JP2005109362A - Processing liquid, and substrate processing method and apparatus using processing liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing liquid and a substrate processing method and apparatus using the processing liquid whereby any water mark can be suppressed from being formed on the surface of a low-permittivity material (low-k material). <P>SOLUTION: The processing liquid is the one for processing the substrate wherein a low-permittivity material is exposed to the external at least in a portion of the surface thereof. The processing liquid has at least a hydrophilic group and a hydrophobic group respectively in its one molecule, and includes an organic substance having volatility at a room temperature. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a treatment liquid for treating a substrate having a low dielectric constant material exposed on the surface, and in particular, a treatment liquid that can be suitably used for a post-treatment of a polishing process, a pre-treatment or a post-treatment of a plating process, The present invention also relates to a substrate processing method and a substrate processing apparatus using the processing liquid.

  As the performance and speed of semiconductor devices increase, it is required to further reduce the delay of signals passing through wiring. This signal delay is determined by the wiring resistance and the capacitance between wirings (capacitance), and in order to realize a faster semiconductor device, it is necessary to make the wiring resistance and the capacitance between the wirings as small as possible. Therefore, in recent years, as a wiring material for forming a wiring, a movement that uses copper (Cu) having a low electrical resistivity and a high electromigration resistance in place of aluminum or an aluminum alloy has become prominent. As copper is used as a wiring material, a low-k material (low dielectric constant material) having a lower dielectric constant than that of a TEOS film is being used as an interlayer insulating film.

  In general, the copper wiring is formed by embedding copper in a fine recess provided on the surface of the substrate. As a method for forming this copper wiring, plating is generally used. For example, when copper wiring is formed by electrolytic plating, a seed layer as a power feeding layer for electrolytic plating is formed on the surface of a barrier layer made of TaN or the like, and a copper film is formed on the surface of the seed layer. Thereafter, the surface of the substrate is polished flat by CMP (chemical mechanical polishing) to remove unnecessary copper films. Thereby, the copper wiring and the interlayer insulating film are exposed on the surface of the substrate after the CMP process.

  After the CMP process is completed, the substrate is transported to a cleaning device and cleaned by a roll scrub or the like while supplying a cleaning solution (chemical solution containing water as a main component) and DIW (Deionized water) to the substrate. Thereafter, the substrate is transported to a drying apparatus, the substrate is rinsed with DIW, and the substrate is further rotated to remove DIW adhering to the substrate by centrifugal force and dry.

  However, when a low-k material is used as the interlayer insulating film, the following problems occur after the drying process. That is, the Low-k material has a hydrophobic surface because a hydrophobic group such as a methyl group appears on the surface thereof. If droplets are locally present on the surface of such a low-k material, after the substrate is dried, spots are formed at the locations where the droplets were present. This stain is called a watermark and is considered a kind of defect that reduces the yield of the product. In general, it is known that this watermark is likely to occur on the hydrophobic surface of the substrate, and hardly occurs on the hydrophilic surface. For this reason, on the surface of the low-k material which shows hydrophobicity, there existed a problem that many watermarks will arise after a drying process.

  A silicon oxide film such as a TEOS film, which has been widely used as an interlayer insulating film, is hydrophilic. For this reason, even if spin drying was performed after DIW rinsing, no watermark was generated on the surface of the TEOS film. With the increase in the speed and integration of semiconductor devices, low-k materials tend to be widely used as interlayer insulating films. Therefore, defects due to watermarks are expected to become more apparent in the future.

  The present invention has been made in view of the above-described conventional problems, and provides a treatment liquid capable of suppressing the formation of a watermark on the surface of a low dielectric constant material (Low-k material). For the purpose. Another object of the present invention is to provide a substrate processing method and a substrate processing apparatus using such a processing solution.

  In order to achieve the above-described object, one embodiment of the present invention is a treatment liquid for treating a substrate in which a low dielectric constant material is exposed on at least a part of a surface, and includes a hydrophilic group and a hydrophobic group in one molecule. And an organic material having volatility at room temperature.

In a preferred aspect of the present invention, the organic substance is an organic acid or an alcohol.
A preferred embodiment of the present invention is characterized in that the organic acid or alcohol has 5 or less carbon atoms.
In a preferred aspect of the present invention, the contact angle of the treatment liquid with respect to the surface of the substrate is 50 degrees or less.
In a preferred aspect of the present invention, the low dielectric constant material has a relative dielectric constant of 3 or less.

  Another aspect of the present invention is a substrate processing method for processing a substrate in which a low dielectric constant material is exposed on at least a part of the surface, and supplying a chemical solution and / or a rinsing solution to the substrate to perform a predetermined process. After being performed, the processing liquid is supplied to the substrate.

In a preferred aspect of the present invention, the processing liquid is supplied to the substrate in the form of a mist.
In a preferred aspect of the present invention, the processing liquid is supplied to the substrate as vapor.
In a preferred aspect of the present invention, the rinse liquid is pure water.
In a preferred aspect of the present invention, the rinse liquid is an aqueous solution in which at least one of H ₂ gas, O ₂ gas, CO ₂ gas, and N ₂ gas is dissolved in pure water. .
In a preferred aspect of the present invention, after the supply of the processing solution is stopped, the substrate is rotated at 2000 mim ⁻¹ or less to dry the substrate.
In a preferred aspect of the present invention, the substrates are dried one by one.

  Another aspect of the present invention is a substrate processing method for polishing a substrate on which a low dielectric constant material and a metal film formed on the low dielectric constant material are formed, the polishing liquid being supplied to the substrate And polishing the substrate while supplying the treatment liquid to the substrate.

Another aspect of the present invention is a substrate processing method for polishing a substrate on which a low dielectric constant material and a metal film formed on the low dielectric constant material are formed, and after polishing the substrate, A predetermined process is performed while supplying the processing liquid to the substrate.
In a preferred aspect of the present invention, the predetermined process is a roll scrub process.

Another aspect of the present invention is a substrate processing method for polishing a substrate on which a low dielectric constant material and a metal film formed on the low dielectric constant material are formed, the step of polishing the substrate, A step of supplying the treatment liquid to the polished substrate; and a step of rotating the substrate at 1500 mim ⁻¹ or less and drying the substrate after stopping the supply of the treatment liquid.

  Another aspect of the present invention is a substrate processing method for plating a substrate on which a low dielectric constant material is exposed on at least a part of the surface, wherein the treatment liquid is used as a pretreatment before plating on the substrate. It supplies to a board | substrate, It is characterized by the above-mentioned.

  Another aspect of the present invention is a substrate processing method for plating a substrate on which a low dielectric constant material is exposed on at least a part of the surface, and after the plating is performed on the substrate, the processing liquid is used as a post-treatment. It supplies to a board | substrate, It is characterized by the above-mentioned.

Another aspect of the present invention is a substrate processing method for processing a substrate in which a low dielectric constant material is exposed on at least a part of a surface, wherein the treatment liquid is applied to at least a part of the surface of the low dielectric constant material. And a step of hydrophilizing at least a part of the surface of the low dielectric constant material with the treatment liquid.
In a preferred aspect of the present invention, the method further comprises the step of removing the treatment liquid from the surface of the substrate after hydrophilizing at least a part of the surface of the low dielectric constant material.
In a preferred aspect of the present invention, the processing liquid is removed from the surface of the substrate by volatilizing the processing liquid from the surface of the substrate.

  Another aspect of the present invention is a substrate processing apparatus for polishing a substrate on which a low dielectric constant material and a metal film formed on the low dielectric constant material are formed, and a polishing section for polishing the substrate; And a post-processing unit that performs post-processing of the polished substrate, and a processing liquid supply unit that supplies the processing liquid to at least one of the polishing unit and the post-processing unit.

  Another aspect of the present invention is a substrate processing apparatus for plating a substrate on which a low dielectric constant material is exposed on at least a part of the surface, the plating unit for plating the substrate, and before plating the substrate A pretreatment unit for performing a predetermined pretreatment on the substrate, a posttreatment unit for performing a predetermined posttreatment on the plated substrate, and at least one of the pretreatment unit and the posttreatment unit. And a processing liquid supply unit to be supplied.

  According to the present invention, a hydrophobic group and an organic substance having hydrophilicity are adsorbed on the surface of a low dielectric constant material exhibiting hydrophobicity, so that hydrophilicity can be imparted to the surface of the low dielectric constant material. Accordingly, the wettability of the surface of the substrate can be improved, and the number of watermarks formed on the surface of the low dielectric constant material can be greatly reduced in the drying step after the wet treatment.

Hereinafter, a processing liquid, a substrate processing apparatus, and a substrate processing method according to embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing a substrate processing apparatus according to a first embodiment of the present invention. The substrate processing apparatus according to this embodiment is configured as a polishing apparatus that polishes the surface of the substrate.

  As shown in FIG. 1, the substrate processing apparatus (polishing apparatus) includes a pair of polishing units (polishing units) 1a and 1b for polishing a semiconductor wafer (substrate) and a pair of cleaning units (for polishing the polished semiconductor wafer). Post-processing units) 7a and 7b and cleaning units (post-processing units) 8a and 8b for further cleaning and drying the semiconductor wafers cleaned by the cleaning units 7a and 7b are provided. In this substrate processing apparatus, polishing units 1a and 1b are disposed on one end side of a base on a floor having a rectangular shape as a whole, and a cassette (not shown) for storing a plurality of semiconductor wafers is placed on the other end side. Four load / unload units 2a, 2b, 2c and 2d are arranged. A transfer robot 4c is installed in front of these load / unload units 2a, 2b, 2c, 2d, and semiconductors stored in cassettes of the load / unload units 2a, 2b, 2c, 2d by the transfer robot 4c. Wafers are taken out one by one.

  On the line connecting the polishing units 1a, 1b, the load / unload unit, and 2a, 2b, 2c, 2d, the transfer robots 4a, 4b for transferring the semiconductor wafer and the semiconductor when the semiconductor wafer is transferred between the units. Temporary placement tables 5a and 5b for temporarily placing the wafer are arranged. Each of the transfer robots 4a and 4b has a joint arm that can be bent in a horizontal plane, and each joint arm has two gripping portions (a dry finger and a wet finger) arranged vertically. The above-described cleaning units 7a and 7b and the cleaning units 8a and 8b are arranged on both sides of these transfer robots 4a and 4b.

  The polishing units 1a and 1b basically have the same configuration. These polishing units 1a and 1b include a polishing table 11 having a polishing surface on its upper surface, a top ring unit 12 that holds a semiconductor wafer as an object to be polished by vacuum suction, and presses the semiconductor wafer on the polishing table 11. Dressing units (not shown in FIG. 1) for dressing the polished surface on the table 11 are provided. Further, the polishing units 1a and 1b are provided with pushers 14a and 14b for transferring the semiconductor wafer between the top ring unit 12 and the transfer robots 4a and 4b, respectively. Reversing machines 6a and 6b are installed between the polishing units 1a and 1b and the cleaning units 7a and 7b. These reversing machines 6a and 6b are respectively located at positions where the joint arms of the transfer robots 4a and 4b can reach. Is arranged.

  A low-k material (low dielectric constant material) as an interlayer insulating film is formed on the surface of the semiconductor wafer to be processed, and copper (Cu) is formed in advance on the low-k material by electrolytic plating or the like. Yes. In the present embodiment, a low-k material having a relative dielectric constant of 3 or less such as SiOCH is preferably used, and is formed on the surface of the semiconductor wafer by CVD (chemical vapor deposition), spin coating, or the like.

A substrate processing apparatus according to this embodiment includes a processing liquid supply unit (processing liquid supply unit) 9 that selectively supplies a predetermined processing liquid to the polishing units 1a and 1b, the cleaning units 7a and 7b, and the cleaning units 8a and 8b. Is further provided. The processing liquid supply unit 9 is connected to the polishing units 1a and 1b, the cleaning units 7a and 7b, and the cleaning units 8a and 8b through a pipe 49, respectively. The polishing units 1a, 1b, the cleaning units 7a, 7b, and the cleaning units 8a, 8b are each provided with a processing liquid supply nozzle (described later) for supplying a processing liquid. From these processing liquid supply nozzles, the polishing unit 1a, The processing liquid is supplied to the semiconductor wafer introduced into 1b, the cleaning units 7a and 7b, and the cleaning units 8a and 8b. The processing liquid supply unit 9 stores IPA (isopropyl alcohol, (CH ₃ ) ₂ CHOH) as a processing liquid. This IPA has an alkyl group (CH ₃ —) which is a hydrophobic group and a hydroxyl group (—OH) which is a hydrophilic group. That is, IPA is an organic substance having properties as a surfactant.

  Thus, since IPA has a property as a surfactant, IPA supplied to the semiconductor wafer is adsorbed on the hydrophobic surface of the low-k material exposed on the surface of the semiconductor wafer, and thereby low- Hydrophilicity is imparted to the hydrophobic surface of the k material. Therefore, the wettability of the surface of the Low-k material is improved, and the treatment liquid is prevented from existing in the form of droplets on the surface of the Low-k material. In this embodiment, IPA is used as the processing liquid. However, the processing liquid may be configured by adding an organic substance such as IPA to an existing cleaning liquid or rinsing liquid. Examples of the organic substance include organic acids (carboxylic acids) such as formic acid and acetic acid having a carboxyl group (—COOH) which is a hydrophilic group, methanol having a hydroxyl group, ethanol, and alcohols such as the above-described IPA.

  The amount of the organic substance added (the concentration of the organic substance in the treatment liquid) is determined by the contact angle representing the degree of hydrophilicity. That is, the organic substance is added to the treatment liquid so that the contact angle of the treatment liquid is 50 degrees or less. Here, the contact angle generally refers to the angle of the surface of the droplet with respect to the contact surface. Thus, if the contact angle is 50 degrees or less, preferable hydrophilicity can be secured on the surface of the low-k material, and the generation of watermarks can be suppressed.

  Generally, at the time of spin drying after rinsing, it is necessary to remove the rinsing liquid from the surface of the semiconductor wafer sufficiently and quickly. Since the IPA used in the present embodiment has 3 carbon atoms, the intermolecular force is weak and volatile at room temperature (for example, 18 ° C. to 25 ° C.). Therefore, when IPA is used as the rinse liquid, IPA volatilizes more quickly from the surface of the semiconductor wafer than when DIW is used. As described above, the organic acid and alcohol added to the treatment liquid preferably have volatility at room temperature, and specifically, the organic acid and alcohol preferably have 5 or less carbon atoms. In order to promote volatilization of IPA (treatment liquid), a negative pressure mechanism that forms a negative pressure around the semiconductor wafer may be provided.

  Next, the above-described polishing units 1a and 1b will be described with reference to FIG. FIG. 2 is a schematic view showing the polishing unit 1a shown in FIG. Hereinafter, only the polishing unit 1a will be described, but the polishing unit 1b has the same configuration as the polishing unit 1a.

  As shown in FIG. 2, the polishing unit 1 a holds a polishing table 11 having a polishing surface 10 on an upper surface and a semiconductor wafer W as an object to be polished by vacuum suction, and presses this against the polishing table 11 to polish it. A top ring unit 12 and a dressing unit 13 for dressing (conditioning) the polishing surface 10 on the polishing table 11 are provided. The polishing table 11 is connected to a motor (not shown) via a table shaft 11a, and the polishing table 11 is rotatable around the table shaft 11a as indicated by an arrow C in FIG. The polishing surface 10 for polishing the semiconductor wafer W is constituted by a polishing pad (for example, a polishing cloth) 9. Here, the polishing cloth refers to a polyurethane foam or a non-woven fabric that does not contain abrasive grains inside.

  A polishing liquid supply nozzle 15, a dressing liquid supply nozzle 16, and a processing liquid supply nozzle 24 are disposed above the polishing table 11. A polishing liquid is supplied from the polishing liquid supply nozzle 15 and a dressing liquid (for example, DIW) is supplied from the dressing liquid supply nozzle 16 onto the polishing surface 10 on the polishing table 11. The processing liquid supply nozzle 24 is connected to the processing liquid supply unit 9 via the pipe 49 described above, and IPA (processing liquid) is supplied from the processing liquid supply nozzle 24 onto the polishing surface 10 on the polishing table 11. Is done.

  The top ring unit 12 includes a rotatable support shaft 20, a swing arm 21 coupled to the upper end of the support shaft 20, a top ring shaft 22 depending from the free end of the swing arm 21, and a top ring shaft 22. It is comprised from the substantially disc shaped top ring 23 connected with a lower end. The top ring 23 moves in the horizontal direction along with the swing of the swing arm 21 due to the rotation of the support shaft 20, and can reciprocate between the pusher 14 a and the polishing position on the polishing surface 10. Further, the top ring 23 is connected to a motor and a lifting cylinder (not shown) provided inside the swing arm 21 via the top ring shaft 22, and thereby, as shown by arrows D and E in FIG. 2. It can move up and down and can rotate around the top ring shaft 22. Further, the semiconductor wafer W to be polished is held on the lower end surface of the top ring 23 by vacuum. With such a configuration, while the top ring 23 rotates, the semiconductor wafer W held on its lower surface is pressed against the rotating polishing surface 10 with an arbitrary pressure for polishing.

  The dressing unit 13 is connected to a rotatable support shaft 30, a swing arm 31 connected to the upper end of the support shaft 30, a dresser shaft 32 depending from the free end of the swing arm 31, and a lower end of the dresser shaft 32. And a dresser 33 to be used. The dresser 33 moves in the horizontal direction along with the swing of the swing arm 31 by the rotation of the support shaft 30, and can reciprocate between the dressing position on the polishing surface 10 and the retracted position outside the polishing table 11. ing.

  As shown in FIG. 2, a dressing member 34 that slides on the polishing surface 10 and performs dressing of the polishing surface 10 is disposed on the lower surface of the dresser 33. The dresser 33 performs dressing (sharpening) of the polishing surface 10 by pressing the dressing member 34 against the rotating polishing surface 10 with an arbitrary pressure and rotating. Diamond particles are attached to the lower surface of the dressing member 34 by electrodeposition or welding.

  FIG. 3A is a side view schematically showing the cleaning units 7a and 7b shown in FIG. The cleaning units 7a and 7b are of a roll scrub type in which the front and back surfaces of the semiconductor wafer are wiped with a roll brush with a sponge. Only the cleaning unit 7a will be described below, but the cleaning unit 7b has the same configuration as the cleaning unit 7a. As shown in FIG. 3A, the cleaning unit 7 a horizontally contacts the cylindrical roll brushes 40 a and 40 b disposed on the upper and lower sides of the semiconductor wafer W and the peripheral edge of the semiconductor wafer W. And a plurality of rollers 41 to be held. Each of the rollers 41 is configured to rotate in the same speed and in the same direction, and the semiconductor wafer W rotates in a horizontal plane by rotating the rollers 41 in contact with the peripheral edge of the semiconductor wafer W. The cleaning unit 7a also supplies cleaning liquid supply nozzles 42a and 42b for supplying a cleaning liquid (chemical solution) to the semiconductor wafer W, DIW supply nozzles 43a and 43b for supplying DIW to the semiconductor wafer W, and IPA (treatment liquid) for the semiconductor wafer. Treatment liquid supply nozzles 44a and 44b for supplying W are provided. The roll brushes 40a and 40b are configured to be movable in the vertical direction, and are configured to rotate around the axis while contacting the upper and lower surfaces of the semiconductor wafer W. The semiconductor wafer W is rotated by a roller 41. In this state, the upper and lower surfaces of the semiconductor wafer W are cleaned by rotating the roll brushes 40a and 40b while supplying a cleaning liquid or the like to the semiconductor wafer W.

FIG. 3B is a perspective view schematically showing the cleaning units 8a and 8b shown in FIG. The cleaning units 8a and 8b are of a spin type that supplies a rinse liquid such as DIW while rotating the semiconductor wafer W in a horizontal plane. Only the cleaning unit 8a will be described below, but the cleaning unit 8b has the same configuration as the cleaning unit 8a. As shown in FIG. 3B, the cleaning unit 8a supplies the semiconductor wafer W with a plurality of rollers 45 that abut against the peripheral edge of the semiconductor wafer W and hold the semiconductor wafer W horizontally, and a rinse liquid such as DIW. A rinsing liquid supply nozzle 46 for supplying the liquid, and a processing liquid supply nozzle 47 for supplying IPA (processing liquid) to the semiconductor wafer W. Instead of the processing liquid supply nozzle 47, a processing liquid supply mechanism that supplies the IPA (processing liquid) to the semiconductor wafer W in the form of mist or vapor may be provided. Each roller 45 is configured to rotate in the same speed and in the same direction, and the semiconductor wafer W rotates in a horizontal plane by rotating the roller 45 in contact with the peripheral edge of the semiconductor wafer W. ing. As the rinsing liquid, DIW or an aqueous solution in which at least one of H ₂ gas, O ₂ gas, CO ₂ gas, and N ₂ gas is dissolved in DIW is used.

The cleaning unit 8a also functions as a spin drying unit (drying unit) that rotates the semiconductor wafer W to remove and dry the rinsing liquid adhering to the surface of the semiconductor wafer W by centrifugal force. In this case, in order to prevent the rinse liquid jumping out from the semiconductor wafer W from reattaching to the semiconductor wafer, it is preferable to rotate the semiconductor wafer within a range of 50 to 1500 min ⁻¹ during spin drying. Instead of the roller 45, a clamp mechanism that grips and rotates the peripheral edge of the semiconductor wafer W may be used. As shown in FIGS. 3A and 3B, the cleaning units 7a and 7b and the cleaning units 8a and 8b adopt a single-wafer type configuration for processing semiconductor wafers one by one.

Next, the operation of the above-described substrate processing apparatus will be described with reference to FIGS. FIG. 4 is a flowchart showing a first processing sequence of the substrate processing apparatus according to the first embodiment of the present invention.
First, a plurality of semiconductor wafers each having a device portion made of Cu as a wiring material and a low-k film as an interlayer insulating film are housed in a cassette, and the cassette is loaded into the loading / unloading unit 2a (and / or loading). Place on the unload units 2b, 2c, 2d) (step 1 in FIG. 4). One semiconductor wafer is taken out from the load / unload unit 2a by the transfer robot 4c. The semiconductor wafer is temporarily placed on the temporary table 5a by the transfer robot 4c, and then transferred to the polishing unit 1a by the transfer robot 4a. In addition, this semiconductor wafer is conveyed to the reversing machine 6a as necessary, and reversed so that the surface of the semiconductor wafer on which the device portion is formed faces downward. The semiconductor wafer is transferred to the pusher 14a of the polishing unit 1a by the transfer robot 4a and placed on the pusher 14a. Thereafter, the swing arm 21 is swung, the top ring 23 is moved directly above the pusher 14 a, the pusher 14 a is raised, and the semiconductor wafer on the pusher 14 a is attracted and held on the lower surface of the top ring 23. Thereafter, with the semiconductor wafer held by the top ring 23, the swing arm 21 is swung to move the top ring 23 above the polishing table 11.

  Next, the top ring 23 is lowered, and the semiconductor wafer held on the top ring 23 is pressed against the polishing surface 10 (see FIG. 2) of the polishing table 11 with a predetermined pressing force. In this state, the polishing table 11 and the top ring 23 are rotated, and at the same time, the polishing liquid is supplied onto the polishing surface 10 from the polishing liquid supply nozzle 15 (see FIG. 2). Chemical mechanical polishing (primary CMP treatment) is performed (step 2 in FIG. 4). Then, when it is detected that the film thickness of copper (Cu) formed on the surface of the semiconductor wafer has reached a predetermined value, the top ring 23 is raised. Then, the rotation of the polishing table 11 and the top ring 23 is stopped, the supply of the polishing liquid is stopped, and the primary CMP process of the semiconductor wafer is completed.

  After the completion of the primary CMP process, the swing arm 21 is swung, and the top ring 23 holding the polished semiconductor wafer is moved above the pusher 14a. The semiconductor wafer is transferred from the top ring 23 to the pusher 14a, and is transferred from the pusher 14a to the cleaning unit 7a by the transfer robot 4a. In the cleaning unit 7a, roll brushes 40a and 40b (see FIG. 3A) are rotated while supplying DIW to the semiconductor wafer to perform roll scrub cleaning (primary cleaning processing) (step 3 in FIG. 4). By this primary cleaning process, copper shavings and polishing liquid adhering to the surface of the semiconductor wafer are removed.

  After the primary cleaning process is completed, the semiconductor wafer is transferred to the polishing unit 1b by the transfer robot 4a via the pusher 14b. Then, the semiconductor wafer is further polished by the polishing unit 1b, and the barrier layer and the like are removed until the low-k material is exposed on the surface of the semiconductor wafer (secondary CMP process, step 4 in FIG. 4). Next, the semiconductor wafer is transferred to the cleaning unit 7b, and roll scrub cleaning (secondary cleaning processing) is performed by rotating the roll brushes 40a and 40b while supplying the chemical liquid and DIW as cleaning liquid to the semiconductor wafer in this order (second cleaning process). Step 5 in FIG.

  After the secondary cleaning process is completed, the semiconductor wafer is transferred to the cleaning unit 8b by the transfer robot 4b. In the cleaning unit 8b, DIW is supplied to the semiconductor wafer as a rinsing liquid while rotating the semiconductor wafer at a low speed, and IPA (treatment liquid) is further supplied to the semiconductor wafer as a rinsing liquid. Thereafter, the semiconductor wafer is rotated at a high speed, and the IPA adhering to the semiconductor wafer is removed by centrifugal force (drying process, step 6 in FIG. 4). Thereafter, the semiconductor wafer is returned from the cleaning unit 8b to the cassette of the load / unload unit 2a by the transfer robots 4b and 4c via the temporary table 5b (step 7 in FIG. 4).

Thus, in the cleaning unit 8b, hydrophilicity can be imparted to the surface of the low-k material exhibiting hydrophobicity by supplying IPA to the semiconductor wafer before spin drying. Therefore, IPA is prevented from locally remaining on the surface of the low-k material after spin drying. Further, as described above, since IPA is volatile at room temperature, the semiconductor wafer is sufficiently and quickly dried even if the rotation speed of the semiconductor wafer is reduced to 1500 min ⁻¹ or less during spin drying. be able to.

  In the polishing unit 1a, the dressing process of the polishing surface 10 is performed while the next semiconductor wafer is transferred to the polishing unit 1a after the completion of the secondary CMP process of the semiconductor wafer. In this dressing process, as shown in FIG. 3, the dressing member 34 is brought into contact with the polishing surface 10 with a predetermined pressing force while the dresser 33 and the polishing table 11 are independently rotated. At this time, before or when the dressing member 34 comes into contact with the polishing surface 10, the dressing solution (for example, pure water) is supplied from the dressing solution supply nozzle 16 to the upper surface of the polishing surface 10 and remains on the polishing surface 10. The polishing surface 10 is regenerated while washing away the copper shavings and polishing liquid.

  In this substrate processing apparatus, the series of processes described above are continuously performed. That is, the plurality of semiconductor wafers stored in the cassette of the load / unload unit 2a are sequentially transferred to the polishing unit 1a, the cleaning unit 7a, the cleaning unit 8a, and the like at predetermined intervals.

FIG. 5 is a flowchart showing a second processing sequence of the substrate processing apparatus according to the first embodiment of the present invention.
The second processing sequence is the same as the first processing sequence shown in FIG. 4 from step 1 to step 4. In step 5 of the second processing sequence, roll scrub cleaning is performed while supplying the chemical solution to the semiconductor wafer, and then rinse treatment is performed by supplying IPA to the semiconductor wafer. Here, roll scrub cleaning with DIW may be performed between the roll scrub cleaning with the chemical solution and the rinse treatment with IPA. In step 6, if necessary, rinse treatment by IPA is performed again, and then the semiconductor wafer is dried by spin drying.

FIG. 6 is a flowchart showing a third processing sequence of the substrate processing apparatus according to the first embodiment of the present invention.
The third processing sequence is the same as the first processing sequence shown in FIG. 4 from step 1 to step 3. In step 4 of the third processing sequence, first, the surface of the semiconductor wafer is polished while supplying the polishing liquid to the polishing surface 10 (see FIG. 2) of the polishing table 11. Next, the supply of the polishing liquid is stopped, and the surface of the semiconductor wafer is polished while supplying IPA onto the polishing surface 10. Thereby, the polishing liquid adhering to the semiconductor wafer can be replaced with IPA. Note that Step 5 and subsequent steps in the third processing sequence are the same as those in the second processing sequence.

  In general, copper is susceptible to corrosion and oxidation. In particular, when copper comes into contact with a polishing liquid containing an oxidizing agent, corrosion and oxidation of copper are promoted. Therefore, in order to prevent corrosion and oxidation of the exposed surface of the copper wiring formed on the surface of the semiconductor wafer, in the third processing sequence, after the supply of the polishing liquid is stopped, IPA is immediately supplied to the polishing surface 10. While polishing the semiconductor wafer. Thereby, the polishing liquid adhering to the surface of the semiconductor wafer can be replaced with IPA, and the exposed surface of the copper wiring can be prevented from being corroded and oxidized.

  FIG. 7 is a graph showing the number of watermarks (defects) generated on the surface of the Low-k material. In FIG. 7, in the conventional processing sequence, IPA is not used as the processing liquid, and rinsing with DIW is performed before spin drying. As shown in FIG. 7, it can be seen that the number of watermarks generated by the above-described first to third processing sequences is significantly reduced as compared with the case of the conventional processing sequence.

Next, a substrate processing apparatus according to a second embodiment of the present invention will be described.
FIG. 8 is a schematic view showing a substrate processing apparatus according to the second embodiment of the present invention. The substrate processing apparatus according to the present embodiment is configured as an electroless plating apparatus that performs so-called cap plating, which selectively forms a wiring protective film on wiring metal exposed on the surface of the substrate. The substrate to be processed is a semiconductor wafer in which wiring is formed in a recess formed in the surface of the low-k material.

  As shown in FIG. 8, the substrate processing apparatus (electroless plating apparatus) is divided into three areas: a load / unload area 50, a cleaning area 52, and a plating process area 54. In the load / unload area 50, two load / unload units 58 on which a cassette 56 containing semiconductor wafers (substrates) is placed, a first reversing device 60 that flips the semiconductor wafers up and down, A first transfer robot 62 that transfers semiconductor wafers between the cassette 56, the first reversing device 60, and the temporary placement table 64 is installed.

  Within the cleaning area 52, temporary cleaning tables 64 positioned on the load / unload area 50 side are positioned on both sides of the temporary mounting table 64, and two cleaning devices for cleaning the semiconductor wafer after cap plating treatment A pre-cleaning device 68 for pre-cleaning the semiconductor wafer before plating and a second reversing machine 70 for inverting the semiconductor wafer up and down are disposed on the plating processing area 54 side. The cleaning device 66 includes a roll cleaning device 66a and a pencil cleaning device 66b, which can perform two-stage cleaning on the semiconductor wafer after the plating process and spin-dry it. Further, a second transfer robot 76 for transferring the semiconductor wafer between the temporary placement table 64, the two cleaning devices 66, the pre-cleaning device 68, and the second reversing device 70 is disposed at the center of the cleaning area 52. Has been.

  The basic configuration of the roll cleaning device 66a is the same as that of the cleaning units 7a and 7b according to the first embodiment described above. Here, the configuration of the pencil cleaning device 66b will be described with reference to FIG. FIG. 9 is a perspective view schematically showing a pencil cleaning apparatus incorporated in a substrate processing apparatus according to the second embodiment of the present invention.

  As shown in FIG. 9, the pencil cleaning device 66b includes a spin chuck (clamp mechanism) 90 that contacts the peripheral edge of the semiconductor wafer W, a swing arm 91 disposed above the spin chuck 90, and the swing arm. And a cleaning member 92 attached to the lower end of the rotary shaft 96 depending from the free end 91. The semiconductor wafer W that is the object to be cleaned is held horizontally by the spin chuck 90. The spin chuck 90 is rotationally driven by a drive source (not shown), so that the semiconductor wafer W held on the spin chuck 90 is rotated. The swing arm 91 is fixed to a drive shaft 95 having a drive source therein, and the swing arm 91 swings around the drive shaft 95 by the drive shaft 95.

  The rotating shaft 96 is connected to a driving source (not shown), and the cleaning member 92 is rotated via the rotating shaft 96 by the driving source. The lower surface of the cleaning member 92 is configured to contact the surface of the semiconductor wafer W held by the spin chuck 90. With such a configuration, the cleaning member 92 moves on the surface of the semiconductor wafer W as the swinging arm 91 swings while rotating around the rotating shaft 96 while contacting the surface of the semiconductor wafer W. .

The pencil cleaning device 66b includes a cleaning liquid supply nozzle 93 that supplies a cleaning liquid (chemical liquid), a DIW supply nozzle 94 that supplies DIW, and a processing liquid supply nozzle 97 that supplies IPA (processing liquid). In such a configuration, the surface of the semiconductor wafer W can be cleaned by rotating the cleaning member 92 while supplying the cleaning liquid or DIW to the surface of the semiconductor wafer W. The pencil cleaning device 66b also functions as a spin drying unit (drying unit) that rotates the semiconductor wafer W at a high speed to remove IPA and DIW adhering to the surface of the semiconductor wafer W by centrifugal force and dry it. In this case, it is preferable to rotate the semiconductor wafer within a range of 50 to 2000 min ^{−1 in} order to prevent IPA or the like jumping out of the semiconductor wafer W from reattaching to the semiconductor wafer. As described above, since IPA is volatile at room temperature, the semiconductor wafer W can be sufficiently and quickly dried even if the semiconductor wafer W is rotated at a relatively low rotational speed.

  In the plating processing area 54, a first pretreatment unit 78 for applying a catalyst to the surface of the semiconductor wafer, a second pretreatment unit 80 for performing a chemical treatment on the surface of the semiconductor wafer to which the catalyst is applied, and a semiconductor wafer Two electroless plating units 82 for performing electroless plating on the surface are arranged in parallel. A plating solution supply device 84 is installed at the end in the plating area 54. Further, a traveling type third transfer robot 86 is disposed in the central portion of the plating process area 54. The third transfer robot 86 includes a pre-cleaning device 68, a first pre-processing unit 78, and a second pre-processing. The semiconductor wafer is delivered between the unit 80, the electroless plating unit 82, and the second reversing machine 70.

  In the substrate processing apparatus according to the present embodiment, a predetermined processing liquid is supplied to the roll cleaning device 66a, the pencil cleaning device 66b, the precleaning device 68, the first preprocessing unit 78, and the second preprocessing unit 80 through the pipe 49. A processing liquid supply unit 9 for selectively supplying is further provided. The roll cleaning device 66a, the pencil cleaning device 66b, the pre-cleaning device 68, the first pre-processing unit 78, and the second pre-processing unit 80 are processing liquid supply nozzles (other than the processing liquid supply nozzle 97) that supply the processing liquid to the semiconductor wafer. (Not shown). The processing liquid stored in the processing liquid supply unit 9 is IPA as in the first embodiment described above. In addition, since the components and properties of the processing liquid used in this embodiment are the same as those in the first embodiment described above, a duplicate description thereof is omitted.

  Next, the operation of the substrate processing apparatus (electroless plating apparatus) according to this embodiment will be described with reference to FIGS. FIG. 10 is a flowchart showing a first processing sequence of the substrate processing apparatus according to the second embodiment of the present invention. In this example, a case where a wiring protective layer (cover material) is formed on the exposed surface of the wiring to protect the wiring is shown.

  First, a plurality of semiconductor wafers are stored in the cassette 56 mounted on the load / unload unit 58 so that the surface on which the wiring is formed faces upward (face up) (step 1 in FIG. 10). Then, one substrate is taken out from the cassette 56 by the first transfer robot 62 and transferred to the first reversing device 60, and the semiconductor wafer is reversed by the first reversing device 60 so that the surface thereof is face down. And placed on the temporary table 64. Then, the substrate placed on the temporary table 64 is transported to the pre-cleaning device 68 by the second transport robot 76.

The pre-cleaning device 68 holds the semiconductor wafer face down and performs pre-cleaning (primary pretreatment) on the surface. That is, for example, the substrate is immersed in an acid solution (chemical solution) such as 0.5 M H ₂ SO ₄ at a liquid temperature of 25 ° C., for example, for 1 minute, and CMP such as copper remaining on the surface of the low-k material Remove any residue. Thereafter, IPA (treatment liquid) is supplied to the surface of the semiconductor wafer to impart hydrophilicity to the surface of the low-k material (step 2 in FIG. 10). Before supplying IPA to the semiconductor wafer, a rinse liquid such as DIW may be supplied to the semiconductor wafer and cleaned as necessary.

Next, the semiconductor wafer after the primary pretreatment is transported to the first pretreatment unit 78 by the third transport robot 86, where the semiconductor wafer is held face down, and a catalyst application treatment (secondary treatment is performed on this surface). Perform pre-processing. This catalyst application is performed, for example, by immersing the semiconductor wafer in a mixed solution of 0.005 g / L PdCl ₂ and about 0.7 wt% HCl, for example, for about 1 minute at a liquid temperature of 25 ° C. Is called. Thereby, Pd (palladium) as a catalyst adheres to the surface of the wiring (Cu), and a Pd nucleus as a catalyst nucleus (seed) is formed on the surface of the wiring. Thereafter, the exposed surface of the wiring is activated, and the surface of the semiconductor wafer is further cleaned with DIW (step 3 in FIG. 10).

Then, the substrate provided with the catalyst is transferred to the second pretreatment unit 80 by the third transfer robot 86, where the semiconductor wafer is held face down, and a chemical treatment (third pretreatment, FIG. (Not shown). In this chemical treatment, for example, a semiconductor wafer is immersed in a solution such as 20 g / L of Na ₃ C ₆ H ₅ O ₇ .2H ₂ O (sodium citrate) at a liquid temperature of 25 ° C. This is performed by subjecting the surface of the semiconductor wafer to water washing with ultrapure water or the like. In addition, after washing with water, you may supply IPA (processing liquid) to a semiconductor wafer as needed.

  In this way, the semiconductor wafer subjected to the pretreatment for electroless plating is transported to the electroless plating processing unit 82 by the third transport robot 86, where the semiconductor wafer is held face-down, and the surface is electrolessly electrolyzed. A plating process is performed (step 4 in FIG. 10). As this electroless plating treatment, for example, a semiconductor wafer is immersed in a Co—WP plating solution having a liquid temperature of 80 ° C. for about 120 seconds, and the surface of the activated wiring is selectively electroless plated ( (Electroless Co-WP cover plating) is performed, and then the surface of the semiconductor wafer is cleaned with a cleaning liquid such as ultrapure water. As a result, a wiring protection layer (cap plating layer) made of a Co—WP alloy film can be selectively formed on the surface of the wiring to protect the wiring.

  Next, the semiconductor wafer after the electroless plating treatment is transferred by the third transfer robot 86 to the second reversing machine 70, where the semiconductor wafer is turned over so that the surface thereof is face up. The inverted semiconductor wafer is transferred by the second transfer robot 76 to the roll cleaning device 66a. In this roll cleaning device 66a, while supplying a cleaning liquid (chemical solution) and DIW to the semiconductor wafer sequentially, a roll brush (not shown) is rotated to remove particles and unnecessary substances adhering to the surface of the semiconductor wafer (FIG. 10). Step 5). Thereafter, the semiconductor wafer is transferred to the pencil cleaning device 66b by the second transfer robot 76, where DIW rinsing of the surface of the semiconductor wafer is performed, and then spin drying is performed (step 6 in FIG. 10).

  The semiconductor wafer after the spin drying is transferred to the temporary table 64 by the second transfer robot 76, and the semiconductor wafer placed on the temporary table 64 is mounted on the load / unload unit 58 by the first transfer robot 62. Return to the cassette 56 (step 7 in FIG. 10).

  In this embodiment, a Co—WP alloy film is used as the wiring protection layer, but the present invention is not limited to this, and Co—B, Ni—B, Ni—WB, Co—WB, etc. You may make it form the wiring protective layer of another alloy. Further, the wiring material is not limited to copper, and copper alloy, silver, silver alloy, gold, gold alloy, and the like may be used.

FIG. 11 is a flowchart showing a second processing sequence of the substrate processing apparatus according to the second embodiment of the present invention.
The second processing sequence is different from the first processing sequence in Step 2, Step 5, and Step 6. That is, as shown in FIG. 11, in step 2 of the second processing sequence, the semiconductor wafer is immersed in an acid solution (chemical solution) such as H ₂ SO ₄ as the primary pretreatment, and then the surface of the semiconductor wafer. DIW is supplied to wash away the acid solution (chemical solution).

  In step 5 of the second processing sequence, roll scrub cleaning is performed while supplying a chemical solution to the semiconductor wafer, and then roll scrub processing is performed while supplying DIW to the semiconductor wafer as necessary. Thereafter, an IPA (treatment liquid) is supplied to the semiconductor wafer to perform a rinsing process. In step 6 of the second processing sequence, the rinsing process using DIW is not performed, and the rinsing process using IPA is performed as necessary, and then the semiconductor wafer is dried by spin drying.

  FIG. 12 is a graph showing the number of watermarks (defects) generated on the surface of the Low-k material. In FIG. 12, in the conventional processing sequence, IPW is not used as the rinse liquid, but DIW is used. As shown in FIG. 12, it can be seen that the number of watermarks generated in the above-described first and second processing sequences is reduced as compared with the case of the conventional processing sequence. In particular, by supplying IPA to the surface of the semiconductor wafer immediately before spin drying, the number of watermarks can be greatly reduced.

  The first and second embodiments are examples in which the processing liquid according to the present invention is used for cleaning processing and rinsing processing. However, the processing liquid according to the present invention is wet for removing a polymer after dry etching. It can also be used for processing. That is, in the step of forming a fine wiring groove in the low-k material formed on the surface of the substrate, a resist is applied to the surface of the low-k material, exposed, and patterned. Thereafter, a wiring trench is formed in the low-k material by dry etching. At this time, in order to perform anisotropic dry etching, the dry etching is performed while generating a polymer on the side surface of the wiring groove. After the wiring groove is formed, the resist is removed, but the polymer remains on the side surface of the wiring groove. Therefore, in order to remove the polymer, a wet process using a chemical solution is performed. Even in such a case, by supplying the treatment liquid according to the present invention to the substrate after the wet treatment, hydrophilicity can be imparted to the Low-k material, and the generation of watermarks can be suppressed.

  Next, a substrate processing apparatus according to a third embodiment of the present invention will be described with reference to FIGS. 13 (a) to 13 (c). FIG. 13A is an enlarged view showing the main part of the substrate processing apparatus according to the third embodiment of the present invention, FIG. 13B is a cross-sectional view taken along the line XIIIb-XIIIb of FIG. FIG. 13C is a cross-sectional view taken along line XIIIc-XIIIc in FIG. The substrate used in this embodiment is a semiconductor wafer in which the Low-k material is exposed on at least a part of its surface.

  The substrate processing apparatus according to this embodiment is an apparatus for processing a semiconductor wafer by supplying a cleaning liquid or an etching liquid onto the semiconductor wafer. As shown in FIGS. 13A to 13C, the substrate processing apparatus includes cleaning nozzles 101 and 102 arranged above and below the semiconductor wafer W. These cleaning nozzles 101 and 102 have working surfaces K1 and K2, respectively, and fluid (liquid) supply ports 103 and suction ports 104 are alternately and linearly aligned on the respective working surfaces K1 and K2. Are arranged. As shown in FIG. 13C, each supply port 103 is connected to a common liquid supply pipe 105, and as shown in FIG. 13B, each suction port 104 is similarly connected to a common drain pipe 106. Has been. Therefore, when a liquid is supplied to the liquid supply pipe 105, the liquid is supplied onto the semiconductor wafer W from each supply port 103. The drainage pipe 106 communicates with a vacuum source (not shown) and is sucked by vacuum, and sucks the liquid supplied to the surface of the semiconductor wafer W from each suction port 104.

  As described above, each of the cleaning nozzles 101 and 102 has two working surfaces K1 and K2 each having a supply port 103 and a suction port 104, and is configured to be able to use two types of liquids. ing. That is, each of the cleaning nozzles 101 and 102 includes two drainage pipes 106 and 106 and two liquid supply pipes 105 and 105. One of the two liquid supply pipes 105 communicates with the supply port 103 that opens to the working surface K1, and similarly, one of the two drainage pipes 106 connects to the suction port 104 that opens to the working surface K1. Communicate. On the other hand, the other liquid supply pipe 105 communicates with the supply port 103 that opens to the working surface K2, and similarly, the other drain pipe 106 communicates with the suction port 104 that opens to the working surface K2. In the present embodiment, a plurality of supply ports 103 and suction ports 104 are provided, but one supply port 103 and one suction port 104 may be provided on each of the working surfaces K1 and K2.

  The cleaning nozzles 101 and 102 are configured to be able to rotate by a quarter (90 degrees) about their respective axes by a rotation mechanism (not shown). Thereby, the operation surfaces K1 and K2 can be switched. Therefore, it is possible to perform processing with different liquids using the same cleaning nozzles 101 and 102. For example, the cleaning liquid is sucked from the semiconductor wafer W through the suction port 104 while supplying the cleaning liquid to the semiconductor wafer W from the supply port 103 disposed on the working surface K1. On the other hand, on the working surface K2, following the process on the working surface K1, the IPA as the processing liquid described above is supplied onto the semiconductor wafer W, and the cleaning liquid remaining on the semiconductor wafer W in the process on the working surface K1 is supplied. You may make it replace with IPA.

1 is a schematic view showing a substrate processing apparatus according to a first embodiment of the present invention. It is the schematic which shows the grinding | polishing unit shown in FIG. FIG. 3A is a side view schematically showing the cleaning units 7a and 7b shown in FIG. 1, and FIG. 3B is a perspective view schematically showing the cleaning units 8a and 8b shown in FIG. It is a flowchart which shows the 1st process sequence of the substrate processing apparatus which concerns on the 1st Embodiment of this invention. It is a flowchart which shows the 2nd process sequence of the substrate processing apparatus which concerns on the 1st Embodiment of this invention. It is a flowchart which shows the 3rd processing sequence of the substrate processing apparatus which concerns on the 1st Embodiment of this invention. It is a graph which shows the number of the watermark which generate | occur | produced on the surface of Low-k material. It is the schematic which shows the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a perspective view which shows typically the pencil cleaning apparatus incorporated in the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a flowchart which shows the 1st process sequence of the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a flowchart which shows the 2nd process sequence of the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a graph which shows the number of the watermark which generate | occur | produced on the surface of Low-k material. FIG. 13A is an enlarged view showing the main part of the substrate processing apparatus according to the third embodiment of the present invention, FIG. 13B is a cross-sectional view taken along the line XIIIb-XIIIb of FIG. FIG. 13C is a cross-sectional view taken along line XIIIc-XIIIc in FIG.

Explanation of symbols

1a, 1b Polishing unit (polishing part)
2a to 2d Load / unload units 4a to 4c Transfer robots 5a and 5b Temporary placement tables 6a and 6b Inverters 7a and 7b Cleaning units (cleaning units)
8a, 8b Cleaning unit (drying section)
9 Treatment liquid supply unit 10 Polishing surface 11 Polishing table 11a Table shaft 12 Top ring unit 13 Dressing units 14a and 14b Pusher 15 Polishing liquid supply nozzle 16 Dressing liquid supply nozzles 20 and 30 Support shafts 21 and 31 Swing arm 22 Top ring shaft 23 Top ring 24 Treatment liquid supply nozzle 32 Dresser shaft 33 Dresser 34 Dressing members 40a and 40b Roll brushes 41 and 45 Rollers 42a and 42b Cleaning liquid supply nozzles 43a and 43b DIW supply nozzles 44a and 44b Treatment liquid supply nozzle 46 Rinse liquid supply nozzle 47 Treatment liquid supply nozzle 49 Piping 50 Load / unload area 52 Cleaning area 54 Plating treatment area 56 Cassette 58 Load / unload unit 60 First reversing machine 62 64 Temporary table 66 Cleaning device 66a Roll cleaning device 66b Pencil cleaning device 68 Pre-cleaning device 70 Second reversing machine 76 Second transfer robot 78 First pre-processing unit 80 Second pre-processing unit 82 Electroless plating processing unit 84 Plating Liquid supply device 86 Third transport robot 90 Spin chuck 91 Oscillating arm 92 Cleaning member 95 Drive shaft 93 Cleaning liquid supply nozzle 94 DIW supply nozzle 97 Treatment liquid supply nozzles 101 and 102 Cleaning nozzle 103 Supply port 104 Suction port 105 Supply liquid tube 106 Drainage pipe

Claims (23)

A processing solution for processing a substrate in which a low dielectric constant material is exposed on at least a part of a surface,
A processing solution comprising an organic substance having at least one hydrophilic group and one hydrophobic group in each molecule and having volatility at room temperature.   The treatment liquid according to claim 1, wherein the organic substance is an organic acid or an alcohol.   The treatment liquid according to claim 2, wherein the organic acid or alcohol has 5 or less carbon atoms.   The treatment liquid according to claim 1, wherein a contact angle of the treatment liquid with respect to a surface of the substrate is 50 degrees or less.   The processing liquid according to claim 1, wherein the low dielectric constant material has a relative dielectric constant of 3 or less. A substrate processing method for processing a substrate in which a low dielectric constant material is exposed on at least a part of a surface,
6. A substrate processing method, comprising: supplying a processing solution according to any one of claims 1 to 5 to a substrate after supplying a chemical solution and / or a rinsing solution to the substrate and performing a predetermined processing.   The substrate processing method according to claim 6, wherein the processing liquid is supplied to the substrate in the form of a mist.   The substrate processing method according to claim 6, wherein the processing liquid is supplied to the substrate as vapor.   The substrate processing method according to claim 6, wherein the rinse liquid is pure water. The substrate according to claim 6, wherein the rinse liquid is an aqueous solution in which at least one of H ₂ gas, O ₂ gas, CO ₂ gas, and N ₂ gas is dissolved in pure water. Processing method. The substrate processing method according to claim 6, wherein after the supply of the processing solution is stopped, the substrate is rotated at 2000 mim ⁻¹ or less to dry the substrate.   The substrate processing method according to claim 11, wherein the substrates are dried one by one. A substrate processing method for polishing a substrate having a low dielectric constant material and a metal film formed on the low dielectric constant material formed on a surface thereof,
Polishing the substrate while supplying the polishing liquid to the substrate;
A substrate processing method comprising: a step of polishing a substrate while supplying the processing liquid according to claim 1 to the substrate. A substrate processing method for polishing a substrate having a low dielectric constant material and a metal film formed on the low dielectric constant material formed on a surface thereof,
6. A substrate processing method comprising: performing a predetermined process while supplying the processing liquid according to claim 1 to the substrate after the substrate is polished.   The substrate processing method according to claim 14, wherein the predetermined process is a roll scrub process. A substrate processing method for polishing a substrate having a low dielectric constant material and a metal film formed on the low dielectric constant material formed on a surface thereof,
Polishing the substrate;
Supplying the treatment liquid according to any one of claims 1 to 5 to a polished substrate;
And a step of drying the substrate by rotating the substrate at 1500 mim ⁻¹ or less after stopping the supply of the treatment liquid. A substrate processing method for plating a substrate having a low dielectric constant material exposed on at least a part of a surface thereof,
A substrate processing method comprising supplying the processing liquid according to any one of claims 1 to 5 to a substrate as a pretreatment before plating the substrate. A substrate processing method for plating a substrate having a low dielectric constant material exposed on at least a part of a surface thereof,
6. A substrate processing method comprising supplying the processing liquid according to claim 1 to the substrate as post-processing after plating the substrate. A substrate processing method for processing a substrate in which a low dielectric constant material is exposed on at least a part of a surface,
Supplying the treatment liquid according to any one of claims 1 to 5 to at least a part of a surface of the low dielectric constant material;
And a step of hydrophilizing at least part of the surface of the low dielectric constant material with the treatment liquid.   The substrate processing method according to claim 19, further comprising the step of removing the processing liquid from the surface of the substrate after hydrophilizing at least a part of the surface of the low dielectric constant material.   21. The substrate processing method according to claim 20, wherein the processing liquid is removed from the surface of the substrate by volatilizing the processing liquid from the surface of the substrate. A substrate processing apparatus for polishing a substrate on which a low dielectric constant material and a metal film formed on the low dielectric constant material are formed.
A polishing section for polishing the substrate;
A post-processing section that performs post-processing of the polished substrate;
6. A substrate processing apparatus comprising: a processing liquid supply unit that supplies the processing liquid according to claim 1 to at least one of the polishing unit and the post-processing unit. A substrate processing apparatus for plating a substrate having a low dielectric constant material exposed on at least a part of a surface thereof,
A plating section for plating the substrate;
A pretreatment unit that performs a predetermined pretreatment on the substrate before plating the substrate;
A post-processing section that performs predetermined post-processing on the plated substrate;
6. A substrate processing apparatus comprising: a processing liquid supply unit that supplies the processing liquid according to claim 1 to at least one of the pre-processing unit and the post-processing unit.

Images