JP7182880B2 - Substrate processing method and substrate processing apparatus - Google Patents

Description

The present invention relates to a substrate processing method and substrate processing apparatus for processing a substrate. Substrates to be processed include, for example, semiconductor wafers, liquid crystal display device substrates, FPD (Flat Panel Display) substrates such as organic EL (Electroluminescence) display devices, optical disk substrates, magnetic disk substrates, and magneto-optical disk substrates. Substrates such as substrates, substrates for photomasks, ceramic substrates, and substrates for solar cells are included.

In substrate processing by a single substrate processing apparatus, substrates are processed one by one. Specifically, the spin chuck holds the substrate substantially horizontally. After the upper surface of the substrate is treated with the chemical solution, the upper surface of the substrate is rinsed with the rinse solution. After that, a spin dry process is performed in which the substrate is rotated at high speed to dry the upper surface of the substrate.
When a fine pattern is formed on the surface of the substrate, there is a possibility that the spin drying process cannot remove the rinsing liquid that has entered the inside of the pattern. This may result in poor drying. The liquid surface (interface between air and liquid) of the rinse liquid that has entered the inside of the pattern is formed within the pattern. Therefore, the surface tension of the liquid acts on the contact position between the liquid surface and the pattern. When this surface tension is large, the pattern tends to collapse. Since water, which is a typical rinse liquid, has a large surface tension, it cannot be ignored that the pattern collapses in the spin-drying process.

Therefore, a method using isopropyl alcohol (IPA), which is a low surface tension liquid whose surface tension is lower than that of water, has been proposed (see, for example, Patent Document 1 below). Specifically, IPA is supplied to the upper surface of the substrate to replace water that has entered the interior of the pattern with IPA, and then the IPA is removed to dry the upper surface of the substrate. However, even if the water that has entered the pattern is replaced with IPA, the pattern may collapse if the surface tension acts for a long time or if the pattern has low strength.

In view of this, Patent Document 2 discloses a substrate treatment in which the top surface of the substrate is hydrophobized with a silylating agent (hydrophobizing agent) to reduce the surface tension applied to the pattern and prevent the pattern from collapsing. Specifically, the silylating agent is supplied to the upper surface of the substrate, and the silylating agent supplied to the upper surface of the substrate flows on the upper surface of the substrate so as to spread from the center to the periphery due to the rotation of the substrate. This renders the entire top surface of the substrate hydrophobic. After that, the silylating agent remaining on the upper surface of the substrate is washed away with IPA, and then the substrate is dried.

JP 2016-21597 A JP 2012-222329 A

However, recent studies have revealed that pattern collapse may occur even after such a hydrophobic treatment. Moreover, it has been found that a relatively large number of particles are observed on the surface of the substrate that has been subjected to the hydrophobizing treatment and dried.
The inventor's hypothesis about this cause is as follows.
If an oxide adheres to the surface of the substrate to be hydrophobized, the surface of the substrate is uneven due to the oxide. When such a substrate surface is subjected to hydrophobizing treatment, the functional groups of the hydrophobizing agent react with the substrate material on the exposed surface of the substrate, and react with the oxide surface on the portion covered with oxide. to form a hydrophobized film covering the exposed portions of the substrate and the oxide on the substrate surface. However, since the hydrophobizing agent is made of a material having a large molecular weight, the surface of the hydrophobizing film not only inherits the unevenness caused by the oxide but also has larger unevenness. That is, if the substrate surface has roughness due to oxides, the roughness is further deteriorated by the hydrophobizing treatment.

If a liquid (IPA in the example of Patent Document 2) is supplied to such a surface with poor roughness, or if a previously supplied liquid (for example, water or IPA) remains, these liquids Pattern collapse due to surface tension occurs.
Further, the roughness amplified by the hydrophobizing treatment may be detected as particles when the substrate surface is observed using a particle counter or the like.

Accordingly, one embodiment of the present invention provides a substrate processing method and substrate processing apparatus capable of improving the problem of pattern collapse and particles.

An embodiment of the present invention includes a heating modification step of heating a substrate having an oxide on the surface to modify the surface, supplying a treatment liquid to the modified surface of the substrate, and Provided is a substrate processing method including a surface cleaning step of cleaning the surface of a substrate and a hydrophobizing step of supplying a hydrophobizing agent to the cleaned surface of the substrate to hydrophobize the surface of the substrate.
According to this method, the surface of the substrate is modified by heating the substrate. The surface modification by heating removes oxides on the substrate or decomposes and recombines the oxides on the substrate, thereby flattening the surface of the substrate. The surface flattened by this surface modification is washed with a treatment liquid, and then hydrophobized with a hydrophobizing agent. In this way, the surface of the substrate is modified to be hydrophobic while the unevenness of the substrate surface caused by the oxide is eliminated, so that the modified surface of the substrate is uniformly hydrophobic and flat with little roughness. becomes the surface. Thereby, the problem of pattern collapse and the problem of particles can be solved.

In one embodiment of the present invention, the thermal modification step includes a thermal removal step of removing at least part of the oxide on the surface of the substrate by heating.
In this method, oxide removal reduces or eliminates substrate surface irregularities. Oxides are decomposed by thermal energy. More specifically, thermal energy can be used to unbond the substrate material from the oxide and remove the oxide. The removal of oxides by heating is advantageous in that there is no loss (film reduction) of the substrate material due to the etching action, as compared with the case of using a chemical solution.

In one embodiment of the present invention, the thermal modification step includes a planarization step of reducing unevenness caused by oxide on the surface of the substrate by heating. In this method, unevenness on the substrate surface caused by oxides is flattened by heating.
In one embodiment of the present invention, the thermal modification step includes a heating removal step of removing at least part of the oxide on the surface of the substrate by heating, and a new oxide on the surface of the substrate after the heating removal step. so that the oxygen concentration in the atmosphere around the substrate in the oxide film forming step is higher than the oxygen concentration in the atmosphere around the substrate in the oxide film forming step and the heating removal step, and controlling the atmosphere around the substrate.
In one embodiment of the present invention, the surface cleaning step includes a chemical cleaning step of supplying a chemical solution for cleaning to the surface of the substrate , and a rinse solution supplied to the surface of the substrate to replace the chemical solution with the rinse solution. and a rinsing step.

Accordingly, the surface of the substrate can be hydrophobized after the substrate is cleaned with the chemical solution. Since the surface of the substrate is modified by heating the substrate before cleaning with the chemical solution, the surface of the substrate presents a good hydrophobic surface. Therefore, substrate cleaning using a chemical solution can be performed while avoiding the problem of pattern collapse and the problem of particles.
In one embodiment of the present invention, the dissolved oxygen concentration in the treatment liquid is 100 ppb or less. As a result, oxidation of the substrate material caused by dissolved oxygen in the treatment liquid can be suppressed or prevented, and the roughness of the substrate surface before the hydrophobizing treatment is improved. As a result, the substrate surface after the hydrophobization treatment has excellent hydrophobic performance.

In one embodiment of the present invention, the hydrophobizing step includes a hydrophobizing agent supplying step of supplying a liquid hydrophobizing agent in which a hydrophobizing substance is dissolved in a solvent. The method further includes a pre-organic solvent supplying step of supplying an organic solvent miscible with the solvent of the hydrophobizing agent to the surface of the substrate after the surface cleaning step and before the hydrophobizing step.
In this method, the treatment liquid on the surface of the substrate is replaced with an organic solvent, and then a liquid hydrophobizing agent is supplied to the substrate surface. Since the organic solvent is miscible (that is, has compatibility) with the solvent of the hydrophobizing agent, the hydrophobizing agent efficiently replaces the organic solvent on the substrate surface. More specifically, even when a pattern is formed on the substrate surface, the organic solvent in the pattern can be replaced with a hydrophobizing agent.

In one embodiment of the present invention, the method further comprises an organic solvent supplying step after the hydrophobizing step, supplying an organic solvent to the surface of the substrate to wash off excess hydrophobizing agent on the substrate. include. As a result, the substrate surface can be hydrophobized with an appropriate amount of the hydrophobizing agent, so that deterioration of the roughness of the substrate surface and deterioration of the hydrophobic performance due to excessive hydrophobizing agent can be avoided.
In one embodiment of the invention, the dissolved oxygen concentration in the organic solvent is 100 ppb or less. As a result, oxidation of the substrate material caused by dissolved oxygen in the organic solvent can be suppressed or prevented, thereby improving the roughness of the substrate surface before the hydrophobizing treatment. As a result, the substrate surface after the hydrophobization treatment has excellent hydrophobic performance.

In one embodiment of the present invention, the dissolved oxygen concentration in the hydrophobizing agent is 100 ppb or less. As a result, oxidation of the substrate material due to dissolved oxygen in the hydrophobizing agent can be suppressed or prevented in the hydrophobizing agent supply step.
In one embodiment of the present invention, the method further includes an atmosphere control step of controlling the atmosphere around the substrate to a low-oxygen atmosphere having an oxygen concentration lower than that of the air during the period from the surface cleaning step to the hydrophobizing step. As a result, after the surface of the substrate is modified by the heat treatment, the surface of the substrate can be modified to be hydrophobic while suppressing the growth of new oxides on the surface.

In one embodiment of the present invention, the low-oxygen atmosphere is an atmosphere having an oxygen concentration in which oxygen does not dissolve in the treatment liquid. As a result, oxygen from the atmosphere does not dissolve into the processing liquid in the surface cleaning step, so that growth of oxide on the surface of the substrate can be suppressed or prevented in the surface cleaning step.
In one embodiment of the present invention, a cooling step of cooling the substrate is included after the thermal modification step, and the surface cleaning step is performed on the substrate after the cooling step. As a result, the substrate is cooled before the surface cleaning process, so that oxidation of the substrate material during the surface cleaning process can be suppressed more reliably.

In one embodiment of the present invention, after the hydrophobizing step, a heat dehydration step of heating and dehydrating the hydrophobizing agent on the surface of the substrate is included. As a result, in the heating and dehydration process, the solvent of the hydrophobizing agent on the surface of the substrate can be blown off to reduce the size of the foreign matter, and the incomplete bonding of the hydrophobizing agent caused by excessive moisture can be eliminated. Thereby, a surface having excellent hydrophobicity can be provided.

An embodiment of the present invention includes a heat treatment unit that heats a substrate having an oxide on its surface to modify the surface, and a treatment liquid for cleaning the surface that is supplied to the modified surface of the substrate. and a hydrophobizing agent supply unit for supplying a hydrophobizing agent to the surface of the cleaned substrate to hydrophobize the surface of the substrate.
In one embodiment of the invention, the thermal processing unit heats the substrate such that at least part of the oxide on the surface of the substrate is removed by heating.

In one embodiment of the present invention, the heat treatment unit heats the substrate so as to reduce unevenness caused by oxides on the surface of the substrate by heating.
In one embodiment of the present invention, the heat treatment unit controls the atmosphere around the substrate to be a low-oxygen atmosphere, and heats the substrate so as to remove at least part of the oxide on the surface of the substrate by heating. Then, after at least part of the oxide is removed, the atmosphere around the substrate is controlled to have a higher oxygen concentration than the low-oxygen atmosphere to form a new oxide film on the surface of the substrate.
In one embodiment of the present invention, the processing liquid supply unit includes a chemical liquid supply unit that supplies a chemical liquid for cleaning to the surface of the substrate, and a rinse liquid that replaces the chemical liquid with a rinse liquid to the surface of the substrate. and a rinse liquid supply unit.

In one embodiment of the present invention, the processing liquid supply unit supplies the processing liquid having a dissolved oxygen concentration of 100 ppb or less to the surface of the substrate.
In one embodiment of the present invention, the hydrophobizing agent supply unit supplies a liquid hydrophobizing agent in which a hydrophobizing substance is dissolved in a solvent. Further, after the substrate processing apparatus cleans the surface of the substrate and before hydrophobizing the surface of the substrate, an organic solvent that is miscible with the solvent of the hydrophobizing agent is supplied to the surface of the substrate. Further includes a supply unit.

In one embodiment of the present invention, after the surface of the substrate is hydrophobized, it further comprises a post-organic solvent supply unit for supplying an organic solvent to the surface of the substrate to wash off excess hydrophobizing agent on the substrate. .
In one embodiment of the invention, the dissolved oxygen concentration in the organic solvent is 100 ppb or less.

In one embodiment of the present invention, the dissolved oxygen concentration in the hydrophobizing agent is 100 ppb or less.
In one embodiment of the present invention, the substrate processing apparatus comprises a period in which a processing liquid is supplied to the surface of the substrate by the processing liquid supply unit, and a hydrophobizing agent is applied to the surface of the substrate by the hydrophobizing agent supply unit. It further includes an atmosphere control unit for controlling the atmosphere around the substrate to be a low-oxygen atmosphere having an oxygen concentration lower than that in the atmosphere during the supply period.

In one embodiment of the present invention, the atmosphere control unit controls the atmosphere around the substrate to a low-oxygen atmosphere having an oxygen concentration in which oxygen does not dissolve in the processing liquid.
An embodiment of the present invention further comprises a cooling unit for cooling the substrate after being heated by the thermal processing unit and before cleaning the surface.
In one embodiment of the present invention, the substrate processing apparatus further includes a post-heating unit that heats the substrate to heat and dehydrate the hydrophobizing agent on the surface of the substrate after the surface is hydrophobized. .

1A to 1D are explanatory diagrams for explaining the principle of substrate processing according to one embodiment of the present invention. 2A to 2C are explanatory diagrams for explaining another principle of substrate processing according to one embodiment of the present invention. 3A to 3D are explanatory diagrams for explaining still another principle of substrate processing according to one embodiment of the present invention. FIG. 4 is an illustrative plan view for explaining the internal layout of the substrate processing apparatus according to one embodiment of the present invention. FIG. 5 is an illustrative cross-sectional view for explaining a structural example of a heat treatment unit provided in the substrate processing apparatus. FIG. 6 is a schematic cross-sectional view for explaining a configuration example of a processing unit provided in the substrate processing apparatus. FIG. 7 is a block diagram for explaining the electrical configuration of the main part of the substrate processing apparatus. FIG. 8A is a flowchart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 8B is a flowchart for explaining another example of substrate processing by the substrate processing apparatus. FIG. 9A is an illustrative cross-sectional view for explaining the state of the chemical solution treatment (surface cleaning step). FIG. 9B is an illustrative cross-sectional view for explaining the state of the rinse treatment (surface cleaning step) after the chemical solution treatment. FIG. 9C is an illustrative cross-sectional view for explaining the state of the first organic solvent treatment. FIG. 9D is a schematic cross-sectional view for explaining how the hydrophobization treatment is performed. FIG. 9E is an illustrative cross-sectional view for explaining the state of the second organic solvent treatment. FIG. 9F is an illustrative cross-sectional view for explaining the state of the post-substrate heat treatment. FIG. 9G is a schematic cross-sectional view for explaining the state of the post-substrate cooling process. FIG. 10A is a schematic cross-sectional view for explaining the state of chemical treatment (oxide removal process, surface cleaning process). FIG. 10B is an illustrative cross-sectional view for explaining the rinsing process after the chemical solution process. FIG. 11 is a sequence diagram for explaining an example of control operation. FIG. 12 is a diagram for explaining the desolvation action by the post-substrate heat treatment. FIG. 13 is a diagram for explaining the dehydration effect of the post-substrate heat treatment.

BEST MODE FOR CARRYING OUT THE INVENTION Below, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
1A to 1D are explanatory diagrams for explaining the principle of substrate processing according to one embodiment of the present invention. The substrates to be processed are typically silicon wafers, and more commonly substrates having on their surface materials that are susceptible to oxidation, such as silicon, germanium, and the like. The surface of the substrate may be, for example, the surface of a silicon wafer or the surface of a pattern containing an easily oxidizable material such as silicon.

FIG. 1A shows the surface state of a silicon wafer W before processing. Oxide Ox is formed on the surface of the wafer W, and unevenness is caused by this oxide Ox. The oxide Ox may be a natural oxide or an oxide produced by a chemical reaction with a chemical solution. Therefore, on the surface of the wafer W, there are a silicon exposed portion Wsi where the substrate material silicon is exposed and an oxide portion Wox which is the surface of the oxide Ox.

FIG. 1D shows the surface state in the case where the surface state shown in FIG. 1A is maintained, that is, when the wafer W having the uneven surface due to the oxide Ox is subjected to the hydrophobizing treatment by supplying the hydrophobizing agent. is considered to be That is, the functional groups (for example, silanol groups) of the hydrophobizing substance Sm combine with the OH groups (hydroxy groups) on the exposed silicon portion Wsi or the OH groups on the surface of the oxide Ox, and the molecules of the hydrophobizing substance Sm are combined with each other. Thereby, a hydrophobized film covering the exposed silicon portion Wsi and the oxide portion Wox is formed. Since the molecules of the hydrophobizing substance Sm are relatively large, the surface of the hydrophobizing film is formed with unevenness larger than that of the original surface of the wafer W, thereby deteriorating the roughness. Therefore, the contact angle of the liquid is not so large, and sufficient hydrophobic performance cannot be obtained. In addition, amplified roughness may be detected as particles when observed with a particle counter.

In this processing example, a processing for removing the oxide Ox is performed as the thermal reforming processing for the wafer W in FIG. 1A (heating removal step). As a result, as shown in FIG. 1B, substantially the entire surface of the wafer W becomes an exposed silicon portion Wsi due to the exposure of the substrate material, and the roughness of the surface of the wafer W is improved. When a hydrophobizing agent is supplied to the surface of the wafer W in this state to perform the hydrophobization treatment, as shown in FIG. Bonds uniformly with groups. As a result, the molecules of the hydrophobizing substance Sm are uniformly aligned along the surface of the wafer W, and a hydrophobized surface without unevenness is obtained. Such a surface has a large liquid contact angle, sufficient hydrophobicity, and does not have irregularities that may be detected as particles.

Note that it is not always necessary to remove all of the oxide Ox on the wafer W, and the hydrophobic treatment may be performed after partially removing the oxide Ox to improve the roughness of the surface.
2A to 2C are explanatory diagrams for explaining another principle of substrate processing according to one embodiment of the present invention. FIG. 2A shows the surface state of the silicon wafer W before processing, which is the same as FIG. 1A.

In this example, a process for planarizing the oxide Ox is performed as the thermal modification process for the wafer W in FIG. 2A (flattening process). More specifically, by subjecting the wafer W to appropriate heat treatment, the oxide Ox is decomposed and recombined. As a result, as shown in FIG. 2B, the oxide Ox having a uniform thickness is formed over substantially the entire surface of the wafer W, and the roughness of the surface of the wafer W is improved. When the hydrophobizing agent is supplied to the surface of the wafer W in this state and the hydrophobization treatment is performed, the functional groups of the hydrophobizing substance Sm become OH of the oxide portion Wox over almost the entire surface of the wafer W, as shown in FIG. 2C. Bonds uniformly with groups.

As a result, the molecules of the hydrophobizing substance Sm are uniformly aligned along the surface of the wafer W, and a hydrophobized surface without unevenness is obtained. Such a surface has a large liquid contact angle, sufficient hydrophobicity, and does not have irregularities that may be detected as particles.
3A to 3C are explanatory diagrams for explaining still another principle of substrate processing according to one embodiment of the present invention. FIG. 3A shows the surface state of the silicon wafer W before processing, which is the same as FIG. 1A.

In this processing example, a processing for removing the oxide Ox is performed as the thermal reforming processing for the wafer W in FIG. 3A (heating removal step). As a result, as shown in FIG. 3B, substantially the entire surface of the wafer W becomes an exposed silicon portion Wsi due to the exposure of the substrate material, and the roughness of the surface of the wafer W is improved.
On the surface of the wafer W in this state, a new oxide film Oxn is formed with a uniform thickness, as shown in FIG. 3C. The new oxide film Oxn may be formed by heating in an oxygen-containing atmosphere (an example of a thermal reforming step).

The new oxide film Oxn thus formed inherits the roughness of the exposed silicon portion Wsi in the state of FIG. 3B, and presents a surface with improved roughness. When the surface of the wafer W in this state, that is, the surface of the new oxide film Oxn is subjected to a hydrophobizing treatment by supplying a hydrophobizing agent, almost the entire surface of the wafer W is covered with the hydrophobizing agent Sm, as shown in FIG. 3D. are uniformly bonded to the OH groups on the surface of the new oxide film Oxn.

As a result, the molecules of the hydrophobizing substance Sm are uniformly aligned along the surface of the wafer W, and a hydrophobized surface without unevenness is obtained. Such a surface has a large liquid contact angle, sufficient hydrophobicity, and does not have irregularities that may be detected as particles.
FIG. 4 is an illustrative plan view for explaining the internal layout of the substrate processing apparatus 1 according to one embodiment of the present invention. The substrate processing apparatus 1 is a single-wafer type apparatus that processes silicon wafers W, which are an example of substrates, one by one. In this embodiment, the wafer W is a disk-shaped substrate. The substrate processing apparatus 1 includes a thermal processing unit 100 that thermally processes a wafer W, and a plurality of (three in this embodiment) processing units 2 that process the wafer W with a processing liquid. The substrate processing apparatus 1 further includes a load port LP on which a carrier C containing a plurality of wafers W to be processed by the thermal processing unit 100 and the processing unit 2 is placed, the load port LP, the thermal processing unit 100 and the processing unit 2. and a control unit 3 for controlling the substrate processing apparatus 1 . The transfer robot IR transfers the wafer W between the carrier C and the transfer robot CR. The transfer robot CR transfers the wafer W between the transfer robot IR and the processing unit 2 . A plurality of processing units 2 have, for example, the same configuration. The thermal processing unit 100 can be used to heat the wafer W to perform a thermal reforming process of reforming the surface thereof.

The transport robot CR loads the unprocessed wafer W received from the transport robot IR into the thermal processing unit 100 . Then, the transfer robot CR unloads the wafer W subjected to the thermal modification process by the heat treatment unit 100 from the heat treatment unit 100 and carries it into the treatment unit 2 . Further, the transfer robot CR takes out the wafer W processed by the processing unit 2 from the processing unit 2 and transfers it to the transfer robot IR.

FIG. 5 is an illustrative cross-sectional view for explaining a configuration example of the heat treatment unit 100. As shown in FIG. The thermal processing unit 100 may be a so-called annealing device. More specifically, the thermal processing unit 100 includes a sealable chamber 101, a susceptor 102 that supports the wafer W within the chamber 101, and a lamp heater unit 103 (for example, a halogen lamp heater unit). The chamber 101 is provided with an openable/closable gate 107 , and the wafer W can be taken in and out of the chamber 101 by opening the gate 107 . The thermal processing unit 100 may further include a flash lamp unit 104 (eg, a xenon flash lamp unit, a krypton flash lamp unit, etc.) for flash heating the surface of the wafer W supported by the susceptor 102 .

The thermal processing unit 100 further comprises an exhaust unit 105 for exhausting the atmosphere inside the chamber 101 . The exhaust unit 105 includes an exhaust pipe 105a that communicates with the interior of the chamber 101, and an exhaust valve 105b that opens and closes the flow path of the exhaust pipe 105a. Furthermore, the heat treatment unit 100 includes an inert gas supply unit 106 that supplies inert gas into the chamber 101 . The inert gas supply unit 106 includes an inert gas supply pipe 106a that communicates with the interior of the chamber 101, and an inert gas valve 106b that opens and closes the flow path of the inert gas supply pipe 106a. By exhausting the atmosphere in the chamber 101 with the exhaust unit 105 and supplying inert gas into the chamber 101 with the inert gas supply unit 106, the atmosphere in the chamber 101 can be made into a low-oxygen atmosphere. That is, the exhaust unit 105 and the inert gas supply unit 106 constitute an atmosphere control unit. Moreover, by supplying an inert gas from the inert gas supply unit 106, the wafer W after the heat treatment can be cooled. That is, the inert gas supply unit 106 is an example of a cooling unit that cools the wafer W after heat treatment.

FIG. 6 is a schematic cross-sectional view for explaining a configuration example of the processing unit 2. As shown in FIG. The processing unit 2 includes a chamber 4 (see FIG. 4), a spin chuck 5, a facing member 6, a support member 7, an inert gas supply unit 8, a first processing liquid supply unit 30, and a second processing liquid. It includes a supply unit 40 , an organic solvent supply unit 10 , a hydrophobic agent supply unit 11 , a support member elevating unit 12 , a processing cup 13 and a heater unit 110 .

The spin chuck 5 rotates the wafer W around a vertical rotation axis A1 passing through the center of the wafer W while holding the wafer W in a horizontal posture. The spin chuck 5 is housed inside the chamber 4 (see FIG. 4). The chamber 4 is formed with an entrance (not shown) for loading the wafer W into the chamber 4 and unloading the wafer W from the chamber 4 . The chamber 4 is provided with a shutter unit (not shown) that opens and closes this entrance.

The spin chuck 5 includes a substrate holding unit 24 , a rotating shaft 22 and an electric motor 23 . The substrate holding unit 24 holds the wafer W horizontally. The substrate holding unit 24 includes a spin base 21 and multiple chuck pins 20 . The spin base 21 has a disk shape along the horizontal direction. A plurality of chuck pins 20 are arranged at intervals in the circumferential direction on the upper surface of the spin base 21 . The rotating shaft 22 is connected to the center of the lower surface of the spin base 21 . The rotation shaft 22 extends vertically along the rotation axis A1. The electric motor 23 applies rotational force to the rotating shaft 22 . The rotation of the rotating shaft 22 by the electric motor 23 causes the spin base 21 of the substrate holding unit 24 to rotate. Thereby, the wafer W is rotated in the rotation direction S around the rotation axis A1. The electric motor 23 constitutes a substrate rotation unit that rotates the wafer W around the rotation axis A1.

The facing member 6 has a substantially circular shape in plan view. The rotation axis A1 is a vertical axis passing through the center of the opposing member 6 . The facing member 6 is made of resin in this embodiment. PEEK (polyether ether ketone) or the like can be used as the resin forming the opposing member 6 . The facing member 6 is an example of a shielding member that shields the atmosphere in the space 65 between the facing member 6 and the upper surface of the wafer W from the ambient atmosphere.

The opposing member 6 can be engaged with the substrate holding unit 24 by magnetic force, for example. Specifically, the facing member 6 includes a plurality of first engaging portions 66 . The first engaging portion 66 extends downward from the facing surface 60 a of the facing portion 60 . The plurality of first engaging portions 66 are spaced apart from each other in the rotational direction S. As shown in FIG. The substrate holding unit 24 includes a plurality of second engaging portions 76 that can engage with the plurality of first engaging portions 66 in concave-convex manner. The plurality of second engaging portions 76 are spaced apart from each other in the rotational direction S and fixed to the spin base 21 .

The opposing member 6 can rotate integrally with the substrate holding unit 24 in a state where each first engaging portion 66 of the opposing member 6 is engaged with the corresponding second engaging portion 76 of the substrate holding unit 24 . When the opposing member 6 and the substrate holding unit 24 are engaged with each other, the electric motor 23 rotates the spin base 21 , thereby rotating the opposing member 6 together with the substrate holding unit 24 . That is, the electric motor 23 also functions as a facing member rotation unit that rotates the facing member 6 around the rotation axis A1.

The facing member 6 includes a facing portion 60 , an extension portion 61 , a cylindrical portion 62 and a plurality of flange portions 63 . The facing portion 60 faces the upper surface of the wafer W from above. The facing portion 60 is formed in a disc shape. The facing portion 60 is arranged substantially horizontally above the spin chuck 5 . The facing portion 60 has a facing surface 60a that faces the upper surface of the wafer W. As shown in FIG. The facing surface 60 a is the lower surface of the facing portion 60 . The extending portion 61 extends downward from the peripheral edge portion of the facing portion 60 and is annularly formed around the rotation axis A1. An inner peripheral surface 61a of the extending portion 61 forms a tapered surface that is inclined with respect to the vertical direction so as to extend downward in a radial direction about the rotation axis A1. The outer peripheral surface of the extended portion 61 extends along the vertical direction.

Hereinafter, the radially inward direction about the rotation axis A1 is simply referred to as "radially inward", and the radially outward direction about the rotational axis A1 is simply referred to as "radial outward". When the opposing member 6 is engaged with the substrate holding unit 24 , the extended portion 61 surrounds the wafer W radially inwardly of the first guard 17 and extends laterally (radially outwardly) along the periphery of the wafer W. ) to face each other (see the two-dot chain line in FIG. 6).

The tubular portion 62 is fixed to the upper surface of the facing portion 60 . The plurality of flange portions 63 are arranged at the upper end of the tubular portion 62 so as to be spaced apart from each other in the circumferential direction (rotational direction S) of the tubular portion 62 . Each flange portion 63 extends horizontally from the upper end of the tubular portion 62 .
The processing liquid used in the substrate processing apparatus 1 includes a chemical liquid, a rinse liquid, an organic solvent, a hydrophobizing agent, and the like.

The first processing liquid supply unit 30 and the second processing liquid supply unit 40 supply the chemical liquid and the rinse liquid (processing liquid) to the central region of the upper surface of the wafer W. As shown in FIG. The central area of the upper surface of wafer W is an area near the center of the upper surface of wafer W including the intersection position of the upper surface of wafer W and rotation axis A1.
The first processing liquid supply unit 30 includes a processing liquid nozzle 33 that discharges the processing liquid toward the central region of the upper surface of the wafer W, a chemical liquid supply pipe 31 coupled to the processing liquid nozzle 33, and a chemical liquid supply pipe 31 connected to the processing liquid nozzle 33. It includes a combined rinse liquid supply pipe 34 , a chemical liquid valve 32 interposed in the chemical liquid supply pipe 31 , and a rinse liquid valve 35 interposed in the rinse liquid supply pipe 34 . The chemical supply pipe 31 is supplied with an acid-based chemical such as hydrofluoric acid (aqueous hydrogen fluoride: HF) from a chemical supply source. The chemical liquid valve 32 opens and closes the flow path in the chemical liquid supply pipe 31 . A rinse liquid such as DIW (deionized water) is supplied to the rinse liquid supply pipe 34 from a rinse liquid supply source. The rinse liquid valve 35 opens and closes the flow path in the rinse liquid supply pipe 34 . The first processing liquid supply unit 30 is an example of a processing liquid supply unit that supplies the surface of the wafer W with a processing liquid for cleaning the surface of the wafer W in this embodiment. In particular, the portion of the first processing liquid supply unit 30 related to chemical supply constitutes a chemical liquid supply unit, and the portion related to rinse liquid supply constitutes a rinse liquid supply unit.

The second processing liquid supply unit 40 includes a processing liquid nozzle 43 that discharges the processing liquid toward the center region of the upper surface of the wafer W, a chemical liquid supply pipe 41 coupled to the processing liquid nozzle 43, and a chemical liquid supply pipe 41 connected to the processing liquid nozzle 43. It includes a combined rinse liquid supply pipe 44 , a chemical liquid valve 42 interposed in the chemical liquid supply pipe 41 , and a rinse liquid valve 45 interposed in the rinse liquid supply pipe 44 . An alkaline chemical such as SC1 (ammonia-hydrogen peroxide mixture) is supplied from a chemical supply source to the chemical supply pipe 41 . The chemical liquid valve 42 opens and closes the flow path in the chemical liquid supply pipe 41 . A rinse liquid such as _CO2 water (carbonated water) is supplied to the rinse liquid supply pipe 44 from a rinse liquid supply source. The rinse liquid valve 45 opens and closes the flow path in the rinse liquid supply pipe 44 . The second processing liquid supply unit 40 is an example of a processing liquid supply unit that supplies the surface of the wafer W with a processing liquid for cleaning the surface of the wafer W in this embodiment. In particular, the portion of the second processing liquid supply unit 40 related to chemical supply constitutes a chemical liquid supply unit, and the portion related to rinse liquid supply constitutes a rinse liquid supply unit.

Examples of chemicals are not limited to hydrofluoric acid and SC1. Chemical liquids discharged from the processing liquid nozzles 33 and 43 include sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, buffered hydrofluoric acid (BHF), dilute hydrofluoric acid (DHF), ammonia water, hydrogen peroxide water, organic alkali ( For example, it may be a liquid containing at least one of TMAH (tetramethylammonium hydroxide, etc.), a surfactant, and a corrosion inhibitor. Examples of chemical liquids in which these are mixed include SPM (sulfuric acid-hydrogen peroxide solution mixture), SC1 (ammonia-hydrogen peroxide solution mixture), SC2 (hydrochloric acid-hydrogen peroxide solution mixture), and the like. However, when using an acid-based chemical solution and an alkaline-based chemical solution, it is possible to supply the respective chemical solutions from the first and second processing solution supply units 30 and 40 so as to avoid their mixing. preferable.

Further, the rinse liquid discharged from the processing liquid nozzles 33 and 43 is not limited to DIW or _CO2 water. For example, the rinse liquid discharged from the treatment liquid nozzles 33 and 43 may be electrolytic ion water, ozone water, ammonia water, hydrochloric acid water with a diluted concentration (for example, about 10 ppm to 100 ppm), or reduced water (hydrogen water). good. The rinse contains water.
The organic solvent supply unit 10 is a unit that supplies an organic solvent to the central region of the upper surface of the wafer W. As shown in FIG. The organic solvent supply unit 10 includes an organic solvent nozzle 50 for discharging an organic solvent toward the central region of the upper surface of the wafer W, an organic solvent supply pipe 51 coupled to the organic solvent nozzle 50 , and an organic solvent supply pipe 51 interposed therebetween. and an installed organic solvent valve 52 . An organic solvent such as IPA is supplied to the organic solvent supply pipe 51 from an organic solvent supply source. The organic solvent valve 52 opens and closes the flow path inside the organic solvent supply pipe 51 . In this embodiment, the organic solvent supply unit 10 is an example of a pre-organic solvent supply unit that supplies the organic solvent before the surface of the wafer W is hydrophobized, and the organic solvent is supplied after the surface of the wafer W is hydrophobized. It is an example of a post-supply organic solvent supply unit.

The organic solvent discharged from the organic solvent nozzle 50 is not limited to IPA. The organic solvent discharged from the organic solvent nozzle 50 is an organic solvent other than IPA that does not chemically react (has poor reactivity) with the upper surface of the wafer W and the pattern (not shown) formed on the wafer W. good too. More specifically, the organic solvent discharged from the organic solvent nozzle 50 is a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and Trans-1,2-dichloroethylene. It may be a solvent. However, the organic solvent supplied from the organic solvent nozzle 50 is preferably an organic solvent that is miscible (that is, has compatibility) with the solvent of the hydrophobizing agent supplied from the hydrophobizing agent supply unit 11 . Furthermore, the organic solvent supplied from the organic solvent nozzle 50 is an organic solvent that is miscible (that is, has compatibility) with the rinsing liquid (DIW, _CO2 water, etc.) supplied from the processing liquid supply units 30 and 40. is preferred.

The hydrophobizing agent supply unit 11 is a unit that supplies a liquid hydrophobizing agent to the center region of the upper surface of the wafer W. As shown in FIG. The hydrophobizing agent supply unit 11 includes a hydrophobizing agent nozzle 80 for discharging a hydrophobizing agent toward the central region of the upper surface of the wafer W, a hydrophobizing agent supply pipe 81 coupled to the hydrophobizing agent nozzle 80, and a hydrophobizing agent. and a hydrophobizing agent valve 82 interposed in the agent supply pipe 81 . A hydrophobizing agent supply pipe 81 is supplied with a liquid hydrophobizing agent from a hydrophobizing agent supply source. The hydrophobizing agent valve 82 opens and closes the channel in the hydrophobizing agent supply pipe 81 .

The hydrophobizing agent discharged from the hydrophobizing agent nozzle 80 is a liquid obtained by dissolving a hydrophobizing substance in a solvent. As the hydrophobizing agent, for example, a silicon hydrophobizing agent that hydrophobizes silicon itself and a compound containing silicon, or a metal hydrophobizing agent that hydrophobizes metal itself and a compound containing metal can be used. The metal hydrophobizing agent includes, for example, at least one of an amine having a hydrophobic group and an organosilicon compound as a hydrophobizing substance. A silicon-based hydrophobizing agent is, for example, a silane coupling agent. The silane coupling agent includes at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilane, alkyldisilazane, and non-chloro hydrophobizing agent as a hydrophobizing substance. . Non-chloro hydrophobizing agents include, for example, dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethylaminotrimethylsilane, N-( At least one of trimethylsilyl)dimethylamine and an organosilane compound is included as a hydrophobizing agent. The solvent for dissolving the hydrophobizing substance may be at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, esters, alcohols, ethers and the like. More specifically, methanol, ethanol, IPA, butanol, ethylene glycol, propylene glycol, NMP (N-methyl-2-pyrrolidone), DMF (N,N-dimethylformamide), DMA (dimethylacetamide), DMSO (dimethyl sulfoxide), hexane, toluene, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol molar methyl ether), PGPE (propylene glycol monopropyl ether), PGEE (propylene glycol monoethyl ether), GBL (γ-butyrolactone), selected from the group consisting of acetylacetone, 3-pentanone, 2-heptanone, ethyl lactate, cyclohexanone, dibutyl ether, HFE (hydrofluoroether), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, and m-xylene hexafluoride At least one type may be used.

A degassing unit is provided in order to reduce dissolved oxygen in the processing liquid (chemical liquid, rinse liquid, organic solvent, and hydrophobizing agent) supplied to the wafer W. FIG. That is, degassing units 36, 46, 37, 47, 53, and 83 are interposed in the chemical solution supply pipes 31, 41, the rinse solution supply pipes 34, 44, the organic solvent supply pipe 51, and the hydrophobizing agent supply pipe 81, respectively. is dressed. Therefore, the processing liquid in which the dissolved oxygen is reduced is supplied to the surface of the wafer W. As shown in FIG. A degassing unit may be provided at each processing liquid source. The degassing unit may be configured to discharge oxygen dissolved in the treatment liquid by introducing an inert gas into each treatment liquid (for example, by bubbling).

The inert gas supply unit 8 includes an inert gas nozzle 90 for discharging an inert gas toward the central region of the upper surface of the wafer W, an inert gas supply pipe 91 coupled to the inert gas nozzle 90, and an inert gas supply unit 8. and an inert gas valve 92 interposed in tube 91 . An inert gas such as nitrogen gas is supplied to the inert gas supply pipe 91 from an inert gas supply source. The inert gas valve 92 opens and closes the flow path inside the inert gas supply pipe 91 .

The processing liquid nozzles 33 and 43, the organic solvent nozzle 50, the hydrophobizing agent nozzle 80, and the inert gas nozzle 90 are commonly housed in the nozzle housing member 38 in this embodiment. A lower end portion of the nozzle accommodating member 38 faces the central region of the upper surface of the wafer W. As shown in FIG.
The support member 7 includes a facing member support portion 70 that supports the facing member 6, a nozzle support portion 72 that is provided above the facing member support portion 70 and supports the nozzle accommodating member 38, the facing member support portion 70, and the nozzle support. and a vertically extending wall portion 71 connecting the portion 72 . A space 75 is defined by the opposing member support portion 70 , the wall portion 71 and the nozzle support portion 72 . The space 75 accommodates the upper end portion of the tubular portion 62 and the flange portion 63 . The opposing member support portion 70 constitutes the lower wall of the support member 7 . The nozzle support portion 72 constitutes the upper wall of the support member 7 . The nozzle housing member 38 is attached substantially in the center of the nozzle support portion 72 . The tip of the nozzle housing member 38 is located below the nozzle support portion 72 . The ejection openings of the nozzles 33, 43, 50, 80, and 90 are arranged downward at the lower end of the nozzle housing member 38, respectively. These outlets face the central region of the wafer W from above vertically through a space in the cylindrical portion 62 of the opposing member 6 and a through hole 60 b formed in the center of the opposing portion 60 .

The opposing member support portion 70 supports the opposing member 6 (more specifically, the flange portion 63) from below. A tubular portion insertion hole 70 a through which the tubular portion 62 is inserted is formed in the central portion of the opposing member support portion 70 . Each flange portion 63 is formed with a positioning hole 63a penetrating through the flange portion 63 in the vertical direction. Engagement protrusions 70 b that can be engaged with the positioning holes 63 a of the corresponding flange portion 63 are formed on the opposing member support portion 70 . The opposing member is positioned with respect to the supporting member in the rotational direction S by engaging the engaging projection 70b corresponding to each positioning hole 63a.

The supporting member elevating unit 12 elevates the opposing member 6 together with the supporting member 7 . The supporting member elevating unit 12 functions as an opposing member elevating unit that raises and lowers the opposing member 6 . Therefore, the support member elevating unit 12 functions as a shielding member placement unit that disposes the opposing member 6 as a shielding member at a position close to the surface of the wafer W so as to face it. The support member elevating unit 12 includes, for example, a ball screw mechanism (not shown) and an electric motor (not shown) that applies a driving force to the ball screw mechanism.

The support member elevating unit 12 can position the support member 7 at a predetermined height position between the upper position and the lower position. The lower position is the position where the support member 7 is closest to the upper surface of the substrate holding unit 24 within the movable range of the support member 7 . The upper position is the position indicated by the solid line in FIG. Specifically, the upper position is the position where the support member 7 is farthest from the upper surface of the substrate holding unit 24 in the movable range of the support member 7 .

The support member 7 suspends and supports the opposing member 6 in the upper position. In this state, the facing member 6 is separated upward from the substrate holding unit 24 . The support member 7 is moved up and down by the support member elevating unit 12 to pass through the engagement position between the upper position and the lower position. The engagement position is a position indicated by a two-dot chain line in FIG. The engaging position is the height position of the supporting member 7 when the opposing member 6 is supported by the supporting member 7 from below and the opposing member 6 and the substrate holding unit 24 are engaged with each other. When the support member 7 is positioned at the lower position, the support member 7 is spaced downward from the opposing member 6 engaged with the substrate holding unit 24 .

When the support member 7 is moved up and down between the upper position and the engaging position, the opposing member 6 moves up and down integrally with the support member 7 . The support member 7 is spaced downward from the opposing member 6 when positioned between the engagement position and the lower position. The opposing member 6 is maintained in a state of being engaged with the substrate holding unit 24 when the supporting member 7 is positioned between the engaging position and the lower position.
The processing cup 13 is arranged radially outward of the wafer W held by the spin chuck 5 . The processing cup 13 includes an exhaust tub 26, a plurality of cups 14-16, a plurality of guards 17-19, and a plurality of guard lifting units 27-29. The plurality of cups includes first cup 14 , second cup 15 and third cup 16 . The multiple guards include first guard 17 , second guard 18 and third guard 19 . The multiple guard lifting units include a first guard lifting unit 27 , a second guard lifting unit 28 and a third guard lifting unit 29 .

The exhaust trough 26 surrounds the spin chuck 5 . The exhaust tub 26 is connected to an exhaust pipe (not shown) for discharging the air flowing into the chamber 4 (see FIG. 4) to the outside of the chamber 4 . A plurality of cups 14 - 16 and a plurality of guards 17 - 19 are arranged between the spin chuck 5 and the exhaust tub 26 . Each of the plurality of cups 14-16 surrounds the wafer W. As shown in FIG. Each of the plurality of guards 17-19 surrounds the wafer W. As shown in FIG.

Each of the guards 17 to 19 receives the processing liquid that scatters radially outward from the wafer W held by the spin chuck 5 . The second guard 18 is arranged radially outward of the first guard 17 . The third guard 19 is arranged radially outward of the second guard 18 .
The first guard 17 includes a first tubular portion 17A that surrounds the spin chuck 5 radially inwardly of the exhaust tub 26, and a first tubular portion 17A that extends radially inward and upward from the first tubular portion 17A. 1 inclined portion 17B. The second guard 18 includes a second tubular portion 18A that surrounds the spin chuck 5 radially inwardly of the exhaust tub 26 and radially outwardly of the first tubular portion 17A, and a second tubular portion 18A that extends radially inward. and a second inclined portion 18B extending upward from the second cylindrical portion 18A. The third guard 19 includes a third tubular portion 19A that surrounds the spin chuck 5 radially inward of the exhaust tub 26 and radially outward of the second tubular portion 18A, and a radially inward and a third inclined portion 19B extending upward from the third cylindrical portion 19A.

The first inclined portion 17B faces the second inclined portion 18B from below. The second inclined portion 18B faces the third inclined portion 19B from below.
Each cup 14-16 has an upwardly opening annular groove. The second cup 15 is arranged radially outward of the first cup 14 . The third cup 16 is arranged radially outward of the second cup 15 . The third cup 16 is provided integrally with the second guard 18 . A recovery line (not shown) or a discharge line (not shown) is connected to the groove of each cup 14-16. The processing liquid received by the corresponding guards 17-19 is led to the bottom of each cup 14-16. The processing liquid led to the bottom of each cup 14-16 is recovered or discarded through recovery piping or discharge piping.

The plurality of guard lifting units 27-29 drive the lifting and lowering of the plurality of guards 17-19, respectively. Each guard lifting unit 27 to 29 includes, for example, a ball screw mechanism (not shown) and an electric motor (not shown) that provides driving force to it.
A heater unit 110 is used to heat the wafer W held by the spin chuck 5 . The heater unit 110 can be used as a post-heating unit that heats the wafer W after the hydrophobic treatment.

The heater unit 110 has the shape of a disc-shaped hot plate. The heater unit 110 has a facing surface 110a that faces the lower surface of the wafer W from below.
Heater unit 110 includes a plate body 111 and a heater 112 . The plate body 111 is slightly smaller than the wafer W in plan view. The surface of the plate body 111 forms the facing surface 110a. The heater 112 may be a resistor built in the plate body 111 . By energizing the heater 112, the facing surface 110a is heated. Electric power is supplied to the heater 112 from a heater power supply unit 113 via a power supply line.

The heater unit 110 is arranged above the spin base 21 . The processing unit 2 includes a heater elevating unit 114 that elevates the heater unit 110 relative to the spin base 21 . Heater elevating unit 114 includes, for example, a ball screw mechanism and an electric motor for driving it.
An elevating shaft 115 extending vertically along the rotation axis A<b>1 is coupled to the lower surface of the heater unit 110 . The elevating shaft 115 is inserted through a through hole 21 a formed in the center of the spin base 21 and the hollow rotary shaft 22 . A power supply line 116 is passed through the elevation shaft 115 . The heater elevating unit 114 raises and lowers the heater unit 110 via the elevating shaft 115 so that the heater unit 110 can be arranged at a lower position, an upper position, and any intermediate position therebetween. When the heater unit 110 is positioned at the lower position, the distance between the facing surface 110a and the lower surface of the wafer W is 15 mm, for example. Since the heater unit 110 moves (elevates) relative to the spin base 21, the distance between the lower surface of the wafer W and the facing surface 110a of the heater unit 110 changes.

The substrate processing apparatus 1 further includes a bottom surface inert gas supply unit 120 that supplies an inert gas such as nitrogen gas toward the center of the bottom surface of the wafer W held by the spin chuck 5 . The lower surface inert gas supply unit 120 includes an inert gas supply pipe 121 and an inert gas valve 122 interposed in the inert gas supply pipe 121 . The inert gas supply pipe 121 passes through a hollow elevating shaft 115 and passes through a central opening (not shown) of the heater unit 110. At the upper end of the inert gas supply pipe 121, there is a discharge port facing the center of the lower surface of the wafer W from below. have.

FIG. 7 is a block diagram for explaining the electrical configuration of the main part of the substrate processing apparatus 1. As shown in FIG. The control unit 3 has a microcomputer, and controls the control objects provided in the substrate processing apparatus 1 according to a predetermined program. More specifically, the control unit 3 includes a processor (CPU) 3A and a memory 3B in which programs are stored. configured to perform control. In particular, the control unit 3 controls the operations of the transport robots IR and CR, the electric motor 23, the support member elevating unit 12, the guard elevating units 27-29, the valves 32, 35, 42, 45, 52, 82, 92, 122, and the like. Control. In addition, the control unit 3 controls energization of each part of the heat treatment unit 100, particularly the lamp heater unit 103 and the flash lamp unit 104, controls the exhaust operation by the exhaust unit 105, and controls the inert gas supply unit 106. Programmed to control the gas supply. Further, the control unit 3 is programmed to control the energization of the heater 112 by the heater energization unit 113 and to control the operation of the heater elevating unit 114 .

FIG. 8A is a flowchart for explaining an example of substrate processing by the substrate processing apparatus 1 of this embodiment, and mainly shows processing realized by the control unit 3 executing a program. 9A to 9G are schematic cross-sectional views for explaining the substrate processing example.
In substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 8A, substrate loading (S21), substrate heating (S22), substrate cooling (S23), substrate transfer (S24), chemical solution processing (S25), Rinsing treatment (S26), first organic solvent treatment (S27), hydrophobic treatment (S28), second organic solvent treatment (S29), drying treatment (S30), post-substrate heating treatment (S31), post-substrate cooling treatment ( S32) and unloading of the substrate (S33) are executed in this order.

More specifically, an unprocessed wafer W is taken out from the carrier C by the transfer robot IR. The transport robot CR receives the unprocessed wafer W from the transport robot IR, loads it into the chamber 101 of the thermal processing unit 100, places it on the susceptor 102, and retreats (S21: substrate loading). The control unit 3 heats the wafer W by, for example, energizing the lamp heater unit 103 (S22: substrate heating process). This substrate heating process is performed so as to supply the wafer W with thermal energy necessary to break the bond between the material (eg, silicon) of the wafer W and oxygen. That is, the substrate heating treatment (S22) may be a heating removal step (oxide removal step) for removing at least part of the oxide on the surface of the wafer W by heating (see FIG. 1B). More specifically, the wafer W is heated to 300° C. or higher, more preferably 500° C. or higher, still more preferably 700° C. or higher. For example, energization to lamp heater unit 103 may be controlled so that wafer W is held at 750° C. for a predetermined time (for example, 20 seconds). If necessary, flash heating by the flash lamp unit 104 may also be used.

The substrate heating process (S22) may be a planarization process that splits and recombines the oxide on the surface of the wafer W to planarize the oxide (see FIG. 2B).
Prior to the substrate heating process (S22), the control unit 3 operates the exhaust unit 105 to exhaust the atmosphere in the chamber 101, and causes the inert gas supply unit 106 to supply inert gas into the chamber 101. . Accordingly, atmosphere control (S35) is performed to maintain the atmosphere around the wafer W at a low-oxygen atmosphere. This atmosphere control continues until the wafer W is unloaded from the thermal processing unit 100 .

After the substrate heating process (S22), a substrate cooling process (S23, cooling step) is performed to bring the wafer W closer to room temperature. Specifically, the control unit 3 stops energizing the lamp heater unit 103 . Meanwhile, the supply of inert gas by the inert gas supply unit 106 and the evacuation of the chamber 101 by the evacuation unit 105 are continued. Thereby, the wafer W is cooled by heat exchange between the wafer W and the inert gas.

Then, after a predetermined cooling time has passed, the control unit 3 takes out the wafer W after the cooling process from the heat treatment unit 100 and carries it into one of the process units 2 (S24: substrate transfer).
Before or during the substrate cooling process (S23), air (oxygen) may be introduced into the chamber 101 to form a new oxide film Oxn (see FIG. 3C) on the surface of the wafer W (heating An example of a reforming process). A uniform oxide film Oxn can be formed on the surface of the wafer W by placing the wafer W at a high temperature in an atmosphere in which the oxygen concentration is controlled.

Before the wafer W is loaded into the processing unit 2, the relative positions of the opposing member 6 and the substrate holding unit 24 in the rotational direction S are adjusted so that the opposing member 6 and the substrate holding unit 24 can be engaged. be. Specifically, the position of the substrate holding unit 24 in the rotation direction S is adjusted by the electric motor 23 so that the first engaging portion 66 of the opposing member 6 and the second engaging portion 76 of the substrate holding unit 24 overlap in plan view. adjust.

On the other hand, an unprocessed wafer W is transported from the heat treatment unit 100 to the processing unit 2 by the transport robot CR (see FIG. 4) and transferred to the spin chuck 5 (S24: substrate transport). After that, the wafer W is held horizontally with a gap above the upper surface of the spin base 21 by the chuck pins 20 until it is unloaded by the transfer robot CR (substrate holding step).

Then, the support member elevating unit 12 lowers the support member 7 positioned at the upper position toward the lower position. The support member 7 passes through the engagement position before moving to the lower position. When the support member 7 reaches the engagement position, the opposing member 6 and the substrate holding unit 24 are engaged by magnetic force. Accordingly, the opposing member 6 is supported from below by the substrate holding unit 24 whose height position is fixed. When the opposing member 6 is engaged with the substrate holding unit 24, the opposing portion 60 of the opposing member 6 is arranged close to the upper surface of the wafer W and faces the upper surface of the wafer W from above. On the other hand, the extending portion 61 of the opposing member 6 faces the wafer W from the radially outer side and surrounds the peripheral edge of the wafer W. As shown in FIG. Further, when the opposing member 6 is engaged with the substrate holding unit 24, the lower end of the extension 61 faces the spin base 21 from above. A small gap is provided between the lower end portion of the extension portion 61 and the upper surface of the spin base 21 . In this manner, the support member lifting unit 12 arranges the facing member 6 at a position where the inner peripheral surface of the extension portion 61 faces the wafer W from the outside in the radial direction (blocking member arranging step).

When the support member 7 is further lowered from the engagement position, the opposing member 6 is released from the support by the support member 7 . Specifically, the facing member supporting portion 70 of the supporting member 7 is retracted downward from the flange portion 63 of the facing member 6 .
Then, as shown in FIG. 9A, the support member 7 reaches its lower position. Then, the electric motor 23 is driven and the spin base 21 of the substrate holding unit 24 starts rotating. Thereby, the horizontally held wafer W rotates (substrate rotation step). The first engaging portion 66 provided on the opposing member 6 is engaged with the second engaging portion 76 provided on the spin base 21 . Therefore, the opposing member 6 rotates synchronously with the wafer W (opposing member rotating step). Synchronous rotation means rotating in the same direction at the same rotational speed.

Furthermore, the control unit 3 opens the inert gas valve 92 to cause the inert gas nozzle 90 to discharge the inert gas. As a result, the air in the processing space 65 between the spin base 21 and the facing portion 60 is replaced with the inert gas atmosphere. As a result, the surroundings of the wafer W become a low-oxygen atmosphere in which the oxygen concentration is lower than the atmospheric pressure. Thus, the atmosphere control step ( S<b>36 ) for controlling the space around wafer W to a low-oxygen atmosphere is continued until wafer W is unloaded from processing unit 2 .

While maintaining such a low-oxygen atmosphere, chemical treatment (S25: chemical cleaning process, surface cleaning process) is started. The number of rotations of the wafer W is controlled to the chemical solution processing speed (for example, 300 rpm). In the chemical liquid process (S25), the upper surface of the wafer W is subjected to the chemical liquid cleaning process by supplying SC1 as the chemical liquid onto the wafer W from the processing liquid nozzle 43. FIG. The SC1 supplied at this time is low oxygen concentration SC1 in which the dissolved oxygen concentration in the liquid has been reduced by the degassing unit 46 . Specifically, the dissolved oxygen concentration in SC1 discharged from the processing liquid nozzle 43 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

More specifically, referring to FIG. 9A, the third guard lifting unit 29 places the third guard 19 at the upper position, and the second guard lifting unit 28 places the second guard 18 at the upper position. do. Then, the first guard elevating unit 27 arranges the first guard 17 at a height position where the processing liquid can be received (guard arrangement step).
In this state, the chemical valve 42 is opened. As a result, the chemical liquid (SC1) is supplied from the processing liquid nozzle 43 to the central region of the upper surface of the wafer W in the rotating state. The chemical solution spreads over the entire upper surface of the wafer W due to centrifugal force.

The chemical liquid scatters radially outward from the wafer W due to centrifugal force. The chemical liquid scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extending portion 61 of the facing member 6 facing the wafer W from the radially outer side. Since the facing member 6 rotates together with the wafer W, the chemical solution adhering to the inner peripheral surface 61a of the extending portion 61 scatters radially outward from the extending portion 61 due to centrifugal force. The chemical solution scattered radially outward from the extending portion 61 is received by the first guard 17 . The liquid medicine received by the first guard 17 is guided to the first cup 14 along the first tubular portion 17A.

After the chemical solution treatment (S25) for a certain period of time, the rinse treatment (S26; rinse step, surface cleaning step) is performed. The number of rotations of wafer W is controlled to the rinse processing speed (eg, 300 rpm). In the rinsing process, the upper surface of the wafer W is rinsed by replacing the SC1 (chemical solution) on the wafer W with CO ₂ water as a rinsing solution. The rinsing liquid supplied at this time is a low-oxygen-concentration rinsing liquid (for example, CO ₂ water) whose dissolved oxygen concentration has been reduced by the degassing unit 47 . Specifically, the dissolved oxygen concentration in the rinse liquid discharged from the processing liquid nozzle 43 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

At the start of the rinsing process (S26), the chemical liquid valve 42 is closed, and the discharge of SC1 from the processing liquid nozzle 43 is stopped. Referring to FIG. 9B, the third guard lifting unit 29 maintains the third guard 19 at the upper position, and the second guard lifting unit 28 maintains the second guard 18 at the upper position. Then, the first guard elevating unit 27 arranges the first guard 17 at a height position where the processing liquid can be received (guard arrangement step).

In this state, the rinse liquid valve 45 is opened. As a result, the rinsing liquid is supplied from the processing liquid nozzle 43 toward the central region of the upper surface of the wafer W in the rotating state. The rinse liquid spreads over the entire upper surface of the wafer W due to centrifugal force. As a result, the chemical liquid on the wafer W is replaced with the rinse liquid.
The mixture of the chemical solution and the rinse solution or the rinse solution on the wafer W is spattered radially outward from the wafer W due to the centrifugal force. The mixture of the chemical liquid and the rinse liquid or the rinse liquid scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extended portion 61 of the opposing member 6 facing the wafer W from the radially outward direction. Since the facing member 6 rotates together with the wafer W, the liquid mixture of the chemical liquid and the rinse liquid or the rinse liquid adhering to the inner peripheral surface 61a of the extension portion 61 is radially displaced from the extension portion 61 by centrifugal force. scatter to the outside. The first guard 17 receives the mixture of the chemical liquid and the rinse liquid or the rinse liquid that is scattered radially outward from the extending portion 61 . The mixture of the chemical solution and the rinse solution or the rinse solution received by the first guard 17 is guided to the first cup 14 along the first cylindrical portion 17A.

After the rinse treatment (S26) for a certain period of time, the first organic solvent treatment (S27; pre-organic solvent supply step) is performed. The rotation speed of the wafer W is controlled to the organic solvent processing speed (eg, 300 rpm). In the first organic solvent process (S27), the rinse liquid on the wafer W is replaced with an organic solvent such as IPA. This organic solvent is an organic solvent that is miscible with (has compatibility with) _CO2 water, which is the rinse liquid used in the rinse process (S26).

Specifically, the rinse liquid valve 45 is closed. As a result, the discharge of the rinse liquid from the processing liquid nozzle 43 is stopped. Then, referring to FIG. 9C, the first guard lifting unit 27 places the first guard 17 at the lower position. The second guard lifting unit 28 places the second guard 18 at the lower position. Furthermore, the third guard lifting unit 29 arranges the third guard 19 at a height position where it can receive the treatment liquid.

Then, the organic solvent valve 52 is opened. As a result, the organic solvent is supplied from the organic solvent nozzle 50 of the organic solvent supply unit 10 toward the center region of the upper surface of the wafer W in the rotating state. The organic solvent spreads over the entire upper surface of the wafer W due to centrifugal force. As a result, the rinse liquid on the wafer W is replaced with the organic solvent. The organic solvent supplied at this time is a low oxygen concentration organic solvent in which the dissolved oxygen concentration in the liquid has been reduced by the degassing unit 53 . Specifically, the dissolved oxygen concentration in the organic solvent discharged from the organic solvent nozzle 50 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

The mixture of the rinsing liquid and the organic solvent or the organic solvent on the wafer W scatters outward in the radial direction from the wafer W due to the centrifugal force. The mixture of the rinsing liquid and the organic solvent or the organic solvent scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extended portion 61 of the facing member 6 that faces the wafer W from the radially outer side. Since the facing member 6 rotates together with the wafer W, the mixture of the rinsing liquid and the organic solvent or the organic solvent adhering to the inner peripheral surface 61a of the extension portion 61 has a larger diameter than the extension portion 61 due to centrifugal force. Scatter outward. The third guard 19 receives the mixture of the rinse liquid and the organic solvent or the organic solvent that is scattered radially outward from the extended portion 61 . The mixture of the rinsing liquid and the organic solvent or the organic solvent received by the third guard 19 is guided to the third cup 16 along the third cylindrical portion 19A.

After the first organic solvent treatment (S27) for a certain period of time, a hydrophobic treatment (S28) is performed. The number of rotations of the wafer W is controlled at a hydrophobic processing speed (eg, 500 rpm). In the hydrophobizing process (S28), the organic solvent on the wafer W is replaced with a hydrophobizing agent. A hydrophobizing agent is a liquid in which a hydrophobizing substance is dissolved in a solvent. The solvent for the hydrophobizing agent is preferably a solvent, such as PGMEA, which is miscible (has compatibility) with IPA supplied in the first organic solvent treatment (S27). Thereby, the organic solvent (IPA) on the wafer W can be replaced.

The organic solvent valve 52 is closed during the hydrophobic treatment (S28). As a result, the discharge of the organic solvent from the organic solvent nozzle 50 is stopped. Then, referring to FIG. 9D, the first guard lifting unit 27 maintains the first guard 17 at the lower position, and the second guard lifting unit 28 maintains the second guard 18 at the lower position. Then, the third guard elevating unit 29 arranges the third guard 19 at a height position where it can receive the treatment liquid.

The hydrophobizing agent valve 82 is then opened. As a result, the hydrophobizing agent is supplied from the hydrophobizing agent nozzle 80 of the hydrophobizing agent supply unit 11 toward the central region of the upper surface of the rotating wafer W (hydrophobizing agent supply step). The hydrophobizing agent spreads over the entire upper surface of the wafer W due to centrifugal force. As a result, the organic solvent on the wafer W is replaced with the hydrophobizing agent. The hydrophobizing agent supplied at this time is a low oxygen concentration hydrophobizing agent in which the concentration of dissolved oxygen in the liquid has been reduced by the degassing unit 83 . Specifically, the dissolved oxygen concentration in the hydrophobizing agent discharged from the hydrophobizing agent nozzle 80 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

The mixture of the organic solvent and the hydrophobizing agent or the hydrophobizing agent on the wafer W is spattered radially outward from the wafer W due to the centrifugal force. The mixture of the organic solvent and the hydrophobizing agent or the hydrophobizing agent scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extended portion 61 of the facing member 6 facing the wafer W from the radially outer side. . Since the opposing member 6 rotates together with the wafer W, the mixture of the organic solvent and the hydrophobizing agent or the hydrophobizing agent adhering to the inner peripheral surface 61a of the extension 61 is removed from the extension 61 by centrifugal force. also scatter radially outward. The third guard 19 receives the mixed liquid of the organic solvent and the hydrophobizing agent or the hydrophobizing agent scattered radially outward from the extending portion 61 . The mixture of the organic solvent and the hydrophobizing agent or the hydrophobizing agent received by the third guard 19 is guided to the third cup 16 along the third tubular portion 19A.

After the hydrophobization treatment (S28) for a certain period of time, the second organic solvent treatment (S29; post-organic solvent supply step) is performed. The rotation speed of the wafer W is controlled to the organic solvent processing speed (eg, 300 rpm). In the second organic solvent treatment, the hydrophobizing agent on the wafer W is replaced with the organic solvent. This organic solvent is miscible (has compatibility) with the solvent of the hydrophobizing agent used in the hydrophobizing treatment (S28), and is, for example, IPA.

Specifically, the hydrophobizing agent valve 82 is closed. Then, referring to FIG. 9E, the first guard lifting unit 27 maintains the first guard 17 at the lower position, and the second guard lifting unit 28 maintains the second guard 18 at the lower position. Then, the third guard 19 is arranged at a height position where the treatment liquid can be received by the third guard elevating unit 29 (guard arrangement step).

Then, the organic solvent valve 52 is opened. As a result, the organic solvent is discharged from the organic solvent nozzle 50 toward the central region of the upper surface of the wafer W in the rotating state. The organic solvent spreads over the entire upper surface of the wafer W due to centrifugal force. As a result, the hydrophobizing agent on the wafer W is replaced with the organic solvent. The organic solvent supplied at this time is a low oxygen concentration organic solvent in which the dissolved oxygen concentration in the liquid has been reduced by the degassing unit 53 . Specifically, the dissolved oxygen concentration in the organic solvent discharged from the organic solvent nozzle 50 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

The mixture of the organic solvent and the hydrophobizing agent or the organic solvent on the wafer W is spattered radially outward from the wafer W due to the centrifugal force. The mixed liquid of the organic solvent and the hydrophobizing agent or the organic solvent scattered radially outward from the wafer W reaches the inner peripheral surface of the extended portion 61 of the facing member 6 facing the wafer W from the radially outer side. Since the facing member 6 rotates together with the wafer W, the mixture of the organic solvent and the hydrophobizing agent or the organic solvent adhering to the inner peripheral surface of the extension 61 is caused to have a diameter larger than that of the extension 61 due to centrifugal force. Scatter outward. The third guard 19 receives the mixture of the organic solvent and the hydrophobizing agent or the organic solvent that scatters radially outward from the extending portion 61 . The mixture of the organic solvent and the hydrophobizing agent or the organic solvent received by the third guard 19 is guided to the third cup 16 along the third cylindrical portion 19A.

After the second organic solvent treatment (S29) for a certain period of time, a drying treatment (S30) is performed in which liquid components on the upper surface of the wafer W are shaken off by centrifugal force. Specifically, after the organic solvent valve 52 is closed, the wafer W is rotated at a high speed (drying processing speed, eg, 2000 rpm).
After the drying process (S30) for a certain period of time, the control unit 3 decelerates the rotation of the wafer W (to 300 rpm, for example), and heats the wafer W by the heater unit 110 as shown in FIG. 9F. As a result, a post-substrate heating process (S31, heat dehydration step) is performed to volatilize the solvent component of the hydrophobizing agent remaining on the wafer W. FIG.

After a certain period of time, the control unit 3 stops heating by the heater unit 110, accelerates the rotation of the wafer W again (for example, to 2000 rpm), and cools the wafer W down to room temperature. A substrate cooling process (S32) is executed. As shown in FIG. 9G, in the post-substrate cooling process (S32), the inert gas is blown to the upper and lower surfaces of the wafer W by opening the inert gas valves 92 and 122 . At this time, it is preferable that the guards 17 to 19 are all positioned at the lower position so that the atmosphere in the processing space 65 can be quickly replaced. After a certain period of time has passed, the control unit 3 controls the electric motor 23 to stop the rotation of the wafer W. FIG.

When the post-substrate cooling process (S32) ends, the control unit 3 closes the inert gas valves 92 and 122 to stop the supply of the inert gas, and ends the atmosphere control process (S36).
Thereafter, the transfer robot CR enters the processing unit 2, picks up the processed wafer W from the spin chuck 5, and carries it out of the processing unit 2 (S31: substrate unloading). The wafer W is transferred from the transfer robot CR to the transfer robot IR and stored in the carrier C by the transfer robot IR.

As shown in FIG. 8B, before the chemical cleaning process (S25) by SC1 and the rinsing process (S26) to wash away SC1, the chemical process using hydrofluoric acid (S41: chemical cleaning) and the rinsing process for rinsing off hydrofluoric acid (S42) are performed. ) may be executed. As a result, a small amount of oxide on the surface of the wafer W can be removed by the etching action of hydrofluoric acid. Further, when an oxide film is formed on the surface of the wafer W, the surface can be flattened by light etching using hydrofluoric acid. In this case, the atmosphere control process (S36) is started before the oxide removal process (S41) using the chemical solution.

In the chemical solution treatment (S41) and the subsequent rinse treatment (S42), the chemical solution (hydrofluoric acid) and the rinse solution are supplied from the first treatment solution supply unit 30, for example.
That is, the chemical treatment (S41) is started while maintaining the low-oxygen atmosphere. The number of rotations of the wafer W is controlled to the chemical solution processing speed (for example, 300 rpm). In the chemical liquid processing (S41), the upper surface of the wafer W is subjected to processing such as etching by supplying hydrofluoric acid (HF) as a chemical liquid onto the wafer W from the processing liquid nozzle 33 . More specifically, by supplying hydrofluoric acid, it is possible to etch off the oxide present on the surface of the wafer W and planarize the surface of the oxide film on the surface. This supply of hydrofluoric acid may also serve as a chemical cleaning step for cleaning the surface of the wafer W. FIG. The supplied hydrofluoric acid is a low-oxygen-concentration hydrofluoric-acid aqueous solution in which the dissolved oxygen concentration in the liquid has been reduced by the degassing unit 36 . Specifically, the dissolved oxygen concentration in the hydrofluoric acid discharged from the processing liquid nozzle 33 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

More specifically, referring to FIG. 10A, the first guard lifting unit 27 places the first guard 17 at the lower position, and the third guard lifting unit 29 places the third guard 19 at the upper position. do. Then, the second guard elevating unit 28 arranges the second guard 18 at a height position where the processing liquid can be received (guard arrangement step).
In this state, the chemical valve 32 is opened. As a result, the chemical solution (hydrofluoric acid) is supplied from the processing solution nozzle 33 to the center region of the upper surface of the wafer W in the rotating state. The chemical solution spreads over the entire upper surface of the wafer W due to centrifugal force.

The chemical liquid scatters radially outward from the wafer W due to centrifugal force. The chemical liquid scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extending portion 61 of the facing member 6 facing the wafer W from the radially outer side. Since the facing member 6 rotates together with the wafer W, the chemical solution adhering to the inner peripheral surface 61a of the extending portion 61 scatters radially outward from the extending portion 61 due to centrifugal force. The chemical liquid scattered radially outward from the extending portion 61 is received by the second guard 18 . The liquid medicine received by the second guard 18 is guided to the second cup 15 along the second cylindrical portion 18A.

After the chemical solution treatment (S41) for a certain period of time, the rinse treatment (S42) is performed. The number of rotations of wafer W is controlled to the rinse processing speed (eg, 300 rpm). In the rinsing process, the upper surface of the wafer W is rinsed by replacing the hydrofluoric acid (chemical solution) on the wafer W with DIW as a rinsing solution. The rinse liquid to be supplied is a low-oxygen-concentration rinse liquid (for example, DIW) whose dissolved oxygen concentration has been reduced by the degassing unit 37 . Specifically, the dissolved oxygen concentration in the rinse liquid discharged from the processing liquid nozzle 33 is preferably 100 ppb or less, thereby avoiding oxidation of the surface of the wafer W due to dissolved oxygen.

At the start of the rinsing process (S42), the chemical liquid valve 32 is closed, and the discharge of hydrofluoric acid from the processing liquid nozzle 33 is stopped. Referring to FIG. 10B, first guard lifting unit 27 maintains first guard 17 at the lower position, and third guard lifting unit 29 maintains third guard 19 at the upper position. Then, the second guard elevating unit 28 arranges the second guard 18 at a height position where the processing liquid can be received (guard arrangement step).

In this state, the rinse liquid valve 35 is opened. As a result, the rinse liquid is supplied from the processing liquid nozzle 33 toward the center region of the upper surface of the wafer W in the rotating state. The rinse liquid spreads over the entire upper surface of the wafer W due to centrifugal force. As a result, the chemical liquid on the wafer W is replaced with the rinse liquid.
The mixture of the chemical solution and the rinse solution or the rinse solution on the wafer W is spattered radially outward from the wafer W due to the centrifugal force. The mixture of the chemical liquid and the rinse liquid or the rinse liquid scattered radially outward from the wafer W reaches the inner peripheral surface 61a of the extended portion 61 of the opposing member 6 facing the wafer W from the radially outward direction. Since the facing member 6 rotates together with the wafer W, the liquid mixture of the chemical liquid and the rinse liquid or the rinse liquid adhering to the inner peripheral surface 61a of the extension portion 61 is radially displaced from the extension portion 61 by centrifugal force. scatter to the outside. The second guard 18 receives the mixture of the chemical liquid and the rinse liquid or the rinse liquid that is scattered radially outward from the extending portion 61 . The mixture of the chemical liquid and the rinse liquid or the rinse liquid received by the second guard 18 is guided to the second cup 15 along the second cylindrical portion 18A.

FIG. 11 is a sequence diagram (time chart) for explaining an example of the control operation of the processing unit 2 by the control unit 3. Mainly, the number of rotations of the wafer W by the spin chuck 5 and the heating of the wafer W by the heater unit 110 are shown. Shows the control contents related to and.
The initial position of the heater unit 110 is the lower position (see FIG. 6), where the distance from the lower surface of the wafer W to the facing surface 110a is long. For example, when the wafer W to be processed is loaded, the control unit 3 starts energizing the heater unit 110 . The control unit 3 holds the heater unit 110 in the lower position during the chemical liquid treatment (S25, S41) and the rinse treatment (S26, S42) (see FIGS. 9A and 9B). Therefore, wafer W is not substantially heated.

During the period of the first organic solvent treatment (S27) and the second organic solvent treatment (S29), the control unit 3 raises the heater unit 110 and places it at a position close to the lower surface of the wafer W (FIGS. 9C, See Figure 9E). A space is ensured between the lower surface of the wafer W, thereby allowing the wafer W to rotate. The rotation speed of the wafer W during the first organic solvent treatment (S27) and the second organic solvent treatment (S29) is, for example, 300 rpm. The wafer W is heated by arranging the heater unit 110 close to the wafer W. FIG. As a result, the replacement of the rinsing liquid with the organic solvent can proceed efficiently.

The control unit 3 holds the heater unit 110 in the lower position during the hydrophobic treatment (S28) (see FIG. 9D). Therefore, wafer W is not substantially heated. As a result, volatilization of the solvent of the hydrophobizing agent can be suppressed, the hydrophobizing agent can be spread over the entire surface of the wafer W, and the organic solvent can be replaced by the hydrophobizing agent. The rotation speed of the wafer W during the hydrophobic treatment is, for example, 500 rpm.

In the drying process (S30), the rotation speed of wafer W is accelerated to, for example, 2000 rpm. As a result, the organic solvent on the wafer W is removed outside the wafer W by centrifugal force.
In the post-substrate heating process (S31), control unit 3 reduces the rotation speed of wafer W to, for example, 300 rpm. Furthermore, the control unit 3 raises the heater unit 110 and places it in the approach position close to the lower surface of the wafer W, as shown in FIG. 9F. Thereby, the temperature of the wafer W is raised to about 200° C., for example. By such a post-substrate heating process (S31), the solvent component and water in the hydrophobizing agent film formed on the surface of the wafer W are evaporated. That is, the post-substrate heat treatment (S31) is solvent removal treatment and dehydration treatment. The post-substrate heating process is preferably a process for raising the temperature of the wafer W to at least the boiling point of the solvent of the hydrophobizing agent liquid or higher. For example, the solvent of the hydrophobizing agent liquid may be PGMEA, in which case the boiling point is about 110.degree.

In the subsequent post-substrate cooling process (S32), control unit 3 accelerates the rotation speed of wafer W to, for example, 2000 rpm. As shown in FIG. 9G, the heater unit 110 is placed in the lower position. As a result, the wafer W exchanges heat with the inert gas supplied from above and below, and is cooled to room temperature. When the post-substrate cooling process is completed, the control unit 3 stops the rotation of the wafer W, that is, the rotation of the spin chuck 5, and causes the transport robot CR to unload the processed wafer W from the processing unit 2. FIG.

FIG. 12 is a diagram for explaining the desolvation action by the post-substrate heat treatment (S31). When the surface of the wafer W is treated with a hydrophobizing agent, the surface of the wafer W is silylated to become a hydrophobic surface. Dust 130 tends to adhere to this hydrophobic surface. The main component of the dust 130 is C (carbon), and it is considered to be in the form of latex containing the solvent 131 when excessive solvent is present. Therefore, by evaporating the solvent 131 in the dust 130 by the post-substrate heating process (S31), the dust 130 can be shrunk, thereby improving the particle performance.

FIG. 13 is a diagram for explaining the dehydration effect of the post-substrate heat treatment (S31). If moisture remains on the surface of the wafer W, water molecules 141 intervene in the bond between the hydrophobizing agent molecules 140 and the material (eg, silicon) of the wafer W, resulting in an incomplete bond. The post-substrate heat treatment (S31) has a dehydrating effect that removes water molecules 141 intervening in bonds, thereby reducing or eliminating incomplete bonds. For example, in a state in which the molecules 140 of the hydrophobizing agent are present in an incompletely bonded state, reaction residues of organic substances may easily adhere to the hydrophobizing agent film. By reducing or eliminating imperfect bonding by dehydration, deterioration of particle performance due to imperfect bonding can be avoided.

As described above, according to this embodiment, the surface modification treatment (S21) is performed by the heat treatment unit 100 on the wafer W having oxide on the surface, whereby the oxide on the wafer W is removed. The surface of the wafer W is flattened by decomposing and recombining the oxide on the wafer W. Thereafter, a surface cleaning step (S25, S26, S41, S42) is performed to clean the surface of the wafer W with the processing liquid. In the hydrophobizing step (S5) performed after the surface cleaning step, a hydrophobizing agent is supplied to the surface of the wafer W to modify the surface of the wafer W to be hydrophobic.

In this way, the surface of the wafer W is modified to be hydrophobic while the unevenness of the surface of the wafer W caused by the oxide is eliminated, so that the modified surface of the wafer W is uniformly made hydrophobic. , and a flat surface with less roughness. This can suppress or prevent the pattern on the surface of the wafer W from collapsing in the second organic solvent treatment (S29) or the like. In addition, since the roughness of the surface is small, it is possible to suppress or prevent the occurrence of irregularities on the surface of wafer W that may be detected as particles.

The processing liquid (chemical liquid, rinse liquid, organic solvent, hydrophobizing agent) used in the processing unit 2 has a low dissolved oxygen content (for example, 100 ppb or less) and does not oxidize the material of the wafer W. No new oxides due to are formed. Also, during the period from the surface cleaning process to the hydrophobic process, the atmosphere around the wafer W is controlled to be a low-oxygen atmosphere (S36). Therefore, the surface of the wafer W can be modified to be hydrophobic while suppressing the growth of new oxide on the surface of the wafer W. FIG.

A low-oxygen atmosphere is an atmosphere having an oxygen concentration in which oxygen does not dissolve in the processing liquid. Thereby, the growth of oxide on the surface of the wafer W can be suppressed or prevented.
Further, in this embodiment, after the hydrophobizing treatment (S28), the organic solvent is supplied to the surface of the wafer W, and the excess hydrophobizing agent on the wafer W is washed off. solvent supply step) is performed. As a result, the surface of the wafer W can be hydrophobized with an appropriate amount of the hydrophobizing agent, thereby avoiding deterioration of the surface roughness of the wafer W and deterioration of the hydrophobic performance due to excessive hydrophobizing agent. can.

Further, in this embodiment, in the atmosphere control step (S36), the facing member 6 is arranged to face the surface of the wafer W at a position close to it, thereby limiting the space where the surface of the wafer W faces. . An inert gas is then supplied to the restricted space. As a result, the surface of the wafer W is placed in an atmosphere with a low oxygen concentration, thereby suppressing or preventing the growth of oxide on the surface of the wafer W during processing.

Furthermore, in this embodiment, when the facing member 6 is arranged to face the surface of the wafer W close to the surface of the wafer W, the space facing the surface of the wafer W is restricted by the facing portion 60 from the normal direction of the surface. It is bounded by an annular extension 61 from a direction parallel to the surface. As a result, the space facing the surface of the wafer W forms a substantially closed space, and the inert gas is supplied to this closed space. Therefore, the surface of the wafer W is placed in a stable atmosphere with a low oxygen concentration, and the surface cleaning process and the like are performed in that state. Therefore, it is possible to more reliably suppress or prevent the growth of oxide on the surface of the wafer W being processed.

Although one embodiment of the present invention has been described above, the present invention can also be implemented in other forms.
For the post-substrate heating process (S31), instead of or in addition to heating by the heater unit 110, heating by an infrared lamp, laser, heating vapor (steam), or the like may be applied. The heating of the wafer W does not have to be performed from the bottom surface, and heating from the top surface may be applied. For example, an infrared lamp may be placed above the wafer W. FIG.

Further, the post-substrate heating process (S31) does not need to be performed in the processing unit 2, and may be performed by being transported to another unit by the transport robot CR.
Further, in the processes of FIGS. 8A and 8B, the post-substrate heating process (S31) and the post-substrate cooling process (S32) may be omitted.
The atmosphere in the transfer chamber in which the transfer robot CR is arranged may be controlled to be a low-oxygen atmosphere to suppress or prevent oxide growth during transfer.

The heat treatment unit 100 does not have to be incorporated in the substrate processing apparatus 1 . That is, the heat treatment for surface modification of the wafer W may be performed in an apparatus other than the substrate processing apparatus 1 .
In addition, various design changes can be made within the scope of the matters described in the claims.

W Wafer Ox Oxide Oxn New oxide film Wsi Exposed silicon portion Wox Oxide portion Sm Hydrophobic substance IR Transfer robot CR Transfer robot 1 Substrate processing apparatus 2 Processing unit 3 Control unit 4 Chamber 5 Spin chuck 6 Opposing member 7 Supporting member 8 Inert gas supply unit 10 Organic solvent supply unit 11 Hydrophobizing agent supply unit 12 Support member elevating unit 20 Chuck pin 21 Spin base 22 Rotating shaft 23 Electric motor 24 Substrate holding unit 26 Exhaust tank 30 First processing liquid supply unit 31 Chemical liquid supply Pipe 32 Chemical liquid valve 33 Processing liquid nozzle 34 Rinse liquid supply pipe 35 Rinse liquid valve 36 Degassing unit 37 Degassing unit 40 Second processing liquid supply unit 41 Chemical liquid supply pipe 42 Chemical liquid valve 43 Processing liquid nozzle 44 Rinse liquid supply pipe 45 Rinse Liquid valve 46 Degassing unit 47 Degassing unit 50 Organic solvent nozzle 51 Organic solvent supply pipe 52 Organic solvent valve 53 Degassing unit 60 Opposing part 61 Extension part 62 Cylindrical part 70 Opposing member supporting part 72 Nozzle supporting part 80 Hydrophobicization agent nozzle 81 hydrophobizing agent supply pipe 82 hydrophobizing agent valve 83 degassing unit 90 inert gas nozzle 91 inert gas supply pipe 92 inert gas valve 100 heat treatment unit 101 chamber 102 susceptor 103 lamp heater unit 104 flash lamp unit 105 exhaust unit 106 Inert gas supply unit 110 Heater unit 113 Heater energizing unit 114 Heater elevating unit 120 Lower surface inert gas supply unit 121 Inert gas supply pipe 122 Inert gas valve

Claims (24)

a heating modification step of heating the substrate having an oxide on the surface to modify the surface;
a surface cleaning step of supplying a processing liquid to the modified surface of the substrate and cleaning the surface of the substrate with the processing liquid;
a hydrophobizing step of supplying a hydrophobizing agent to the washed surface of the substrate to hydrophobize the surface of the substrate ;
The substrate processing method , wherein the thermal modification step includes a flattening step of reducing unevenness caused by oxide on the surface of the substrate by heating . a heating modification step of heating the substrate having an oxide on the surface to modify the surface;
a surface cleaning step of supplying a processing liquid to the modified surface of the substrate and cleaning the surface of the substrate with the processing liquid;
a hydrophobizing step of supplying a hydrophobizing agent to the washed surface of the substrate to hydrophobize the surface of the substrate;
The heat reforming step is
a heating removal step of removing at least part of the oxide on the surface of the substrate by heating;
an oxide film forming step of forming a new oxide film on the surface of the substrate after the heating and removing step;
a step of controlling the atmosphere around the substrate so that the oxygen concentration in the atmosphere around the substrate in the oxide film forming step is higher than the oxygen concentration in the atmosphere around the substrate in the heating removal step; , a substrate processing method. The surface cleaning step includes a chemical cleaning step of supplying a chemical solution for cleaning to the surface of the substrate , and a rinsing step of supplying a rinse solution to the surface of the substrate and replacing the chemical solution with the rinse solution. The substrate processing method according to claim 1 or 2 . 4. The substrate processing method according to claim 1, wherein the processing liquid has a dissolved oxygen concentration of 100 ppb or less . The hydrophobizing step includes a hydrophobizing agent supply step of supplying a liquid hydrophobizing agent in which a hydrophobizing substance is dissolved in a solvent,
5. The method according to any one of claims 1 to 4 , further comprising a pre-organic solvent supply step of supplying an organic solvent miscible with the solvent of the hydrophobizing agent to the surface of the substrate after the surface cleaning step and before the hydrophobizing step. 1. The substrate processing method according to claim 1. 6. The method according to any one of claims 1 to 5 , further comprising a post organic solvent supply step of supplying an organic solvent to the surface of the substrate after the hydrophobizing step to wash off excess hydrophobizing agent on the substrate. The substrate processing method described in . 7. The substrate processing method according to claim 5 , wherein the dissolved oxygen concentration in said organic solvent is 100 ppb or less. The substrate processing method according to any one of claims 1 to 7 , wherein the dissolved oxygen concentration in the hydrophobizing agent is 100 ppb or less. 9. The method according to any one of claims 1 to 8 , further comprising an atmosphere control step of controlling the atmosphere around the substrate to a low-oxygen atmosphere having an oxygen concentration lower than that of the air during the period from the surface cleaning step to the hydrophobizing step. 1. The substrate processing method according to item 1. 10. The substrate processing method according to claim 9 , wherein said low-oxygen atmosphere is an atmosphere having an oxygen concentration in which oxygen does not dissolve in said processing liquid. including a cooling step of cooling the substrate after the thermal reforming step;
The substrate processing method according to any one of claims 1 to 10 , wherein the surface cleaning step is performed on the substrate after the cooling step. 12. The substrate processing method according to claim 1, further comprising a heat dehydration step of heating and dehydrating the hydrophobizing agent on the surface of the substrate after the hydrophobizing step. a heat treatment unit that heats a substrate having an oxide on its surface to modify the surface;
a processing liquid supply unit that supplies the modified surface of the substrate with a processing liquid for cleaning the surface;
a hydrophobizing agent supply unit for supplying a hydrophobizing agent to the surface of the cleaned substrate to hydrophobize the surface of the substrate;
including
The substrate processing apparatus, wherein the thermal processing unit heats the substrate so as to reduce unevenness caused by oxide on the surface of the substrate by heating . a heat treatment unit that heats a substrate having an oxide on its surface to modify the surface;
a processing liquid supply unit that supplies the modified surface of the substrate with a processing liquid for cleaning the surface;
a hydrophobizing agent supply unit for supplying a hydrophobizing agent to the surface of the cleaned substrate to hydrophobize the surface of the substrate;
including
The heat treatment unit is
The atmosphere around the substrate is controlled to be a low-oxygen atmosphere, and the substrate is heated so as to remove at least part of the oxide on the surface of the substrate by heating, and at least part of the oxide is removed. A substrate processing apparatus for forming a new oxide film on the surface of the substrate by controlling the atmosphere around the substrate to an atmosphere having a higher oxygen concentration than the low-oxygen atmosphere. The processing liquid supply unit includes a chemical liquid supply unit that supplies a chemical liquid for cleaning to the surface of the substrate, and a rinse liquid supply unit that supplies a rinse liquid that replaces the chemical liquid with a rinse liquid to the surface of the substrate. 15. The substrate processing apparatus according to claim 13 or 14. 16. The substrate processing apparatus according to any one of claims 13 to 15 , wherein said processing liquid supply unit supplies a processing liquid having a dissolved oxygen concentration of 100 ppb or less to the surface of the substrate. The hydrophobizing agent supply unit supplies a liquid hydrophobizing agent in which a hydrophobizing substance is dissolved in a solvent,
3. The apparatus further comprises a pre-organic solvent supply unit that supplies an organic solvent that is miscible with the solvent of the hydrophobizing agent to the surface of the substrate after cleaning the surface of the substrate and before hydrophobizing the surface of the substrate. 17. The substrate processing apparatus according to any one of 13 to 16 . 18. The method according to any one of claims 13 to 17 , further comprising a post-organic solvent supply unit for supplying an organic solvent to the surface of the substrate after hydrophobizing the surface of the substrate to wash away excess hydrophobizing agent on the substrate. 1. The substrate processing apparatus according to claim 1. 19. The substrate processing apparatus according to claim 17 , wherein the dissolved oxygen concentration in said organic solvent is 100 ppb or less. The substrate processing apparatus according to any one of claims 13 to 19 , wherein the dissolved oxygen concentration in said hydrophobizing agent is 100 ppb or less. During a period in which the processing liquid supply unit supplies the processing liquid to the surface of the substrate and a period in which the hydrophobizing agent supply unit supplies the hydrophobizing agent to the surface of the substrate, the atmosphere around the substrate is replaced with the air. 21. The substrate processing apparatus according to any one of claims 13 to 20 , further comprising an atmosphere control unit for controlling the low-oxygen atmosphere having an oxygen concentration lower than medium. 22. The substrate processing apparatus according to claim 21 , wherein said atmosphere control unit controls the atmosphere around said substrate to a low-oxygen atmosphere having an oxygen concentration in which oxygen does not dissolve in said processing liquid. The substrate processing apparatus according to any one of claims 13 to 22 , further comprising a cooling unit that cools the substrate after being heated by the thermal processing unit and before cleaning the surface. 24. The method according to any one of claims 13 to 23 , further comprising a post-heating unit for heating the substrate to heat and dehydrate the hydrophobizing agent on the surface of the substrate after the surface is hydrophobized. Substrate processing equipment.

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