KR102010262B1 - Apparatus and method for manufacturing cleaning solution - Google Patents

Abstract

The present invention relates to a cleaning liquid production method for producing a cleaning liquid for cleaning a substrate. Method for preparing a cleaning liquid according to an embodiment of the present invention comprises the steps of mixing the surfactant chemical and pure water at a first temperature, and then mixing the surfactant and pure water while cooling to a second temperature lower than the first temperature; And after the surfactant and the pure water are cooled and mixed for a predetermined time at a second temperature, adding a surfactant chemical liquid to prepare a cleaning liquid.

Description

Apparatus and method for manufacturing cleaning solution {APPARATUS AND METHOD FOR MANUFACTURING CLEANING SOLUTION}

The present invention relates to an apparatus and method for producing a cleaning liquid for cleaning a substrate.

Contaminants such as particles, organic contaminants, and metal contaminants remaining on the substrate surface have a great influence on the characteristics and production yield of semiconductor devices. For this reason, the cleaning process for removing various contaminants adhering to the substrate surface is very important in the semiconductor manufacturing process, and the process for cleaning the substrate is carried out at the front and rear stages of each unit process for manufacturing the semiconductor. In general, the substrate is cleaned using a cleaning solution to remove metal foreign matter, organic matter, or particles remaining on the substrate, a rinse process to remove the cleaning solution remaining on the substrate using pure water, and an organic solvent. And a drying step of drying the substrate using a supercritical fluid, nitrogen gas, or the like.

The cleaning liquid used in the cleaning liquid treatment process described above is prepared by mixing a surfactant chemical liquid containing a surfactant with pure water. Particles are formed in the cleaning liquid when such a surfactant chemical liquid is mixed with pure water to prepare the cleaning liquid. The resulting particles facilitate particle removal during substrate cleaning.

The present invention is to provide a cleaning liquid production apparatus and method that can increase the size of the plate-shaped particles in the cleaning liquid to increase the efficiency of removing contaminants.

Moreover, this invention is providing the cleaning liquid manufacturing apparatus and method which can shorten cleaning liquid manufacturing time.

The problem to be solved by the present invention is not limited to the above-described problem, and the objects not mentioned may be clearly understood by those skilled in the art from the present specification and the accompanying drawings. will be.

According to one aspect of the present invention, there is provided a method of preparing a cleaning liquid for cleaning a substrate, wherein the surfactant chemical liquid and pure water are mixed at a first temperature, and then the surfactant chemical liquid and pure water are mixed with the first temperature. Mixing while cooling to a second temperature that is lower and the temperature difference from the first temperature is less than 14 ° C .; And after the surfactant and the pure water are cooled and mixed for a set time at the second temperature, adding a surfactant chemical liquid to prepare the cleaning liquid.

The first temperature may be lower than 30 ° C, and the second temperature may be higher than 16 ° C and lower than 20 ° C.

The mixing ratio of the surfactant chemical liquid mixed with the pure water at the first temperature may be greater than 0.3% (v.v) and less than 0.7% (v / v) with respect to pure water.

The preparation of the cleaning liquid by further adding the surfactant chemical liquid may be performed immediately before discharging the cleaning liquid onto the substrate through the nozzle, or before a set time from the start of cleaning liquid discharge, or through the nozzle. Can be performed during discharge.

By further adding the surfactant chemical solution to prepare the cleaning solution, the surfactant particles of the plate-like lamellar crystal structure having an average size of 30 ㎛ or more in the cleaning solution is increased, the initial contaminant removal performance of the cleaning solution May be at least 90%.

The adding of the surfactant chemical liquid to prepare the cleaning liquid may include adding an additional surfactant stock solution once or a plurality of times.

According to another aspect of the invention, the apparatus for producing a cleaning liquid, comprising: a chemical liquid tank having a liquid mixing space therein; A first supply member for supplying a surfactant chemical liquid into the chemical liquid tank; A second supply member for supplying pure water into the chemical tank; A mixing unit for mixing the surfactant chemical liquid and the pure water supplied in the chemical liquid tank; A temperature regulating member for controlling the temperature of the surfactant chemical liquid and the pure water supplied into the chemical liquid tank; And a controller for controlling the first supply member, the second supply member, the mixing unit, and the temperature regulating member, wherein the controller is configured to firstly supply the surfactant chemical liquid and the pure water supplied into the liquid mixing space. A first step of mixing at a temperature, a second step of cooling the surfactant chemical liquid and the pure water mixed in the first step to a second temperature lower than the first temperature, and the surfactant and the pure water The first supply member, the second supply member, the mixing unit and the temperature adjusting member are cooled to mix at a temperature for 2 hours and then mixed with the surfactant chemical liquid to perform the third step of preparing the cleaning liquid. There is provided a cleaning liquid production apparatus for controlling.

The controller may further add a surfactant chemical liquid just before discharging the cleaning liquid on the substrate through the nozzle in the third step, or additionally add the surfactant chemical liquid before the time set from the time point at which the cleaning liquid is discharged, or It may be configured to further add a surfactant chemical liquid while the cleaning liquid is discharged through the nozzle.

According to an embodiment of the present invention, there is provided a cleaning liquid production apparatus and method that can increase the size of the plate-shaped particles in the cleaning liquid to increase the efficiency of removing contaminants.

Moreover, according to the Example of this invention, the washing | cleaning liquid manufacturing apparatus and method which can shorten washing liquid manufacturing time are provided.

1 is a plan view schematically showing an example of a substrate processing apparatus using a cleaning liquid prepared according to an embodiment of the present invention.
2 is a cross-sectional view illustrating an example of a substrate processing apparatus provided in the process chamber of FIG. 1.
3 is a view schematically showing a cleaning liquid manufacturing apparatus according to an embodiment of the present invention.
Figure 4 is a flow chart showing a cleaning liquid manufacturing method according to an embodiment of the present invention.
FIG. 5 is a graph showing changes in size and conductivity of surfactant particles according to cooling of surfactant chemicals and pure water according to an embodiment of the present invention.
6 is a graph showing a change in particle removal efficiency (PRE) according to the cooling temperature of the cleaning liquid.
7 is an image taken by the optical microscope of the surfactant particles after the addition of the surfactant chemical in accordance with an embodiment of the present invention.
Figure 8 is a graph showing the measurement of the change in cleaning performance for each method of adding a surfactant chemical solution.
9 is a CLD particle size analysis result of the cleaning solution prepared according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. The embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. This embodiment is provided to more completely explain the present invention to those skilled in the art. Therefore, the shape of the elements in the drawings are exaggerated to emphasize a more clear description.

In an embodiment of the present invention, an example of a substrate processing apparatus for performing a process of cleaning a substrate and a cleaning liquid manufacturing apparatus for manufacturing a cleaning liquid will be described. However, the present invention is not limited to this, and can be applied to various kinds of apparatuses for cleaning a substrate using a cleaning liquid.

1 is a plan view schematically showing an example of a substrate processing apparatus using a cleaning liquid prepared according to an embodiment of the present invention.

Referring to FIG. 1, the substrate treating apparatus 1 includes an index module 10 and a process treating module 20. The index module 10 includes a load port 120 and a transfer frame 140. The load port 120, the transfer frame 140, and the process module 20 are sequentially arranged in a row. Hereinafter, the direction in which the load port 120, the transfer frame 140, and the process module 20 are arranged is referred to as a first direction 12. When viewed from the top, the direction perpendicular to the first direction 12 is referred to as the second direction 14, and the direction perpendicular to the plane including the first direction 12 and the second direction 14 is referred to as the third direction. It is called (16).

The carrier 18 in which the substrate is accommodated is mounted in the load port 120. A plurality of load ports 120 are provided and they are arranged in a line along the second direction 14. In FIG. 1, four load ports 120 are provided. However, the number of load ports 120 may increase or decrease depending on conditions such as process efficiency and footprint of the process module 20. The carrier 18 is formed with a slot provided to support the edge of the substrate. A plurality of slots are provided along the third direction 16, and the substrates are positioned in the carrier 18 to be stacked in a spaced apart state along the third direction 16. As the carrier 18, a front opening unified pod (FOUP) may be used.

The process module 20 has a buffer unit 220, a transfer chamber 240, and a process chamber 260. The transfer chamber 240 is disposed in parallel with the first direction 12 in the longitudinal direction thereof. Process chambers 260 are disposed on one side and the other side of the transfer chamber 240 along the second direction 14, respectively. Process chambers 260 located on one side of the transfer chamber 240 and process chambers 260 located on the other side of the transfer chamber 240 are provided to be symmetrical with respect to the transfer chamber 240. Some of the process chambers 260 are disposed along the longitudinal direction of the transfer chamber 240. In addition, some of the process chambers 260 are arranged to be stacked on each other. That is, the process chambers 260 may be arranged in an array of A X B (A and B are one or more natural numbers) on one side of the transfer chamber 240. Where A is the number of process chambers 260 provided in a line along the first direction 12 and B is the number of process chambers 260 provided in a line along the third direction 16. When four or six process chambers 260 are provided at one side of the transfer chamber 240, the process chambers 260 may be arranged in an array of 2 × 2 or 3 × 2. The number of process chambers 260 may increase or decrease. Unlike the above, the process chamber 260 may be provided only on one side of the transfer chamber 240. In addition, unlike the above-described process chamber 260 may be provided as a single layer on one side and both sides of the transfer chamber 240.

The buffer unit 220 is disposed between the transfer frame 140 and the transfer chamber 240. The buffer unit 220 provides a space where the substrate W stays between the transfer chamber 240 and the transfer frame 140 before the substrate W is transferred. The buffer unit 220 is provided with a slot (not shown) in which the substrate W is placed therein, and a plurality of slots are provided to be spaced apart from each other along the third direction 16. Surfaces facing the transfer frame 140 and surfaces facing the transfer chamber 240 are opened in the buffer unit 220.

The transfer frame 140 transports the substrate W between the carrier 18 seated on the load port 120 and the buffer unit 220. The transfer frame 140 is provided with an index rail 142 and an index robot 144. The index rail 142 is provided in parallel with the second direction 14 in the longitudinal direction thereof. The index robot 144 is installed on the index rail 142 and is linearly moved in the second direction 14 along the index rail 142. The index robot 144 has a base 144a, a body 144b, and an index arm 144c. The base 144a is installed to be movable along the index rail 142. Body 144b is coupled to base 144a. The body 144b is provided to be movable along the third direction 16 on the base 144a. In addition, the body 144b is provided to be rotatable on the base 144a. The index arm 144c is coupled to the body 144b and provided to move forward and backward with respect to the body 144b. The plurality of index arms 144c are provided to be individually driven. The index arms 144c are stacked to be spaced apart from each other along the third direction 16. Some of the index arms 144c may be used when conveying the substrate from the processing module 20 to the carrier 18, and others may be used when conveying the substrate from the carrier 18 to the processing module 20. have. This may prevent particles generated from the substrate before the process treatment from being attached to the substrate after the process treatment while the index robot 144 loads and unloads the substrate.

The transfer chamber 240 transports the substrate W between the buffer unit 220 and the process chamber 260 and between the process chambers 260. The transfer chamber 240 is provided with a guide rail 242 and a main robot 244. The guide rail 242 is disposed such that its length direction is parallel to the first direction 12. The main robot 244 is installed on the guide rail 242 and moves linearly along the first direction 12 on the guide rail 242. The main robot 244 has a base 244a, a body 244b, and a main arm 244c. The base 244a is installed to be movable along the guide rail 242. Body 244b is coupled to base 244a. The body 244b is provided to be movable along the third direction 16 on the base 244a. In addition, the body 244b is provided to be rotatable on the base 244a. The main arm 244c is coupled to the body 244b, which is provided to be capable of moving forward and backward with respect to the body 244b. A plurality of main arms 244c are provided to be individually driven. The main arms 244c are stacked to be spaced apart from each other along the third direction 16. The main arm 244c used to convey the substrate W from the buffer unit 220 to the process chamber 260 and the substrate W used to convey the substrate W from the process chamber 260 to the buffer unit 220. The main arms 244c may be different from each other.

2 is a cross-sectional view illustrating an example of a substrate processing apparatus provided in the process chamber of FIG. 1. 1 and 2, a substrate processing apparatus 300 performing a cleaning process on a substrate W is provided in a process chamber 260. The substrate processing apparatus 300 provided in each process chamber 260 may have a different structure according to the type of cleaning process to be performed. Optionally, the substrate processing apparatus 300 in each process chamber 260 may have the same structure. Optionally, the process chambers 260 are divided into a plurality of groups so that the substrate processing apparatuses 300 provided in the process chambers 260 belonging to the same group have the same structure and are provided to the process chambers 260 belonging to different groups. The substrate processing apparatuses 300 may have different structures from each other. For example, when the process chamber 260 is divided into two groups, one side of the transfer chamber 240 is provided with process chambers 260 of the first group, and the other side of the transfer chamber 240 is provided with the second group. Process chambers 260 may be provided. Optionally, a first group of process chambers 260 may be provided at a lower layer, and a second group of process chambers 260 may be provided at a lower layer at each of one side and the other side of the transfer chamber 240. The process chamber 260 of the first group and the process chamber 260 of the second group may be classified according to the type of chemicals used or the type of cleaning method.

The substrate processing apparatus 300 includes a housing 320, a support unit, a lifting unit 360, and an injection member 380.

The housing 320 provides a space in which a substrate treatment process is performed, and an upper portion thereof is opened. The housing 320 has an inner recovery container 322, an intermediate recovery container 324, and an external recovery container 326. Each recovery container 322, 324, 326 recovers different treatment liquids from among treatment liquids used in the process. The inner recovery container 322 is provided in an annular ring shape surrounding the spin head 340, and the intermediate recovery container 324 is provided in an annular ring shape surrounding the inner recovery container 322, and the outer recovery container 326. ) Is provided in an annular ring shape surrounding the intermediate collection vessel 324. Inner space 322a of the inner recovery container 322, space 324a between the inner recovery container 322 and the intermediate recovery container 324 and the space between the intermediate recovery container 324 and the external recovery container 326 ( 326a functions as an inlet through which the treatment liquid flows into the inner recovery container 322, the intermediate recovery container 324, and the external recovery container 326, respectively. Each recovery container 322, 324, 326 is connected to the recovery line (322b, 324b, 326b extending vertically in the bottom direction). Each of the recovery lines 322b, 324b and 326b discharges the treatment liquid introduced through the respective recovery vessels 322, 324 and 326. The discharged treatment liquid may be reused through an external treatment liquid regeneration system (not shown).

The support unit is provided in the housing. In the support unit, the substrate W is placed. The support unit may be provided to the spinhead 340. According to one embodiment, the spin head 340 is disposed in the housing 320. The spin head 340 supports the substrate W and rotates the substrate W during the process. Spin head 340 has a body 342, a support pin 334, a chuck pin 346, and a support shaft 348. Body 342 has a top surface that is provided generally circular when viewed from the top. A support shaft 348 rotatable by the motor 349 is fixedly coupled to the bottom of the body 342. A plurality of support pins 334 are provided. The support pins 334 are spaced at predetermined intervals at the edges of the upper surface of the body 342 and protrude upward from the body 342. The support pins 334 are arranged to have an annular ring shape as a whole by combining with each other. The support pin 334 supports the rear edge of the substrate W so that the substrate W is spaced apart from the upper surface of the body 342 by a predetermined distance. A plurality of chuck pins 346 are provided. The chuck pin 346 is disposed farther from the support pin 334 at the center of the body 342. The chuck pins 346 are provided to protrude upward from the body 342. The chuck pin 346 supports the side of the substrate W so that the substrate W does not deviate laterally from its position when the spin head 340 is rotated. The chuck pins 346 are provided to be linearly movable between the standby position and the support position along the radial direction of the body 342. The standby position is a position far from the center of the body 342 relative to the support position. When the substrate W is loaded or unloaded to the spin head 340, the chuck pins 346 are positioned at the standby position, and when the process is performed on the substrate W, the chuck pins 346 are positioned at the support position. . The chuck pins 346 are in contact with the side of the substrate W at the support position.

The lifting unit 360 linearly moves the housing 320 in the vertical direction. As the housing 320 is moved up and down, the relative height of the housing 320 relative to the spin head 340 is changed. The lifting unit 360 has a bracket 362, a moving shaft 364, and a driver 366. The bracket 362 is fixedly installed on the outer wall of the housing 320, and the movement shaft 364 which is moved in the vertical direction by the driver 366 is fixedly coupled to the bracket 362. The housing 320 is lowered so that the spin head 340 protrudes above the housing 320 when the substrate W is placed on the spin head 340 or lifted from the spin head 340. In addition, when the process is in progress, the height of the housing 320 is adjusted to allow the processing liquid to flow into the predetermined recovery container 360 according to the type of processing liquid supplied to the substrate W. For example, when different first processing liquids, second processing liquids, and third processing liquids are supplied to the substrates, the substrates W are disposed in the inner recovery container 322 while the substrates W are being treated with the first processing liquids. It is located at a height corresponding to the inner space (322a) of. In addition, during the processing of the substrate W with the second processing liquid and the third processing liquid, the substrate W may have a space 324a and an intermediate recovery between the inner recovery container 322 and the intermediate recovery container 324, respectively. It may be located at a height corresponding to the space 326a between the barrel 324 and the outer collection container 326. Unlike the above, the lifting unit 360 may move the spin head 340 in the vertical direction instead of the housing 320.

The injection member 380 supplies liquid to the substrate W during the substrate treating process. The injection member 380 has a nozzle support 382, a nozzle 384, a support shaft 386, and a driver 388. The support shaft 386 has a longitudinal direction along the third direction 16, and a driver 388 is coupled to a lower end of the support shaft 386. The driver 388 rotates and lifts the support shaft 386. The nozzle support 382 is vertically coupled with the opposite end of the support shaft 386 coupled with the driver 388. The nozzle 384 is installed at the bottom of the end of the nozzle support 382. The nozzle 384 is moved by the driver 388 to a process position and a standby position. The process position is where the nozzle 384 is disposed vertically above the housing 320, and the standby position is where the nozzle 384 deviates from the vertical upper portion of the housing 320. One or a plurality of injection members 380 may be provided. When a plurality of injection members 380 are provided, different liquids may be injected.

The nozzle 384 supplies a cleaning liquid, which is one of the processing liquids used in the substrate processing apparatus 300, to the substrate W placed on the spin head 340. According to an embodiment of the present invention, the cleaning liquid is prepared by mixing a surfactant chemical liquid and a pure water containing a surfactant. Hereinafter, a cleaning liquid manufacturing apparatus according to an embodiment of the present invention.

3 is a view schematically showing a cleaning liquid manufacturing apparatus according to an embodiment of the present invention. Referring to FIG. 3, the cleaning solution manufacturing apparatus 400 manufactures a cleaning solution for cleaning a substrate. The cleaning liquid manufacturing apparatus 400 includes a chemical liquid tank 410, a first supply member 420, a second supply member 430, a mixing unit 440, a temperature control member 450, and a controller 460.

The chemical liquid tank 410 has a liquid mixing space in which the liquids supplied therein are mixed with each other. The wall of the chemical tank 410 may be insulated in order to minimize heat exchange with the outside to facilitate temperature control of the liquid supplied in the liquid mixing space. The chemical liquid tank 410 may be provided with a temperature sensor that measures the temperature of the liquid in the liquid mixing space. The temperature of the liquid measured by the temperature sensor is transmitted to the controller 460.

The first supply member 420 supplies the surfactant chemical liquid into the liquid mixing space. The second supply member 430 supplies pure water into the liquid mixing space.

The mixing unit 440 mixes the surfactant chemical liquid and the pure water supplied in the liquid mixing space. According to one embodiment, the mixing unit 440 includes a circulation line 441 and a pump 442.

The circulation line 441 is provided so that both ends are connected to the liquid mixing space, and the liquid supplied to the liquid mixing space flows therein. The circulation line 441 may be provided insulated to minimize heat exchange between the inside and the outside. According to an embodiment, the supply line 470 connected to the nozzle 384 is connected to the circulation line 441. The circulation line 441 is provided with an on / off valve 471.

The pump 442 provides power to circulate the liquid in the liquid mixing space into the circulation line 441. The mixing unit 440 mixes the surfactant chemical liquid and the pure water supplied into the liquid mixing space by circulating through the circulation line 441 and back into the liquid mixing space.

The temperature regulating member 450 adjusts the temperatures of the surfactant chemical liquid and the pure water supplied to the liquid mixing space. According to one embodiment, the temperature regulating member 450 may be provided outside the chemical liquid tank 410. For example, the temperature regulating member 450 may be connected to the circulation line 441 so as to adjust the temperature of the liquid flowing in the circulation line 441. Alternatively, the temperature adjusting member 450 may be provided in the chemical liquid tank 410 to directly adjust the temperature of the liquid staying in the liquid mixing space. The temperature regulating member 450 may include various kinds of members capable of heating and cooling the surfactant chemical liquid and the pure water supplied to the liquid mixing space. For example, the temperature regulating member 450 may include a heat fluid flow path through which a hot wire or a heat fluid flows to generate heat by a current supplied to heat the surfactant chemical and the pure water. In addition, the temperature regulating member 450 may include a cooling channel through which a thermoelectric element or a cooling fluid flows to cool the surfactant chemical liquid and the pure water. The temperature control member 450 may be provided with a temperature sensor that measures the temperature of the surfactant chemical liquid and the pure water passing through the inside. The temperature measured at the temperature sensor is transferred to the controller 460.

The controller 460 is provided with a first supply member 420, a second supply member 430, a mixing unit 440, a temperature regulating member 450, and an opening / closing valve 471 to produce the cleaning liquid according to the cleaning liquid manufacturing method to be described below. ).

Hereinafter, the cleaning solution manufacturing method according to an embodiment of the present invention will be described using the cleaning solution manufacturing apparatus 400 of FIG. 3. The washing | cleaning liquid manufacturing method produces the washing | cleaning liquid which wash | cleans a board | substrate.

Figure 4 is a flow chart showing a cleaning liquid manufacturing method according to an embodiment of the present invention. Referring to FIGS. 3 and 4, the cleaning solution manufacturing method includes a first step S10, a second step S20, and a third step S30.

In the first step S10, the surfactant chemical and the pure water are mixed at the first temperature. According to one embodiment, in the first step S10 the controller 460 is the first supply member 420 to mix the surfactant chemical liquid and pure water supplied in the liquid mixing space of the chemical liquid tank 410 at a first temperature The second supply member 430, the mixing unit 440, and the temperature regulating member 450 are controlled. The first temperature is higher than room temperature and lower than 30 ° C. According to one embodiment, the first temperature is preferably higher than 25 ° C. and lower than 27 ° C. For example, a 1st temperature is 26.5 degreeC. By mixing the surfactant chemical and the pure water at a temperature higher than room temperature, the size of the particles formed in the cleaning liquid can be made larger than that of mixing at room temperature. When the surfactant chemical liquid and the pure water are mixed at a temperature higher than 30 ° C., the particles may be dissolved, so it is necessary to manage the first temperature at 30 ° C. or lower.

According to an embodiment, the first step S10 includes a pure water supply step S11, a pure water heating step S12, a surfactant chemical liquid supply step S13, and a mixing step S14.

In the pure water supply step S11, the controller 460 controls the second supply member 430 to supply pure water to the liquid mixing space of the chemical liquid tank 410.

Thereafter, the pure heating step S12 is performed. In the pure water heating step (S12), pure water supplied to the liquid mixing space is heated to the first temperature. According to one embodiment, in the pure water heating step S12, the controller 460 is configured to pump the pump 442 and the temperature regulating member so that the pure water supplied to the liquid mixing space is circulated into the circulation line 441 and heated to the first temperature. 450).

Thereafter, the surfactant chemical liquid supply step (S13) is performed. In the surfactant chemical supply step S13, the surfactant chemical is supplied to the liquid mixing space of the housing 410. According to one embodiment, in the surfactant chemical liquid supply step (S13), the controller 460 controls the first supply member 420 to supply the surfactant chemical liquid to the liquid mixing space of the housing 410. While pure water is supplied to the liquid mixing space, the controller 460 pumps the temperature regulating member 450 and the pump such that the surfactant chemical liquid and pure water of the chemical liquid tank 410 are circulated in the circulation line 441 while maintaining the first temperature. Control 442.

Thereafter, the mixing step S14 is performed. In the mixing step S14, the surfactant chemical liquid and the pure water supplied to the liquid mixing space of the chemical liquid tank 410 are mixed while maintaining the first temperature. According to one embodiment, in the mixing step S14, the controller 460 is configured to adjust the temperature regulating member 450 to circulate in the circulation line 441 while maintaining the surfactant chemical liquid and the pure water in the liquid mixing space at the first temperature. Control the pump 442. The surfactant chemical and the pure water are mixed with each other by circulating in the circulation line 441. The mixing step S14 is performed for a certain time. According to one embodiment, the mixing step S14 is performed for a time longer than 25 minutes and shorter than 35 minutes.

In the second step S20, the surfactant chemical liquid and the pure water mixed in the first step are mixed while cooling to the second temperature. According to an embodiment, in the second step S20, the controller 460 circulates into the circulation line 441 while cooling the surfactant chemical liquid and the pure water mixed in the first step S10 to a second temperature lower than room temperature. The temperature regulating member 450 and the pump 442 are controlled to be effective. According to one embodiment, the second temperature is preferably higher than 17 ° C and lower than 19 ° C. For example, the second temperature is 18 ° C.

FIG. 5 is a graph showing changes in size and conductivity of surfactant particles according to cooling of surfactant chemicals and pure water according to an embodiment of the present invention. As the surfactant chemical and the pure water are cooled, the size of the surfactant particles increases, and the conductivity decreases. This action is considered to be because the solubility of the surfactant particles is reduced by cooling to induce crystallization, and the formation of lamellar crystalline structured particles in the cleaning liquid is accelerated. If not undergoing the cooling process (S20), it takes approximately 1 hour or more to increase the surfactant particles to the appropriate size (eg, 30 μm or more) required to achieve 90% or more of contaminant removal performance. When performing the process (S20), the time required to increase the size of the surfactant particles can be shortened to about 40 minutes or less.

6 is a graph showing a change in particle removal efficiency (PRE) according to the cooling temperature of the cleaning liquid. Referring to FIG. 6, when the cooling temperature (second temperature) for growing the size of the surfactant particles is 20 ° C., the particle generation rate is slower than the cooling temperature is 18 ° C., and the extent of reduction of the pollutant removal performance is reduced. It can also be seen that it is large. Also, when the cooling temperature (second temperature) is 16 ° C., the initial pollutant removal performance is also lower than the cooling temperature is 18 ° C., and the reduction is also large. Thus, the second temperature may be set above 16 ° C. and below 20 ° C., more preferably 17 ° C. to 19 ° C., in order to grow the size of the plate-shaped surfactant particles and maximize the pollutant removal performance.

After the second step S20 is completed, the particles in the cleaning liquid are deformed while waiting until the cleaning liquid discharge starts, and the contaminant removal performance PRE of the cleaning liquid gradually decreases over time. The surfactant particles grow in a direction for thermodynamically stable form, and the lamellar structure eventually transforms into spherulites, the most stable state, and is vortexed onto the surface of the particle as it deforms. This is because amorphous particles are grown in the form of spiral). As more particles are deformed, the wafer cleaning effect is reduced.

In order to prevent the reduction of the cleaning performance as described above, the step (S30) of additionally adding the surfactant chemical liquid into the chemical liquid tank 410 is performed. As the surfactant is added, a source for forming a lamellar crystalline structure in the nuclei-shaped particles is generated, and the plate-shaped lamellar crystal structure particles are increased in size and thickness.

7 is an image taken by the optical microscope of the surfactant particles after the addition of the surfactant chemical in accordance with an embodiment of the present invention. At this time, the surfactant stock solution was added at a ratio of 0.2% (v / v) to the total volume of the cleaning liquid in the chemical tank 410, and the ratio of the surfactant in the cleaning solution before the addition of the surfactant stock solution is 0.5 compared to the pure water. % (v / v). The surfactant chemical liquid used in the experiment is the "AP 1.0" chemical liquid of "Dongwoo Finechem Co., Ltd.". As shown in FIG. 7, it can be seen that due to the addition of the surfactant chemical liquid, most of the particles in the cleaning liquid retain the lamellar crystal structure particles of the plate type.

In order to confirm whether the effect of maintaining the cleaning performance due to the addition of the surfactant is due to the addition of the surfactant, the mixing ratio of the surfactant chemical liquid to the pure water is 0.3, 0.5, 0.7% (v / v). The experiment was performed while changing to). Table 1 below summarizes the results.

Mixing ratio 0.3% (v / v) 0.5% (v / v) 0.7% (v / v) Initial PRE 73% 90% 75% Surfactant Particle Size 21 μm 33 μm 24 μm

After cooling in the second step (S20) with the mixing ratio of the surfactant at 0.5% (v / v) in the first step (S10), 0.2% (v / v) of the surfactant is added in the third step (S30). When added, the size of the surfactant particles was as large as 33 μm, and the initial cleaning performance (PRE) was as high as 90%. On the other hand, when the mixing ratio of the surfactant was cooled to 0.7% (v / v) from the first step (S10), the initial cleaning performance (PRE) was reduced to 75%. This is considered to be because the amount of IPA in the surfactant chemical liquid mixed in the pure water in the first step (S10) is rather hindered the production of plate-shaped particles. Even when the ratio of the surfactant chemical liquid mixed in the pure water in the first step (S10) is 0.3% (v / v), it can be seen that the initial PRE is low as 73%. In the first step (S10), it is preferable that the ratio of the surfactant chemical liquid mixed with pure water is more than 0.3% (v / v) and less than 0.7% (v / v). In the third step (S30), the ratio of the surfactant stock solution additionally added to the cleaning solution may be 0.1% (v / v) or more, but less than 1% (v / v), but is not limited thereto.

The third step S30 may be performed immediately before the cleaning liquid is discharged through the nozzle 384, before a predetermined time from the cleaning liquid discharge start time, or may be performed while being discharged through the nozzle 340. In the third step S30, the surfactant chemical liquid may be additionally added to the chemical liquid tank 410 at a time, or the surfactant chemical liquid may be additionally added in a plurality of times at set intervals.

Figure 8 is a graph showing the measurement of the change in cleaning performance for each method of adding a surfactant chemical solution. When the surfactant stock solution (590 mL) was added to the 0.2% (v / v) chemical tank at a time immediately before discharging the washing liquid (add. × 1), the same amount (588 mL) of the surfactant stock solution was It can be seen that the drop in cleaning performance decreases over time and maintains high cleaning performance in all cases where 147 mL is added and added to the chemical tank (add. × 4) over time.

The controller 460 controls the closing valve 471 to be closed while the first step S10 and the second step S20 are performed. While the third step S30 is completed or the third step S30 is being performed, the controller 460 controls the opening / closing valve 471 to be opened so that the cleaning liquid in the circulation line 441 is supplied to the nozzle 384. . As described above, after the surfactant particles and the pure water are mixed at the first temperature, the mixture is cooled to the second temperature and the mixing is performed, so that the size of the particles in the cleaning liquid is larger than the case where only the mixing at the first temperature is performed. It is formed large and the time until the particles are formed in the same size is shortened. For example, by the apparatus and method of the present invention, the particles in the cleaning liquid may be formed to be 30 mu m or more in length. That is, when the particles are provided in the shape of a square plate, the average length of the long sides may be provided at 30 μm or more. In addition, after the cleaning solution is cooled, a surfactant chemical solution is further added to maintain a high cleaning performance (PRE) of 90% or more.

9 is a CLD particle size analysis result of the cleaning solution prepared according to an embodiment of the present invention. In FIG. 9, the red graph is a result measured before the addition of the surfactant chemical solution, and the rest shows the change in the particle size distribution over time after the addition of the surfactant chemical solution at 59 minutes. In FIG. 9, Unweighted CLD is a particle size distribution of fine particles, and Square-Weighted CLD is a particle size distribution of coarse particles. After the addition of the surfactant chemicals, the number and size of the particles increased in both the fine particles and the coarse particles, and it can be seen that the particle size of the coarse particles having a great effect on the cleaning performance was increased significantly.

400: cleaning liquid production apparatus 410: chemical liquid tank
420: first supply member 430: second supply member
440: mixing unit 441: circulation line
442: pump 450: temperature control member
460: controller 470: supply line
471: on-off valve

Claims (10)

In the method of manufacturing the cleaning liquid for cleaning the substrate,
Mixing the surfactant chemical and the pure water at a first temperature, followed by mixing the surfactant chemical and the pure water while cooling to a second temperature lower than the first temperature; And
And after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature, adding a surfactant chemical liquid to prepare the cleaning liquid.
The said 2nd temperature is a washing | cleaning liquid manufacturing method whose temperature difference with said 1st temperature is less than 14 degreeC. In the method of manufacturing the cleaning liquid for cleaning the substrate,
Mixing the surfactant chemical and the pure water at a first temperature, followed by mixing the surfactant chemical and the pure water while cooling to a second temperature lower than the first temperature; And
And after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature, adding a surfactant chemical liquid to prepare the cleaning liquid.
The first temperature is lower than 30 ° C.,
The said 2nd temperature is the temperature of more than 16 degreeC and less than 20 degreeC. In the method of manufacturing the cleaning liquid for cleaning the substrate,
Mixing the surfactant chemical and the pure water at a first temperature, followed by mixing the surfactant chemical and the pure water while cooling to a second temperature lower than the first temperature; And
And after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature, adding a surfactant chemical liquid to prepare the cleaning liquid.
The mixing ratio of the surfactant chemical liquid mixed in the pure water at the first temperature is more than 0.3% (vv) and less than 0.7% (v / v) compared to the pure water. The method according to claim 1 or 2,
The addition of the surfactant chemical solution to prepare the cleaning solution,
20. A method of manufacturing a cleaning liquid which is performed immediately before the cleaning liquid is discharged onto the substrate through a nozzle, before a set time from a cleaning liquid discharge start time, or while the cleaning liquid is discharged through the nozzle. The method according to claim 1 or 2,
By further adding the surfactant chemical solution to prepare the cleaning solution, the surfactant particles of the plate-like lamellar crystal structure having an average size of 30 ㎛ or more in the cleaning solution is increased, the initial contaminant removal performance of the cleaning solution 90% or more of the cleaning solution manufacturing method. The method according to claim 1 or 2,
The addition of the surfactant chemical solution to prepare the cleaning solution,
Method for producing a cleaning solution comprising the step of further adding a surfactant stock solution once or a plurality of times. In the apparatus for producing a cleaning liquid,
A chemical tank having a liquid mixing space therein;
A first supply member for supplying a surfactant chemical liquid into the chemical liquid tank;
A second supply member for supplying pure water into the chemical tank;
A mixing unit for mixing the surfactant chemical liquid and the pure water supplied in the chemical liquid tank;
A temperature regulating member for controlling the temperature of the surfactant chemical liquid and the pure water supplied into the chemical liquid tank; And
A controller for controlling the first supply member, the second supply member, the mixing unit, and the temperature regulating member,
The controller may include a first step of mixing the surfactant chemical liquid and the pure water supplied into the liquid mixing space at a first temperature, and the surfactant chemical liquid and the pure water mixed in the first step than the first temperature. To perform a second step of cooling to a low second temperature, and a third step of preparing the cleaning solution by further adding a surfactant chemical liquid after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature. To control the first supply member, the second supply member, the mixing unit and the temperature regulating member,
The said 2nd temperature, The cleaning liquid manufacturing apparatus whose temperature difference with said 1st temperature is less than 14 degreeC. In the apparatus for producing a cleaning liquid,
A chemical tank having a liquid mixing space therein;
A first supply member for supplying a surfactant chemical liquid into the chemical liquid tank;
A second supply member for supplying pure water into the chemical tank;
A mixing unit for mixing the surfactant chemical liquid and the pure water supplied in the chemical liquid tank;
A temperature regulating member for controlling the temperature of the surfactant chemical liquid and the pure water supplied into the chemical liquid tank; And
A controller for controlling the first supply member, the second supply member, the mixing unit, and the temperature regulating member,
The controller may include a first step of mixing the surfactant chemical liquid and the pure water supplied into the liquid mixing space at a first temperature, and the surfactant chemical liquid and the pure water mixed in the first step than the first temperature. To perform a second step of cooling to a low second temperature, and a third step of preparing the cleaning solution by further adding a surfactant chemical liquid after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature. To control the first supply member, the second supply member, the mixing unit and the temperature regulating member,
The first temperature is lower than 30 ° C.,
The said 2nd temperature is more than 16 degreeC, The cleaning liquid manufacturing apparatus which is less than 20 degreeC. In the apparatus for producing a cleaning liquid,
A chemical tank having a liquid mixing space therein;
A first supply member for supplying a surfactant chemical liquid into the chemical liquid tank;
A second supply member for supplying pure water into the chemical tank;
A mixing unit for mixing the surfactant chemical liquid and the pure water supplied in the chemical liquid tank;
A temperature regulating member for controlling the temperature of the surfactant chemical liquid and the pure water supplied into the chemical liquid tank; And
A controller for controlling the first supply member, the second supply member, the mixing unit, and the temperature regulating member,
The controller may include a first step of mixing the surfactant chemical liquid and the pure water supplied into the liquid mixing space at a first temperature, and the surfactant chemical liquid and the pure water mixed in the first step than the first temperature. To perform a second step of cooling to a low second temperature, and a third step of preparing the cleaning solution by further adding a surfactant chemical liquid after the surfactant and the pure water are cooled and mixed for a predetermined time at the second temperature. To control the first supply member, the second supply member, the mixing unit and the temperature regulating member,
The mixing ratio of the surfactant chemical liquid mixed in the pure water at the first temperature is more than 0.3% (vv) and less than 0.7% (v / v) compared to the pure water. The method according to claim 7 or 8,
The controller,
In the third step, the surfactant chemical is additionally added immediately before the cleaning liquid is discharged onto the substrate through the nozzle, or the surfactant chemical is additionally added before the time set from the cleaning liquid discharge start time, or through the nozzle. A cleaning liquid production apparatus configured to further add a surfactant chemical liquid while the cleaning liquid is discharged.