation part 712 Second sublimation part 721 Storage part 722 Raw material gas supply part 724 Diluting part 761a, 761b Concentration sensor 762 Weight sensor 772 Sublimation control part Central axis S11-S16, S21-S22, S31-S32, S211-S212, S215-S217, S221-S222 Steps

Claims (22)

A processing liquid generator that generates a processing liquid used in a substrate processing device that processes a liquid on a substrate.
A sublimation part that sublimates a solid raw material containing a solid solute to generate a raw material gas,
A treatment liquid generation unit that dissolves the raw material gas in a solvent to generate a treatment liquid,
A gas supply flow path that guides the raw material gas from the sublimation section to the treatment liquid generation section,
A processing liquid generator, which comprises. The treatment liquid generator according to claim 1.
The solid raw material further contains low sublimation temperature impurities having a lower sublimation point than the solute.
The sublimation part
The first sublimation portion that sublimates the solid raw material at a temperature higher than the sublimation point of the low sublimation point impurity and lower than the sublimation point of the solute.
A second sublimation section that generates the raw material gas by sublimating the solid raw material after the sublimation treatment in the first sublimation section at a temperature higher than the sublimation point of the solute.
A processing liquid generator, which comprises. The treatment liquid generator according to claim 1.
The solid raw material further contains low sublimation temperature impurities having a lower sublimation point than the solute.
The sublimation part
A first sublimation section that sublimates the solid raw material to generate an intermediate gas,
A coagulation portion for coagulating the solute by setting the temperature of the intermediate gas to a temperature between the sublimation point of the low sublimation point impurity and the sublimation point of the solute.
A second sublimation section that produces the raw material gas by sublimating the coagulant obtained in the coagulation section, and
A processing liquid generator, which comprises. The treatment liquid generator according to any one of claims 1 to 3.
The solid raw material further contains high sublimation point impurities having a higher sublimation point than the solute.
A processing liquid generating apparatus characterized in that, in the sublimation section, the solid raw material is sublimated at a temperature higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity. The treatment liquid generator according to any one of claims 1 to 4.
A processing liquid generation device further comprising a heat retaining unit that maintains the temperature of the gas supply flow path at a temperature higher than the sublimation point of the solute. The treatment liquid generator according to any one of claims 1 to 5.
A concentration sensor that measures the concentration of the solute in the gas flowing through the gas supply flow path or the concentration of the solute dissolved in the solvent.
A sublimation control unit that controls the sublimation speed of the solid raw material in the sublimation unit based on the measurement result of the concentration sensor,
A processing liquid generator, which further comprises. The treatment liquid generator according to any one of claims 1 to 6.
A weight sensor that measures the weight of the solid raw material in the sublimation section,
A sublimation control unit that controls the sublimation speed of the solid raw material in the sublimation unit based on the measurement result of the weight sensor,
A processing liquid generator, which further comprises. The treatment liquid generator according to any one of claims 1 to 7.
The treatment liquid generation unit
A storage unit that stores the solvent and
A raw material gas supply unit that supplies the raw material gas in nanobubbles to the solvent stored in the storage unit,
A processing liquid generator, which comprises. The treatment liquid generator according to any one of claims 1 to 8.
The treatment liquid generation unit
A raw material solution generating unit that generates a raw material solution by dissolving the raw material gas supplied from the gas supply flow path in a solvent.
A diluting unit for producing the treatment liquid by diluting the raw material solution produced in the raw material solution generating unit with the solvent, and a diluting unit.
A processing liquid generator, which comprises. A substrate processing device that processes liquid on a substrate.
The treatment liquid generator according to any one of claims 1 to 9.
A substrate holding part that holds a substrate with a pattern formed on the upper surface in a horizontal state,
A treatment liquid discharge unit that discharges the treatment liquid generated by the treatment liquid generation device onto the upper surface of the substrate,
A film-forming portion that forms a solute film by embedding a solute in the gap of the pattern by vaporizing the solvent from the treatment liquid on the upper surface of the substrate.
A substrate processing apparatus comprising. The substrate processing apparatus according to claim 10.
A film thickness measuring unit for measuring the film thickness of the solute film and
A film thickness control unit that controls the concentration of the solute in the treatment liquid or the discharge time of the treatment liquid from the treatment liquid discharge unit based on the measurement result by the film thickness measurement unit.
A substrate processing apparatus characterized by further comprising. It is a treatment liquid generation method for generating a treatment liquid used in liquid treatment of a substrate.
a) A process of sublimating a solid raw material containing a solid solute to generate a raw material gas, and
b) A step of dissolving the raw material gas supplied through the gas supply flow path in a solvent to generate a treatment liquid, and
A method for producing a treatment liquid, which comprises. The treatment liquid generation method according to claim 12.
The solid raw material further contains low sublimation temperature impurities having a lower sublimation point than the solute.
The step a) is
c) A step of sublimating the solid raw material at a temperature higher than the sublimation point of the low sublimation point impurity and lower than the sublimation point of the solute.
d) A step of producing the raw material gas by sublimating the solid raw material at a temperature higher than the sublimation point of the solute after the step c).
A method for producing a treatment liquid, which comprises. The treatment liquid generation method according to claim 12.
The solid raw material further contains low sublimation temperature impurities having a lower sublimation point than the solute.
The step a) is
e) A step of sublimating the solid raw material to generate an intermediate gas,
f) A step of coagulating the solute by setting the temperature of the intermediate gas to a temperature between the sublimation point of the low sublimation impurity and the sublimation point of the solute.
g) The step of producing the raw material gas by sublimating the coagulant obtained in the step f), and
A method for producing a treatment liquid, which comprises. The treatment liquid generation method according to any one of claims 12 to 14.
The solid raw material further contains high sublimation point impurities having a higher sublimation point than the solute.
A method for producing a treatment liquid, which comprises sublimating the solid raw material at a temperature higher than the sublimation point of the solute and lower than the sublimation point of the high sublimation point impurity in the step a). The treatment liquid generation method according to any one of claims 12 to 15.
A method for producing a treatment liquid, characterized in that the temperature of the gas supply flow path is maintained higher than the sublimation point of the solute. The treatment liquid generation method according to any one of claims 12 to 16.
The sublimation rate of the solid raw material in the step a) is controlled based on the concentration of the solute in the gas flowing through the gas supply flow path or the concentration of the solute dissolved in the solvent. Treatment liquid generation method. The treatment liquid generation method according to any one of claims 12 to 17.
A method for producing a treatment liquid, which comprises controlling the sublimation rate of the solid raw material in the step a) based on the weight change of the solid raw material. The treatment liquid generation method according to any one of claims 12 to 18.
A method for producing a treatment liquid, which comprises supplying the raw material gas in nanobubbles to the solvent stored in the storage unit in the step b). The treatment liquid generation method according to any one of claims 12 to 19.
The step b) is
h) A step of dissolving the raw material gas in the solvent to generate a raw material solution, and
i) A step of diluting the raw material solution with the solvent to produce the treatment liquid, and
A method for producing a treatment liquid, which comprises. It is a substrate processing method that performs liquid treatment of the substrate.
j) A process of holding a substrate with a pattern formed on the upper surface in a horizontal state, and
k) A step of discharging the treatment liquid generated by the treatment liquid generation method according to any one of claims 12 to 20 onto the upper surface of the substrate.
l) A step of embedding a solute in the gap of the pattern by vaporizing a solvent from the treatment liquid on the upper surface of the substrate to form a solute film.
A substrate processing method comprising. The substrate processing method according to claim 21.
m) A step of measuring the film thickness of the solute film after the step l)
n) A step of controlling the concentration of the solute in the treatment liquid or the discharge time of the treatment liquid in the k) step based on the measurement result in the m) step.
A substrate processing method characterized by further comprising.

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