JP2014017280A - Substrate contamination recovery method, substrate contamination recovery apparatus, and substrate contamination recovery analysis system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To unfailingly recover only a contamination metal adhering to a peripheral part of a substrate and accurately analyze the contamination metal adhering to the peripheral part of the substrate.SOLUTION: A liquid is supplied only to a peripheral part of a substrate W1. Droplets contact with the peripheral part of the substrate W1. This process causes a contamination metal adhering to the peripheral part of the substrate W1 to be taken in the droplets. Then, the droplets contacting with the peripheral part of the substrate W1 are cooled to be freezed. This process changes the droplets contacting with the peripheral part of the substrate W1 to an ice block. The ice block taking in the metal contamination is peeled from the substrate W1 to be analyzed by an analyzer.

Description

The present invention relates to a substrate contamination recovery method and contamination recovery apparatus for recovering contaminated metal adhering to the peripheral edge of a substrate. Furthermore, the present invention relates to a substrate contamination recovery analysis system for recovering and analyzing contaminated metals attached to the peripheral edge of the substrate.
Examples of target substrates include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and photomask substrates. Substrates, ceramic substrates, solar cell substrates and the like are included.

In a manufacturing process of a semiconductor device or a liquid crystal display device, a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is contaminated with a contaminant such as a metal. Patent Document 1 discloses an analysis method for analyzing a metal element of a semiconductor wafer by a total reflection fluorescent X-ray analysis method.
In the analysis method of Patent Document 1, hydrofluoric acid is dropped onto the surface (upper surface) of the semiconductor wafer, and the hydrofluoric acid is scattered at a plurality of positions in the semiconductor wafer. Thereafter, the tip of the recovery rod is moved inward along the surface of the semiconductor wafer while the semiconductor wafer is rotated. The plurality of droplets on the semiconductor wafer are collected at the central portion of the semiconductor wafer as the recovery rod moves along the surface of the semiconductor wafer. Then, after the collected hydrofluoric acid droplets are dried on the semiconductor wafer, the contaminated metal deposited from the hydrofluoric acid is irradiated with X-rays. Thereby, the contaminated metal of a semiconductor wafer is collect | recovered by the center part of a semiconductor wafer, and the collect | recovered contaminated metal is analyzed.

JP 2005-249546 A

In the total reflection X-ray fluorescence analysis method, X-rays are irradiated on the sample at an angle of total reflection, and fluorescent X-rays emitted from the sample by X-ray irradiation are detected. If the portion irradiated with X-rays is not sufficiently flat, a large amount of scattered X-rays are generated and the analysis accuracy is lowered.
When only the contaminating metal adhering to the peripheral edge of the substrate is analyzed by the total reflection fluorescent X-ray analysis method, a method of irradiating the peripheral edge of the substrate with X-rays can be considered. However, since the peripheral edge of the substrate is not flat and inclined, this method cannot accurately analyze contaminated metals.

Although the method of recovering the contaminated metal adhering to the peripheral portion of the substrate to the central portion of the flat substrate by adopting the analysis method of Patent Document 1 can be considered, the peripheral portion of the substrate is not flat. In some cases, the hydrofluoric acid supplied to the peripheral edge of the metal wraps around the lower surface of the substrate. Therefore, it is not possible to reliably recover only the contaminated metal adhering to the peripheral edge of the substrate.
In order to collect only contaminated metal adhering to the peripheral edge of the substrate, a liquid such as hydrofluoric acid is supplied only to the peripheral edge of the substrate, and all the liquid including the liquid that wraps around the lower surface of the substrate is sucked with a dropper. However, in this method, there is a possibility that contamination in the dropper is mixed in the liquid. Therefore, it is not possible to reliably recover only the contaminated metal adhering to the peripheral edge of the substrate.

Therefore, an object of the present invention is to provide a substrate contamination recovery method and a contamination recovery device that can reliably recover only the contaminated metal adhering to the peripheral edge of the substrate.
Another object of the present invention is to provide a contamination recovery and analysis system for a substrate that can reliably collect only the contaminated metal adhering to the peripheral portion of the substrate and can accurately analyze the contaminated metal adhering to the peripheral portion of the substrate. It is.

  In order to achieve the above object, the invention according to claim 1 is a substrate contamination recovery method for recovering contaminated metal adhering to the peripheral portion of the substrate (W1), wherein droplets are brought into contact with the peripheral portion of the substrate. A liquid contacting step, a freezing step of changing the droplets in contact with the peripheral portion of the substrate into an ice block, and a peeling step of peeling the ice block in contact with the peripheral portion of the substrate from the substrate A method for collecting contamination of a substrate.

  According to this method, the liquid is supplied only to the peripheral edge of the substrate, and the droplet contacts the peripheral edge of the substrate. Thereby, the contaminated metal adhering to the peripheral part of the substrate is taken into the droplet. Thereafter, the droplet in contact with the peripheral edge of the substrate is cooled and frozen. Thereby, the droplet which is contacting the peripheral part of a board | substrate changes into an ice lump. Then, the ice block incorporating the contaminated metal is peeled off from the substrate and analyzed by the analyzer. In this way, since the droplets that have taken in the contaminated metal are separated from the substrate in a frozen state, even if the droplets circulate on both the front side and the back side of the substrate, the droplets can be reliably removed together with the contaminated metal. Can be recovered. Therefore, the contaminated metal adhering to the peripheral part of the substrate can be reliably recovered.

The invention described in claim 2 further includes a liquid moving step of moving the droplets in contact with the peripheral portion of the substrate along the peripheral portion of the substrate before the freezing step. The method for recovering contamination of a substrate as described in 1. above.
According to this method, the droplets are moved along the peripheral edge of the substrate before the droplets in contact with the peripheral edge of the substrate are frozen. The region where the droplet moves may be the entire circumference of the substrate, or may be an area shorter than the entire circumference of the substrate (an area of less than 360 degrees). In either case, since the droplets move along the peripheral edge of the substrate, the contaminated metal can be recovered from a wider area within the peripheral edge of the substrate.

According to a third aspect of the present invention, in the liquid movement step, the contact member (8, 208) is in contact with the liquid droplet that is in contact with the peripheral edge of the substrate. The substrate contamination recovery method according to claim 2, further comprising a step of relatively moving the two.
According to this method, since the contact member is in contact with the droplet, a force (surface tension or the like) for holding the droplet on the contact member is generated. Therefore, when the substrate and the contact member move relative to each other while the peripheral edge of the substrate and the contact member are in contact with the liquid droplet, the peripheral edge of the substrate moves relative to the liquid droplet. Thereby, the droplet moves along the peripheral edge of the substrate, and the contaminated metal is recovered from a wider area in the peripheral edge of the substrate.

  According to a fourth aspect of the present invention, in the freezing step, at least one of the contact member in contact with the liquid droplet in contact with the peripheral edge portion of the substrate and the substrate is in contact with the peripheral edge portion of the substrate. The substrate contamination recovery method according to any one of claims 1 to 3, further comprising a step of changing the droplet in contact with the peripheral edge of the substrate into an ice block by cooling in a state where the substrate is cooled. It is.

  According to this method, one of the substrate and the contact member, or both the substrate and the contact member is cooled in a state where the peripheral edge portion of the substrate and the contact member are in contact with the droplet. Thereby, the droplet is indirectly cooled and frozen. Thus, since the droplets are indirectly cooled, it is not necessary to spray the coolant onto the droplets or to bring the cooling member into contact with the droplets. Therefore, it is possible to suppress or prevent the droplets from being blown off by the coolant or contamination of the cooling member from being mixed into the droplets.

  According to a fifth aspect of the present invention, in the freezing step, the liquid that is in contact with the peripheral portion of the substrate is in contact with the droplet that is in contact with the peripheral portion of the substrate. A step of changing droplets into ice blocks, wherein the peeling step contacts the peripheral edge of the substrate by moving the substrate and the contact member relative to each other in a direction away from each other. The substrate contamination recovery method according to any one of claims 1 to 4, further comprising a step of peeling the ice block from the substrate.

  According to this method, the droplet is frozen while the peripheral edge of the substrate and the contact member are in contact with the droplet. Thereby, the droplet freezes on the contact member. Then, with the droplets frozen, the substrate and the contact member are relatively moved in a direction away from each other. Thereby, the force which peels an ice block from a board | substrate applies to an ice block from a contact member, and an ice block peels from a board | substrate. Therefore, the ice block that takes in the contaminated metal adhering to the peripheral edge of the substrate is recovered from the substrate.

The invention according to claim 6 is the method according to any one of claims 1 to 5, wherein the liquid contact step includes a step of bringing a droplet of a solution for dissolving the substrate into contact with a peripheral portion of the substrate. This is a substrate contamination recovery method.
According to this method, the solution for dissolving the substrate is supplied only to the peripheral portion of the substrate, and the droplets of the solution come into contact with the peripheral portion of the substrate. Therefore, the contaminated metal adhering to the peripheral portion of the substrate peels off (lifts off) from the substrate together with the surface layer portion of the substrate, and is reliably captured in the solution. Therefore, the recovery rate of contaminated metals can be increased from the peripheral edge of the substrate.

  The invention according to claim 7 is a substrate contamination recovery apparatus for recovering contaminant metals adhering to the peripheral edge of the substrate (W1), the substrate holding means (7) for holding the substrate, and the substrate holding means. Liquid contact means (9, 9A) for bringing the droplet into contact with the peripheral edge of the substrate held on the substrate, and cooling the droplet in contact with the peripheral edge of the substrate held on the substrate holding means A freezing means (10, 10A, 10B) for changing into ice blocks, and a peeling means (4) for peeling off the ice blocks in contact with the peripheral edge of the substrate held by the substrate holding means. Is a substrate contamination recovery apparatus (2). According to this configuration, it is possible to achieve an effect similar to the effect described with respect to the invention of claim 1.

  The invention according to claim 8 is a substrate contamination recovery analysis system for recovering contaminated metal adhering to the peripheral portion of the substrate (W1) and analyzing the recovered contaminated metal, and holding the substrate Means (7), liquid contact means (9, 9A) for bringing droplets into contact with the peripheral edge of the substrate held by the substrate holding means, and the peripheral edge of the substrate held by the substrate holding means Freezing means (10, 10A, 10B) that changes the droplets that are in contact with the ice into ice blocks, and the ice blocks that are in contact with the peripheral edge of the substrate held by the substrate holding means. A substrate contamination recovery and analysis system (1, 201, 301) including a peeling means (4) for peeling from the substrate and an analysis means (3) for analyzing a contaminated metal taken in the ice block.

  According to this configuration, the liquid from the liquid contact unit is supplied only to the peripheral portion of the substrate held by the substrate holding unit, and the droplet contacts the peripheral portion of the substrate. Thereby, the contaminated metal adhering to the peripheral part of the substrate is taken into the droplet. Then, after the droplets are frozen by the freezing means and changed into ice blocks, the ice blocks in contact with the peripheral edge of the substrate are peeled off from the substrate by the peeling means. Therefore, the contaminated metal adhering to the peripheral part of the substrate can be reliably recovered. And the contaminated metal adhering to the peripheral part of the board | substrate contained in the peeled ice block is analyzed by an analyzer. Therefore, the contaminated metal adhering to the peripheral edge portion of the substrate can be analyzed with high accuracy.

  In this section, alphanumeric characters in parentheses represent reference numerals of corresponding components in the embodiments described later, but the scope of the claims is not limited by these reference numerals.

1 is a schematic diagram of a recovery analysis system according to a first embodiment of the present invention. It is an enlarged view which shows the contact state of the board | substrate and contact member with respect to the collection | recovery liquid in 1st Embodiment of this invention. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram of the collection | recovery analysis system which concerns on 2nd Embodiment of this invention. It is an enlarged view which shows the contact state of the board | substrate and contact member with respect to the collection | recovery liquid in 2nd Embodiment of this invention. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram which shows the process after collect | recovering the contaminated metal adhering to the peripheral part of a board | substrate until it analyzes. It is a schematic diagram of the collection | recovery analysis system which concerns on 3rd Embodiment of this invention. It is an enlarged view which shows the contact state of the board | substrate and contact member with respect to the collection | recovery liquid in 3rd Embodiment of this invention. It is an enlarged view which shows the contact state of the board | substrate and contact member with respect to the collection | recovery liquid in other embodiment of this invention. It is an enlarged view which shows the contact state of the board | substrate and contact member with respect to the collection | recovery liquid in further another embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a contamination recovery analysis system 1 according to the first embodiment of the present invention. FIG. 2 is an enlarged view showing a contact state of the substrate W1 and the contact member 8 with respect to the recovered liquid in the first embodiment of the present invention.
As shown in FIG. 1, a contamination recovery analysis system 1 includes a contamination recovery device 2 that recovers a contaminated metal adhering to the peripheral portion of the substrate W1, and a contamination analysis device 3 that analyzes the contaminated metal recovered by the contamination recovery device 2. And a control device for controlling the operation of the device provided in the pollution recovery analysis system 1 and the opening and closing of the valves, and the transfer device 4 for transferring the contaminated metal recovered by the pollution recovery device 2 from the pollution recovery device 2 to the pollution analysis device 3. Device 5.

  As shown in FIG. 1, the contamination recovery analysis system 1 includes a recovery chamber 6 having an internal space. The contamination recovery apparatus 2 includes a spin chuck 7 that holds a substrate W1 in a vertical posture in a recovery chamber 6 and rotates the substrate W1 around a rotation axis A1 that passes through the center of the substrate W1, and a substrate W1 that is held by the spin chuck 7. A contact member 8 that contacts the peripheral portion with the recovery liquid, a recovery liquid nozzle 9 that supplies the recovery liquid to the contact member 8, and a cooling nozzle 10 that freezes the liquid droplets in contact with the peripheral portion of the substrate W1 are included.

As shown in FIG. 1, the collection chamber 6 includes a partition wall 11 provided with an opening, a shutter 12 that closes the opening, and an opening / closing device (not shown) that opens and closes the opening by moving the shutter 12. including. Loading and unloading of the substrate W1 by a transfer robot (not shown) is performed through the opening.
As shown in FIG. 1, the spin chuck 7 has a spin base 13 that holds the substrate W1 in a vertical posture by adsorbing the back surface of the substrate W1, which is a non-device forming surface, and a rotation axis A1 orthogonal to the substrate W1. And a spin motor 14 that rotates the substrate W1 held on the spin base 13 about the rotation axis A1 by rotating the spin base 13 to the rotation base A1. The control device 5 controls the rotation angle of the substrate W1 by controlling the spin motor 14.

  As shown in FIG. 2, the contact member 8 includes a contact surface 15 that comes into contact with the recovered liquid. The contact surface 15 is made of a fluororesin such as PTFE (polytetrafluoroethylene). Polytetrafluoroethylene is an example of a hydrophobic material (a material having a water contact angle larger than 30 degrees). The contact surface 15 may be made of a hydrophilic material such as PVC (polyvinyl chloride) (a material having a water contact angle smaller than 30 degrees). The contact surface 15 forms a recess 16 that opens upward. The recess 16 is disposed below the substrate W1 held by the spin chuck 7. The recess 16 faces the lower end of the substrate W1 (a part of the peripheral end surface of the substrate W1) in the vertical direction. The recess 16 has a longitudinal section (a section when cut along a vertical plane) along the peripheral edge of the substrate W1. The lower end of the substrate W1 is immersed in the collected liquid stored in the recess 16. Thereby, a part of peripheral edge part of the board | substrate W1 contacts collection liquid.

  As shown in FIG. 1, the transport device 4 is connected to the contact member 8. Although not shown, the transport device 4 includes an actuator such as a motor or a cylinder, and a transmission member that transmits the power of the actuator to the contact member 8. The transfer device 4 moves the contact member 8 in the collection chamber 6 with the concave portion 16 facing upward. Further, the transport device 4 moves the contact member 8 between the contamination collection device 2 and the contamination analysis device 3, and moves the contact member 8 within the contamination analysis device 3. The conveying device 4 can move the contact member 8 in a state in which the posture of the contact member 8 is kept constant, and between the upward posture in which the concave portion 16 faces upward and the downward posture in which the concave portion 16 faces downward. Thus, the posture of the contact member 8 can be changed.

  As shown in FIG. 1, the transport device 4 includes, for example, a contact position (a position indicated by a two-dot chain line) where the recovered liquid held by the contact member 8 contacts the peripheral edge of the substrate W1 and a peripheral edge of the substrate W1. Between the peeling position (solid line position) away from the collected liquid held by the contact member 8 and the liquid supply position (dotted line position) where the collected liquid from the collected liquid nozzle 9 is supplied to the contact member 8. The contact member 8 is moved. The contact position is a position below the substrate W1, and the peeling position is a position below the contact position. The liquid supply position is a position on the side of the peeling position.

  As shown in FIG. 1, the recovery liquid nozzle 9 is connected to a recovery liquid pipe 18 in which a recovery liquid valve 17 is interposed. When the recovered liquid valve 17 is opened, the recovered liquid guided from the recovered liquid pipe 18 to the recovered liquid nozzle 9 is discharged downward from a recovered liquid discharge port provided at the lower end of the recovered liquid nozzle 9. Further, when the recovery liquid valve 17 is closed, the discharge of the recovery liquid from the recovery liquid nozzle 9 is stopped. When the recovery liquid nozzle 9 discharges the recovery liquid while the contact member 8 is located at the liquid supply position, the recovery liquid discharged from the recovery liquid nozzle 9 is accumulated in the recess 16 of the contact member 8.

  As shown in FIG. 1, the recovered liquid supplied to the recovered liquid nozzle 9 is hydrofluoric acid (hydrofluoric acid) having a concentration of 50%, which is an example of etching. The melting point of hydrofluoric acid having a concentration of 50% is −34 ° C. The recovery liquid supplied to the recovery liquid nozzle 9 may be a solution for dissolving the substrate W1 other than hydrofluoric acid, or pure water (deionized water), carbonated water, electrolytic ion water, hydrogen water. , Ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm) may be used.

  As shown in FIG. 1, the cooling nozzle 10 is connected to a cooling pipe 20 in which a cooling valve 19 is interposed. When the cooling valve 19 is opened, the coolant guided from the cooling pipe 20 to the cooling nozzle 10 is discharged from the discharge port of the cooling nozzle 10 toward the substrate W1. Further, when the cooling valve 19 is closed, the discharge of the coolant from the cooling nozzle 10 is stopped. The coolant supplied to the cooling nozzle 10 is a cooling gas whose temperature is equal to or lower than the melting point of the recovered liquid. The cooling gas is a carbon dioxide gas of about −79 ° C. generated from solid carbon dioxide. The cooling gas is not limited to carbon dioxide, but may be nitrogen gas generated from liquid nitrogen, or may be gas other than carbon dioxide and nitrogen gas.

  When the coolant is sprayed on the substrate W1, the substrate W1 is rapidly cooled. Therefore, when the cooling liquid is discharged by the cooling nozzle 10 in a state where the recovered liquid held by the contact member 8 is in contact with the peripheral edge portion of the substrate W1, the recovered liquid that is in contact with the substrate W1 is rapidly absorbed by the substrate W1. To be cooled. Furthermore, since the recovered liquid is cooled, the contact member 8 holding the recovered liquid is also rapidly cooled. As a result, the recovered liquid in contact with the substrate W1 is frozen. That is, the recovered liquid in contact with the substrate W1 changes to a solid ice block. Further, as shown in FIG. 1, the coolant discharged from the cooling nozzle 10 is sprayed onto a portion (non-contact portion) other than the portion in contact with the recovered liquid in the substrate W1, and thus is held by the contact member 8. It is possible to suppress or prevent the recovered liquid from being blown off by the coolant.

  As shown in FIG. 1, the pollution analyzer 3 is a total reflection X-ray fluorescence analyzer that analyzes contaminated metals by a total reflection X-ray fluorescence analysis method. The pollution analyzer 3 is not limited to a total reflection X-ray fluorescence analyzer, but may be an inductively coupled plasma mass spectrometer that analyzes contaminated metals by inductively coupled plasma mass spectrometry (ICP-MS), or a total reflection fluorescence. An apparatus for analyzing contaminated metals by a method other than X-ray analysis and ICP-MS may be used.

  As shown in FIG. 1, the contamination recovery analysis system 1 includes an analysis chamber 21 having an internal space. The contamination analyzer 3 includes a holding unit 22 that holds the measurement substrate W2 (a disk having the same shape as the substrate W1) in the analysis chamber 21 in a horizontal posture, and a heating device that evaporates the liquid dropped on the upper surface of the measurement substrate W2. 23, an X-ray source 24 that irradiates the upper surface of the measurement substrate W2 with X-rays at an angle of total reflection, and a detector 25 that detects fluorescent X-rays emitted by irradiation of the measurement substrate W2 with X-rays. . The analysis chamber 21 includes a partition wall 26 provided with an opening, a shutter 27 that closes the opening, and an opening / closing device (not shown) that opens and closes the opening by moving the shutter 27. Loading and unloading of the contact member 8 by the transport device 4 is performed through the opening.

3A to 3H are schematic views showing steps from collecting the contaminated metal adhering to the peripheral edge of the substrate W1 to analyzing it. In the following, reference is made to FIG. 3A to 3H will be referred to as appropriate. Hereinafter, an example in which the substrate W1 and the measurement substrate W2 are silicon wafers will be described.
When the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered, a holding step of holding the contact member 8 with hydrofluoric acid, which is an example of the recovered liquid, is performed. Specifically, the control device 5 moves the contact member 8 to the liquid supply position (the position indicated by the one-dot chain line) by the transport device 4. Then, the control device 5 opens the recovered liquid valve 17 in a state where the contact member 8 is located at the liquid supply position, and discharges hydrofluoric acid from the recovered liquid nozzle 9 toward the contact member 8. Thereby, as shown in FIG. 3A, a very small amount (for example, about several milliliters) of hydrofluoric acid is supplied to the contact member 8, and the hydrofluoric acid accumulates in the recess 16 of the contact member 8.

  Next, a liquid contact step for bringing hydrofluoric acid into contact with the peripheral edge of the substrate W1 is performed. Specifically, the control device 5 moves the contact member 8 from the liquid supply position to the peeling position (solid line position) by the transport device 4 in a state where hydrofluoric acid is held in the recess 16 of the contact member 8. Further, the position is moved from the peeling position to the contact position (the position of the two-dot chain line). As a result, as shown in FIG. 3B, the hydrofluoric acid in the recess 16 approaches the peripheral edge of the substrate W1, and the peripheral edge of the substrate W1 is immersed in the hydrofluoric acid in the recess 16. Therefore, the peripheral edge portion of the substrate W1 comes into contact with hydrofluoric acid held by the contact member 8.

  Next, a liquid movement process is performed in which the substrate W1 and the contact member 8 are relatively rotated in the circumferential direction of the substrate W1 while the substrate W1 and the contact member 8 are in contact with hydrofluoric acid. Specifically, as shown in FIG. 3C, the control device 5 controls the spin chuck 7 so that the substrate W1 is rotated 360 degrees around the rotation axis A1 while the contact member 8 is stationary at the contact position. Turn above. When the substrate W1 rotates 360 degrees or more, the control device 5 stops the rotation of the substrate W1 by controlling the spin chuck 7.

  The contaminated metal adhering to the peripheral portion of the substrate W1 is taken into hydrofluoric acid that is in contact with the peripheral portion of the substrate W1. When the substrate W1 rotates while the contact member 8 is stationary, the position of the substrate W1 in contact with the hydrofluoric acid changes at the peripheral edge of the substrate W1, and the hydrofluoric acid held in the recess 16 of the contact member 8 changes to the substrate W1. It moves in the circumferential direction of the substrate W1 along the peripheral edge. Therefore, when the substrate W1 rotates 360 degrees or more, the contaminated metal adhering to the peripheral portion of the substrate W1 is collected in hydrofluoric acid from the entire periphery of the substrate W1. Thereby, the contaminated metal adhering to the peripheral portion of the substrate W1 is captured by the hydrofluoric acid.

  Further, since hydrofluoric acid dissolves the substrate W1, the surface layer portion of the substrate W1 is dissolved in hydrofluoric acid by contact between the substrate W1 and hydrofluoric acid. Therefore, the contaminated metal adhering to the peripheral portion of the substrate W1 is peeled off (lifted off) from the substrate W1 together with the surface layer portion, and is reliably captured by hydrofluoric acid. Therefore, the contaminated metal can be recovered in a shorter time than when the recovered liquid is pure water. Further, since the hydrophobic base is exposed by peeling off the natural oxide film of silicon oxide constituting the surface layer portion of the substrate W1, hydrofluoric acid moves smoothly in the circumferential direction of the substrate W1. . Therefore, hydrofluoric acid hardly remains in a portion other than between the substrate W1 and the contact member 8. Therefore, the contaminated metal adhering to the peripheral portion of the substrate W1 is reliably collected in the hydrofluoric acid that is in contact with the substrate W1 and the contact member 8.

  Next, a freezing step is performed in which the hydrofluoric acid in contact with the substrate W1 and the contact member 8 is frozen to change into an ice block. Specifically, the control device 5 opens the cooling valve 19 so that carbon dioxide, which is an example of a coolant, is directed toward a portion (non-contact portion) other than the portion in contact with hydrofluoric acid in the substrate W1. It is discharged from the cooling nozzle 10. Thereby, as shown to FIG. 3D, a carbon dioxide gas is sprayed on a non-contact part, and the board | substrate W1 is cooled. Therefore, the hydrofluoric acid that is in contact with the substrate W1 and the contact member 8 that holds the hydrofluoric acid are indirectly cooled. Thereby, the droplets of hydrofluoric acid held on the contact member 8 are in contact with the peripheral edge of the substrate W1, and the ice mass (the ice mass solidified by cooling the hydrofluoric acid below the melting point: It is called “ice block”. Furthermore, since carbon dioxide gas is sprayed on the non-contact portion, it is possible to suppress or prevent the hydrofluoric acid from being blown off by the carbon dioxide gas.

  Next, a peeling process for peeling the ice block from the peripheral edge of the substrate W1 is performed. Specifically, the control device 5 controls the transport device 4 to move the contact member 8 from the contact position to the peeling position (solid line position). Since the ice block freezes on the contact member 8, the ice block in contact with the substrate W <b> 1 and the contact member 8 moves together with the contact member 8. Therefore, as shown in FIG. 3E, the ice block is peeled off from the peripheral edge of the substrate W <b> 1 while being held by the contact member 8. Thereby, the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered from the substrate W1 while being confined in the ice block.

  Next, a dropping step is performed in which the ice block containing the contaminating metal is thawed and dropped onto the measurement substrate W2. Specifically, the control device 5 controls the transport device 4 to move the contact member 8 from the contamination collection device 2 to the contamination analysis device 3 with the hydrofluoric acid frozen and the recess 16 facing upward. Thus, the contact member 8 is moved above the flat portion (for example, the central portion) of the measurement substrate W2. Thereafter, the control device 5 changes the posture of the contact member 8 so that the concave portion 16 is directed downward above the measurement substrate W2. As shown in FIG. 3F, the ice block held in the recess 16 melts above the measurement substrate W2 and falls from the contact member 8. The control device 5 may melt the ice block by heating by the heating device 23, or may wait the contact member 8 above the measurement substrate W2 until the ice block is melted.

  Next, an evaporation step is performed in which the hydrofluoric acid droplets dropped on the measurement substrate W2 are evaporated on the measurement substrate W2. Specifically, the control device 5 controls the heating device 23 to heat the hydrofluoric acid droplets on the measurement substrate W2. Thereby, as shown in FIG. 3G, the hydrofluoric acid on the measurement substrate W2 evaporates, and only the contaminated metal contained in the hydrofluoric acid remains on the measurement substrate W2. The control device 5 stops the heat generation of the heating device 23 by controlling the heating device 23 after the hydrofluoric acid on the measurement substrate W2 has evaporated.

  Next, an irradiation step of irradiating the measurement substrate W2 with X-rays is performed. Specifically, as shown in FIG. 3H, the control device 5 controls the X-ray source 24 to irradiate the region in the upper surface of the measurement substrate W2 where the contaminated metal remains, with X-rays. Thereby, fluorescent X-rays are emitted from the region irradiated with X-rays, and the emitted fluorescent X-rays are detected by the detector 25. Therefore, the contaminated metal on the measurement substrate W2 is analyzed. In this way, the contaminated metal adhering to the peripheral edge of the substrate W1 is recovered by the contamination recovery device 2, and the contaminated metal recovered by the contamination recovery device 2 is analyzed by the contamination analyzer 3.

  As described above, in the first embodiment, the recovery liquid is supplied only to the peripheral portion of the substrate W1, and the droplet contacts the peripheral portion of the substrate W1. Thereby, the contaminated metal adhering to the peripheral portion of the substrate W1 is taken into the droplet. Thereafter, the droplet in contact with the peripheral edge of the substrate W1 is cooled and frozen. Thereby, the droplet which is contacting the peripheral part of the board | substrate W1 changes to an ice lump. Then, the ice block incorporating the contaminated metal is peeled off from the substrate W1, and the contaminated metal contained in the ice block is analyzed. In this way, since the droplets that have taken in the contaminated metal are separated from the substrate W1 in a frozen state, even if the droplets circulate on both the front side and the back side of the substrate W1, the droplets together with the contaminated metal are removed. It can be reliably recovered. Therefore, the contaminated metal can be reliably recovered only from the peripheral portion of the substrate W1, and the contaminated metal attached to the peripheral portion of the substrate W1 can be analyzed with high accuracy.

[Second Embodiment]
Next, a second embodiment of the present invention will be described. In FIG. 4 to FIG. 6H below, components equivalent to those shown in FIG. 1 to FIG. 3H are given the same reference numerals as those in FIG.
FIG. 4 is a schematic diagram of a contamination recovery analysis system 201 according to the second embodiment of the present invention. FIG. 5 is an enlarged view showing a contact state of the substrate W1 and the contact member 208 with respect to the recovered liquid in the second embodiment of the present invention.

  As shown in FIG. 4, the contamination recovery analysis system 201 has the same configuration as the contamination recovery analysis system 1 according to the first embodiment except for the recovery chamber 6 and the analysis chamber 21. That is, the contamination recovery analysis system 201 includes a recovery analysis chamber 206 that houses the contamination recovery device 2 and the contamination analysis device 3 in place of the recovery chamber 6 and the analysis chamber 21 according to the first embodiment.

  As shown in FIG. 4, the contamination recovery apparatus 2 includes a contact member 208 that contacts the recovered liquid that is in contact with the peripheral portion of the substrate W1, instead of the contact member 8 according to the first embodiment. The contact member 208 is disposed above the substrate W1 held by the spin chuck 7. As shown in FIG. 5, the contact member 208 includes a contact surface 215 that contacts the recovered liquid. Contact surface 215 is made of a fluororesin such as polytetrafluoroethylene. The contact surface 215 is a horizontal flat surface. The width of the contact surface 215 (the length in the thickness direction of the substrate W1 in FIG. 5) is wider than the thickness of the substrate W1. The contact surface 215 is not limited to a flat surface, and may be a concave surface that is recessed upward. The contact surface 215 faces the upper end of the substrate W1 (a part of the peripheral end surface of the substrate W1) with an interval in the vertical direction.

  As shown in FIG. 4, the transport device 4 is connected to the contact member 208. The transfer device 4 moves the contact member 208 in the collection analysis chamber 206 with the contact surface 215 facing downward. For example, the transport device 4 includes a contact position (a position indicated by a two-dot chain line) where the contact member 208 comes into contact with the collected liquid held on the peripheral portion of the substrate W1, and a peeling position where the contact member 208 moves away from the peripheral portion of the substrate W1. The contact member 208 is moved between (the position indicated by the solid line) and the liquid supply position (the position indicated by the alternate long and short dash line) where the recovery liquid from the recovery liquid nozzle 9 is supplied to the peripheral edge of the substrate W1. The contact position is a position above the substrate W1, and the peeling position is a position above the contact position. The liquid supply position is a position on the side of the peeling position. The recovery liquid nozzle 9 is disposed above the substrate W1 with the recovery liquid discharge port facing downward.

6A to 6H are schematic views showing steps from collecting the contaminated metal adhering to the peripheral edge of the substrate W1 to analyzing it. In the following, reference is made to FIG. 6A to 6H will be referred to as appropriate. Hereinafter, an example in which the substrate W1 and the measurement substrate W2 are silicon wafers will be described.
When the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered, a holding step of holding hydrofluoric acid, which is an example of the recovered liquid, at the peripheral portion of the substrate W1 is performed. Specifically, the control device 5 moves the contact member 208 to the liquid supply position (the position indicated by the alternate long and short dash line) by the transport device 4. Then, the control device 5 opens the recovered liquid valve 17 in a state where the contact member 208 is located at the liquid supply position, and discharges hydrofluoric acid from the recovered liquid nozzle 9 toward the peripheral edge of the substrate W1. Thereby, as shown in FIG. 6A, a small amount of hydrofluoric acid is supplied to the peripheral edge of the substrate W1, and the supplied hydrofluoric acid is held on the peripheral edge of the substrate W1.

  Next, a liquid contact process for bringing hydrofluoric acid into contact with the contact member 208 is performed. Specifically, the control device 5 moves the contact member 208 from the liquid supply position to the peeling position (solid line position) by the transport device 4 while the hydrofluoric acid is held at the peripheral edge of the substrate W1, And move from the peeling position to the contact position (the position of the two-dot chain line). As a result, as shown in FIG. 6B, the contact member 208 approaches the hydrofluoric acid held at the peripheral edge of the substrate W1, and the contact surface 215 comes into contact with the hydrofluoric acid.

  Next, a liquid moving step is performed in which the substrate W1 and the contact member 208 are relatively rotated in the circumferential direction of the substrate W1 while the substrate W1 and the contact member 208 are in contact with hydrofluoric acid. Specifically, as shown in FIG. 6C, the control device 5 controls the spin chuck 7 so that the substrate W1 is rotated 360 degrees around the rotation axis A1 while the contact member 208 is stationary at the contact position. Turn above. When the substrate W1 rotates 360 degrees or more, the control device 5 stops the rotation of the substrate W1 by controlling the spin chuck 7.

  Since the width of the contact surface 215 is wider than the thickness of the substrate W1, the contact area between the contact member 208 and hydrofluoric acid is wider than the contact area between the substrate W1 and hydrofluoric acid. Therefore, when the substrate W1 rotates while the contact member 208 is stationary, the substrate W1 rotates while the hydrofluoric acid is held by the contact member 208. Therefore, the contaminated metal adhering to the peripheral portion of the substrate W1 is collected in hydrofluoric acid from the entire periphery of the substrate W1. Further, since the hydrofluoric acid dissolves the substrate W1, the contaminated metal adhering to the peripheral edge of the substrate W1 is peeled off from the substrate W1 together with the surface layer portion and is reliably captured by the hydrofluoric acid, as in the first embodiment. Furthermore, since the hydrophobic base is exposed by peeling off the surface layer portion of the substrate W1, hydrofluoric acid moves smoothly in the circumferential direction of the substrate W1 along the peripheral edge of the substrate W1.

  Next, a freezing process is performed in which the hydrofluoric acid in contact with the substrate W1 and the contact member 208 is frozen into ice blocks. Specifically, the control device 5 opens the cooling valve 19 so that carbon dioxide, which is an example of a coolant, is directed toward a portion (non-contact portion) other than the portion in contact with hydrofluoric acid in the substrate W1. It is discharged from the cooling nozzle 10. Thereby, as shown to FIG. 6D, a carbon dioxide gas is sprayed on a non-contact part, and the board | substrate W1 is cooled. Therefore, the hydrofluoric acid that is in contact with the substrate W1 and the contact member 208 that holds the hydrofluoric acid are indirectly cooled. Thereby, the droplets of hydrofluoric acid held by the contact member 208 are in contact with the peripheral edge of the substrate W1, and the ice mass (the ice mass solidified by cooling the hydrofluoric acid below the melting point: It is called “ice block”. Furthermore, since carbon dioxide gas is sprayed on the non-contact portion, it is possible to suppress or prevent the hydrofluoric acid from being blown off by the carbon dioxide gas.

  Next, a peeling process for peeling the ice block from the peripheral edge of the substrate W1 is performed. Specifically, the control device 5 controls the transport device 4 to move the contact member 208 from the contact position to the peeling position (solid line position). Since the ice block freezes on the contact member 208, the ice block contacting the substrate W1 and the contact member 208 moves together with the contact member 208. Therefore, as shown in FIG. 6E, the ice block is peeled off from the peripheral edge of the substrate W1 while being held by the contact member 208. Thereby, the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered from the substrate W1 while being confined in the ice block.

  Next, a dropping step is performed in which the ice block containing the contaminating metal is thawed and dropped onto the measurement substrate W2. Specifically, the control device 5 controls the transfer device 4 so that the hydrofluoric acid is frozen and the contact surface 215 faces downward, and the contact member 208 is moved to the flat portion (for example, the center of the measurement substrate W2). Part). As shown in FIG. 6F, the ice block held by the contact member 208 melts above the measurement substrate W2 and falls from the contact member 208. The control device 5 may melt the ice block by heating by the heating device 23, or may make the contact member 208 wait above the measurement substrate W2 until the ice block melts.

  Next, an evaporation step is performed in which the hydrofluoric acid droplets dropped on the measurement substrate W2 are evaporated on the measurement substrate W2. Specifically, the control device 5 controls the heating device 23 to heat the hydrofluoric acid droplets on the measurement substrate W2. Thereby, as shown in FIG. 6G, the hydrofluoric acid on the measurement substrate W2 evaporates, and only the contaminating metal contained in the hydrofluoric acid remains on the measurement substrate W2. The control device 5 stops the heat generation of the heating device 23 by controlling the heating device 23 after the hydrofluoric acid on the measurement substrate W2 has evaporated.

  Next, an irradiation step of irradiating the measurement substrate W2 with X-rays is performed. Specifically, as shown in FIG. 6H, the control device 5 controls the X-ray source 24 to irradiate the region in the upper surface of the measurement substrate W2 where the contaminated metal remains, with X-rays. Thereby, fluorescent X-rays are emitted from the region irradiated with X-rays, and the emitted fluorescent X-rays are detected by the detector 25. Therefore, the contaminated metal on the measurement substrate W2 is analyzed. In this way, the contaminated metal adhering to the peripheral edge of the substrate W1 is recovered by the contamination recovery device 2, and the contaminated metal recovered by the contamination recovery device 2 is analyzed by the contamination analyzer 3.

[Third Embodiment]
Next, a third embodiment of the present invention will be described. 7 and 8, the same components as those shown in FIGS. 1 to 6H described above are denoted by the same reference numerals as those in FIG. 1 and the description thereof is omitted.
FIG. 7 is a schematic diagram of a contamination recovery analysis system 301 according to the third embodiment of the present invention. FIG. 8 is an enlarged view showing a contact state of the substrate W1 and the contact member 208 with respect to the recovered liquid in the third embodiment of the present invention.

  As shown in FIG. 7, the pollution recovery analysis system 301 has the same configuration as the pollution recovery analysis system 201 according to the second embodiment. Specifically, in the third embodiment, the spin chuck 7 is disposed so that the substrate W1 is held in a horizontal posture. The contact member 208 is disposed below the substrate W1 held by the spin chuck 7 with the contact surface 215 facing upward. An inner portion (portion on the center side of the substrate W1) of the contact surface 215 is disposed below the substrate W1, and an outer portion (portion opposite to the center of the substrate W1) of the contact surface 215 is from the substrate W1. Is also located outside. Therefore, the substrate W1 and the contact surface 215 overlap each other in plan view.

  As shown in FIG. 7, for example, the transport device 4 includes a contact position (a position indicated by a two-dot chain line) where the contact member 208 comes into contact with the collected liquid held on the peripheral portion of the substrate W1, and the contact member 208 is the substrate W1. The contact member 208 is moved between the peeling position (solid line position) away from the peripheral edge. The contact position is a position below the substrate W1, and the peeling position is a position outside the contact position (a direction away from the center of the substrate W1). The recovery liquid nozzle 9 is disposed above the contact member 208 with the recovery liquid discharge port facing downward. The cooling nozzle 10 is disposed above the substrate W1 with the discharge port directed downward.

  When the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered, the control device 5 recovers the recovered liquid from the recovered liquid nozzle 9 toward the peripheral portion of the substrate W1 with the contact member 208 positioned at the contact position. To discharge. As shown in FIG. 8, the recovered liquid discharged from the recovered liquid nozzle 9 is applied to the contact surface 215 of the contact member 208 and contacts the peripheral edge of the substrate W1 (liquid contact process). After stopping the discharge of the recovery liquid from the recovery liquid nozzle 9, the control device 5 makes contact with the substrate W1 and the contact member 208 by relatively rotating the substrate W1 and the contact member 208 in the circumferential direction of the substrate W1. The recovered liquid is moved along the peripheral edge of the substrate W1 (liquid moving step). At this time, the control device 5 may rotate the substrate W1 around the rotation axis A1 by the spin chuck 7 while the contact member 208 is stationary, or the contact member by the transport device 4 while the substrate W1 is stationary. 208 may be moved in the circumferential direction of the substrate W1. Further, the control device 5 may rotate the substrate W1 and move the contact member 208 in the circumferential direction of the substrate W1.

  In any case, the recovered liquid that is in contact with the substrate W1 and the contact member 208 is held by the contact member 208 along the peripheral edge of the substrate W1 as the substrate W1 and the contact member 208 move relative to each other. Move. Thereby, the contaminated metal adhering to the peripheral portion of the substrate W1 is collected in the recovery liquid from the entire periphery of the substrate W1. The control device 5 collects the contaminated metal in the recovered liquid, and then sprays the coolant from the cooling nozzle 10 onto the substrate W1, thereby freezing the recovered liquid. Thereafter, the control device 5 causes the contamination analyzer 3 to analyze the contaminated metal contained in the recovered liquid, as in the second embodiment.

[Other Embodiments]
The description of the first to third embodiments of the present invention is as described above, but the present invention is not limited to the contents of the first to third embodiments, and various modifications can be made within the scope of the claims. Is possible.
For example, in the first embodiment, the case where the contamination recovery apparatus 2 and the contamination analysis apparatus 3 are accommodated in separate chambers has been described. However, as in the second and third embodiments, the contamination recovery apparatus 2 and The contamination analyzer 3 may be accommodated in a common chamber. In the second and third embodiments, the case where the contamination recovery apparatus 2 and the contamination analysis apparatus 3 are accommodated in a common chamber has been described. However, the contamination recovery apparatus 2 and the contamination analysis apparatus 3 are the first embodiment. Like the form, it may be housed in a separate chamber. Further, ice blocks containing contaminating metals may be stored in a frozen state. In this case, a plurality of ice blocks may be collectively measured at another opportunity.

In the first to third embodiments, the case where the recovery liquid discharged from the recovery liquid nozzle 9 is supplied to the peripheral edge of the substrate W1 has been described. However, as shown in FIG. A recovery liquid discharge port 9A may be provided in the contact member 8, and the recovery liquid discharged from the recovery liquid discharge port 9A may be supplied to the peripheral portion of the substrate W1.
Moreover, although 1st-3rd embodiment demonstrated the case where the collection | recovery liquid which is contacting the peripheral part of the board | substrate W1 was cooled by spraying the cooling gas which is an example of a coolant on the board | substrate W1, cooling gas May be cooled to the contact member 8 to cool the recovered liquid in contact with the peripheral edge of the substrate W1. Further, as shown in FIG. 10, the contact member 8 is cooled by circulating a cooling gas or a coolant (a liquid whose temperature is equal to or lower than the melting point of the recovered liquid) through a cooling channel 10 </ b> A provided inside the contact member 8. May be. Further, as shown in FIG. 10, the cooling member 10 </ b> B provided with a flow path through which the cooling gas or the coolant flows is brought into contact with at least one of the substrate W <b> 1 and the contact member 8, thereby bringing the peripheral edge of the substrate W <b> 1 The recovered liquid in contact may be cooled.

  In the first to third embodiments, the case where the contaminated metal adhering to the peripheral portion of the substrate W1 is recovered from the entire periphery of the substrate W1 is described. However, the region where the contaminated metal is recovered is the peripheral portion of the substrate W1. It may be a part of Specifically, for example, the contaminated metal may be recovered only from a continuous region of less than 360 degrees, or the contaminated metal is recovered only from the landing region where the recovered liquid discharged from the recovered liquid nozzle 9 is deposited. It ’s okay.

Further, in the case where the contaminated metal is recovered only from the landing area where the recovered liquid is deposited, the droplets need not be moved along the peripheral edge of the substrate W1. Further, when collecting the contaminated metal only from the liquid deposition region, after freezing the droplet in a state where the contact member is separated from the droplet, the ice mass is removed from the periphery of the substrate W1 using tweezers as the contact member. You can peel it off the part.
In the first to third embodiments, the case where the substrate W1 and the measurement substrate W2 are disk-shaped has been described, but the substrate W1 and the measurement substrate W2 may be polygonal.

  In addition, various design changes can be made within the scope of matters described in the claims.

1: Contamination recovery analysis system 2: Contamination recovery device 3: Contamination analysis device (analysis means)
4: Conveying device (peeling means)
7: Spin chuck (substrate holding means)
8: Contact member 9: Recovery liquid nozzle (liquid contact means)
9A: Recovery liquid discharge port (liquid contact means)
10: Cooling nozzle (freezing means)
10A: Cooling flow path (freezing means)
10B: Cooling member (freezing means)
23: Heating device 24: X-ray source 25: Detector 201: Contamination recovery analysis system 208: Contact member 301: Contamination recovery analysis system W1: Substrate

Claims (8)

A substrate contamination recovery method for recovering contaminant metals adhering to the peripheral edge of a substrate,
A liquid contact step of bringing a droplet into contact with the peripheral edge of the substrate;
A freezing step of changing the droplets in contact with the peripheral edge of the substrate into ice blocks by cooling;
A substrate contamination recovery method comprising: a peeling step of peeling off the ice block in contact with a peripheral edge of the substrate from the substrate.   2. The substrate contamination recovery method according to claim 1, further comprising a liquid moving step of moving the liquid droplet contacting the peripheral edge of the substrate along the peripheral edge of the substrate before the freezing step.   The said liquid movement process includes the process of relatively moving the said board | substrate and the said contact member in the state which the contact member is contacting the said droplet which is contacting the peripheral part of the said board | substrate. Substrate contamination recovery method.   In the freezing step, at least one of the contact member in contact with the liquid droplet in contact with the peripheral edge of the substrate and the substrate is cooled in a state where the liquid droplet is in contact with the peripheral edge of the substrate. The substrate contamination recovery method according to any one of claims 1 to 3, further comprising a step of changing the droplet in contact with the peripheral edge of the substrate into an ice block. The freezing step includes a step of changing the droplet in contact with the peripheral portion of the substrate into an ice block in a state where a contact member is in contact with the droplet in contact with the peripheral portion of the substrate. ,
The peeling step includes a step of peeling the ice block coming into contact with the peripheral portion of the substrate from the substrate by relatively moving the substrate and the contact member in a direction in which the substrate and the contact member are separated from each other. The substrate contamination recovery method according to any one of claims 1 to 4, further comprising:   6. The substrate contamination recovery method according to claim 1, wherein the liquid contact step includes a step of bringing a droplet of a solution for dissolving the substrate into contact with a peripheral portion of the substrate. A substrate contamination recovery apparatus for recovering contaminated metal adhering to the peripheral edge of the substrate,
Substrate holding means for holding the substrate;
Liquid contact means for bringing droplets into contact with the peripheral edge of the substrate held by the substrate holding means;
Freezing means for changing into droplets of ice by cooling the droplets contacting the peripheral edge of the substrate held by the substrate holding means;
A substrate contamination recovery apparatus, comprising: a peeling unit that peels off the ice block in contact with the peripheral edge of the substrate held by the substrate holding unit. A substrate contamination recovery analysis system for recovering contaminated metal adhering to the peripheral edge of a substrate and analyzing the recovered contaminated metal,
Substrate holding means for holding the substrate;
Liquid contact means for bringing droplets into contact with the peripheral edge of the substrate held by the substrate holding means;
Freezing means for changing into droplets of ice by cooling the droplets contacting the peripheral edge of the substrate held by the substrate holding means;
Peeling means for peeling off the ice blocks coming in contact with the peripheral edge of the substrate held by the substrate holding means;
A substrate contamination recovery analysis system, comprising: an analysis means for analyzing a contaminated metal taken in the ice block.

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