JP2010020014A - Method of delivering semiconductor manufacturing composite solution, manufacturing method, pipe line and manufacturing apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of delivering a semiconductor manufacturing composite solution, a manufacturing method, a pipe line and a manufacturing apparatus, thoroughly restraining the mixing-in of a foreign matter that can cause a defect in a manufacturing process, and remarkably reducing a content of the foreign matter. <P>SOLUTION: The solution is delivered using the pipe line the inner surface of which satisfies the following relational expression: Ra<X between the value (Ra:μm) of arithmetic mean roughness showing the surface smoothness and the size (X:μm) of the foreign matter in the delivered semiconductor manufacturing composite solution. Alternatively, the solution is delivered using the pipe line the inner surface of which satisfies the following relational expression: Rz<3X between the value (Rz:μm) of a ten-point height of irregularities showing the surface smoothness and the size (X:μm) of the foreign matter in the semiconductor manufacturing composite solution. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for feeding a composition solution for semiconductor production, a production method, piping used in the method, and a production apparatus. Specifically, a polymer solution for photoresist, a photoresist composition solution, or an immersion composition used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photolithography processes. The present invention relates to a method for producing a physical solution or the like.

  In recent years, as functions of electronic materials, display materials, and the like have been rapidly advanced, compositions used for producing these have been regarded as important. In the field of microfabrication represented by the manufacture of integrated circuit elements, lithography technology capable of finer processing is required to obtain a higher degree of integration. For example, in order to enable fine processing at a level of 0.10 μm or less, use of radiation having a shorter wavelength and immersion exposure are being studied. Many resin compositions suitable for this application have been proposed and used. For example, a resist composition containing a radiation-sensitive resin composition for resist formation and an immersion composition containing a resin composition for forming an upper layer film in a multilayer resist are used.

  In such a miniaturization method, patterning with higher resolution has been required, and it has become impossible to ignore the defect of the resist pattern. One of the causes of this defect is the presence of solids such as oligomers and low molecular weight polymers by-produced during polymerization of the resin in the resist resin-containing solution, and dust and fine particles mixed in from piping and valves of production facilities. It is mentioned that the foreign material of a shape exists. Note that “defect” refers to all defects detected when the resist pattern after development is observed from above.

  Among these foreign substances that can cause defects, as a method for reducing oligomers by-produced during resin polymerization and low molecular weight polymers, a precipitation purification method (Patent Document 1) for purifying the resin solution using a poor solvent, A purification method using a precipitation step and / or a washing filtration step (Patent Document 2) has been proposed. Also, as a method of reducing solid foreign matters such as dust and fine particles mixed in from pipes and valves, the amount of fine particles in the resist composition is circulated by circulating the resist composition in a closed system where a filter is installed. Has been proposed (Patent Document 3).

Japanese Patent No. 3810428 JP 2005-13297 A Japanese Patent Laid-Open No. 2002-62667

  However, in the field of manufacturing semiconductor devices where miniaturization is rapidly progressing, even if the above-described method is used, it cannot be said that the effect of suppressing the occurrence of defects is sufficient. Problems still remain in terms of obtaining a photoresist composition having a low foreign matter content. In particular, solid foreign matters such as dust and fine particles mixed from production equipment such as piping and valves have not been sufficiently reduced.

  The present invention has been made in view of such problems of the prior art, has high productivity, can sufficiently suppress the entry of foreign substances that can be a cause of defects in the manufacturing process, and has a foreign substance content as much as possible. A liquid feeding method, a manufacturing method, piping, and a manufacturing apparatus for a reduced semiconductor manufacturing composition solution are provided.

  As a result of intensive investigations to solve the problems of the prior art as described above, the present inventors have confirmed that many foreign substances that can cause defects in these resist patterns are mixed from the inside of the pipe. It has been found that foreign matters remain in the pipe before the production, and these foreign matters are mixed into the product when the composition solution at the time of production sends the pipe.

  The cause of foreign matter remaining in the piping is that foreign matter is mixed in the piping during pipe manufacturing, pipe assembly, and installation, and the product solution cannot be sufficiently cleaned by the normal cleaning method when the equipment is started up. When foreign matter is mixed in and / or the pre-produced composition remains in the pipe and cannot be sufficiently washed by the pre-production washing, and the remaining composition feeds the product solution. It was confirmed that it may be mixed as a foreign object.

  In order to prevent these foreign matters from entering the piping, it is possible to increase the number of cleaning liquids and increase the number of cleaning times or cleaning time. It was found that the effect of reducing foreign matter sufficient to achieve the level required for the above was not observed.

  Accordingly, as a result of further intensive studies, the present inventors have determined that the arithmetic average roughness (Ra) or ten-point average roughness (Rz), which is an index of the surface smoothness of the pipe inner surface, and the foreign matter size The present inventors have found that there is a correlation between the values and completed the present invention. Specifically, the arithmetic average roughness (Ra), which is an index of the surface smoothness of the inner surface of the pipe, is made smaller than the foreign matter size, or the ten-point average roughness (Rz) is given by three times the foreign matter size. It was found that the foreign matter is less than the target standard by reducing. That is, according to the present invention, there are provided the following method for feeding a composition solution for semiconductor production, a production method, piping, and a production apparatus.

[1] The following relational expression Ra <between the arithmetic mean roughness value (Ra; μm) indicating the surface smoothness and the foreign substance size (X; μm) in the composition solution for semiconductor production to be fed. X
A method for feeding a composition solution for semiconductor production, which uses a pipe on the inner surface that satisfies the above.

[2] The following relational expression Rz <3X between the ten-point average roughness value (Rz; μm) indicating the surface smoothness and the foreign material size (X; μm) in the composition for semiconductor production
A method for feeding a composition solution for semiconductor production, which uses a pipe on the inner surface that satisfies the above.

[3] The composition for manufacturing a semiconductor according to [1] or [2], wherein an inner surface of the pipe is subjected to any of electrolytic polishing treatment of stainless steel, glass lining treatment, and lining treatment with polytetrafluoroethylene. Solution delivery method.

[4] A method for producing a composition solution for semiconductor production, which is produced using the method for feeding a composition solution for semiconductor production according to any one of [1] to [3].

[5] A pipe used in the method for feeding a semiconductor solution composition according to any one of [1] to [3].

[6] When the arithmetic mean roughness Ra value of the inner surface of the pipe for sending the semiconductor solution composition solution is 0.5 μm or less and the foreign matter size in the semiconductor solution composition is X (μm) An apparatus for producing a composition solution for semiconductor production, wherein the ten-point average roughness Rz value is smaller than 3X (μm) and 1.5 μm or less.

  The liquid feeding method and the manufacturing method of the present invention can sufficiently suppress the mixing of foreign substances that can cause a defect in a resist pattern in the manufacturing process, and obtain a composition solution for semiconductor manufacturing in which the impurity content is reduced as much as possible. Can do.

  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.

In the method for feeding a composition solution for semiconductor production according to the present invention, the arithmetic average roughness value (Ra; μm) indicating the surface smoothness is a foreign matter size (X; μm) and the following relational expression (0.1X <) Ra <X
In this method, the liquid is fed by using the piping on the inner surface that satisfies the above. Ra needs to be smaller than X, but practically larger than 0.1X is sufficient.

  In the present specification, the arithmetic average roughness value (Ra; μm) indicating the surface smoothness of the inner surface of the pipe is from the average line to the measurement curve in the range of the reference length L μm in the direction of the average line from the roughness curve. It is an index of surface roughness defined by an average value obtained by summing absolute values of deviations, and is defined by JIS B0601: 1994. The reference length L (μm) in the present invention is 10,000 to 100,000 μm.

Alternatively, in the method for feeding a composition solution for semiconductor production of the present invention, the value of ten-point average roughness (Rz; μm) indicating the surface smoothness is a foreign matter size (X; μm) in the composition solution for semiconductor production. ) And the following relational expression (0.1X <) Rz <3X
In this method, the liquid is fed by using the piping on the inner surface that satisfies the above. Rz needs to be smaller than 3X, but practically larger than 0.1X is sufficient.

  The ten-point average roughness value (Rz; μm) indicating the surface smoothness of the inner surface of the pipe in this specification is the highest peak from the average line in the range of the reference length L μm in the direction of the average line from the roughness curve. Is an index of surface roughness defined by the sum of the absolute value of the height (Yp) of the top from the bottom to the fifth and the average of the absolute values of the depth (Yv) of the bottom from the bottom to the fifth. Yes, as defined in JIS B0601: 1994. The reference length L (μm) in the present invention is 10,000 to 100,000 μm.

  Moreover, the apparatus for producing a composition solution for semiconductor production according to the present invention has an arithmetic average roughness Ra value of 0.5 μm or less on the inner surface of a pipe for feeding the composition solution for semiconductor production, and the composition for semiconductor production. When the foreign matter size in the solution is X (μm), the ten-point average roughness Rz value may be smaller than 3X (μm) and 1.5 μm or less.

  The foreign substance size of the foreign substance in this specification is a value evaluated by measuring using a particle counter (scattered light detection type). The foreign particle size may be, for example, an automatic particle measuring device (Ks-41 type) manufactured by Rion Co., Ltd., a liquid particle counter.

FIG. 1 shows a cross-sectional view of an embodiment of the piping of the present invention. The pipe 1 has the following relational expression between the value of the arithmetic mean roughness (Ra; μm) indicating the surface smoothness and the foreign substance size (X; μm) in the composition solution for semiconductor production to be fed ( 0.1X <) Ra <X
Has an inner surface such that

Alternatively, the piping 1 has the following relational expression (0) between the value of the ten-point average roughness (Rz; μm) indicating the surface smoothness and the foreign substance size (X; μm) in the composition solution for semiconductor production. .1X <) Rz <3X
Has an inner surface such that

  A pipe 1 in FIG. 1 is an embodiment in which a lining treatment is performed, and is a non-metallic lining pipe in which an inner surface of a metal pipe 2 is covered with a lining 3 made of a non-metallic material such as glass or resin. Examples of the non-metallic material used as the lining material include glass and polytetrafluoroethylene (registered trademark: Teflon). That is, the pipe 1 is subjected to a glass lining process, a lining process using polytetrafluoroethylene, and the like. In this specification, the term “lining” includes coating (less than 1 mm of film thickness) in addition to lining (film thickness of 1 mm or more). The material for the metal pipe is not particularly limited.

  Alternatively, the pipe 1 may be subjected to an electrolytic polishing treatment of stainless steel on the inner surface. By performing these treatments, it is possible to suppress the mixing of metallic foreign matters into the product.

  Most of the foreign matters mixed in the composition solution for semiconductor production such as the resin-containing solution for photoresist and the composition solution for immersion are mainly caused by the solid matter and the pre-batch composition remaining on the inner surface of the pipe. These foreign matters have entered the irregularities on the pipe surface, and the foreign matters cannot be completely removed by a normal cleaning process. For this reason, by increasing the surface smoothness in the piping, it is effective to eliminate the intrusion of the surface, and even if foreign matter adheres to the piping surface, it can be washed easily. is there.

  In general, in order to achieve microfabrication, the size of foreign matters is defined within a range of 0.1 to 0.5 μm, and if the number of foreign matters within this range exceeds 100 / ml, the number of occurrences of defects is increased. It becomes unacceptable. Therefore, the size and the amount of foreign matter are strictly controlled, and it is essential to achieve 100 / ml or less of foreign matter in the range of 0.15 μm to 0.5 μm in order to achieve ultrafine processing. In other words, in manufacturing a high-performance semiconductor material, it is essential to reduce and manage foreign matter mixed in the semiconductor composition solution. For example, foreign matter having a size of 0.15 μm or more is 100 pieces / ml or less. In addition, specifications are required that foreign matter having a size of 1 μm or more is 10 pieces / ml or less and foreign matter having a size of 2 μm or more is 5 pieces / ml or less.

  Therefore, by supplying the composition for semiconductor production through a pipe having an inner surface with an arithmetic average roughness and a ten-point average roughness satisfying the above formula for the required foreign material size, the semiconductor production composition is used. It is possible to reduce foreign matters mixed in the composition and satisfy the required specifications. That is, by the production method of the present invention, a composition solution for semiconductor production in which the number of foreign matters having a foreign matter size (X; μm) in the range of 0.15 to 0.5 μm is 100 / ml or less is produced. Can do. The basic surface smoothness of the inner surface of the pipe can be evaluated by the value of the arithmetic average roughness Ra, and local flaws or dents on the inner surface of the pipe can be evaluated by the Rz value of the ten-point average roughness. It is more preferable to apply both Ra and Rz values to foreign matter management.

  Therefore, when the arithmetic mean roughness Ra value of the inner surface of the pipe 1 for feeding the semiconductor manufacturing composition solution is 0.5 μm or less and the foreign matter size in the semiconductor manufacturing composition solution is X (μm), it is sufficient. You may comprise so that a point average roughness Rz value may be smaller than 3X (micrometer) and 1.5 micrometers or less.

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

The photoresist resin-containing solution contains at least a photoresist 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 ultraviolet rays such as g-line and i-line, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV, etc. For photolithography such as a positive or negative resist composition capable of forming a resist, and a resin composition for forming an upper layer film or a lower layer film (antireflection film, etc.) containing an immersion composition in a multilayer resist. Examples of the resin composition used include a resin solution containing a photoresist resin used in these compositions.

  Examples of the photoresist resin include acrylate resins, methacrylate resins, hydroxystyrene resins, novolac resins, and the like. 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.

  Furthermore, in the manufacturing method of the composition for semiconductor manufacture of this invention, it is still more preferable to filter before obtaining a final product. The number and properties of the filters used for filtration are not particularly limited as long as the resist composition and the like can be filtered. The number of the filters is usually one, but may be two or more. Preferably, the filter material is polyethylene (PE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UPE), polypropylene (PP), polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether. A polymer (PFA), nylon (NYLON), and a composite film of PE and NYLON. The filter made of the above material is preferable because the elution of the filter component can be suppressed even when the resist composition contacts the filter. The pore size of the filter is usually 0.005 μm to 1 μm, preferably 0.005 μm to 0.1 μm. It is preferable for the pore size of the filter to be in the above-mentioned range since the required foreign matter collecting ability is exhibited, pressure loss is small, and productivity of the resist composition and the like can be increased. The “pore size” of the filter refers to the average pore size determined by the removal rate of standard particles (PSL). However, the value less than 30 nm is a value estimated by a bubble point or the like.

  In FIG. 2, one Embodiment of the manufacturing apparatus of the composition solution for semiconductor manufacture using the piping 1 of this invention is shown. The manufacturing apparatus 30 includes the adjustment tank 10 and a filtration unit 20 having, for example, the above-described HDPE filter on the downstream side. The adjustment tank 10 includes an upper valve 15 a and a chemical solution supply nozzle 11, and can supply a chemical solution into the adjustment tank 10. In addition, a stirring device 12 for stirring the chemical solution and a tank lower valve 15b for discharging the chemical solution are provided.

  The adjustment tank 10 and the filtration unit 20 are connected by the pipe 1 of the present invention, and a liquid feed pump 13 is provided between them, so that the liquid can be fed from the adjustment tank 10 to the filtration unit 20.

  A valve 15c is provided downstream of the filtration unit 20, and a valve 15d and a filling nozzle 14 are further provided as filling equipment. In addition, a circulation line 28 is provided so that the chemical solution can be returned to the adjustment tank 10.

  For example, the inner surface of the pipe 1 is subjected to a lining treatment with polytetrafluoroethylene, and the surface is formed so as to satisfy at least one of the arithmetic average roughness Ra and the ten-point average roughness Rz. ing.

  First, after the tank lower valve 15b of the preparation device is closed, the upper valve 15a is opened, for example, an immersion composition is introduced from the chemical solution supply nozzle 11, and the valve 15a is closed. Stir at 12 until the concentration of the contents is uniform.

  Thereafter, the tank lower valve 15b is opened, and the solution is circulated by the circulation line 28 by the liquid feed pump 13 and is subjected to circulation filtration, whereby an immersion composition solution can be produced. After the circulation, the valve 15c and the valve 15d are opened, the immersion composition solution is fed, and the composition solution is filled into the filling bottle 24 while measuring the weight with the weigh scale 23, for immersion as a product. A composition solution can be obtained.

  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, an apparatus as shown in FIG. 2 was assembled. The pipe inner surface used in the examples was subjected to Teflon lining treatment (lining treatment with polytetrafluoroethylene), and pipe 1 having an Ra value of 0.03 μm and an Rz value of 0.19 μm was used. In addition, the three-dimensional measurement was implemented using the non-contact film thickness meter (the Ryoko company make, NH-3), and the surface roughness was calculated | required according to JIS specification (B0601: 1994). The reference length was 20000 μm.

  First, after closing the tank lower valve 15b of the preparation device, the upper valve 15a is opened, and the liquid immersion composition (2-methyl-acrylic acid 4,4,4-trifluoro-3 -Hydroxy-1-methyl-3-trifluoromethyl-butyl and vinyl sulfonic acid copolymer, 4-methyl-2-pentanol containing 20% of Mw 10000) was charged in 30 kg, and 4-methyl-2 was further added. -After charging 30 kg of pentanol and closing the valve 15a, the mixture was stirred with the stirring device 12 for 3 hours until the concentration of the contents became uniform.

Thereafter, the tank lower valve 15b was opened, and circulation filtration was performed by the liquid feed pump 13 over 4 hours. The filter used was an HDPE membrane (pore size: 0.01 μm, filter cloth area: 0.24 m ² ). After the circulation, the valve 15c and the valve 15d were opened, and the composition solution was filled in the filling bottle to obtain an immersion composition solution.

(Examples 2-14, Comparative Examples 1-6)
An immersion composition solution was obtained in the same manner as in Example 1 except that a pipe having the surface roughness of the pipe inner surface shown in the following table was used.

(Examples 15 to 23, Comparative Examples 7 to 10)
Similarly, propylene glycol monomethyl ether acetate was added to a copolymer (Mw: 13,000) obtained by copolymerizing 2-methyl-2-adamantyl methacrylate and norbornane lactone methacrylate to obtain a raw solution (solid content). Content: 8% by mass) to obtain a resin-containing composition solution for photoresist.

(Foreign substance evaluation method)
The foreign substance size and the number thereof were evaluated from the fine particle measurement. As an evaluation device, an automatic fine particle measuring device (Ks-41 type) manufactured by Rion Co., Ltd. was used.

  In Tables 1 and 2, those satisfying Ra <X and Rz <3X were evaluated as “◯”, and those not satisfying as “×”. In addition, for a foreign matter size X (μm) to be 100 pieces / ml or less (required specifications mean that foreign matter having a size of X (μm) or more is 100 pieces / ml or less), X (μm) The composition solution in which the number of foreign substances was 100 (pieces / ml) or less was evaluated as “good”, and the composition solution exceeding 100 (pieces / ml) was evaluated as “poor”. For those satisfying Ra <X or Rz <3X with respect to the foreign matter size X, the number of foreign matters in 1 ml of X (μm) or more was 100 or less, and good results were obtained. For example, in Example 10 and Example 14, the Ra value is 0.5 μm or less, the ten-point average roughness Rz value is less than 3 × (μm) and 1.5 μm or less, and the number of foreign matters is 100 ( Pieces / ml) or less.

  The liquid feeding method and manufacturing method of the composition solution for semiconductor production according to the present invention are used for applications such as strict sub-quarter micron level microfabrication with respect to contamination such as foreign matters such as metallic foreign matters and impurities such as metallic components. It is suitably used for the production of a resist resin-containing solution, a liquid immersion composition solution, an upper layer film-forming composition, and the like.

It is sectional drawing which shows one Embodiment of piping of this invention. It is a schematic diagram which shows the manufacturing apparatus of the composition solution for semiconductor manufacture.

Explanation of symbols

1: piping, 2: metal piping, 3: lining, 10: adjustment tank, 11: chemical supply nozzle, 12: stirring device, 13: liquid feed pump, 14: filling nozzle, 15a, 15b, 15c, 15d: valve, 20: Filtration unit, 23: Weigh scale, 24: Filling bottle, 28: Circulation line, 30: Production equipment.

Claims (6)

The following relational expression Ra <X between the value of the arithmetic mean roughness (Ra; μm) indicating the surface smoothness and the foreign substance size (X; μm) in the composition solution for semiconductor production to be fed
A method for feeding a composition solution for semiconductor production, which uses a pipe on the inner surface that satisfies the above. The following relational expression Rz <3X between the 10-point average roughness value (Rz; μm) indicating the surface smoothness and the foreign material size (X; μm) in the composition solution for semiconductor production
A method for feeding a composition solution for semiconductor production, which uses a pipe on the inner surface that satisfies the above.   The method for feeding a composition solution for semiconductor production according to claim 1 or 2, wherein an inner surface of the pipe is subjected to any of electrolytic polishing treatment of stainless steel, glass lining treatment, and lining treatment with polytetrafluoroethylene.   The manufacturing method of the composition solution for semiconductor manufacture manufactured using the liquid feeding method of the composition solution for semiconductor manufacture of any one of Claims 1-3.   The piping used for the liquid feeding method of the composition solution for semiconductor manufacture of any one of Claims 1-3.   Ten point average when the arithmetic mean roughness Ra value of the inner surface of the pipe for feeding the semiconductor manufacturing composition solution is 0.5 μm or less and the foreign matter size in the semiconductor manufacturing composition solution is X (μm) An apparatus for producing a composition solution for semiconductor production, having a roughness Rz value smaller than 3X (μm) and 1.5 μm or less.

Images