JP2010111002A - Manufacturing method for resin composition solution, and manufacturing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method and a manufacturing apparatus for a resin composition solution which can effectively remove particulates contained in the resin composition solution, which could become a defect factor, and can suppress the generation of defects. <P>SOLUTION: The resin composition solution which is housed in a tank 10 for housing the resin composition solution is discharged from the tank 10 and circulate-filtered by a circulation path having a liquid feeding means and a filtering means by this manufacturing method for resin composition solution. As the liquid feeding means, a diaphragm pump 13 is used, and in addition, the circulation-filtering is performed by the circulation path having a first damper 30 on a pump discharging line 28p on the downstream side of the diaphragm pump 13 in the manufacturing method. More preferably, a second damper 13c is installed in the diaphragm pump 13. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a resin composition solution and a production apparatus. Specifically, the present invention relates to a method for producing a resin composition solution such as a photoresist resin-containing solution, a liquid immersion composition solution, and an upper layer film-forming composition, and a production apparatus.

  In the manufacture of semiconductor elements and liquid crystal display elements, miniaturization is progressing rapidly due to advances in lithography technology. Examples of the method for miniaturization include shortening the wavelength of exposure light and using an immersion exposure method. However, in such a miniaturization method, when a conventional resist material is used, there is a problem that defects (defects) are likely to occur on the surface of the resist pattern to be formed. Note that “defect” refers to all defects detected when the resist pattern after development is observed from above.

  In recent years, patterning with higher resolution has been required, and it has become impossible to ignore defects, and attempts have been made to improve it. This defect factor includes a solution containing a resist resin, an oligomer or a low molecular weight polymer by-produced during the polymerization of the resin, a polymer having a higher molecular weight than the target mass average molecular weight, a purification process, etc. The presence of solid foreign matters such as dust and fine particles mixed from devices, piping, valves, and the like.

  As a method for removing such a defect factor, a solution containing a resist resin is passed through a filter having a pore size of a micron unit and filled in a container while being filtered to produce a product. The filtration method is known. However, in the single-pass filtration, since the fine particles from the filter to the filling are mixed in the resist material, it is necessary to cut off sufficiently and there is a problem in productivity.

  In addition, as a method for removing the defect factor, there is a method of circulating in a closed system in which a filter is installed to reduce the amount of fine particles in the resist composition (see Patent Document 1). At that time, if the wetted part of the equipment is a metal, the metal is eluted, and the lithography material is caused to have poor performance due to the metal. At that time, it is preferred that all the wetted parts should be made of a fluorine-based resin with little metal elution rather than metal. Therefore, diaphragm pumps, Levitro pumps, etc. are regarded as useful as pumps with little metal elution. However, diaphragm pumps are prone to pulsation and flow fluctuations because of their driving methods, so a method of installing a pulsation preventing damper has been taken (patented) Reference 2)

Japanese Patent Laid-Open No. 2002-62667 JP-A-10-288160

  However, in the field of manufacturing semiconductor devices and liquid crystal display devices that are rapidly miniaturized, even when the above-described method is used, the pulsation slightly occurs and the fine particles are removed. However, the current situation is not enough.

  The present invention has been made in view of the above circumstances, and provides a method and apparatus for producing a resin composition solution that can effectively remove fine particles that can be a defect factor contained in the resin composition solution. Objective.

  The present inventors have found that the above problem can be solved by using a diaphragm pump and performing circulation filtration in a circulation path having a damper in a pump discharge line downstream of the diaphragm pump. That is, according to this invention, the manufacturing method and manufacturing apparatus of the following resin composition solutions are provided.

[1] A method for producing a resin composition solution, wherein the resin composition solution contained in a tank is discharged from the tank and circulated and filtered through a circulation path having a liquid feeding means and a filtering means, As a means, a resin composition that uses a diaphragm pump, and further performs circulation filtration in a circulation path including a first damper for attenuating pulsation of the resin composition solution in a pump discharge line downstream of the diaphragm pump. A method for producing a product solution.

[2] The method for producing a resin composition solution according to [1], wherein circulation filtration is performed using the diaphragm pump including a second damper on a discharge side from which the resin composition solution is discharged.

[3] The method for producing a resin composition solution according to [1] or [2], wherein the damper and the diaphragm pump are driven by supplying driving air having different pressures.

[4] The method for producing a resin composition solution according to any one of [1] to [3], wherein the diaphragm pump in which a flow path of the resin composition solution is formed of a fluorine-based polymer is used.

[5] The method for producing a resin composition solution according to any one of [1] to [4], wherein the diaphragm pump has a pump design maximum flow rate of 1 to 100 L / min.

[6] A tank containing the resin composition solution, a circulation line for circulating the resin composition solution discharged from the tank to the tank, and the resin composition solution provided in the circulation line Liquid feeding means for liquid, filtration means for filtering the resin composition solution provided in the circulation line, filling means for filling the resin composition solution in a container, The liquid feeding means is a diaphragm pump, and further includes a first damper for attenuating pulsation of the resin composition solution in a pump discharge line downstream of the diaphragm pump, and circulation filtration is performed in the circulation line. Then, the apparatus for producing a resin composition solution in which a container is filled with the resin composition solution by the filling means.

[7] The apparatus for producing a resin composition solution according to [6], wherein the diaphragm pump includes a second damper on a discharge side from which the resin composition solution is discharged.

[8] The apparatus for producing a resin composition solution according to [6] or [7], further including driving air supply means for supplying driving air having different pressures to the damper and the diaphragm pump.

[9] The apparatus for producing a resin composition solution according to any one of [6] to [8], wherein the diaphragm pump has a flow path of the resin composition solution formed of a fluorine-based polymer.

[10] The apparatus for producing a resin composition solution according to any one of [6] to [9], wherein the diaphragm pump has a pump design maximum flow rate of 1 to 100 L / min.

  When the resin composition solution pulsates during circulation filtration, it is difficult to sufficiently reduce the fine particles and reduce the number of foreign substances in the filtration means, etc., but the method and apparatus for producing the resin composition solution of the present invention According to the present invention, the diaphragm pump is used as the liquid feeding means, and the pulsation of the resin composition solution can be suppressed by installing the first damper in the pump discharge line. Can be provided efficiently. Further, by providing the diaphragm pump with the second damper, it is possible to more effectively suppress pulsation and manufacture a resin composition solution with reduced fine particles.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be added without departing from the scope of the invention.

  The schematic diagram of one Embodiment of the manufacturing apparatus of the resin composition solution of this invention is shown in FIG. The resin composition solution manufacturing apparatus 1 (hereinafter also simply referred to as the manufacturing apparatus 1) includes a tank 10 that contains the resin composition solution, and a circulation line that circulates the resin composition solution discharged from the tank 10 to the tank 10. 28. And the liquid feeding pump 13 as a liquid feeding means for feeding the resin composition solution provided in the circulation line 28, and a filtering means for filtering the resin composition solution provided in the circulation line And a filling nozzle 14 as a filling means for filling the container with the resin composition solution. The liquid feed pump 13 as a liquid feed means uses a diaphragm pump, and has a first damper 30 in the pump discharge line 28p downstream of the diaphragm pump 13 for attenuating the pulsation of the resin composition solution. . It is preferable that the diaphragm pump 13 is accompanied by a pulsation prevention damper (second damper 13c) (a diaphragm pump with a pulsation prevention damper). The first damper 30 is installed at a location separated from the liquid feed pump 13, and the second damper 13 c is installed along with the liquid feed pump 13. The pump discharge line 28p means a line downstream of the liquid feed pump 13 and upstream of the filtration device 20.

  In addition, the manufacturing apparatus 1 includes an air source 33 for supplying air to the diaphragm pump 13, the first damper 30, and the second damper 13c to drive them. The air supply line for supplying air from the air source 33 to the diaphragm pump 13, the first damper 30, and the second damper 13c is provided with a regulator 34 for supplying air of different pressures to each. ing. The air source 33 and the regulator 34 are driving air supply means.

  The tank 10 includes an upper valve 15 a and a chemical liquid supply nozzle 11, and can supply chemical liquid into the tank 10. Moreover, the stirring apparatus 12 which stirs a chemical | medical solution, and the lower valve | bulb 15b which discharges | emits a chemical | medical solution are provided.

  The tank 10 and the filtration device 20 are connected by piping, and are provided with a liquid feed pump 13 therebetween, so that liquid can be fed from the tank 10 to the filtration device 20.

  A filling nozzle 14 is provided downstream of the filtration device 20 as a filling means. Further, the circulation line 28 is constituted by piping, and the resin composition solution can be returned to the tank 10.

  The filtering device 20 as a filtering means is provided with a filter, and the types of the filter are polyethylene (PE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UPE), polypropylene (PP), polytetrafluoroethylene. (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), nylon (NYLON), and a composite film of PE and NYLON. Use of a filter made of these materials is advantageous in that it has high chemical resistance and is difficult to elute foreign substances such as metals.

  Further, the pore diameter of the filter is preferably 0.005 to 1 μm in order to remove foreign matters.

  The piping material of the piping constituting the circulation line 28 is preferably SUS304, SUS316, SUS316L, or SUS304 + PFA coating in order to remove foreign matters.

  The liquid feed pump 13 is preferably a diaphragm pump, and the diaphragm pump 13 preferably has a damper 13c for preventing pulsation (integrated type). The liquid contact member material (material of the resin composition solution flow path) of the diaphragm pump 13 and the damper 13c is preferably a fluorine-based polymer with little metal elution, and for example, PFA and PTFE are preferable.

  Moreover, it is preferable that the pump design maximum flow volume of the diaphragm pump 13 is 1-100 L / min. When the flow rate of the diaphragm pump 13 is 1 to 100 L / min, the capacity of the diaphragm in the pump is increased, and the pulsation of the diaphragm pump 13 itself is increased, so that the effect of the present invention is greatly obtained. When the flow rate exceeds 100 L / min, since the flow rate is large, the foreign matter once collected from the filter comes out, and the foreign matter cannot be effectively removed.

  The diaphragm pump 13 used as the liquid feed pump 13 drives the diaphragm in the pump by the driving air from the air source 33, and sucks the resin composition solution discharged from the tank 10 from the suction port 13a. It discharges from the discharge port 13b. It is preferable that a discharge-side discharge port 13b for discharging the resin composition solution is provided with a damper 13c for preventing pulsation, and the damper 13c is also configured to be driven by drive air from an air source 33. And the pulsation of the resin composition solution resulting from the drive of the diaphragm of the diaphragm pump 13 can be attenuated by the damper 13c.

  Further, a first damper 30 is provided downstream of the damper 13c via a pipe. The damper 30 is also an air damper configured to be driven by driving air from the air source 33. The structure and operation of the damper 30 will be described with reference to FIGS. 2A and 2B. The same applies to the second damper 13c.

  As shown in FIG. 2A, the damper 30 includes an introduction port 30a through which the resin composition solution is introduced, a flow path 30c through which the introduced resin composition solution flows, and a discharge port 30b through which the resin composition solution is discharged. Moreover, the air chamber 30h separated by the diaphragm 30d which forms the flow path 30c is provided. The air chamber 30h includes an air inlet 30g for introducing air from the air source 33, a valve 30f, and an air outlet 30i for discharging air. The valve 30f is configured to be raised by a diaphragm support portion 30e connected to the diaphragm 30d.

  When the resin composition solution is introduced from the inlet 30a of the damper 30, the diaphragm 30d forming the flow path 30c is pushed up by the hydraulic pressure, and the diaphragm support portion 30e connected to the diaphragm 30d opens the valve 30f. . Thereby, driving air from the air source 33 is introduced into the air chamber 30h from the air introduction port 30g.

  As shown in FIG. 2B, when the resin composition solution introduced into the flow path 30c from the introduction port 30a decreases, the diaphragm 30d is pushed down by the air pressure in the air chamber 30h, so that the resin composition solution is discharged from the discharge port 30b. Therefore, a decrease in hydraulic pressure is prevented. When the diaphragm 30d is pushed down, the valve 30f is closed, and the air in the air chamber 30h is discharged from the air discharge port i, so that when the liquid pressure from the liquid feed pump 13 increases, the diaphragm is pushed up again. Thereby, the pulsation of the resin composition solution can be reduced.

  The apparatus 1 for producing a resin composition solution of the present invention is provided with a pressure gauge 31 for measuring the liquid pressure of the resin composition solution to be sent upstream and downstream of the filtration device 20 in the circulation line 28. Yes. Thereby, it is possible to monitor the pulsation of the resin composition solution that causes a reduction in the efficiency of collecting the fine particles.

  Further, the circulation line is provided with a flow meter 32 for measuring the amount of the resin composition solution to be fed.

  Examples of the resin composition solution in the method for producing a resin composition solution of the present invention include a resist resin-containing solution, an immersion composition solution, an upper layer film forming composition solution, and a lower layer film forming composition solution.

The resist resin-containing solution contains at least a resist resin and a solvent, and may further contain other additives such as an acid generator and an acid diffusion controller. Specifically, for example, it is suitable for microfabrication by various types of radiation such as ultraviolet rays such as g-line and i-line, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV, etc. Resin composition used for photolithography such as a positive or negative resist composition capable of forming a resist, a resin composition for forming an upper layer film or a lower layer film (antireflection film, etc.) in a multilayer resist, Examples thereof include a resin solution containing a crude resist resin for obtaining a resist resin used in these compositions.

  Examples of the resist resin include acrylate resins, methacrylate resins, hydroxystyrene resins, and novolak resins. Such a resist resin can be obtained, for example, by polymerizing a predetermined polymerizable compound such as a polymerizable compound (monomer) having an ethylenically unsaturated bond in the presence of a solvent.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, glyme, and propylene glycol monomethyl ether; esters such as ethyl acetate and ethyl lactate; propylene glycol Examples include ether esters such as methyl ether acetate, and lactones such as γ-butyrolactone. These solvents may be used alone or in combination of two or more.

  The immersion composition liquid used in the immersion exposure process has a refractive index at a wavelength of 193 nm that is equal to or higher than the refractive index of water, and the refractive index at a wavelength of 193 nm has a refractive index of water (1.44). Although it has the above refractive index, an alicyclic hydrocarbon compound and an alicyclic hydrocarbon compound are mentioned as an immersion composition solution by the manufacturing method of this invention. Furthermore, examples of the alicyclic hydrocarbon compound include trans-decahydronaphthalene, and examples of the alicyclic hydrocarbon compound include exo-tetradicyclopentadiene.

  The upper layer film-forming composition is used to form an upper layer film on the surface of a photoresist film. For example, an acid dissociable group-modified alkali-soluble resin and a radiation-sensitive acid generator are essential components. And a radiation-sensitive resin composition contained therein.

  Next, the manufacturing method of the resin composition solution of this invention is demonstrated. The production method of the present invention is a method for producing a resin composition solution in which a resin composition solution accommodated in a tank 10 is discharged from the tank 10 and circulated and filtered through a circulation path having a liquid feeding means and a filtration means. The diaphragm pump 13 is used as the liquid feeding means, and further, circulation filtration is performed through a circulation path having a damper in the pump discharge line 28p downstream of the diaphragm pump 13.

  Hereinafter, the production method will be specifically described. First, after the lower valve 15b of the preparation device is closed, the upper valve 15a is opened, for example, a chemical solution is introduced from the chemical solution supply nozzle 11, and the valve 15a is closed. Stir until the concentration of becomes uniform.

  Thereafter, the lower valve 15b is opened, and the solution is circulated through the circulation line 28 by the liquid feed pump 13, and is subjected to circulation filtration to produce an immersion composition solution.

  The circulation filtration is performed by circulating the resin composition solution stored in the tank 10 through a circulation path that has a liquid feeding means and a filtration means and circulates the resin composition solution discharged from the tank 10 to the tank 10. .

  At this time, unlike FIG. 1, it is possible not to install the second damper 13c. It is also possible to perform circulation filtration without installing the regulator 34 on the air supply line from the air source 33 that supplies the liquid feed pump 13, the first damper 30, and the second damper 13c. However, as shown in FIG. 1, it is preferable to install not only the first damper 30 installed at a position separated from the diaphragm pump 13 but also the second damper 13 c integrated with the diaphragm pump 13. Furthermore, installing a regulator 34 on the air supply line, adjusting the regulator 34, and supplying air with different pressures to the liquid feed pump 13, the first damper 30, and the second damper 13c prevents pulsation. In order to reduce fine particles (the number of foreign substances), it is preferable. The pump discharge line 28p may be provided with two or more dampers.

  Circulation filtration is performed until the fine particles are reduced below a predetermined standard, and then the resin composition solution is filled into the filling bottle 24 by the filling nozzle 14 of the filling means.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

Example 1
First, as shown in FIG. 1, a 3 m ³ tank 10, a diaphragm pump with a pulsation preventing damper (feed pump 13, second damper 13 c), a filter (in the filtration device 20, manufactured by Entegris: Microguard Plus 0.01 μm) ), A resin composition manufacturing apparatus including a separately installed damper (first damper 30), a pressure gauge 31, and a flow meter 32 in the pump discharge line 28p was assembled. However, unlike FIG. 1, the regulator 34 was not installed on the air supply line from the air source 33 that supplies the liquid feed pump 13, the first damper 30, and the second damper 13c. In the tank 10, an upper film composition for immersion (2-methyl-acrylic acid 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-butyl and vinylsulfonic acid copolymer) , 3 m ^{3 of} Mw (4-methyl-2-pentanol solution containing 4% of polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC)) of 10500 is charged, and circulation filtration is performed at a flow rate of 15 L / min. And the pressure difference of the filter was measured with the pressure gauge 31 upstream and downstream of the filtration apparatus 20 shown in FIG. As shown in FIG. 3, the pressure fluctuation amount with respect to the time of the pressure difference of the filter is represented as ΔP. ΔP is the maximum and minimum difference within the filtration time when the flow rate is constant. Therefore, the smaller the ΔP, the smaller the pressure fluctuation. In addition, the number of foreign matters was measured using an online particle counter. Table 1 shows the number of circulations until the number of foreign matters of 0.15 μm or more is reduced to 100 pieces / 10 ml, the filtration time, and the pressure fluctuation amount ΔP within the filtration time.

(Example 2)
In the apparatus of the first embodiment, a diaphragm pump (feed pump 13), an integrated pulsation prevention damper (second damper 13c) provided in the diaphragm pump 13, and a separately installed damper (first damper 30) of the pump discharge line 28p. The regulator 34 was installed in each of the driving air lines, and air of different pressures was supplied. Circulation filtration was performed in the same manner as in Example 1 except that air of different pressure was supplied. The air drive pressure at this time was 0.3 MPa for the diaphragm pump 13, 0.4 MPa for the integral pulsation prevention damper, and 0.35 MPa for the separate damper. Circulating filtration is performed under the same conditions as in Example 1, the pressure difference and the number of foreign substances are measured, and the number of circulations, the filtration time, and the filtration time until 0.15 μm or more of foreign substances are reduced to 100/10 ml. The pressure fluctuation amount ΔP was investigated.

(Comparative Example 1)
Except for removing the separately installed damper, the same apparatus as in Example 1 was used. Similarly, the measurement of the pressure difference and the number of foreign matters were performed using an online particle counter, and the number of foreign matters of 0.15 μm or more was reduced to 100/10 ml. The number of circulation cycles, filtration time, and pressure fluctuation amount ΔP within the filtration time were examined.

  As shown in Table 1, in Examples 1 and 2 provided with the damper 30, the pressure fluctuation amount ΔP of the pressure difference before and after the filter is smaller than that of the comparative example 1 and 100 foreign matters of 0.15 μm or more are present. The filtration time for reducing to 10 ml and the number of circulations were shortened. Furthermore, the diaphragm pump (liquid feed pump 13), the integrated pulsation prevention damper (second damper 13c) provided in the diaphragm pump 13, and the separately installed damper (first damper 30) of the pump discharge line 28p are different. By supplying pressure air, the pressure fluctuation amount ΔP was reduced, the number of circulations was reduced, and the filtration time could be shortened. That is, by providing a diaphragm pump with a pulsation preventing damper and a damper, and further supplying air with different pressures, it was possible to effectively remove fine particles that could be a defect factor contained in the resin composition solution.

  The method and apparatus for producing the resin composition solution of the present invention is for a photoresist used for fine processing such as strict sub-quarter micron level with respect to contamination of foreign matters such as metallic foreign matters and impurities such as metallic components. It is suitably used for the production of a resin composition solution such as a resin-containing solution, an immersion composition solution, and an upper layer film-forming composition.

It is a schematic diagram which shows one Embodiment of the manufacturing apparatus of the resin composition solution of this invention. It is a schematic diagram which shows the action | operation of a damper. It is a schematic diagram which shows the action | operation of a damper following FIG. 2A. It is a graph which shows the fluctuation | variation of the pressure difference before and behind a filter.

Explanation of symbols

1: resin composition solution manufacturing apparatus, 10: tank, 11: chemical supply nozzle, 12: stirring device, 13: liquid feed pump (diaphragm pump), 13a: suction port, 13b: discharge port, 13c: second Damper, 14: Filling nozzle, 15a: Upper valve, 15b: Lower valve, 20: Filtration device, 24: Filling bottle, 28: Circulation line, 28p: Pump discharge line, 30: First damper, 30a: Inlet, 30b: outlet, 30c: flow path, 30d: diaphragm, 30e: diaphragm support, 30f: valve, 30g: air inlet, 30h: air chamber, 30i: air outlet, 31: pressure gauge, 32: flow meter 33: Air source, 34: Regulator.

Claims (10)

A resin composition solution contained in a tank is discharged from the tank and circulated and filtered in a circulation path having a liquid feeding means and a filtration means,
As the liquid feeding means, a diaphragm pump is used, and further, circulation filtration is performed in a circulation path including a first damper for attenuating pulsation of the resin composition solution in a pump discharge line downstream of the diaphragm pump. The manufacturing method of the resin composition solution to perform.   The method for producing a resin composition solution according to claim 1, wherein circulation filtration is performed using the diaphragm pump including a second damper on a discharge side from which the resin composition solution is discharged.   The method for producing a resin composition solution according to claim 1, wherein the damper and the diaphragm pump are driven by supplying driving air having different pressures.   The manufacturing method of the resin composition solution of any one of Claims 1-3 using the said diaphragm pump in which the flow path of the said resin composition solution is formed with the fluorine-type polymer.   The manufacturing method of the resin composition solution of any one of Claims 1-4 using the said diaphragm pump whose pump design maximum flow rate is 1-100 L / min. A tank containing a resin composition solution;
A circulation line for circulating the resin composition solution discharged from the tank to the tank;
A liquid feeding means for feeding the resin composition solution provided in the circulation line;
A filtering means for filtering the resin composition solution provided in the circulation line;
Filling means for filling a container with the resin composition solution,
The liquid feeding means is a diaphragm pump, and further includes a first damper for attenuating pulsation of the resin composition solution in a pump discharge line downstream of the diaphragm pump,
An apparatus for producing a resin composition solution, wherein the resin composition solution is filled in a container by the filling means after being circulated and filtered in the circulation line.   The said diaphragm pump is a manufacturing apparatus of the resin composition solution of Claim 6 provided with the 2nd damper in the discharge side which the said resin composition solution discharges.   The apparatus for producing a resin composition solution according to claim 6 or 7, further comprising driving air supply means for supplying driving air having different pressures to the damper and the diaphragm pump.   The said diaphragm pump is a manufacturing apparatus of the resin composition solution of any one of Claims 6-8 in which the flow path of the said resin composition solution is formed with the fluorine-type polymer.   The apparatus for producing a resin composition solution according to any one of claims 6 to 9, wherein the diaphragm pump has a pump design maximum flow rate of 1 to 100 L / min.

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