JP4205106B2 - Method and apparatus for cleaning phase shift photomask - Google Patents

Description

  The present invention relates to a photomask cleaning method and a cleaning apparatus that are used as a master in a photoengraving process for manufacturing a semiconductor (LSI) and are required to obtain an extremely clean surface.

  A photomask serves as a master when transferring a pattern of an integrated circuit to the surface of a wafer with a transfer device in a photoengraving process of semiconductor manufacturing. The pattern formed on the surface is defective or unresolved. If there is a foreign matter exceeding the image limit, it will be transferred as a pattern onto the wafer. Therefore, any defect or foreign substance exceeding the resolution limit is not allowed on the surface of the photomask.

  In addition, with the high integration and miniaturization of integrated circuits, the allowable defects and the size of foreign matter have been required up to 0.5 μm.

  Conventional photomask cleaning uses RCA cleaning (cleaning using a mixed solution of acid such as sulfuric acid and hydrogen peroxide solution, or a mixed solution of alkaline chemical solution such as ammonia water and hydrogen peroxide solution) that has been proven in wafer cleaning. A cleaning method based on the base was adopted. The flow of the cleaning process is shown in FIG. A conventional photomask cleaning process will be described with reference to FIG.

  First, in the process of Step 1, organic substances such as resist and solvent residue present on the photomask surface are decomposed, and cleaning using a mixed solution of high-temperature sulfuric acid and hydrogen peroxide solution is performed to remove metal impurities. To do. This process improves the wettability of the photomask surface and increases the efficiency of subsequent cleaning.

  Next, in step 2, rinsing with high-temperature pure water is performed in order to remove residual chemicals such as sulfuric acid remaining on the photomask surface.

  Next, in the process of Step 3, immersion cleaning is performed in a mixed solution of warmed ammonia and hydrogen peroxide water for the purpose of removing the attached foreign matter. At this time, in order to remove foreign substances more effectively, megasonic ultrasonic waves may be applied to the immersion tank.

  Next, also after this process, as shown in the process of step 4, rinsing with pure water is necessary.

  Finally, the photomask rinsed with pure water in step 5 is dried.

  In the process of Step 3, cleaning may be performed by applying ultrasonic waves such as megasonic using only pure water or pure water to which a detergent is added without using a mixed solution of ammonia and hydrogen peroxide.

  In the immersion cleaning method as described above, the efficiency of the cleaning process can be improved by immersing a plurality of photomasks in the tank at the same time. However, the contamination of the heavily contaminated photomask is another relatively clean photomask. May be contaminated.

  In order to improve this point, a chemical solution for cleaning one photomask is disposed as a disposable method, and a chemical solution, pure water, or the like is poured from a fixed or swinging nozzle onto a photomask surface rotated horizontally. A cleaning method (spinning method) in which a chemical solution for cleaning one photomask is disposed is also performed.

  In the spin-type cleaning method, mechanical cleaning such as high-pressure jet pure water rinse or megasonic pure water rinse may be performed as a means for effectively removing foreign matters.

  In the conventional cleaning method as shown in FIG. 11, if sulfuric acid remains on the surface of the photomask because of insufficient cleaning after the treatment with sulfuric acid / hydrogen peroxide solution (step 1), the photomask Cloudiness occurs on the surface.

  When such fogging occurs on the surface of the photomask, the transmittance of the non-patterned portion of the photomask (the portion through which light is transmitted when transferred to the wafer) decreases, and the dimensions of the resist patterned on the wafer vary. This causes a disconnection of wiring in the integrated circuit (LSI) and deteriorates the characteristics of the LSI itself.

  In the conventional cleaning method, a large amount of pure water is rinsed after the treatment with sulfuric acid / hydrogen peroxide solution (step 1) in order to prevent this residual sulfuric acid, or rinse with warm pure water in which pure water is heated (in step 2). Process), but a large amount of pure water was consumed and electric energy for heating the pure water was consumed.

  In addition, in the immersion method cleaning in the ammonia / hydrogen peroxide treatment process (step 3) for the purpose of removing foreign substances, a plurality of photomasks are treated with the same chemical solution, so that the chemical solution is not deteriorated or contaminated. The frequency of chemical replacement increases and the amount of chemical used increases.

  Further, when the cleaning efficiency (cleaning yield) is poor, the number of times of cleaning per photomask increases, so that the amount of chemical solution used, the amount of pure water used, the amount of energy used such as electricity increases.

  Recently, a phase shift photomask has been developed and put into practical use to partially change the phase transmitted through the photomask to increase the resolution of the resist on the wafer.

  The MoSiON film is a material used for a light-shielding film of a halftone photomask that is a kind of this phase shift photomask. However, in the conventional strong alkali cleaning treatment such as immersion treatment in ammonia / hydrogen peroxide water, The transmittance and phase angle fluctuated greatly, and the quality when shipped as a product could not be maintained.

  Therefore, the cleaning process (step 3) using ammonia / hydrogen peroxide solution, which is effective for removing foreign matters, cannot actually be performed on the MoSiON film, and only pure water or cleaning using a detergent is performed. Residual foreign matter was a problem.

The present invention has been made to solve such problems,
(1) The chemical solution (mainly sulfuric acid) remaining on the photomask surface after the cleaning process is effectively removed to improve the quality of the photomask.
(2) With a small amount of chemical solution, the foreign matter removal effect is equivalent to or better than that of conventional cleaning methods, reducing the amount of chemical solution and pure water used.
(3) Moreover, foreign matter removal is effectively performed without changing the transmittance of the light shielding film (MoSiON film) of the phase shift photomask.
An object of the present invention is to provide a photomask cleaning method and a cleaning apparatus that can perform the same.

A phase shift photomask cleaning method according to the present invention is a phase shift photomask cleaning method in which a metal oxynitride film of molybdenum silicide is formed on the surface of a glass substrate, using a mixed solution of sulfuric acid and hydrogen peroxide solution. A first step of cleaning the phase shift photomask; a second step of cleaning the phase shift photomask using anode water; and a third step of cleaning the phase shift photomask using cathode water. And a fourth step of performing a drying process on the phase shift photomask after the first, second and third steps, wherein the third step has an ammonia concentration of less than 0%. large washing the phase shift photomask using 1% or less of the cathode water, the third step, characterized in Rukoto continuously performed after the second step That.

A phase shift photomask cleaning apparatus according to the present invention is a phase shift photomask cleaning apparatus in which a metal oxynitride film of molybdenum silicide is formed on a glass substrate surface. An acid bath for cleaning the phase shift photomask using, a rinse bath for cleaning the phase shift photomask using the anode water generated by the electrolyzed water generating unit, and a cathode water generated by the electrolyzed water generating unit. A foreign matter removal tank that cleans the phase shift photomask using a liquid, a drying tank that performs a drying process on the phase shift photomask, and a cleaning liquid that is supplied to each of the acid tank, the rinse tank, and the foreign substance removal tank Cleaning liquid supply / control means for controlling the concentration to a predetermined concentration or temperature. In the foreign matter removal tank, the ammonia concentration is 0%. Ri is large than 1% of the cathode water is used, said washing with foreign matter removing tank, continuously performed after the washing with the rinse tank is characterized in Rukoto.

  According to the photomask cleaning method of the present invention, even when the anode water is at room temperature (25 ° C.), it has the same ability to remove residual sulfuric acid as when conventional high-temperature pure water is used. In addition, there is no need to heat the anode water as the cleaning liquid to a high temperature, and there is an effect that consumption of electric energy can be reduced.

  In addition, since the third step uses cathodic water, the foreign substance attached to the surface of the photomask can be removed without impairing the transmittance even with respect to the phase shift photomask in which the MoSiON film is formed as a light shielding film. There is an effect that can be done.

  In addition, since the cathode water used in the third step contains ammonia, the foreign matter adhered to the surface of the photomask can be more effectively removed from the phase shift photomask in which the MoSiON film is formed as a light shielding film. In addition to being able to perform the treatment, there is an effect that the amount of chemical liquid or pure water used can be reduced.

  Further, according to the photomask cleaning apparatus of the present invention, the anode water has a high cleaning ability even at about room temperature, so it is not necessary to heat it to a high temperature, and the consumption of electric energy can be reduced.

  Further, since cathode water is used as a cleaning solution, the effect of removing foreign matter adhering to the surface of the photomask can be performed without damaging the transmittance even for the phase shift photomask in which the MoSiON film is formed as a light shielding film. There is.

  In addition, since the cathode water used in the foreign matter removal tank contains ammonia, the foreign matter adhered to the surface of the photomask can be more effectively removed from the phase shift photomask in which the MoSiON film is formed as a light shielding film. Can be used, and the amount of chemical liquid or pure water used can be reduced.

Embodiment 1 FIG.
In the first embodiment, a method for effectively removing residual sulfate ions remaining on the surface of a photomask after treatment with sulfuric acid / hydrogen peroxide solution will be described.

  In FIG. 1, a glass substrate for photomask having a 5 inch square of about 2 mm thickness is dipped in sulfuric acid, and then dipped in various rinsing liquids (pure water, dilute ammonia water, anode water) in an overflow tank. Then, the result of having analyzed the amount of sulfate ion which remained on this glass substrate by ion chromatography is shown.

As shown in FIG.
A1: pure water at room temperature (25 ° C.),
A2: 40 ° C. pure water,
A3: pure water at 60 ° C.
A4: 80 ° C. pure water,
B1: diluted ammonia water at room temperature with a hydrogen ion concentration of pH 10;
B2: A small amount of ammonia water was added to adjust the hydrogen ion concentration pH to about 10.
Room temperature cathode water,
C1: cathode water at room temperature (25 ° C.),
C2: anode water at 30 ° C.
C3: anode water at 40 ° C.
C4: anode water at 60 ° C.
C5: anode water at 80 ° C.,
Was used.

  Anode water is electrolyzed water in which pure water is electrolyzed and oxygen produced in the anode tank is dissolved in a substantially saturated state, and cathode water is hydrogen produced in the cathode tank is dissolved in a substantially saturated state. It is the electrolyzed water of the state which was made, and the production method is mentioned later.

In the figure, the vertical axis represents the amount of residual sulfate ions (unit: ion / cm ² ). As is clear from the figure, the temperature of pure water used in the rinse with pure water (A1 to A4) is room temperature (25 The amount of residual sulfate ions decreases as the temperature increases from 80 ° C. to 80 ° C.

  Further, the amount of residual sulfate ions in the glass substrate similarly rinsed with dilute ammonia water (B1) having a pH of 10 is smaller than that in the case of rinsing with pure water at room temperature, compared with the case of rinsing with pure water (A3) at 60 ° C. However, the residual amount was small.

  Also, using a glass substrate with a CrON film (a kind of general light-shielding film that is not a light-shielding film for phase-shifting photomasks) formed on one side as a light-shielding film, the surface of the glass substrate due to the difference in the rinse treatment after sulfuric acid treatment As a result of an experiment on the occurrence of cloudy weather, it was confirmed that clouding had already occurred 1 day after the completion of cleaning only by rinsing with pure water at room temperature (25 ° C.). In the photomask blank rinsed with pure water at 60 ° C., no clouding was confirmed after 1 day, but thin clouding was confirmed after about 1 month. However, cloudiness was not confirmed even after about one month in the photomask substrate rinsed with diluted ammonia water.

  From the above results, if the amount of sulfuric acid remaining on the photomask substrate surface by rinsing after sulfuric acid treatment is the level of the residual sulfate ion amount achieved with dilute ammonia water (the level indicated by H in FIG. 1), photo It is considered that no fogging occurs on the mask.

  However, as is apparent from FIG. 1, in order to achieve this condition, it is necessary to heat the pure water alone to at least about 60 ° C., preferably about 80 ° C.

  Moreover, as shown in FIG. 1, when the same rinse was performed using the anode water (C1) of room temperature (25 degreeC) produced | generated by electrolyzing pure water, it rinsed with the pure water (A3) of about 60 degreeC. Sulfuric acid can be removed to the same level.

  Further, rinsing with 30 ° C. anode water (C1) can remove residual sulfuric acid to almost the same level (level indicated by H in FIG. 1) when rinsing with about 80 ° C. pure water (A4). I found that I can do it.

  Moreover, if the rinse is performed using anode water (C2 to C5) heated to 30 ° C. or higher, residual sulfate ions can be more effectively removed.

  By using anode water in this way, residual sulfate ions can be effectively removed. That is, compared with the case of pure water alone, a sufficient sulfuric acid removal effect can be obtained with a lower temperature anode water, so that heating as in the case of pure water is not required, and the amount of electricity used can be reduced. Moreover, since the removal effect is improved by changing from pure water to anode water, the rinsing time can be shortened, and the amount of pure water used can be reduced.

  As described above, in the present embodiment, rinsing is performed using anode water to remove residual sulfate ions after the sulfuric acid / hydrogen peroxide solution treatment, so that even if the heating is as low as about 30 ° C. Sulfate ions remaining on the mask surface can be effectively removed.

  Since the removal efficiency of residual sulfate ions is increased in this manner, the processing time can be shortened, and the amount of pure water used and the amount of electric energy consumed for heating can be reduced.

  The anode water is electrolyzed water in which oxygen produced in the anode tank by electrolyzing pure water is dissolved in a substantially saturated state, and the cathode water is hydrogen produced in the cathode tank. Is an electrolyzed water in a substantially saturated state, and an example of the electrolyzed water generating device and its generating mechanism will be described with reference to FIG.

  2, 3 is a positive electrode, 4 is an anode tank (anode tank), 5 is a negative electrode, 6 is a cathode tank (cathode tank), 7 is an intermediate tank, 8 is an in-side pipe for injecting pure water, and 9 is The ion exchange membrane 10 is anode water generated in the anode tank 4, and 11 is cathode water generated in the cathode tank 6. The chemical reaction formula shown in the figure is a reaction formula showing electrolysis of pure water at the positive electrode 3 and the negative electrode 5.

  As shown in the figure, the electrolyzed water generator comprises an anode tank (anode tank) 4 provided with a positive electrode 3, a cathode tank (cathode tank) 6 provided with a negative electrode 5, and an intermediate tank 7 filled with an ion exchange resin. It consists of three tanks. Further, the intermediate tank 7 and the anode tank (anode tank) 4 and the intermediate tank 7 and the cathode tank (cathode tank) 6 are separated by an ion exchange membrane 9, respectively.

When pure water is injected from the in-side pipe 8 and positive and negative potentials are applied to the positive electrode 3 and the negative electrode 5, respectively, the exchange groups adjacent to the exchange groups of the ion exchange resin are H ⁺ and OH ^−. It moves in the direction of the electric field by repeatedly binding / dissociating with the electrode, finally reaches the electrode surface, and becomes an oxygen molecule (O ₂ ) at the positive electrode 3 and a hydrogen molecule (H ₂ ) at the negative electrode 5 by the oxidation-reduction reaction. Dissolve in. The exchange group deprived of H ⁺ and OH ⁻ continuously dissociates pure water to form a new ionic bond.

  By electrolyzing the pure water in this way, anode water 10 in which oxygen is dissolved in a substantially saturated state is obtained from the anode tank 4, and cathode water 11 in which hydrogen is dissolved in a substantially saturated state is obtained from the cathode tank 6. .

  In some cases, an electrolyzed water generating apparatus including two tanks in which the anode tank 4 and the cathode tank 6 are separated by the ion exchange membrane 9 can be used without the intermediate tank 7.

Embodiment 2. FIG.
In the second embodiment, a method for effectively removing fine dust and fine foreign matters such as metal and organic matter adhering to the surface of the photomask (particularly the surface of the light shielding film) during the manufacturing process will be described.

  In general, this step is performed after the step of removing residual sulfate ions remaining on the surface of the photomask after the treatment with sulfuric acid / hydrogen peroxide solution as described in the first embodiment.

FIG. 3 shows a quartz product having an ultrasonic vibrator as shown in FIG. 4 after depositing silica (SiO ₂ ) particles as foreign matter on the surface of a photomask having a CrON film as a light shielding film. 3 shows the removal rate of silica particles when immersed in various chemicals in an overflow tank and subjected to megasonic sonication.

  In FIG. 4, 21 is an ultrasonic transducer, 22 is an inner tank of the overflow tank, and 23 is an outer tank of the overflow tank.

As shown in FIG. 3, chemicals are: A: pure water,
B: Dilute aqueous ammonia (pH 10),
C: 0.1% ammonia water
D: Cathode water,
E: Cathode water having a pH of about 10 by adding a small amount of ammonia,
F: An experiment was performed using cathode water added with 0.1% ammonia, and the removal rate of foreign matters in each case was confirmed.

  The foreign matter removal rate was determined from the value obtained by dividing the number of particles removed by ultrasonic treatment by the number of particles present before the treatment.

  As is clear from the figure, the removal rates were 0.1% and −30% in pure water (A) and dilute ammonia water (B) at pH 10, respectively, and silica particles imitating foreign matter were hardly removed. .

  However, in the cathode water (D) produced by electrolyzing pure water, particles were removed at a removal rate of 30.6%.

  Furthermore, the removal rate improved to 67.2% in the cathode water (E) produced by electrolyzing pure water having a hydrogen ion concentration pH of about 10 by adding a very small amount of ammonia water.

  Further, in the cathode water (F) to which 0.1% of ammonia was added, the removal rate in the ammonia water (C) having a concentration of 0.1% was 52.0%, whereas 99% Particles were removed with a removal rate as high as 2%.

  In this way, by performing megasonic ultrasonic treatment in the cathode water, the particulate foreign matter adhering to the surface of the photomask can be effectively removed.

  It was also found that the removal efficiency of foreign particles adhering to the surface of the photomask can be greatly improved by using cathode water to which a small amount of ammonia is added.

  The concentration of ammonia to be used is about 0.003% at a pH of 10, and the cleaning effect can be improved at such an extremely low concentration, so that the chemical solution can be greatly reduced as compared with the conventional cleaning method.

  In addition, the amount of pure water used for the subsequent rinsing can be greatly reduced as compared with the case where a thick chemical is used.

  Furthermore, the cleaning process time for removing foreign substances can be shortened by improving the cleaning ability, and energy such as electricity can be saved.

Embodiment 3 FIG.
In the third embodiment, an optimum cleaning method for removing foreign matters in the case of a phase shift photomask such as a halftone photomask will be described.

  FIG. 5 shows the change in the transmittance after the cleaning treatment using the alkaline chemical solution of the MoSiON film which is the light shielding film of the halftone photomask.

  The glass substrate on which the MoSiON film was formed to a thickness of about 0.1 μm was immersed in various cleaning solutions for 2 hours, and the variation (%) in transmittance at a wavelength of 248 nm was confirmed.

As the cleaning liquid, as shown in FIG.
A: 1% ammonia water B: Ammonia / hydrogen peroxide water,
C: 5% strength aqueous ammonia,
D: 10% ammonia water,
E: Cathode water,
F: Cathode water with a small amount of ammonia added (pH 10)
The experiment was conducted using

  As a result, the transmittance increased by 1.04% in the treatment of ammonia / hydrogen peroxide solution (B) that was used for the purpose of removing foreign matters in the conventional photomask cleaning.

  Further, in pure water (C) having an ammonia concentration of 5% and pure water (A) having an ammonia concentration of 1%, the transmittances increased by 0.9% and 0.27%, respectively.

  However, the cathode water (E) produced by electrolyzing pure water or the cathode water (F) having a pH of 10 added with a small amount of ammonia increased the transmittance only by 0.02% and 0.1%, respectively.

  If the transmittance of the MoSiON film, which is a light-shielding film formed on the surface of the photomask, fluctuates, the resist shape and dimensions when the circuit pattern is transferred onto the wafer will fluctuate, eventually degrading the LSI characteristics. Therefore, the transmittance is strictly controlled.

  The conventional treatment with ammonia / hydrogen peroxide solution (B) cannot be used for cleaning the photomask on which the MoSiON film is formed because the transmittance varies greatly.

  However, the amount of fluctuation in the cathodic water (E) or the cathodic water (F) having a pH of 10 with a small amount of ammonia added is acceptable.

FIG. 6 shows the removal rate of alumina particles when megasonic ultrasonic treatment in various liquids of alumina (Al ₂ O ₃ ) particles adhered to the MoSiON film as foreign matters is performed.

  The removal rate was calculated from the value obtained by dividing the number of particles removed by the megasonic treatment by the number of particles present before the treatment.

In addition, as shown in FIG.
A: Pure,
B: pH 10 dilute aqueous ammonia,
C: Cathode water,
D: Cathode water having a pH of 10 with a small amount of ammonia added,
E: Cathode water with ammonia concentration of 1%,
F: ammonia / hydrogen peroxide solution,
The experiment was conducted using

  As a result, the removal rates in pure water (A), dilute ammonia water (B), and cathode water (C) were 5.0%, -0.2%, and 0.0%, respectively, and alumina particles as foreign matter Is hardly removed.

  However, it was removed at a removal rate of 31.6% in the cathode water (D) to which a small amount of ammonia was added.

  Further, the amount of ammonia added was increased and the cathode water having an ammonia concentration of 1% was removed at a removal rate of 39.6%.

  In the ammonia / hydrogen peroxide solution (F) effective for removing foreign substances used in the past, it is removed at a removal rate of 30.1%. By using the cathode water (D) to which a small amount of ammonia is added, It has been found that the same foreign matter removing effect as that obtained by the conventional treatment in ammonia / hydrogen peroxide solution (F) can be obtained.

  Therefore, from the results shown in FIGS. 5 and 6, it is known that the transmittance of the MoSiON film is not changed by performing the foreign matter cleaning process using the cathode water to which a small amount of ammonia having a concentration of 0.003% is added. It was found that a cleaning effect equivalent to or better than that can be obtained.

  Further, if the ammonia concentration is 1% or less, it is possible to suppress the fluctuation in transmittance to a control standard (for example, 0.5%) or less and to increase the cleaning efficiency by limiting the cleaning process to a short time.

  In Embodiments 1 to 3, the cleaning effect can be further improved by heating the cleaning chemicals such as cathode water to be used and cathode water to which a small amount of ammonia water is added.

  Further, in Embodiments 1 to 3, by using the overflow tank as shown in FIG. 4 and performing the cleaning process while irradiating ultrasonic waves, the cleaning ability can be further increased.

  In the second or third embodiment, the same effect can be obtained by using a weakly alkaline chemical solution by adding a trace amount of an electrolyte substance such as KOH in place of ammonia added to the cathode water.

Embodiment 4 FIG.
In the fourth embodiment, the entire process of the photomask cleaning process will be described. FIG. 7 is a diagram showing the overall flow of a high-performance cleaning process according to the present invention.

  First, in step 1, a mixed solution of high-temperature sulfuric acid and hydrogen peroxide solution is used to decompose organic substances such as resist and solvent residues on the photomask surface, improve surface wettability, and remove metal impurities. Wash with.

  Next, in the process of Step 2, a cleaning process is performed to remove the remaining chemical such as sulfuric acid remaining on the photomask surface. Specifically, as shown in the first embodiment, the cleaning process is performed using the anode water. Anode water has the ability to remove residual sulfuric acid equivalent to or higher than conventional high-temperature pure water even with a slight heating of about 30 ° C, so that the treatment time can be shortened and the amount of pure water used can be reduced. Electric energy consumption for reduction and heating can be reduced.

  Next, in the step 3, a process for removing the attached foreign matter is performed. Specifically, when the light shielding film formed on the photomask to be cleaned is a CrON film, as shown in the second embodiment, the supersonic wave is added in the cathode water or the cathode water to which a small amount of ammonia is added. By performing the sonic treatment, fine particles adhering to the surface of the photomask can be effectively removed. The concentration of ammonia used is about 0.003% at a pH of 10, and the cleaning effect can be improved at such a very low concentration, so that the chemical solution can be greatly reduced as compared with the conventional cleaning method.

  In addition, the amount of pure water used for the subsequent rinsing can be greatly reduced as compared with the case where a thick chemical is used.

  Furthermore, the cleaning process time for removing foreign substances can be shortened by improving the cleaning ability, and energy such as electricity can be saved.

  Further, when the photomask to be cleaned is a halftone mask and the formed light shielding film is a MoSiON film, the step 3 has a concentration of 0.003% as shown in the third embodiment. Foreign matter cleaning treatment is performed using cathode water to which such a small amount of ammonia is added.

  By processing using such a chemical solution, a cleaning effect equivalent to or higher than that of the prior art can be achieved without changing the transmittance of the MoSiON film.

  Further, if the ammonia concentration is 1% or less, it is possible to suppress the fluctuation in transmittance to a control standard (for example, 0.5%) or less and to increase the cleaning efficiency by limiting the cleaning process to a short time.

  In this case, it goes without saying that it is more effective if megasonic sonication is used in combination.

  Next, in the step 4, the washed photomask is dried to finish.

  As described above, by using such a cleaning process, the removal efficiency of residual sulfuric acid and adhering foreign matters is improved as compared with the conventional treatment, so that the treatment time is shortened, and the amount of pure water used and electric power are reduced. Energy can be reduced. In addition, the amount of chemical used for cleaning can be greatly reduced.

  Further, even when the light shielding film is a MoSiON film, effective cleaning can be performed without changing the transmittance.

Embodiment 5 FIG.
In the fifth embodiment, a cleaning apparatus for realizing the photomask cleaning method according to the first to fourth embodiments will be described.

  FIG. 8 is a diagram showing the configuration of a high-performance photomask cleaning apparatus according to this embodiment. In the figure, reference numeral 100 denotes an apparatus main body, and 200 denotes a cleaning liquid supply / control unit that supplies a chemical liquid or pure water to each tank disposed in the apparatus main body 100 with a predetermined concentration and temperature controlled.

  As shown in the figure, the apparatus main body 100 includes a sender unit 101, an acid tank 102, a rinse tank 103, a foreign matter removal tank 104, a drying tank 105, and a receiver 106.

  The cleaning liquid supply / control unit 200 includes an acid preparation tank 201, an alkali / detergent preparation tank 202, an electrolyzed water generation unit 203, an IPA (isopropyl alcohol) unit 204, and a control unit 205.

  Next, the operation of the apparatus will be described with reference to FIG. The photomask is set on the sender unit 101 of the apparatus main body 100. At this time, one photomask or a plurality of photomasks are set simultaneously.

  The photomask set in the sender unit 101 is sent to the acid tank 102, and the acid tank 102 performs acid treatment with sulfuric acid / hydrogen peroxide solution or the like using sulfuric acid / hydrogen peroxide solution supplied from the acid preparation tank 201. .

  When the treatment in the acid bath 102 is completed, the photomask is then sent to the rinse bath 103, where the anode water is treated to a level at which the sulfuric acid on the photomask substrate is not clouded. Remove. The anode water used at this time is supplied from the electrolyzed water generation unit 203. As described in the first embodiment, the anode water is heated to about 30 ° C. or more, and sulfuric acid / hydrogen peroxide solution or the like. An effective cleaning treatment can be performed so that the residual sulfuric acid after the acid treatment by the above becomes an allowable level or less. Therefore, the control unit 205 of the control unit 200 controls the temperature of the anode water generated by the electrolyzed water generation unit 203 to be heated to about 30 ° C., for example. If the anode water is used for rinsing, residual sulfate ions can be removed more effectively.

  When the processing in the rinsing tank 103 is completed, the photomask is then fed into the foreign substance removal tank 104. The foreign matter removal tank 104 is configured so that the control unit 205 is supplied with cathode water generated by the electrolyzed water generation unit 203 under control and ammonia water set to a predetermined concentration in the alkali / detergent preparation tank. .

  In the foreign matter removal tank 104, as described in Embodiment 3, the particulate foreign matter adhering to the surface of the photomask can be effectively removed by performing megasonic ultrasonic treatment in the cathode water.

  Moreover, the removal efficiency of the foreign particles adhering to the surface of the photomask can be greatly improved by using the cathode water to which a small amount of ammonia is added.

  In this case, the concentration of ammonia used is about 0.003% at pH 10, and the cleaning effect can be improved at such a very low concentration, so that the amount of the chemical solution used can be greatly reduced.

  In addition, the amount of pure water used for the subsequent rinsing can be greatly reduced as compared with the case where a thick chemical is used.

  Furthermore, the cleaning process time for removing foreign substances can be shortened by improving the cleaning ability, and energy such as electricity can be saved.

The acid bath 102, the rinsing bath 103 and the foreign matter removing bath 104 can be combined with an ultrasonic bath as shown in FIG. By overflowing and circulating filtering the chemicals in each tank, the amount of pure water and chemicals used can be saved, and the number of foreign substances in the chemicals can be managed at a low level.
FIG. 9 shows an example of a method for pouring a chemical solution such as anode water, cathode water, or low-concentration ammonia water onto the photomask surface in each tank.

  As shown in FIG. 9, anode water, cathode water, or a small amount of ammonia from the nozzle 31 fixed in the cleaning treatment chamber (tank) or the nozzle fixed to the swinging arm 32 on the surface of the photomask substrate 30 rotated horizontally. Effective treatment can be performed by pouring the cathode water with water added.

  Also, as shown in FIG. 10, a photomask is used in each cleaning tank using a line-type megasonic nozzle 40 with anode water, cathode water or a small amount of ammonia water added with megasonic ultrasonic waves. By rinsing the substrate 30, cleaning using megasonic ultrasonic cleaning is possible.

  Further, the same effect can be obtained by rinsing with an anode water to which megasonic is added from a megasonic ultrasonic oscillation nozzle fixed to the swinging arm 32 in FIG.

  Also, only pure water to which megasonic is added is poured from this megasonic nozzle, and ammonia water, ammonia water / hydrogen peroxide mixture, cathode water, cathode water to which a small amount of ammonia water is added, etc. from another nozzle, etc. It is also possible to remove foreign matters effectively by pouring.

  Further, in order to classify the cleaning pass according to the type of photomask to be processed, a plurality of cleaning tanks may be provided.

  Moreover, the chemical | medical solution supplied from the control part 200 to each washing tank can be heated with heating apparatuses, such as an in-line heater.

  Further, the drying tank 105 is connected to a unit for drying with alcohol such as IPA (isopropyl alcohol) or spin drying for rotating the photomask at a high speed in a horizontal state.

  FIG. 8 shows an apparatus configured to connect to an IPA (isopropyl alcohol) unit 204.

  When the spin drying unit is installed, the IPA unit 204 is omitted.

  The dried photomask is transported to a receiver unit and stored in a dedicated case or the like.

  As described above, the chemical solution used in each cleaning tank is supplied from each chemical solution supply unit (acid preparation tank 201, alkali / detergent preparation tank 202, electrolyzed water generation unit 203) of the cleaning liquid supply / control unit 200 independent of the main body. The

  Each of these chemical solution supply units is provided with a control unit 205 such as a sequencer for optimally controlling the operation of the apparatus.

  The dried photomask is transported to a receiver unit and stored in a dedicated case or the like.

FIG. 4 is a diagram showing the amount of residual sulfate ions after rinsing with various chemical solutions according to the first embodiment. It is a figure for demonstrating the apparatus which produces | generates electrolyzed water, and its production | generation process. It is a figure which shows the removal rate of the foreign material (silica particle) on a CrON film | membrane by the various chemical | medical solutions by Embodiment 2. FIG. It is explanatory drawing of the overflow tank which installed the ultrasonic transducer | vibrator. It is a figure which shows the fluctuation amount of the transmittance | permeability after the alkali process of the MoSiON film | membrane with respect to the various chemical | medical solutions by Embodiment 3. FIG. FIG. 6 is a diagram showing the removal rate of alumina particles on a MoSiON film after cleaning treatment with various chemical solutions according to Embodiment 3. It is a figure which shows the whole process of the photomask cleaning process by Embodiment 4. FIG. 10 is a configuration diagram of a photomask cleaning apparatus according to a fifth embodiment. It is a figure for demonstrating the method to rotate and rotate a photomask horizontally. It is a figure for demonstrating the photomask washing | cleaning method using a line type megasonic nozzle. It is a figure which shows the whole process of the photomask cleaning process by the conventional method.

Explanation of symbols

3 Positive electrode, 4 Anode tank, 5 Negative electrode, 6 Cathode tank, 7 Intermediate tank, 8 Inner side piping, 9 Ion exchange membrane, 10 Anode water, 11 Cathode water, 21 Ultrasonic vibrator, 22 Inner tank, 23 Outside Tank, 30 Photomask substrate, 31 nozzle, 32 arm, 40 line type megasonic nozzle, 100 Cleaning device body, 101 Sender unit, 102 Acid tank, 103 Rinse tank, 104 Foreign substance removal tank, 105 Drying tank, 106 Receiver, 200 Cleaning liquid supply / control unit, 201 acid preparation tank, 203 alkali / detergent preparation tank, 204 IPA unit, 205 control unit.

Claims (4)

A method of cleaning a phase shift photomask in which a metal oxynitride film of molybdenum silicide is formed on a glass substrate surface,
A first step of cleaning the phase shift photomask using a mixed solution of sulfuric acid and hydrogen peroxide;
A second step of cleaning the phase shift photomask using anode water;
A third step of cleaning the phase shift photomask with cathodic water;
A fourth step of performing a drying process on the phase shift photomask after the first, second and third steps;
In the third step, the phase shift photomask is washed with cathode water having an ammonia concentration of more than 0% and 1% or less ,
The third step, the second phase shift photomask cleaning method characterized by Rukoto continuously performed after step. The anode water used in the second step, phase shift photomask cleaning method of claim 1, wherein that it has been heated to 30 ° C. or higher. A phase shift photomask cleaning device in which a metal oxynitride film of molybdenum silicide is formed on a glass substrate surface,
An acid bath for cleaning the phase shift photomask using a mixed solution of sulfuric acid and hydrogen peroxide solution;
A rinsing tank for cleaning the phase shift photomask using anode water generated by an electrolyzed water generation unit;
A foreign matter removal tank that cleans the phase shift photomask using the cathode water produced by the electrolyzed water production unit;
A drying tank for performing a drying process on the phase shift photomask;
Cleaning liquid supply / control means for controlling the cleaning liquid supplied to each of the acid tank, the rinse tank, and the foreign substance removal tank to a predetermined concentration or temperature;
With
In the foreign matter removal tank, cathode water having an ammonia concentration of more than 0% and 1% or less is used,
The washing with the foreign matter removing tank, the continuously performed after washing with rinsing tank you wherein Rukoto position phase shift photomask of the cleaning apparatus. The anode used in the rinsing tank water cleaning device of a phase shift photomask according to claim 3, characterized that you have been heated to 30 ° C. or higher.

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