JP3654478B2 - Washing water manufacturing / supply system, manufacturing / supply method, and cleaning system - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cleaning water production / supply system and a manufacturing / supply method, and more specifically, a cleaning water manufacturing / supply system, a manufacturing / supply method, a cleaning system, and a cleaning system that generate ozone water and hydrogen water in the same apparatus. Regarding the method.
[0002]
[Background]
To remove particles such as organic substances and colloidal silica from semiconductor substrates, liquid crystal substrates, and other various objects to be cleaned, ozone water and OH obtained by electrolysis^-It has recently been reported that ionic water (electrolytic cathode water) is effective.
[0003]
Ozone water is generated by oxygen discharge, etc._ThreeThere is known a method of producing by dissolving in water.
[0004]
On the other hand, a method for producing electrolytic cathodic water obtained by electrolysis as described above is disclosed in JP-A-6-260460.
[0005]
[Problems to be solved by the invention]
However, in the conventional technology described above, the production of ozone water for removing organic substances and the production of electrolytic cathode water for removing particles are different from each other between an ozone water generator and an electrolytic ionic water generator. Therefore, the entire cleaning water supply system becomes large.
[0006]
For this reason, for example, the area occupied by the apparatus in a clean room increases, and the space cost also increases.
[0007]
In addition, efficient use of ozone is difficult, and cleaning efficiency is deteriorated. However, since the half-life of ozone is short, it is preferable that the ozone water production and supply system is in the immediate vicinity of the use point, that is, the cleaning room. However, if the device is large, it cannot be placed in the immediate vicinity.
[0008]
In addition, the production of ozone water and the production of electrolytic ion water are performed in different processes using different apparatuses. That is, two steps are required, and a simpler step is desired. In addition, the consumption of ultrapure water as a raw material is inevitably increased due to the two steps.
[0009]
Moreover, in the electrolyzed cathode water production apparatus, the electrolyzed cathode water is in contact with the electrode, so that the eluted ion water produced is mixed with impurities eluted from the electrode. Therefore, the object to be cleaned is contaminated with the eluted impurities. Therefore, in order to prevent this contamination, a measure for preventing impurity elution on the electrode surface is desired.
[0010]
On the other hand, as a cleaning technique, (1) a technique in which ultrapure water is used as a cleaning liquid and the object to be cleaned is brushed with a brush, and (2) ultrapure water to which a surfactant is added is used as a cleaning liquid. Attempts have been made to perform techniques such as cleaning the brushed object with a brush.
[0011]
However, with the technique (1), it is possible to remove large particles (1 μm or more), but it is not always possible to remove particles with a submicron size (0.5 to 1 μm) that may be due to redeposition. .
[0012]
In the above technique (2), the removability of large particles is good and the re-adhesion of sub-micron particles is small. However, a large amount of ultrapure water for rinsing is required to remove the surfactant, and the rinsing is performed. An oxidative cleaning step is required to remove the slight remaining surfactant later.
[0013]
Conventionally, CO₂A cleaning technique is known in which ultrapure water in which water is dissolved is injected at high pressure. This technology has a high removal capability due to the physical detergency by high-pressure injection. CO₂Is to prevent the generation of static electricity.
[0014]
However, with this technology, CO₂Is CO_Three ^2-As a result, the pH was about 5 and the particles were reattached.
[0015]
SUMMARY OF THE INVENTION An object of the present invention is to provide a very compact cleaning water production / supply system in which cleaning liquids for organic substances and particles can be manufactured by the same apparatus.
[0016]
It is an object of the present invention to provide a cleaning water production / supply system that can perform cleaning with a cleaning liquid that is not contaminated by electrodes.
[0017]
An object of the present invention is to provide a cleaning water production / supply method capable of producing an organic cleaning liquid and a particle cleaning liquid in one step.
[0018]
The present invention provides a cleaning system and a cleaning method capable of removing not only large particles (particles of about 1 μm or more) but also submicron particles (particles of about 0.5 to 1 μm) without using a surfactant. For the purpose.
[0019]
An object of the present invention is to provide a cleaning system and a cleaning method in which reattachment of particles does not occur.
[0020]
[Means for Solving the Problems]
The present invention has an anode chamber and a cathode chamber._Three(Ozone) gas is generated and H is generated in the cathode chamber.₂An electrolysis tank for generating (hydrogen) gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H to discharge gas out of the cathode chamber₂Gas exhaust piping,
H₂H connected to the gas discharge pipe₂Dissolve gas in pure water₂H for producing water₂A gas dissolution tower;
H₂H from gas dissolution tower₂H for introducing water into the washing chamber₂Water piping,
A cleaning water production / supply system characterized by comprising:
[0021]
In the present invention, the cleaning liquids for the organic matter and the particles are manufactured by the same apparatus, and a very compact cleaning water supply system can be configured. As a result of being able to make the conventional large supply system compact, the system can be arranged near the cleaning chamber, in particular, ozone can be used efficiently and the cleaning effect can be enhanced.
[0022]
O_ThreeGas and H₂Each gas is dissolved in pure water in a dissolution tower, and a clean cleaning solution free from contamination by electrodes can be supplied to the cleaning chamber.
[0023]
Where H₂It is preferable to provide means for adding a pH adjusting chemical to water.
[0024]
H₂Since pH adjustment chemicals can be added to water, H₂The pH of water can be adjusted appropriately (for example, pH 7 or more), and a cleaning liquid with high particle removal efficiency can be supplied.
[0025]
Moreover, NH as a pH adjusting chemical solution_FourOH is preferred.
[0026]
Examples of pH adjusting chemicals include NaOH, KOH, NH_FourOH, etc., especially NH_FourOH exhibits a higher particle removal efficiency than other chemicals, and there is no concern about residual alkaline components.
[0027]
The cleaning water production / supply system of the present invention has an anode chamber and a cathode chamber, and in the anode chamber, O_ThreeGas is generated and H in the cathode chamber₂An electrolysis tank for generating gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H produced by dissolving gas in pure water in the cathode chamber₂H for introducing water from the cathode chamber into the cleaning chamber₂Water piping,
It is characterized by having at least.
[0028]
In the present invention, the cleaning liquids for organic substances and particles are manufactured by the same apparatus, and a very compact cleaning water manufacturing / supply system can be configured.
[0029]
H₂Since the gas is configured to be dissolved in pure water directly in the cathode chamber of the electrolysis tank to form hydrogen water and introduced into the cleaning chamber, the gas can be further reduced in size.
[0030]
In the present invention, it is preferable to provide means for adding a pH adjusting chemical to the cathode chamber.
[0031]
In such a case, H₂Since pH adjustment chemicals can be added to water, H₂The pH of water can be adjusted appropriately (for example, pH 7 or more), and a cleaning liquid with high particle removal efficiency can be supplied. In addition, when a pH adjusting chemical solution is added to the cathode chamber of the electrolysis tank, the electric conductivity of ultrapure water is increased, the electrolysis decomposition efficiency is increased, and the decomposition speed is increased, resulting in more efficient. H₂Since gas is obtained, it is more preferable.
[0032]
The present invention can be achieved by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂A method for producing and supplying cleaning water, characterized in that water is sent to a cleaning chamber.
[0033]
In the present invention, the cleaning liquid for removing organic substances and the cleaning liquid for removing particles can be manufactured in a plurality of apparatuses at the same time, not in different processes, so that the cost can be reduced and the raw materials used ( The amount of ultrapure water) used can be reduced.
[0034]
In this invention, H₂It is preferable to add an alkaline solution to water.
[0035]
In this case, H₂H to add pH adjuster to water₂The pH of water can be adjusted appropriately (for example, pH 7 or higher), and a cleaning liquid can be produced and supplied with high particle removal efficiency. In addition, when a pH adjusting chemical solution is added to the cathode chamber of the electrolysis tank, the electric conductivity of ultrapure water is increased, the electrolysis decomposition efficiency is increased, the decomposition rate is increased, and the H efficiency is increased.₂Since gas is obtained, it is more preferable.
[0036]
The pH adjusting chemical solution is NH_FourIt is preferable to use OH.
[0037]
NH_FourWhen OH is used, the particle removal effect is further enhanced.
[0038]
The cleaning system of the present invention has an anode chamber and a cathode chamber._ThreeGas is generated and H in the cathode chamber₂An electrolysis tank for generating gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H to discharge gas out of the cathode chamber₂Gas exhaust piping,
H₂H connected to the gas discharge pipe₂Dissolve gas in pure water₂H for producing water₂A gas dissolution tower;
H₂H from gas dissolution tower₂H for introducing water into the washing chamber₂Water piping,
Having at least
Further, the present invention is characterized in that a brush for slidingly cleaning an object to be cleaned is provided in the cleaning chamber.
[0039]
In the present invention, not only large particles but also small particles can be removed. Further, the adhesion of particles to the brush can be reduced by controlling the pH and oxidation-reduction potential. H₂H if no chemical is added to the water₂No rinsing is required after brush cleaning with water. Further, even when a chemical solution is added, rinsing is extremely easy, and the amount of super water used is 1/10 or less than the conventional amount.
When performing brushing cleaning with a brush,₂By applying ultrasonic waves of 0.2 MHz or more and 5 MHz or less to water, the amount of adhered particles can be further reduced.
[0040]
The cleaning system of the present invention has an anode chamber and a cathode chamber._ThreeGas is generated and H in the cathode chamber₂An electrolysis tank for generating gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H to discharge gas out of the cathode chamber₂Gas exhaust piping,
H₂H connected to the gas discharge pipe₂Dissolve gas in pure water₂H for producing water₂A gas dissolution tower;
H₂H from gas dissolution tower₂H for introducing water into the washing chamber₂Water piping,
Having at least
Furthermore, in the cleaning chamber, H₂A high-pressure jet nozzle for jetting water at a high pressure is provided.
[0041]
In the present invention, H₂Water is jetted at high pressure, physical washing with high pressure, and H₂The redeposition potential of water and the control of pH eliminate the reattachment of particles.
The cleaning system of the present invention has an anode chamber and a cathode chamber._ThreeGas is generated and H in the cathode chamber₂An electrolysis tank for generating gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H to discharge gas out of the cathode chamber₂Gas exhaust piping,
H₂H connected to the gas discharge pipe₂Dissolve gas in pure water₂H for producing water₂A gas dissolution tower;
H₂H from gas dissolution tower₂H for introducing water into the washing chamber₂Water piping,
Having at least
Furthermore, H introduced into the cleaning chamber₂It has the ultrasonic element which provides the ultrasonic wave of 0.2 MHz or more and 5 MHz or less to water.
H₂When cleaning is performed by applying ultrasonic waves to water, the particle removal efficiency is superior to that when cleaning is performed by applying ultrasonic waves to the electrolytic ion cathode water.
Further, in the present invention, ultrapure water does not come into direct contact with the electrode, so that cleaning water with higher purity than electrolytic ion water can be obtained. Therefore, stable cleaning can be performed over a long period of time.
[0042]
Furthermore, unlike electrolytic ionic water, gasified H₂Since gas does not flow, the cleaning efficiency is good, and cleaning can be performed in a shorter time.
[0043]
The cleaning system of the present invention has an anode chamber and a cathode chamber._ThreeGas is generated and H in the cathode chamber₂An electrolysis tank for generating gas;
O generated in the anode chamber_ThreeO to discharge gas out of the anode chamber_ThreeGas exhaust piping,
O_ThreeO connected to the gas exhaust pipe_ThreeGas is dissolved in pure water and O_ThreeO to produce water_ThreeA gas dissolution tower;
O_ThreeO from the gas dissolution tower_ThreeO to introduce water into the washing room_ThreeWater piping,
H generated in the cathode chamber₂H to discharge gas out of the cathode chamber₂Gas exhaust piping,
H₂H connected to the gas discharge pipe₂Dissolve gas in pure water₂H for producing water₂A gas dissolution tower;
H₂H from gas dissolution tower₂H for introducing water into the washing chamber₂Water piping,
Having at least
Furthermore, H introduced into the cleaning chamber₂It has the gas injection nozzle for injecting water to a to-be-cleaned object by gas.
The cleaning water production and supply method of the present invention is performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂It is characterized by sending water to one or more cleaning chambers.
Where H₂It is preferable to add a pH adjusting chemical solution to water, and the pH adjusting chemical solution is NH._FourOH is preferred.
[0044]
The cleaning method of the present invention is performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂Send water to one or more washrooms,
The object to be cleaned is cleaned with a brush in the cleaning chamber.
Further, the cleaning method of the present invention can be performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂Send water to one or more washrooms,
The object to be cleaned is cleaned with a brush in the cleaning chamber.
Furthermore, the cleaning method of the present invention can be performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂Send water to one or more washrooms,
The H in the cleaning chamber₂The object to be cleaned is cleaned by jetting water at a high pressure.
[0045]
Further, the cleaning method of the present invention can be performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, the H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂Send water to one or more washrooms,
H in the cleaning chamber₂The object to be cleaned is cleaned by applying ultrasonic waves of 0.2 MHz to 5 MHz to water.
Furthermore, the cleaning method of the present invention can be performed by electrolysis._ThreeGas and H₂Generate gas,
O_ThreeGas is dissolved in pure water and O_ThreeWhile producing water, H₂Dissolve gas in pure water₂Producing water,
O_ThreeWater and H₂Send water to one or more washrooms,
H in the cleaning chamber₂The object to be cleaned is cleaned by jetting water with a gas.
[0046]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a conceptual diagram showing an embodiment of the cleaning liquid production / supply apparatus of the present invention.
In FIG. 1, 1 is O_ThreeGas and H₂It is an electrolysis tank that generates gas at the same time.
[0047]
2 is O generated in the electrolysis tank 1_ThreeO for dissolving gas in ultrapure water_ThreeIt is a gas dissolution tower. O_ThreeThe gas dissolution tower 2 is connected to the electrolysis tank 1 through the pipe 11 with O._ThreeWhile the gas is supplied, ultrapure water is supplied from the ultrapure water supply pipe 7 via the branch pipe 7b._ThreeDissolve the gas. O that cannot be dissolved_ThreeThe gas is discharged out of the system from the pipe 13 as waste gas.
[0048]
O_ThreeThe ultrapure water (ozone water) in which the gas is dissolved is supplied to the cleaning chamber (not shown) through the ozone water pipe 9.
[0049]
3 is H generated in the electrolysis tank 1₂H for dissolving gas in ultrapure water₂It is a gas dissolution tower. H₂The gas dissolution tower 3 is connected to the H 2 from the electrolysis tank 1 through a pipe 12.₂While supplying gas, ultrapure water is supplied from the ultrapure water supply pipe 7 via the branch pipe 7a, and H is supplied to the ultrapure water.₂Dissolve the gas. H that cannot be dissolved₂The gas is discharged out of the system from the pipe 14 as waste gas. H₂Ultra-pure water (hydrogen water) with dissolved gas is H₂The water is supplied to the cleaning chamber through the water pipes 8 and 10.
[0050]
In this example, H₂A mixing device 5 is provided between the water pipe 8 and the hydrogen water pipe 10. In the mixing device 5, an alkaline solution (preferably NH) is added to hydrogen water._FourOH solution) and H₂The pH of water is 7 or more.
[0051]
Details of the electrolysis tank 1 are shown in FIG.
[0052]
The electrolysis tank 1 has an anode chamber 22 and a cathode chamber 21, and both chambers are separated by an ion exchange membrane 25. The anode chamber 22 is provided with an anode 24, and the cathode chamber 21 is provided with a cathode 23. The electrolysis tank 1 has O_ThreeGas, H₂Ultrapure water serving as a gas raw material is supplied from an ultrapure water supply line 7 through a branch pipe 7c.
[0053]
When a potential is applied from the DC power source 26 between the anode 24 and the cathode 23 in a state where ultrapure water is supplied, the anode chamber 16 is subjected to electrolysis in an O_ThreeGas is generated and H in the cathode chamber 15₂Gas is generated.
[0054]
In the system shown in FIG._ThreeA gas discharge pipe 11 is provided, and the cathode chamber 15 is provided with H.₂A gas exhaust pipe 12 is provided.
[0055]
FIG. 3 shows another embodiment.
[0056]
In this example, the electrolysis tank 1 has an anode chamber 16 and cathode chambers 15a and 15b. O in the anode chamber 16_ThreeGas is generated and H is generated in the cathode chambers 15a and 15b.₂Generate gas.
[0057]
The anode chamber 16 has O 2 generated in the anode chamber 16._ThreeO to discharge gas out of the anode chamber 16_ThreeA gas discharge pipe 11 is provided.
[0058]
2 is O_ThreeGas melting tower, O_ThreeConnected to the gas discharge pipe 11_ThreeGas is dissolved in pure water and O_ThreeIt is a tower for producing water. O_ThreeO from the gas dissolution tower 2_ThreeO to introduce water into the washing room_ThreeA water pipe 9 extends.
[0059]
On the other hand, in this example, unlike the example shown in FIG.₂There is no melting tower. That is, in this example, H generated in the cathode chambers 15a and 15b.₂Gas is dissolved in pure water in the cathode chambers 15a and 15b to form hydrogen water.₂The water pipe 30 introduces the cleaning chamber. In this case, a material that does not elute impurities is selected for the cathode electrode. The material is preferably a rare earth metal oxide. For example, ruthenium and iridium are preferable.
[0060]
In this example,₂Without providing a melting tower,_ThreeWater and H₂Since water can be produced and supplied to the cleaning chamber, the cleaning supply system can be further reduced in size.
[0061]
In this example, the electrolysis tank 1 has a three-chamber configuration including one anode chamber 16 and two cathode chambers 15a and 15b.
[0062]
The pH adjuster is H₂In the cathode chamber 15b where the water pipe 30 is provided, H₂Add to water. Therefore, the efficiency of electrolysis can be improved, and H₂Water can be produced quickly. pH adjustment is H from the electrolysis tank₂The same effect can be obtained even with water.
[0063]
FIG. 4 shows another embodiment.
This example also has a three-chamber configuration, similar to the example shown in FIG.₂H for introducing water into the washroom₂Water piping is provided in both cathode chambers 15a and 15b. Therefore, pH adjusted H₂Water can be used twice as compared to the supply system of FIG.
[0064]
FIG. 5 shows an embodiment of a cleaning system according to the present invention. FIG. 5 shows only the cleaning chamber.
[0065]
Reference numeral 101 denotes a cleaning chamber. In the cleaning chamber 101, brushes 1102 and 103 are provided above and below the object to be cleaned 115.
[0066]
This cleaning chamber 101 has H₂Water pipe 10 is connected and H₂Water is supplied to the upper and lower surfaces of the workpiece 115 via the pipes 118 and 119.
In this example, an upper brush ultrasonic cleaning tank 104 for cleaning the upper brush 102 and a lower brush ultrasonic cleaning tank 105 for cleaning the lower brush 103 are provided. Ultrasonic elements 106 and 107 are provided in the upper brush ultrasonic cleaning tank 104 and the lower brush ultrasonic cleaning tank 105, respectively. This ultrasonic element can oscillate between 0.2 MHz and 5 MHz. When the brushes 102 and 103 need to be cleaned, appropriate treated water (for example, H in the upper brush ultrasonic cleaning tank 104 and the lower brush ultrasonic cleaning tank 105 is used.₂Water, electrolytic ionic water, and ultrapure water) are supplied through pipes 113 and 114, and the brushes 102 and 103 are moved (moved) into the upper brush ultrasonic cleaning tank 104 and the lower brush ultrasonic cleaning tank 105. The means is not particularly shown but may be any appropriate means), and the cleaning may be performed while applying ultrasonic waves.
By appropriately cleaning the brushes in the ultrasonic cleaning tanks 104 and 105, the brushes can always be kept clean, and the object to be cleaned can be effectively cleaned.
[0067]
Note that the inner surface of the cleaning chamber 101 is preferably formed of stainless steel having a passive film formed on the surface.
[0068]
Moreover, it is preferable to set it as the structure which can rotate a to-be-processed object. If the workpiece is rotated and the cleaning liquid is supplied to the front surface (back surface), cleaning with a higher degree of cleanliness becomes possible.
[0069]
The brush may be any brush that does not damage the surface of the object to be cleaned and does not become a contamination source. For example, a brush made of nylon can be used.
[0070]
In FIG. 5, H₂The case where the water pipe 10 is connected to the cleaning chamber is shown.₂The ozone water pipe 9 may be connected to the cleaning chamber together with the water pipe 10. Moreover, you may connect other piping (For example, piping for supplying rinse liquid). The same applies to other embodiments or examples described below.
[0071]
FIG. 6 shows an embodiment of a cleaning system according to the present invention. FIG. 6 shows only the cleaning chamber.
[0072]
Reference numeral 204 denotes a cleaning room. High pressure jet nozzles 210 and 211 are provided in the cleaning chamber 204, and the high pressure jet nozzles 210 and 211 have H₂A water pipe 10 is connected via a pump or the like.
[0073]
The injection pressure is 5 kgw / cm.²~ 150kgw / cm²Is preferable from the standpoint of further improving the cleaning effect, but considering damage on the substrate, it is 30 to 70 kgw / cm.²Is more preferable.
[0074]
The nozzles 210 and 211 are made of stainless steel having a passive film mainly composed of chromium oxide formed on the surface thereof, so that generation of particles and metal elution from the nozzle can be prevented. To preferred. Note that sapphire is preferable for the minute hole at the tip of the nozzle.
[0075]
FIG. 7 shows an embodiment of a cleaning system according to the present invention. FIG. 7 shows only the cleaning chamber. Reference numeral 309 denotes a cleaning chamber.
[0076]
In the example shown in FIG. 7, a quartz ultrasonic cleaning tank 301 is further provided inside the cleaning chamber 309, in which H₂Water 306 is H₂It is supplied via the water pipe 10. The ultrasonic cleaning tank 301 is accommodated in the ultrasonic tank 302 via the ultrasonic transmission liquid 305. 303 and 304 are ultrasonic elements, and in this example, ultrasonic waves are applied to the workpiece 115 in the horizontal direction. The ultrasonic waves from the ultrasonic element 303 are transmitted through the ultrasonic transmission liquid 305 to the H in the ultrasonic cleaning tank 301.₂It is transmitted to the workpiece 115 immersed in the water 306.
[0077]
Reference numeral 311 denotes a holding member for holding the workpiece 115 and can be moved up and down.
[0078]
FIG. 8 shows an embodiment of a cleaning system according to the present invention. FIG. 8 shows only the cleaning chamber. Reference numeral 402 denotes a cleaning chamber.
[0079]
Reference numeral 403 denotes an ultrasonic element. Reference numeral 404 denotes an ultrasonic shower for deriving treated water to which ultrasonic waves are applied in a shower shape. H in this ultrasonic shower 404₂A water pipe 10 is connected, and ultrasonic waves are applied by the ultrasonic element 403.
[0080]
The length a of the ultrasonic shower 404 is preferably larger than the length of the diagonal line of the workpiece 115 (substrate). Thereby, even when the workpiece 115 held by the holding body 407 is rotated, the spray water can always be applied to the entire substrate 115, and reattachment of particles can be prevented. .
[0081]
The drying is preferably performed while spraying an inert gas on the surface of the object to be processed in order to prevent an oxide film from being formed on the surface. Also in this example, a gas inlet 405 for introducing an inert gas is provided. This gas is preferably a gas having a concentration of impurities such as moisture of several ppb or less. Nitrogen gas is preferred from an economic viewpoint.
[0082]
Note that the gas is preferably heated by the heater 406 in order to increase the drying speed.
[0083]
FIG. 9 shows an embodiment of a cleaning system according to the present invention. FIG. 9 shows only the cleaning chamber. Reference numeral 901 denotes a cleaning chamber.
[0084]
In this example, gas injection nozzles 910 and 911 are provided in the cleaning chamber 901.
Details of the gas injection nozzle 910 are shown in FIG. FIG. 10B is a vertical sectional view, and FIG. 10A is an X-X ′ sectional view of FIG.
[0085]
While introducing a gas such as nitrogen or air from the gas inlet 915, H₂Water is introduced from the liquid inlet 917. H for gas flow₂Water is sucked into the gas injection nozzle 910 and flows along the passage 916 in the nozzle together with the gas, and is injected from the nozzle tip 918 at a high pressure.
[0086]
The diameter of the nozzle tip 918 is preferably 0.1 to 0.2 mm. The gas flow rate is preferably 1 to 150 Nl / min, and the gas pressure is 1 to 5 kgw / cm.²Is preferred.
[0087]
By using such injection nozzles 910 and 911, the amount of ultrapure water used and the amount of gas used can be reduced as compared with the conventional one, and submicron particles can be removed and cleaning without reattachment can be performed.
[0088]
【Example】
In this example, the cleaning water supply system shown in FIG._ThreeWater and H₂Water was produced and supplied to the cleaning room to perform a cleaning test.
[0089]
In addition, the brand name "Purezone" (trademark) by Permerec Electrode Co., Ltd. was used as an apparatus shown in FIG.
[0090]
H from the ultrapure water supply line 7 through the branch pipe 7a₂O to the gas dissolution tower 3 through the branch pipe 7b_ThreeUltrapure water was introduced into the electrolysis tank 1 through the branch pipe 7c to the gas dissolution tower 2, respectively.
[0091]
In the electrolysis tank 1, electrolysis is performed under the following conditions.₂Gas and O_ThreeGas was generated.
[0092]
The conditions for electrolysis are as follows.
Voltage: about 3V
Current: about 35A
[0093]
Under these conditions, the generation amount of ozone gas was 1.3 g / hour, and the generation amount of hydrogen gas was 1.3 g / hour.
[0094]
O_ThreeO at the gas dissolution tower 2 outlet_ThreeThe ozone concentration in water was about 10 ppm.
[0095]
This O_ThreeThe removal effect of organic substances in water was tested by the following procedure.
The organic substance removal effect was evaluated by examining the contact angle of water droplets. That is, water droplets were attached to the cleaned and dried substrate surface, the contact angle of the water droplets was examined, and the contact angle was evaluated. The smaller the contact angle, the easier the water droplets get wet.
[0096]
A glass substrate for TFT-LCD was prepared. The contact angle of water droplets at the initial stage (before cleaning) of this substrate was about 20 degrees. This substrate is O_ThreeWashing was performed with water while changing the washing time between 5 and 60 seconds. The contact angle after cleaning was examined. The result is shown in FIG.
[0097]
According to the cleaning with ozone water produced in this example, the contact angle can be made 5 degrees or less if the cleaning time is secured for 5 seconds or more.
[0098]
For comparison, FIG. 11B shows the result of cleaning with ozone generated by ultraviolet irradiation.
[0099]
On the other hand, H₂Gas is also H₂It is dissolved in ultrapure water in the dissolution tower 3 and H₂Water was produced. This H₂H for water₂In the mixing device 5 arranged in the middle of the water pipe, the chemical solution (NH_FourOH) was added.
[0100]
NH in cleaning room_FourOH added H₂The water had the following characteristics:
pH: 10.5
ORP (redox potential): -630 mV vs NHE
H₂Concentration: 0.98ppm
[0101]
The following tests were conducted on the cleaning ability of this hydrogen water.
A glass substrate for TFT-LCD (150 × 150 mm square) was prepared, and this substrate was immersed in an alumina particle suspension to adhere particles to the substrate surface.
[0102]
The substrate on which the particles were adhered was washed while irradiating ultrasonic waves using the hydrogen water, and the number of residual particles after washing was examined.
[0103]
The cleaning conditions are as follows.
Ultrasonic frequency: 1.5 MHz
Hydrogen water flow rate: 0.8L / min
Cleaning time: 1 minute
[0104]
The test results are shown in FIG.
FIG. 12 also shows the result of cleaning with ultrapure water and the result of cleaning with cathode water at pH = 10.5.
[0105]
As can be seen from FIG. 12, H produced and supplied according to the present invention.₂The cleaning effect of the water cleaning solution is the same as the cleaning effect of conventional electrolytic ionic water. Therefore, it can be seen that a compact cleaning liquid production / supply system can be provided without deteriorating the cleaning effect.
[0106]
(Example 2)
Washing water was produced using the apparatus shown in FIG. 3, supplied to the washing chamber, and the same washing as in Example 1 was performed.
[0107]
The same results as in Example 1 were obtained with respect to the effect of removing organic substances and particles.
[0108]
Just H₂After washing with water, 10 deposits of metal considered to be eluted from the electrode as compared with Example 1 were observed.^Tenatms / cm²It was accepted in the order.
[0109]
(Example 3)
Washing water was produced using the apparatus shown in FIG. 4 and supplied to the washing chamber, and the same washing as in Example 1 was performed.
[0110]
The same results as in Example 1 were obtained with respect to the effect of removing organic substances and particles.
[0111]
Just H₂After washing with water, 10 deposits of metal considered to be eluted from the electrode as compared with Example 1 were observed.^Tenatms / cm²It was accepted in the order.
[0112]
Example 4
Brush cleaning was performed under the following conditions by the cleaning system shown in FIGS.
Substrate: Glass with alumina particles attached
Washing water: H₂Water + NH_FourOH
H₂Concentration: 0.98ppm
pH: 10.5
ORP: -630 mV vs NHZ
Flow rate: 2L / min
Brush material: Nylon
[0113]
On the other hand, for comparison, brush cleaning similar to the above was performed using pure water having a specific resistance of 18 MΩcm as cleaning water.
[0114]
The cleaning results are shown in FIG. As shown in FIG.₂Water + NH_FourBrush cleaning with OH shows a cleaning effect superior to brush cleaning with pure water. This is H₂Water + NH_FourThis is because brush cleaning with OH is effective in preventing reattachment of particles.
[0115]
(Example 5)
The following high-pressure jet cleaning was performed by the cleaning system shown in FIGS.
Substrate: Glass with alumina particles attached
Washing water: H₂Water + NH_FourOH
H₂Concentration: 0.98ppm
pH: 10.5
ORP: -630 mV vs NHZ
Flow rate: 150cc / min
Jet pressure: 70kgW
[0116]
On the other hand, for comparison, high-pressure jet cleaning was performed at the same jet pressure using pure water having a specific resistance of 18 MΩcm.
[0117]
The cleaning result is shown in FIG. As shown in FIG.₂Water + NH_FourThe high-pressure jet cleaning with OH shows a cleaning effect superior to the high-pressure jet cleaning with ultrapure water.
[0118]
(Example 6)
The following ultrasonic cleaning was performed by the cleaning system shown in FIGS.
Substrate: Glass with alumina particles attached
Washing water: H₂Water + NH_FourOH
H₂Concentration: 0.98ppm
pH: 10.5
ORP: -630 mV vs NHZ
Flow rate: 0.8L / min
Ultrasonic frequency: 1.5 MHz
[0119]
On the other hand, ultrasonic cleaning was performed at the same frequency using pure water having a specific resistance of 18 MΩcm for comparison.
[0120]
The cleaning result is shown in FIG. As shown in FIG.₂Water + NH_FourUltrasonic cleaning with OH shows a cleaning effect superior to ultrasonic cleaning with ultrapure water. In the case of pure water, static electricity is generated.₂Water + NH_FourIn the case of OH, generation of static electricity can be prevented and the insulating film can be used for cleaning.
[0121]
(Example 7)
The following high-pressure jet cleaning was performed by the cleaning system shown in FIGS.
Substrate: Glass with alumina particles attached
Washing water: H₂Water + NH_FourOH
H₂Concentration: 0.98ppm
pH: 10.5
ORP: -630 mV vs NHZ
Flow rate: 2L / min
Gas flow rate: 10 NL / min
[0122]
On the other hand, for comparison, high-pressure jet cleaning was performed under the same conditions using pure water having a specific resistance of 18 MΩcm.
[0123]
The washing results are shown in FIG. As shown in FIG.₂Water + NH_FourThe high-pressure jet cleaning with OH shows a cleaning effect superior to the high-pressure jet cleaning with ultrapure water. Moreover, rinse properties, such as peeling and etching, were also good.
[0124]
【The invention's effect】
According to the invention, the following various effects are achieved.
[0125]
(1) Cleaning liquids for organic substances and particles are manufactured by the same apparatus, and a very compact cleaning water supply system can be configured. The supply system, which was large in the past, has been made compact. As a result, since the system can be arranged near the cleaning chamber, ozone can be used efficiently and the cleaning effect can be enhanced.
[0126]
O_ThreeGas and H₂Each gas is dissolved in pure water in a dissolution tower, and a clean cleaning solution free from contamination by electrodes can be supplied to the cleaning chamber.
[0127]
▲ 2 ▼ H₂Since pH adjustment chemicals can be added to water, H₂The pH of water can be adjusted appropriately (for example, pH 7 or more), and a cleaning liquid with high particle removal efficiency can be supplied.
[0128]
NH_FourOH exhibits higher particle removal efficiency than other pH adjusting chemicals.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of a cleaning water production / supply system according to an embodiment of the invention.
FIG. 2 is an enlarged view of the electrolysis tank of FIG.
FIG. 3 is a conceptual diagram of a cleaning water production / supply system according to another embodiment of the present invention.
FIG. 4 is a conceptual diagram of a cleaning water production / supply system according to still another embodiment of the present invention.
FIG. 5 is a sectional view of a cleaning system according to an embodiment of the invention.
FIG. 6 is a sectional view of a cleaning system according to another embodiment of the invention.
FIG. 7 is a sectional view of a cleaning system according to another embodiment of the invention.
FIG. 8 is a sectional view of a cleaning system according to another embodiment of the invention.
FIG. 9 is a sectional view of a cleaning system according to another embodiment of the invention.
10A and 10B are cross-sectional views of the high-pressure injection nozzle shown in FIG.
FIGS. 11A and 11B are graphs showing the cleaning effect of ozone water, in which FIG. 11A relates to Example 1 and FIG. 11B relates to a conventional example.
FIG. 12 is a graph showing the cleaning effect of hydrogen water.
13 is a graph showing the cleaning effect of Example 4. FIG.
14 is a graph showing the cleaning effect of Example 5. FIG.
15 is a graph showing the cleaning effect of Example 6. FIG.
16 is a graph showing the cleaning effect of Example 7. FIG.
[Explanation of symbols]
1 electrolysis tank,
2 O_ThreeGas melting tower,
3 H₂Gas melting tower,
4a cathode electrode,
4b Anode electrode,
5 mixing device,
6 pumps,
7 Ultrapure water supply line,
8,10 H₂Water piping,
9 Ozone water piping,
11 O_ThreeGas exhaust piping,
12 H₂Gas exhaust piping,
15 cathode chamber,
15a, 15b cathode chamber,
21 cathode chamber,
22 anode chamber,
23 Cathode side catalyst,
24 anode side catalyst,
25 ion exchange membrane,
26 DC power supply,
30 H₂Water piping,
101 Cleaning room,
102,103 brushes,
104,105 brush washing tank,
106,107 ultrasonic element,
118,119 piping,
204 Cleaning room,
210, 211 high pressure jet nozzle,
301 Ultrasonic cleaning tank,
302 ultrasonic bath,
303,304 ultrasonic element,
305 Ultrasonic transmission liquid,
306 H₂water,
309 Cleaning room,
402 Cleaning room,
403 ultrasonic element,
404 ultrasonic shower,
405 gas inlet,
901 Cleaning room,
910,911 high pressure gas injection nozzle,
915 gas inlet,
916 passage,
917 liquid inlet,
918 nozzle tip,
930 Gas inlet tube.

Claims (16)

An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ (ozone) gas in the anode chamber and generating H ₂ (hydrogen) gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
H ₂ gas discharge piping for discharging H ₂ gas generated in the cathode chamber to the outside of the cathode chamber;
An H ₂ gas dissolution tower connected to the H ₂ gas discharge pipe for dissolving H ₂ gas in pure water to produce H ₂ water;
An H ₂ water pipe for introducing H ₂ water from the H ₂ gas dissolution tower into the cleaning chamber;
A cleaning water production / supply system characterized by comprising: The cleaning water production / supply system according to claim 1, further comprising means for adding NH ₄ OH to the H ₂ water. An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ gas in the anode chamber and generating H ₂ gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
An H ₂ water pipe for introducing H ₂ water produced by dissolving H ₂ gas generated in the cathode chamber into pure water in the cathode chamber from the cathode chamber to the cleaning chamber;
A cleaning water production / supply system characterized by comprising: An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ gas in the anode chamber and generating H ₂ gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
H ₂ gas discharge piping for discharging H ₂ gas generated in the cathode chamber to the outside of the cathode chamber;
An H ₂ gas dissolution tower connected to the H ₂ gas discharge pipe for dissolving H ₂ gas in pure water to produce H ₂ water;
An H ₂ water pipe for introducing H ₂ water from the H ₂ gas dissolution tower into the cleaning chamber;
Having at least
The cleaning system further comprises a brush for slidingly cleaning the object to be cleaned in the cleaning chamber. The cleaning system according to claim 4, further comprising an ultrasonic element that applies an ultrasonic wave of 0.2 MHz to 5 MHz to the H ₂ water introduced into the cleaning chamber. A brush cleaning tank for cleaning the brush is provided in the cleaning chamber, and an ultrasonic element that applies ultrasonic waves of 0.2 MHz to 5 MHz to H ₂ water supplied to the brush cleaning tank is provided. The cleaning system according to claim 4. An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ gas in the anode chamber and generating H ₂ gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
H ₂ gas discharge piping for discharging H ₂ gas generated in the cathode chamber to the outside of the cathode chamber;
An H ₂ gas dissolution tower connected to the H ₂ gas discharge pipe for dissolving H ₂ gas in pure water to produce H ₂ water;
An H ₂ water pipe for introducing H ₂ water from the H ₂ gas dissolution tower into the cleaning chamber;
Having at least
The cleaning system further comprises a high-pressure jet nozzle for injecting H ₂ water at a high pressure into the object to be cleaned. An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ gas in the anode chamber and generating H ₂ gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
H ₂ gas discharge piping for discharging H ₂ gas generated in the cathode chamber to the outside of the cathode chamber;
An H ₂ gas dissolution tower connected to the H ₂ gas discharge pipe for dissolving H ₂ gas in pure water to produce H ₂ water;
An H ₂ water pipe for introducing H ₂ water from the H ₂ gas dissolution tower into the cleaning chamber;
Having at least
The cleaning system further includes an ultrasonic element that applies an ultrasonic wave of 0.2 MHz to 5 MHz to the H ₂ water introduced into the cleaning chamber. An electrolysis tank having an anode chamber and a cathode chamber, generating O ₃ gas in the anode chamber and generating H ₂ gas in the cathode chamber;
And the O ₃ gas discharge pipe for discharging the O ₃ gas generated in the anode chamber to the anode outside,
An O ₃ gas dissolution tower connected to the O ₃ gas discharge pipe for dissolving O ₃ gas in pure water to produce O ₃ water;
An O ₃ water pipe for introducing O ₃ water from the O ₃ gas dissolution tower into the cleaning chamber;
H ₂ gas discharge piping for discharging H ₂ gas generated in the cathode chamber to the outside of the cathode chamber;
An H ₂ gas dissolution tower connected to the H ₂ gas discharge pipe for dissolving H ₂ gas in pure water to produce H ₂ water;
An H ₂ water pipe for introducing H ₂ water from the H ₂ gas dissolution tower into the cleaning chamber;
Having at least
The cleaning system further comprises a gas injection nozzle for injecting the H ₂ water introduced into the cleaning chamber onto the object to be cleaned with gas. O ₃ gas and H ₂ gas are generated by electrolysis,
The O ₃ gas is dissolved in pure water to produce O ₃ water, and the H ₂ gas is dissolved in pure water to produce H ₂ water.
A method for producing and supplying cleaning water, wherein the O ₃ water and the H ₂ water are respectively sent to one or more cleaning chambers. The method for producing and supplying washing water according to claim 10, wherein a pH adjusting chemical solution is added to H ₂ water. The method for producing and supplying washing water according to claim 11, wherein the pH adjusting chemical is NH ₄ OH. O ₃ gas and H ₂ gas are generated by electrolysis,
The O ₃ gas is dissolved in pure water to produce O ₃ water, and the H ₂ gas is dissolved in pure water to produce H ₂ water.
Sending the O ₃ water and the H ₂ water to one or more cleaning chambers,
A cleaning method, wherein an object to be cleaned is cleaned with a brush in the cleaning chamber. O ₃ gas and H ₂ gas are generated by electrolysis,
The O ₃ gas is dissolved in pure water to produce O ₃ water, and the H ₂ gas is dissolved in pure water to produce H ₂ water.
Sending the O ₃ water and the H ₂ water to one or more cleaning chambers,
A cleaning method characterized by cleaning an object to be cleaned by jetting the H ₂ water at a high pressure in a cleaning chamber. O ₃ gas and H ₂ gas are generated by electrolysis,
The O ₃ gas is dissolved in pure water to produce O ₃ water, and the H ₂ gas is dissolved in pure water to produce H ₂ water.
Sending the O ₃ water and the H ₂ water to one or more cleaning chambers,
A cleaning method comprising cleaning an object to be cleaned by applying ultrasonic waves of 0.2 MHz to 5 MHz to the H ₂ water in a cleaning chamber. O ₃ gas and H ₂ gas are generated by electrolysis,
The O ₃ gas is dissolved in pure water to produce O ₃ water, and the H ₂ gas is dissolved in pure water to produce H ₂ water.
Sending the O ₃ water and the H ₂ water to one or more cleaning chambers,
A cleaning method, wherein an object to be cleaned is cleaned by injecting the H ₂ water with a gas in a cleaning chamber.

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