JP6501448B2 - Processing apparatus and processing method - Google Patents

Description

  Embodiments of the present invention relate to a processing apparatus and a processing method.

In the manufacture of semiconductor devices, photomasks, and the like, the surface of an object to be processed is treated using a solution containing sulfate ions. For example, sulfuric acid or a mixture of sulfuric acid and hydrogen peroxide solution (SPM; Sulfuric acid Hydrogen-Peroxide Mixture) is used to remove an object to be removed such as a resist mask on the surface of the object to be treated. .
Then, after treatment with a solution containing sulfate ions, washing with pure water is performed to remove the solution containing sulfate ions remaining on the surface of the object to be treated and the object to be removed which has been dissolved.
However, in the washing using pure water, it is not possible to sufficiently remove the sulfate ion adhering to the surface of the object to be treated.
Therefore, after washing with pure water, a solution containing an alkali (for example, a mixture of pure water, ammonia water, and hydrogen peroxide water; APM; Ammonium Hydrogen-peroxide mixture) is supplied to the surface of the object to be treated. To remove sulfate ions (see, for example, Patent Document 1).
However, when processing is performed using a solution containing an acid and a solution containing an alkali in the same apparatus, a salt is generated by a chemical reaction to form particles. Therefore, it is necessary to separate an apparatus for performing treatment using a solution containing sulfate ion and an apparatus for performing treatment using a solution containing alkali.
As a result, the size and complexity of the system have been increased.
Furthermore, on the surface of the object to be treated, an element (for example, a pattern or the like) made of a material which may be changed in size or damaged by a liquid containing alkali may be exposed. For example, when an element made of quartz, chromium, molybdenum silicide or the like is present on the surface of the object to be treated, the liquid containing the alkali may change or damage the dimension of such an element.
Therefore, there has been a demand for development of a technique that can easily and effectively remove the object to be removed and sulfate ions.

Japanese Patent Application Laid-Open No. 2002-9035

  The problem to be solved by the present invention is to provide a processing apparatus and a processing method capable of performing the removal of the removal target and the removal of the sulfate ion simply and effectively.

A processing apparatus according to an embodiment includes a mounting unit for mounting an object to be processed, and a first supply unit for supplying a solution containing sulfate ions to the surface of the object to be processed mounted on the mounting unit. A second supply unit for supplying a hydrogen peroxide solution to the surface of the processing object placed in the placement unit; a first supply unit; and a second supply unit. A control unit that controls the control unit, the control unit controls the first supply unit and the second supply unit, and a liquid containing the sulfate ion is provided on the surface of the object to be processed; And supplying the mixed solution of the hydrogen peroxide solution, and maintaining the supply of the solution containing the sulfate ion by the first supply unit, while the ratio of the solution containing the sulfate ion in the mixed solution is set to time passage varied to reduce with the, after stopping the supply of the liquid containing the sulfate ion by the first supply unit, the peracid Predetermined time wherein the hydrogen water supplies only the hydrogen peroxide solution from said second supply portion so that the surface of the object is covered.

  According to an embodiment of the present invention, there is provided a processing apparatus and a processing method capable of performing removal of a removal target and removal of sulfate ion in a simple and effective manner.

FIG. 2 is a schematic view for illustrating the processing device 1 according to the present embodiment. It is a graph for illustrating the removal effect of sulfate ion.

Hereinafter, embodiments will be illustrated with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals and the detailed description will be appropriately omitted.
FIG. 1 is a schematic view for illustrating the processing apparatus 1 according to the present embodiment.
As shown in FIG. 1, the processing apparatus 1 is provided with a processing unit 2, a first supply unit 3, a second supply unit 4, and a control unit 5.
The workpiece 100 is, for example, a wafer used for a semiconductor device, a quartz substrate used for a photomask, or the like.

The processing unit 2 is provided with a placement unit 21, a cover 22, and a nozzle 23.
The mounting unit 21 is provided with a mounting table 21 a, a rotating shaft 21 b, and a driving unit 21 c. The mounting table 21a has a plate shape.
Further, on one main surface of the mounting table 21a, a plurality of protruding portions 21a1 for holding the peripheral edge of the object to be processed 100 are provided. The workpiece 100 is placed on the plurality of protrusions 21a1. When the peripheral edge of the object to be processed 100 is held by the plurality of projecting portions 21a1, the portion where the object to be processed 100 contacts the side of the mounting table 21a can be reduced. Therefore, the contamination, damage or the like of the object to be processed 100 can be suppressed.

The rotating shaft 21b has a columnar shape.
One end of the rotary shaft 21b is connected to the surface of the mounting table 21a opposite to the side where the protrusion 21a1 is provided.
The rotation shaft 21 b passes through the inside of the insertion portion 22 b and extends to the outside of the cover 22.
The other end of the rotation shaft 21 b is connected to the drive unit 21 c outside the cover 22.

The drive unit 21c can include a rotating device such as a motor.
The rotational force of the drive unit 21c is transmitted to the mounting table 21a via the rotation shaft 21b.
Therefore, it is possible to rotate the workpiece 100 placed on the mounting table 21a, and hence on the mounting table 21a by the drive unit 21c.
Further, the drive unit 21c can change the rotational speed (rotational speed) as well as start and stop of the rotation. In this case, the drive unit 21c can include a control motor such as a servomotor.

The cover 22 covers the periphery of the mounting table 21a.
The cover 22 is supplied to the surface of the object to be treated 100 and is discharged to the outside of the object to be treated 100 by rotating the object to be treated 100 (liquid 102 containing sulfate ion, hydrogen peroxide solution 103, or Accept these mixed solutions) and the removed objects to be removed.
At an upper portion of the side wall of the cover 22, a bent portion 22a which is bent toward the center direction is provided. If the bending portion 22 a is provided, it is easy to capture the treatment liquid splattering above the object to be treated 100 and the removed object to be removed.
At a central portion of the bottom surface of the cover 22, a cylindrical insertion portion 22 b protruding toward the inside of the cover 22 is provided.
The insertion portion 22 b protrudes toward the inside of the cover 22, so that it is possible to suppress the leakage of the processing liquid from the portion where the rotary shaft 21 b comes out of the cover 22.

A discharge port 22 c is provided on the bottom of the cover 22.
The discharge port 22c can be provided with an on-off valve 22d.
Further, the pipe 22e can be connected to the on-off valve 22d, and the on-off valve 22d can be connected to a factory pipe, a recovery device, etc. (not shown) via the pipe 22e.
In this case, the bottom surface of the cover 22 may be provided with an inclined surface which is inclined toward the discharge port 22c. By providing such an inclined surface, it becomes easy to discharge the processing liquid that has flowed out to the bottom side of the cover 22 and the removed removal target.

Moreover, the raising / lowering apparatus which raises / lowers the cover 22 can also be provided.
By providing a lifting device for lifting and lowering the cover 22, the cover 22 can be lowered at the time of loading and unloading of the object to be processed 100 so that the mounting table 21 a can be exposed from the cover 22.
Therefore, delivery to the mounting base 21a of the to-be-processed object 100 can be made easy.

The nozzle 23 has a discharge port 23 a for discharging the liquid 102 containing sulfate ion, or the hydrogen peroxide solution 103, or the mixed solution of the liquid 102 containing sulfate ion and the hydrogen peroxide solution 103.
The nozzle 23 is provided such that the discharge port 23a faces the mounting table 21a.
Further, the nozzle 23 has a supply port 23 b for supplying the liquid 102 containing sulfate ions, and a supply port 23 c for supplying the hydrogen peroxide solution 103.

Although the case where the solution 102 containing sulfate ion and the hydrogen peroxide solution 103 can be mixed in the nozzle 23 has been exemplified, the solution 102 containing sulfate ion and the hydrogen peroxide solution 103 on the upstream side of the nozzle 23 are illustrated. And may be mixed. For example, the pipe 44 may be connected to the pipe 34.
Alternatively, the mixed solution may be generated on the surface of the object 100 by alternately discharging the solution 102 containing sulfate ion and the hydrogen peroxide solution 103.
The nozzle 23 may be fixed at a predetermined position, or may be provided so as to be movable above the mounting table 21 a.
Alternatively, a nozzle for discharging the solution 102 containing sulfate ions and a nozzle for discharging the hydrogen peroxide solution 103 can be separately provided.
In this case, the liquid 102 containing the sulfate ion discharged from one nozzle and the hydrogen peroxide solution 103 discharged from the other nozzle may be mixed on the surface of the object 100 to generate the mixed liquid. .

In the first supply unit 3, a storage unit 31, a solution supply unit 32, a flow rate control unit 33, and a pipe 34 are provided.
The storage unit 31 stores the solution 102 containing sulfate ion.
The solution 102 containing sulfate ion is used for wet processing such as wet etching, wet ashing, and cleaning.
The solution 102 containing a sulfate ion can be, for example, sulfuric acid or a mixed solution of sulfuric acid and hydrogen peroxide solution (SPM; Sulfuric acid Hydrogen-Peroxide Mixture).
The sulfuric acid may be concentrated sulfuric acid or dilute sulfuric acid. The concentration of sulfuric acid can be appropriately changed according to the components contained in the removal target. The sulfuric acid concentration can be determined, for example, by performing experiments or simulations.

The solution supply unit 32 is connected to the storage unit 31. The solution supply unit 32 supplies the solution 102 containing sulfate ion stored in the storage unit 31 toward the nozzle 23.
The solution supply unit 32 can be a pump or the like having resistance to the solution 102 containing sulfate ions. The solution supply unit 32 can be, for example, a chemical pump.
However, the solution supply unit 32 is not limited to the pump. For example, the solution supply unit 32 may supply a gas to the inside of the storage unit 31 and pressure-feed the solution 102 containing sulfate ions stored in the inside of the storage unit 31.

The flow rate control unit 33 is connected to the solution supply unit 32. The flow rate control unit 33 controls the flow rate of the solution 102 containing sulfate ions supplied by the solution supply unit 32. The flow control unit 33 can be, for example, a flow control valve.
The flow rate control unit 33 can also start and stop the supply of the solution 102 containing sulfate ion.
One end of the pipe 34 is connected to the flow rate control unit 33. The other end of the pipe 34 is connected to the supply port 23 b of the nozzle 23.

In the second supply unit 4, a storage unit 41, a solution supply unit 42, a flow control unit 43, a pipe 44, and a temperature control unit 45 are provided.
The storage unit 41 stores the hydrogen peroxide solution 103.
The hydrogen peroxide solution 103 is used to remove sulfate ions adhering to the surface of the object to be treated 100.
The solution supply unit 42 is connected to the storage unit 41. The solution supply unit 42 supplies the hydrogen peroxide solution 103 stored inside the storage unit 41 toward the nozzle 23.
The solution supply unit 42 can be a pump or the like having resistance to the hydrogen peroxide solution 103. The solution supply unit 42 can be, for example, a chemical pump.
However, the solution supply unit 42 is not limited to the pump. For example, the solution supply unit 42 may supply gas to the inside of the storage unit 41, and pressure-feed the hydrogen peroxide solution 103 stored in the inside of the storage unit 41.

The flow control unit 43 is connected to the solution supply unit 42. The flow rate control unit 43 controls the flow rate of the hydrogen peroxide solution 103 supplied by the solution supply unit 42. The flow control unit 43 can be, for example, a flow control valve.
Further, the flow rate control unit 43 can also start and stop the supply of the hydrogen peroxide solution 103.
One end of the pipe 44 is connected to the flow rate control unit 43. The other end of the pipe 44 is connected to the supply port 23 c of the nozzle 23.

The temperature control unit 45 controls the temperature of the hydrogen peroxide solution 103.
If the temperature of the hydrogen peroxide solution 103 supplied to the surface of the object to be treated 100 is increased, the removal efficiency of sulfate ions can be improved.
On the other hand, if the temperature of the hydrogen peroxide solution 103 supplied to the surface of the object to be treated 100 is too high, the amount of oxygen generated may be large, and stable supply may not be possible.

Here, the boiling point of the hydrogen peroxide solution 103 is about 141 ° C. at a concentration of 90 wt%. However, according to the knowledge obtained by the present inventors, the supply of the hydrogen peroxide solution 103 can not be stabilized unless the temperature of the hydrogen peroxide solution 103 is set to 60 ° C. or less.
The temperature control unit 45 may have a heating function or may have a heating function and a cooling function.

The temperature control unit 45 may be, for example, a heater that generates Joule heat, or a unit that circulates a heat medium. In addition, the temperature control unit 45 can further include, for example, one having a cooling function such as a Peltier device.
As illustrated in FIG. 1, the temperature control unit 45 can be provided to cover the pipe 44. However, the present invention is not limited to this, and the temperature control unit 45 may be provided at a position at which the temperature of the hydrogen peroxide solution 103 supplied to the surface of the object to be treated 100 can be controlled. For example, the temperature control unit 45 can be provided inside the storage unit 41.

In addition, an ultrasonic vibration device may be provided which applies ultrasonic vibration to at least one of the solution 102 containing sulfate ion and the hydrogen peroxide solution 103.
For example, the ultrasonic vibration device can be built in the nozzle 23, the mounting table 21a, and the like. In addition, a recovery device for recovering and reusing the solution 102 containing sulfate ions discharged from the outlet 22c of the cover 22 may be provided.

The control unit 5 controls the operation of the elements provided in the processing device 1.
For example, the control unit 5 controls the drive unit 21c to start the rotation of the mounting table 21a (the object to be processed 100), to stop the rotation, and to change the number of rotations (rotational speed).
The control unit 5 controls the on-off valve 22 d to discharge the solution 102 containing sulfate ions, the hydrogen peroxide solution 103, the mixed solution thereof, and the removed object to be removed from the cover 22.

The control unit 5 controls the first supply unit 3 (the solution supply unit 32) to start the supply of the solution 102 containing sulfate ions, stop the supply, control the supply time, and the like.
The control unit 5 controls the first supply unit 3 (flow rate control unit 33) to control the flow rate (supply amount) of the solution 102 containing sulfate ions.
The control unit 5 controls the second supply unit 4 (the solution supply unit 42) to start the supply of the hydrogen peroxide solution 103, stop the supply, control the supply time, and the like.
The control unit 5 controls the second supply unit 4 (flow rate control unit 43) to control the flow rate (supply amount) of the hydrogen peroxide solution 103.

In this case, the control unit 5 controls the first supply unit 3 to supply the solution 102 containing sulfate ions to the surface of the object 100, and controls the second supply unit 4 to The hydrogen peroxide solution 103 can be supplied to the surface of the object to be processed 100 supplied with the liquid 102 containing H.
Further, the control unit 5 controls the first supply unit 3 and the second supply unit 4 so that the solution 102 containing sulfate ions and the hydrogen peroxide solution 103 are formed on the surface of the object to be treated 100. It is also possible to supply the mixed solution and change the ratio of the solution 102 containing sulfate ion in the mixed solution over time as the surface of one object to be treated 100 decreases.

The control unit 5 controls the temperature control unit 45 so that the temperature of the hydrogen peroxide solution 103 becomes equal to or higher than normal temperature (25 ° C.) and equal to or lower than 60 ° C.
The control unit 5 controls the second supply unit 4 to supply the hydrogen peroxide solution for 300 seconds or more.

Next, the processing method according to the present embodiment will be illustrated together with the operation of the processing apparatus 1. First, the to-be-processed object 100 is mounted by the conveyance apparatus on the protrusion part 21a1 provided in the main surface of the mounting base 21a.
Next, the placement unit 21 is rotated by the drive unit 21 c. By the placement unit 21 rotating, the placed object to be processed 100 rotates.
Next, the solution 102 containing sulfate ion stored in the storage unit 31 is sent toward the nozzle 23 by the solution supply unit 32. At this time, the flow control unit 33 controls the amount of supply of the solution 102 containing sulfate ions.
The solution 102 containing sulfate ions sent to the nozzle 23 is discharged from the nozzle 23 and supplied to the surface of the object 100 to be treated. The solution 102 containing sulfate ions supplied to the surface of the object to be treated 100 removes the object to be removed on the surface of the object to be treated 100. The removed object to be removed and the solution 102 containing sulfate ions are discharged to the outside of the object 100 by the rotation of the object 100.

When the solution 102 containing sulfate ions is sulfuric acid, a mixed solution of the solution 102 containing sulfate ions and the hydrogen peroxide solution 103 can also be generated.
In this case, the hydrogen peroxide solution 103 stored in the storage unit 41 is further sent by the solution supply unit 42 toward the nozzle 23. At this time, the flow rate control unit 43 controls the supply amount of the hydrogen peroxide solution 103.
Then, the solution 102 containing sulfate ion supplied by the solution supply unit 32 and the hydrogen peroxide solution 103 supplied by the solution supply unit 42 are mixed in the interior of the nozzle 23 or on the upstream side of the nozzle 23 and mixed. A liquid is produced.
The generated mixed solution is discharged from the nozzle 23 and supplied to the surface of the object 100 to be treated. The mixed liquid supplied to the surface of the object 100 removes the object to be removed on the surface of the object 100. The removed object to be removed and the mixed liquid are discharged to the outside of the object 100 by the rotation of the object 100.
Further, the mixed solution is generated on the surface of the object to be treated 100 by discharging the solution 102 containing the sulfate ion and the hydrogen peroxide solution 103 from the separate nozzles almost simultaneously onto the surface of the object to be treated 100. It can also be done.

The solution 102 containing sulfate ion and the mixed solution of the solution 102 containing sulfate ion and the hydrogen peroxide solution 103 are discharged to the outside of the object to be treated 100 by the rotation of the object to be treated 100. Sulfate ion remains on the surface.
When the sulfate ion remains on the surface of the object to be treated 100, the sulfate ion may react with the ammonium ion in the air to precipitate ammonium sulfate. Precipitation of ammonium sulfate causes the generation of foreign matter.

Therefore, next, the hydrogen peroxide solution 103 stored in the storage unit 41 is sent by the solution supply unit 42 toward the nozzle 23. At this time, the flow rate control unit 43 controls the supply amount of the hydrogen peroxide solution 103. The hydrogen peroxide solution 103 sent to the nozzle 23 is discharged from the nozzle 23 and supplied to the surface of the workpiece 100. The hydrogen peroxide solution 103 supplied to the surface of the object to be treated 100 removes sulfate ions remaining on the surface of the object to be treated 100.
At this time, the temperature control unit 45 controls the temperature of the hydrogen peroxide solution 103 to be not less than normal temperature (25 ° C.) and not more than 60 ° C.
According to the knowledge obtained by the present inventors, if the time (treatment time) in which the surface of the object to be treated 100 is covered with the hydrogen peroxide solution 103 is set to 300 seconds or more, the removal of sulfate ions can be assured It can be done.
Therefore, the control unit 5 controls the second supply unit 4 to supply the hydrogen peroxide solution 103 for 300 seconds or more.

When a mixture of the solution 102 containing sulfate ion and the hydrogen peroxide solution 103 is formed, the ratio of the solution 102 containing sulfate ion in the mixture solution can be changed. For example, the ratio of the solution 102 containing sulfate ion in the mixture solution is gradually or gradually reduced with time with respect to one object 100 to be treated, and finally only the hydrogen peroxide solution 103 is supplied. It is possible to
In this way, the time for which the surface of the object to be treated 100 is covered with the hydrogen peroxide solution 103 can be substantially lengthened, so that the treatment time can be shortened.
Also, for example, the change rate to reduce the ratio of the solution 102 containing sulfate ions (change rate to increase the ratio of the hydrogen peroxide solution 103) can be changed in the first half and the second half of the treatment to increase the change rate in the second half. . By doing so, in the first half of the treatment in which a large amount of the removal target remains on the surface of the processing object 100, the proportion of the solution 102 containing sulfate ions that can remove the removal target is increased to remove the removal target You can do it. Then, in the second half of the process in which there are few objects to be removed, the proportion of the solution 102 containing sulfate ions is reduced (the proportion of the hydrogen peroxide solution 103 capable of removing the sulfate ions is increased). Ions can be removed.
In addition, the detail regarding the removal effect of a sulfate ion is mentioned later.

Next, the flow control unit 43 stops the supply of the hydrogen peroxide solution 103.
Next, the hydrogen peroxide solution 103 remaining on the surface of the object to be treated 100 is discharged to the outside of the object to be treated 100 by the rotation of the mounting table 21 a. At this time, the rotation speed of the mounting table 21a can be increased. By discharging the hydrogen peroxide solution 103 remaining on the surface of the object to be treated 100, the object to be treated 100 is dried.
Next, the workpiece 100 is unloaded by the transport device.
Thereafter, the processing object 100 is continuously processed by repeating the above-described operation.

Next, the removal effect of sulfate ion will be further described.
FIG. 2 is a graph for illustrating the removal effect of sulfate ion.
The case of the comparative example is a case where pure water is supplied to the surface of the object to be treated 100 to which the mixed solution of sulfuric acid and hydrogen peroxide solution is supplied.
In the case of the present embodiment, the hydrogen peroxide solution 103 is supplied to the surface of the object 100 to which the mixed solution of sulfuric acid and hydrogen peroxide solution is supplied.
Moreover, the removal effect of a sulfate ion measures the quantity of the sulfur in the surface of the to-be-processed object 100 using a total reflection fluorescence X-ray analyzer (Total Reflection X-Ray Fluorescence Spectrometer), A sulfuric acid and a hydrogen-peroxide solution The rate of increase of sulfur from the state prior to the supply of the mixed solution was calculated and evaluated.
It can be seen from FIG. 2 that in the case of the comparative example, sulfur increased by about 100% as compared to the state before supplying the mixed solution of sulfuric acid and hydrogen peroxide solution.
In addition, it can be seen from FIG. 2 that, in the case of the present embodiment, sulfur is reduced by about 20% as compared to the state before supplying the mixed solution of sulfuric acid and hydrogen peroxide solution.
As can be seen from FIG. 2, when the hydrogen peroxide solution 103 is supplied to the surface of the object to be treated 100, the sulfate ions remaining on the surface of the object to be treated 100 can be effectively removed.

As described above, the processing method according to the present embodiment can include the following steps.
Supplying a solution 102 containing sulfate ions to the surface of the object to be treated 100;
A step of supplying a hydrogen peroxide solution 103 to the surface of the object to be treated 100 to which the solution 102 containing a sulfate ion is supplied.
In this case, in the step of supplying the hydrogen peroxide solution 103, the hydrogen peroxide solution 103 at normal temperature (25 ° C.) or more and 60 ° C. or less can be supplied.
Further, in the step of supplying the hydrogen peroxide solution 103, the hydrogen peroxide solution 103 can be supplied for 300 seconds or more.
Further, the processing method according to the present embodiment can also be performed as follows.
A step of supplying a mixed solution of a solution 102 containing sulfate ion and a hydrogen peroxide solution 103 on the surface of the object to be treated 100 is provided to change the ratio of the solution 102 containing sulfate ion in the mixed solution to be reduced. .
In addition, since the content in each process can be made to be the same as that of what was mentioned above, detailed description is abbreviate | omitted.

In the above, the solution 102 containing sulfate ions, the hydrogen peroxide solution 103, or a mixture thereof is supplied to the surface of the to-be-processed object 100 to be rotated, but the rotation of the to-be-processed object 100 is not necessarily required. . For example, the solution 102 containing sulfate ions, the hydrogen peroxide solution 103, or a mixture of these may be supplied to the surface of the processing object 100 in a stationary state.
Further, a processing apparatus including a tank containing a solution 102 containing sulfate ion or a mixture of a solution 102 containing sulfate ion and a hydrogen peroxide solution 103 and a tank containing a hydrogen peroxide solution 103 You can also
Then, the object to be treated 100 is immersed in the bath containing the solution 102 containing sulfate ion or the mixed solution of the solution 102 containing sulfate ion and the hydrogen peroxide solution 103, and then the object to be treated 100 is treated. It may be made to immerse in the tank in which the hydrogen peroxide solution 103 was stored.
In this case, the bath containing the sulfate ion-containing solution 102 or the mixed solution of the sulfate ion-containing solution 102 and the hydrogen peroxide solution 103 functions as the first supply unit 3.
The tank in which the hydrogen peroxide solution 103 is stored functions as the second supply unit 4.
However, if the solution 102 containing sulfate ions, the hydrogen peroxide solution 103, or a mixture of these is supplied to the surface of the rotating object to be treated 100, the removal efficiency can be improved. Moreover, drying of the to-be-processed object 100 can also be performed collectively. Further, the processing device 1 can be miniaturized.

As described above, according to the embodiment of the present invention, there is provided a processing apparatus and a processing method capable of performing removal of a removal target and removal of sulfate ion in a simple and effective manner.
The embodiments have been illustrated above. However, the present invention is not limited to these descriptions.
Those skilled in the art can appropriately add, delete, or change design elements of the above-described embodiment, or can add, omit, or change the process of the components, to which the features of the present invention are included As long as it is included in the scope of the present invention.
For example, the shape, size, material, number, arrangement, and the like of each element included in the processing apparatus 1 are not limited to those illustrated, and can be appropriately changed.
Moreover, each element with which each embodiment mentioned above is equipped can be combined as much as possible, and what combined these is also included in the scope of the present invention as long as the feature of the present invention is included.

  DESCRIPTION OF SYMBOLS 1 processing apparatus, 2 processing part, 3 1st supply part, 4 2nd supply part, 5 control part, 21 mounting part, 21a mounting base, 21b rotary shaft, 21c driving part, 22 cover, 23 nozzle, 31 Storage unit 32 Solution supply unit 33 Flow control unit 41 Storage unit 42 Solution supply unit 43 Flow control unit 45 Temperature control unit 100 Processed object 102 Solution containing sulfate ion 103 Hydrogen peroxide solution

Claims (6)

A placement unit for placing an object to be treated;
A first supply unit for supplying a solution containing sulfate ions to the surface of the object to be treated placed on the placement unit;
A second supply unit configured to supply a hydrogen peroxide solution to the surface of the processing object placed in the placement unit;
A control unit that controls the first supply unit and the second supply unit;
Equipped with
The control unit controls the first supply unit and the second supply unit so that the solution containing the sulfate ion on the surface of the object to be treated and the hydrogen peroxide solution The mixed solution is supplied, and while maintaining the supply of the solution containing the sulfate ion by the first supply unit, the ratio of the solution containing the sulfate ion in the mixed solution is changed to decrease with time. After stopping the supply of the solution containing the sulfate ion by the first supply unit, the hydrogen peroxide from the second supply unit is arranged to cover the surface of the object for a predetermined time by the hydrogen peroxide solution. Processor that supplies only water.   The control unit changes the change rate to reduce the ratio of the solution containing the sulfate ion in the mixed solution between the first half and the second half of the treatment, and increases the change rate in the second half of the treatment. The processor according to 1). It further has a drive unit for rotating the placement unit,
Wherein, after stopping the supply of the hydrogen peroxide solution according to the second supply unit, and controls the drive unit, by increasing the rotational speed of the placement portion, the hydrogen peroxide solution The processing apparatus according to claim 1, wherein the object to be processed which is left is dried. Providing a mixture of a solution containing sulfate ions and a hydrogen peroxide solution on the surface of the object to be treated;
After maintaining the supply of the solution containing the sulfate ion and changing the proportion of the solution containing the sulfate ion in the mixed solution so as to decrease over time, and stopping the supply of the solution containing the sulfate ion, The solution containing the sulfate ion is supplied by supplying only the hydrogen peroxide solution to the surface of the object to be treated on which the solution containing the sulfate ion remains, and covering the surface of the object with the hydrogen peroxide solution for a predetermined time How to remove   In the step of supplying the mixed solution, the change rate to reduce the ratio of the solution containing the sulfate ion in the mixed solution is changed between the first half of the treatment and the second half of the treatment, and the change rate is changed in the second half of the treatment 5. The method of claim 4 wherein said processing is increased. The processing method according to claim 4 or 5, wherein after the supply of the hydrogen peroxide solution is stopped, the rotational speed of the object to be treated is increased to dry the object to be treated in which the hydrogen peroxide solution remains. .

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