JPWO2020086772A5 - - Google Patents

Description

[Technical field]

The present invention relates to a chemical solution manufacturing apparatus and a method for producing a chemical solution using the same.

[Background technology]

The semiconductor industry has achieved a rapid increase in the density of electronic components resulting from the continuous reduction in component size. Ultimately, more and smaller parts can be integrated into a given area. These improvements are largely due to the development of new precision and high resolution processing techniques.

During the manufacture of high resolution integrated circuits (ICs), various treatment liquids come into contact with bare wafers or film coated wafers. For example, the manufacture of a fine metal wiring structure typically involves coating the substrate with a pre-wet solution before the substrate is coated with the composite liquid to form a resist film. These treatment liquids, which contain unique components and various additives, are known as contaminant sources for IC wafers.

Even if a small amount of contaminants are mixed in these chemicals such as wafer prewetting liquid or developer, it can be inferred that the resulting circuit pattern may have defects. It is known that the presence of very low levels of metal impurities of only 1.0 ppt impair the performance and stability of semiconductor devices. Then, depending on the type of metal impurities, the oxidation characteristics are deteriorated, an inaccurate pattern is formed, and the electrical performance of the semiconductor circuit is impaired, which ultimately affects the manufacturing yield.

Impurities such as metal impurities, fine particles, organic impurities, moisture and the like can be unintentionally introduced into the chemical solution during various stages of the chemical solution manufacturing process. Such examples include impurities in raw materials, by-products produced during the manufacture of chemicals, residual unreacted reactants, or the surface of manufacturing equipment and container equipment used for transport, storage and reaction. This includes the case where foreign substances eluted or extracted from the reaction vessel or the like are present. Therefore, reduction or removal of insoluble and soluble contaminants from these chemicals used in the manufacture of high-precision and ultra-fine semiconductor electronic circuits is a basic guarantee for the manufacture of defect-free ICs. ..

In this regard, the standards and quality of the chemicals manufacturing process and the manufacturing equipment applied to the process for forming the high-purity chemicals essential for the production of ultra-fine and highly precise semiconductor electronic circuits have been significantly improved. However, strict control is essential.

Therefore, in order to form a high-precision integrated circuit, the demand for ultra-high-purity chemicals and the quality improvement and control of these liquids are very important. Specific key parameters for quality improvement and control include reduction of trace metals, reduction of liquid particle count, reduction of on-wafer defects, reduction of organic contaminants, etc. It has been shown that all these important parameters are influenced by the required preparation of the manufacturing equipment and the proper design of the manufacturing process.

In view of the above, the present invention particularly provides a chemical solution manufacturing apparatus for preparing a chemical solution for semiconductor production and a method for producing a chemical solution using the same, and the high-purity chemical solution has a predetermined range. Manufactured with the number of particles and the amount of metal impurities in the chemical solution controlled to prevent the introduction of unknown and unwanted substances. Therefore, the generation of residue and / or particle defects is suppressed, and the yield of the semiconductor wafer is improved.

According to some embodiments of the invention, the drug solution manufacturing apparatus comprises at least a first system, the first system being configured to process the material. The first system is a temperature control configured on the upstream side of at least one first filtration medium selected from a first ion exchange membrane and a first ion adsorption membrane and at least one first filtration medium. Including units.

According to some embodiments of the present invention, the method of producing a chemical solution provides a system comprising at least an ion exchange membrane and / or an ion adsorption membrane, and at least an ion exchange membrane and / or at least to regulate the temperature of the material. Alternatively, it includes arranging a temperature control unit on the upstream side of the ion adsorption membrane and processing the material with the system.

According to the present invention, the chemical liquid manufacturing apparatus and the method for manufacturing the chemical liquid using the chemical liquid manufacturing apparatus avoid the introduction or formation of various organic and inorganic contaminants during the manufacturing process, and are applicable to semiconductor manufacturing. Effectively designed and properly configured to produce purity chemicals.

The aspects of the invention are most preferably understood from the following detailed description when read with the accompanying drawings. Note that the various features are not drawn to scale according to industry standard practices. In fact, the dimensions of the various functions are optionally scaled up or down to clarify the description.

FIG. 1 is a schematic diagram showing an exemplary drug solution manufacturing apparatus adopted in a method for manufacturing a drug solution according to some embodiments of the present invention.

FIG. 2 is a flow chart of processing steps in a method for producing an exemplary chemical solution according to some embodiments of the present invention.

FIG. 3 shows the GC-MSMS results.

The following disclosures provide many different embodiments or examples for implementing the different features of the provided subject matter. For the sake of brevity of the present disclosure, specific embodiments of components and arrangements are described below. Of course, these are just examples and are not intended to be limited. For example, when the term "solvent" is used, it refers to a single solvent or a combination of two or more solvents, unless otherwise stated (unless otherwise specified). In addition, the present disclosure may repeat reference numerals and / or characters in various embodiments. This iteration is intended for brevity and clarity and by itself does not specify the relationships between the various embodiments and / or configurations described.

Further, spatial relative terms such as "downward", "lower", "lower", "upper", "upper", etc. relate to one element or function represented in the drawing to another element or function. It is used here to facilitate the description for explanation. Spatial relative terms are intended to include different orientations of the device in use or in operation, in addition to the orientations illustrated in the drawings. The device may be oriented in other ways (rotation 90 degrees or in any other direction), and the spatial relative descriptive terms used herein are interpreted accordingly.

In the present invention, the numerical range indicated by using the term "-" means a range including the numerical values before and after the term "-" as the lower limit value and the upper limit value.

In the present invention, "ppm" means "parts-per-million ( 10-6 )", " ^ppb " means "parts-per-billion ( 10-9 )", and " ^ppt " means "parts". ^{-Per-trillion (10-12} ) "means.

In the present invention, 1 Å (angstrom) corresponds to 0.1 nm (nanometer) and 1 μm (micron) corresponds to 1000 nm.

<Chemical solution>

In the present invention, the chemical solution contains a wafer processing solution such as a pre-wet solution, a developing solution, a rinsing solution, a cleaning solution, a stripping solution, etc., or a raw material solvent used for producing the same.

Prior to undergoing the manufacturing process of the present invention, including but not limited to purification steps, the drug solution may contain undesired amounts of contaminants and impurities. After the drug solution is processed by the manufacturing process of the present invention by adopting the drug solution manufacturing apparatus of the present invention, a considerable amount of contaminants and impurities are removed from the drug solution. The chemical solution before treatment is referred to as "material to be treated" in the present invention. The material to be processed may be obtained on the market through in-house synthesis or purchase from a supplier. The treated chemical solution is referred to as a "treated chemical solution" in the present invention, and is also simply referred to as a "chemical solution". The "treated chemical solution" or "chemical solution" may contain impurities controlled and restricted within a predetermined range.

<Organic solvent>

In the present invention, the chemical solution contains an organic solvent. The type of the organic solvent is not particularly limited, but a well-known organic solvent is applicable. The content of the organic solvent in the chemical solution is not particularly limited, but the organic solvent is contained as the main component. Specifically, the content of the organic solvent is 98% by mass or more with respect to the total mass of the chemical solution. In a particular embodiment, the content of the organic solvent is 99% by mass or more with respect to the total mass of the chemical solution. In another embodiment, the content of the organic solvent is 99.5% by mass or more with respect to the total mass of the chemical solution. In still another embodiment, the content of the organic solvent is 99.8% by mass or more with respect to the total mass of the chemical solution. The upper limit value is not particularly limited, but the upper limit value is usually 99.999% by mass or less.

The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total content thereof is preferably within the above range.

The content of the organic solvent in the chemical solution can be measured by using a gas chromatograph mass spectrometry (GCMS) device.

The boiling point of the organic solvent is not particularly limited. However, the boiling point of the organic solvent is preferably less than 200 ° C. from the viewpoint of improving the manufacturing yield of the semiconductor chip. In the present invention, the boiling point means the boiling point at 1 atm.

The organic solvent is not particularly limited. Examples of organic solvents are methanol, ethanol, 1-propanol, isopropanol, n-propanol, 2-methyl-1-propanol, n-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-Pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-1- Pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4- Methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 2,2-dimethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 2,4- Dimethyl-3-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-3-heptanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-2-hexanol, 2-methyl- 3-hexanol, 5-methyl-1-hexanol, 5-methyl-2-hexanol, 2-ethyl-1-hexanol, methylcyclohexanol, trimethylcyclohexanol, 4-methyl-3-heptanol, 6-methyl-2- Heptanol, 1-octanol, 2-octanol, 3-octanol, 2-propyl-1-pentanol, 2,6-dimethyl-4-heptanol, 2-nonanol, 3,7-dimethyl-3-octanol, ethylene glycol, Propylene glycol, diethyl ether, dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, di -Tert-Butyl ether, dipentyl ether, diisoamyl ether, cyclopentylmethyl ether, cyclohexylmethyl ether, bromomethylmethyl ether, α, α-dichloromethylmethyl ether, chloromethylethyl ether, 2-chloroethylmethyl ether, 2-bromoethyl Methyl ether, 2,2-dichloroethyl methyl ether, 2-chloroethyl ethyl ether, 2-bromoe Chill ethyl ether, (±) -1,2-dichloroethyl ethyl ether, 2,2,2-trifluoroethyl ether, ethyl vinyl ether, butyl vinyl ether, allyl ethyl ether, allyl propyl ether, allyl butyl ether, diallyl ether, 2- Methoxypropen, ethyl-1-propenyl ether, cis-1-bromo-2-ethoxyethylene, 2-chloroethyl vinyl ether, allyl-1,1,2,2-tetrafluoroethyl ether, octane, isooctane, nonane, decane, Methylcyclohexane, decalin, xylene, ethylbenzene, diethylbenzene, cumene, sec-butylbenzene, simene, dipentene, methyl pyruvate, monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether. Acetate, ethyl lactate, methylmethoxypropionate, cyclopentanone, cyclohexanone, butyl acetate, γ-butyrolactone, diisoamyl ether, isoamyl acetate, chloroform, dichloromethane, 1,4-dioxane, hexyl alcohol, 2-heptanone, isoamyl acetate , And tetrahydrofuran.

In a particular embodiment of the invention, the drug solution is a pre-wet solution. The type of pre-wet liquid is not particularly limited. Specific examples of the pre-wet solution include cyclopentanone (CyPe), cyclohexanone (CyH), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol. It contains at least one of monopropyl ether (PGPE) and ethyl lactate (EL). In other embodiments, the drug solution may be a developer such as butyl acetate or a rinse solution such as 4-methyl-2-pentanol (MIBC).

<Impurities>

Impurities contained in the treatment target and / or the chemical solution include metal impurities, particles, organic impurities, moisture and the like.

<Metal impurities>

The most common metal impurities include heavy metals such as iron (Fe), aluminum (Al), chromium (Cr), nickel (Ni) and ionic metals such as sodium (Na) and calcium (Ca). Depending on the type of metal, metal impurities reduce the integrity of the oxide, degrade the MOS gate stack, shorten the life of the device, and the like. In the chemical solution produced by the chemical solution manufacturing apparatus according to the production method of the present invention, the total trace metal content is preferably in the predetermined range of 0 to 300 pt by mass, and more preferably 0 to 150 pt.

In the present invention, the metal impurity refers to a metal impurity provided in the form of a solid (elemental metal, particulate metal-containing compound, etc.).

<Particles>

In the present invention, a counting object having a size of 0.03 μm or more is referred to as “particle” or “fine particle”. The number of "particles" in the liquid medium is counted by a light scattering type liquid particle counter and is called LPC (number of particles in liquid).

Examples of particles include dust, debris, organic solids, inorganic solids. The particles may also contain impurities of colloidal metal atoms. The type of metal atom that is easily colloidalized is not particularly limited, but at least one selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, and Pb. It may contain metal atoms. In the chemical solution prepared by the chemical solution producing apparatus of the present invention, the total number of particles having a size of 0.03 μm or more is preferably within a predetermined range of 100 or less per 1 ml of the chemical solution.

<Organic impurities>

The organic impurity means a compound different from the organic solvent as the main component provided in the chemical solution, and the organic substance contained in the content of 5000 mass ppm or less with respect to the total mass of the chemical solution corresponds to the organic impurity and becomes an organic solvent. Indicates that it does not correspond.

Volatile organic compounds are present in the ambient air even in clean rooms. Some organic impurities are derived from shipping and storage equipment, while others are included in the raw materials from the beginning. Other examples of organic impurities include by-products produced when the organic solvent is synthesized and / or unreacted reactants.

The total content of organic impurities in the chemical solution is not particularly limited. From the viewpoint of improving the manufacturing yield of the semiconductor device, the total content of organic impurities is preferably 0.1 to 5000 mass ppm, more preferably 1 to 2000 mass ppm, based on the total mass of the chemical solution. It is more preferably 1 to 1000 mass ppm, particularly preferably 1 to 500 mass ppm, and most preferably 1 to 100 mass ppm.

The content of organic impurities in the chemical solution can be measured by using a gas chromatograph mass spectrometry (GCMS) device.

<Chemical solution manufacturing equipment>

FIG. 1 is a schematic diagram showing the configuration of an exemplary chemical solution manufacturing apparatus according to some embodiments of the present invention. As shown in FIG. 1, the chemical solution manufacturing apparatus 10 is connected to a processing target supply unit 20 configured to hold or transport a material, for example, a processing target material or a pretreated chemical solution. The material to be treated is processed by the chemical solution manufacturing apparatus 10 in order to generate or produce a chemical solution in which the number of unwanted contaminants such as fine particles, organic impurities, metal impurities and the like is controlled within a predetermined range and is limited. In some embodiments, the drug solution is monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methoxypropionic acid, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl. It includes, but is not limited to, ether, 4-methyl-2-pentanol and the like. The treatment target supply unit 20 is not particularly limited as long as the treatment target material is continuously or intermittently supplied to the chemical solution manufacturing apparatus 10. The processing target supply unit 20 may include a material receiving tank, a sensor such as a level gauge (not shown), a pump (not shown), a valve for controlling the inflow of the processing target material (not shown), and the like. In FIG. 1, the chemical liquid manufacturing apparatus 10 is connected to 20 of one processing target supply unit. However, the present invention is not limited to this. In some embodiments, a plurality of processing target supply units 20 are provided in parallel for each type of processing target material to be processed by the chemical liquid manufacturing apparatus 10.

As shown in FIG. 1, the chemical solution manufacturing apparatus 10 includes at least one first purification system 110. In certain exemplary embodiments, the chemical manufacturing apparatus 10 may include a heat exchanger 100 for setting the temperature of the material to be treated to a particular temperature range. In this way, the material to be processed filled in the chemical liquid manufacturing apparatus 10 is kept at a substantially constant temperature. The heat exchanger 100 is arranged, for example, between the processing target supply unit 20 and the first purification system 110. In some embodiments, the temperature of the material to be treated is ambient temperature (eg, room temperature).

Also referring to FIG. 1, the first purification system 110 has at least one or more filtration media 114 (purification means), each of which has a particular purification function (form or medium of filtration unit) and provides a particular treatment. )including. For example, the purification system 110 may include at least one filtration medium 114 (114a, 114b, or 114c) selected from an ion exchange membrane and an ion adsorption membrane. In some embodiments, the purification system 110 comprises at least one particle removal filter and at least one ion exchange membrane and / or ion adsorption membrane. Further, the one or more filtration media 114 are high quality products commercially available from the supplier.

In certain exemplary embodiments, the one or more filtration media 114 are each compartmentalized and housed in one or more enclosures 112. For example, the first purification system 110 may include at least one enclosure 112 selected from a first enclosure 112a, a second enclosure 112b, and a third enclosure 112c, and may include at least one enclosure. 112 contains and accommodates one or more units of the filtration medium 114 therein. In other words, according to the above example, the first purification system 110 has only one housing 112 (either the first housing 112a, the second housing 112b, or the third housing 112c). Or two housings 112 (any combination of any two of the first housing 112a, the second housing 112b, and the third housing 112c), or the three housings 112 (first housing). 112a, a second housing 112b, a third housing 112c) may be included. Note that the above examples are for illustrative purposes only and the number of enclosures is not limited to the examples shown. In another exemplary embodiment, the first purification system 110 is, for example, 1, 2, 3, in addition to the first, second and / or third enclosures (112a, 112b, 112c) described above. 6 or more, more than 10 enclosures 112 may be included.

In an alternative exemplary embodiment, there is no need for a separate enclosure 112 and one or more filtration media 114 are configured not to be compartmentalized in the first purification system 110. In yet another exemplary embodiment, the first purification system 110 may include one or more filtration media 114 as well as other purification modules (not shown).

Also referring to FIG. 1, the first housing 112a may contain one or more units of the first filtration medium 114a and the second housing 112b contains one or more units of the second filtration medium 114b. The third housing 112c may include one or more units of the third filtration medium 114c, and the first, second, and third filtration media 114a, 114b, 114c have different functions or performances and are different. Purification treatment may be provided, each of which has one or more units of filtration medium 114 (114a, 114b, 114c) housed in each selected enclosure (112a, 112b, 112c) having the same or similar purification function. It has physicochemical properties, pore diameter and / or constituent materials and the like. As an example, the first purification system 110 has one or more particle removal filters and one or more ion exchanges housed in the first housing 112a, the second housing 112b, and the third housing 112c, respectively. The membrane may include one or more ion adsorption membranes. In another example, the first purification system 110 has one or more particle removal filters and one or more ion exchange membranes (or 1) housed in the first housing 112a and the second housing 112b, respectively. The above ion adsorption membrane) may be included. In yet another example, the first purification system 110 comprises one or more ion exchange membranes and one or more ion adsorption membranes housed in the first housing 112a and the second housing 112b, respectively. It's fine. Note that the above examples are for illustrative purposes only and are not intended to be limiting.

As shown in FIG. 1, the first purification system 110 also includes a temperature control unit 180 configured upstream of the entrance of at least one housing 112. According to an embodiment of the present invention, the temperature control unit 180 is configured and configured upstream of the entrance and exit of the selected housing 112 that houses one or more ion exchange membranes or one or more ion adsorption membranes. The temperature of the material to be processed passing through 112 is limited to a predetermined optimum temperature range. The temperature control unit 180 includes a commercially available recirculation heating / cooling unit, a condenser, or, for example, a heat exchanger attached to a pipe, upstream of the inlet of the selected housing 112. Not limited.

In some exemplary embodiments, the temperature control unit 180 includes a cooling unit, the temperature control unit 180 is set to a temperature of about 80 ° F. or less, preferably about 65 ° F. or less, and the temperature of the object to be treated is. When passing through one or more ion exchange membranes or one or more ion adsorption membranes in the selected housing 112, the temperature is limited to about 80 ° F. or less. In another embodiment, the temperature control unit 180 is set within a temperature range of about 30-70 ° F. In yet another embodiment, the temperature control unit 180 is preferably set within a temperature range of about 41-67 ° F. In an alternative embodiment, it is more preferred that the temperature control unit be set within a temperature range of about 50-65 ° F. According to a particular embodiment of the invention, the temperature control unit 180 is prevented from rising above 70 ° F. In some embodiments, the temperature control unit 180 is prevented from rising above 68.5 ° F. In yet another embodiment, the temperature control unit 180 is restricted from rising above 67.5 ° F.

As in the example shown in FIG. 1, the temperature control unit 180 is configured between the first housing 112a and the second housing 112b, and the temperature of the material to be processed is processed by the temperature control unit 180. Target Material The material is adjusted to 65 ° F. or less before being filled and processed in the second housing 112b, and the second housing 112b is one or more ion exchange filtration media or one or more ion adsorption filtration media. Accommodates any of. In the above example, the first housing 112a may include one or more particle removal filters, and the particle removal filter may have, for example, a pore diameter of 20 nm or more. It should be understood that the arrangement order of the housing 112 and the filtration medium 114 exemplified in the above example is for illustrative purposes only and is not intended to be limiting.

Note that the position of the temperature control unit 180 is not limited to the examples shown above. In another exemplary embodiment, the temperature control unit 180 may be configured upstream of the inlet of the first housing 112a, where the first housing 112a is one or more ion exchange membranes or one or more ion adsorption membranes. To accommodate. In this regard, another temperature control unit may or may not be attached downstream of the first enclosure 112a in front of the inlet of subsequent enclosures (eg, enclosure 112b and / or 112c). The configuration of another temperature control unit downstream of the first housing 112a is such that other means or equipment capable of reintroducing thermal energy into the material to be processed, such as a pump, is the first housing 112a and another. Or optional, provided that it is not introduced or placed between an additional ion exchange medium and / or a subsequent enclosure (eg, a second enclosure 112b or a third enclosure 112c) accommodating an ion adsorption medium. Is.

In certain exemplary embodiments, there is no need for a separate enclosure 112 in the first purification system 110, and one or more filtration media 114 are configured not to be partitioned in the first purification system 110. For example, the first purification system 110 is a multi-stage system including replaceable filtration media 114 (114a, 114b, 114c) coupled together inside the first purification system 110, and the material to be processed is a filtration medium. It flows down 114 (114a, 114b, 114c). In this regard, the temperature control unit 180 may be configured at any position upstream of the first ion exchange membrane or ion adsorption membrane through which or flows down the material to be treated. For example, when the first purification system 110 sequentially accommodates the particle removal filter A, the particle removal filter B, the ion exchange membrane A, the ion exchange membrane B, and the ion adsorption membrane A downstream of the supply port 110a, the temperature. The control unit 180 sets the temperature of the material to be treated to about 80 ° F or less, preferably about 80 ° F or less, before the material to be treated passes through the ion exchange membrane A and the subsequent ion exchange membrane B and the ion adsorption membrane A to be treated. It may be configured between the particle removal filter B and the ion exchange membrane A in order to adjust and limit the temperature to 65 ° F or less. Note that the above examples are for illustrative purposes only and are not intended to be limiting.

In another example, in the temperature control unit 180, when the material to be treated is treated by the ion exchange membrane A and the subsequent ion exchange membrane B and the ion adsorption membrane A, the temperature of the material to be treated is in the above-mentioned temperature range, for example, 80. It may be configured upstream of the particle removal filter A or between the particle removal filters A and B as long as it is maintained at ° F or less, preferably 65 ° F or less.

In some exemplary embodiments, the first purification system 110 is re-processed so that the partially purified object is returned to the first purification system 110 and processed again by the first purification system 110. A recirculation conduit 160h for circulation may also be included. Further, another temperature control unit / heat exchanger 170 may be configured along the recirculation conduit 160h. In certain embodiments, the temperature control unit 170 may also be set to a temperature of about 80 ° F. or less, preferably about 65 ° F. or less, and the temperature of the partially purified object is the first purification system. Limited to about 80 ° F or less when recirculated to 110. In the example shown in FIG. 1, the recirculation conduit 160h is located upstream of the outlet 110b of the first purification system 110. In another example, the recirculation conduit 116h may be configured downstream of the outlet 110b. If desired, pumps and valves may be attached to various conduits, outlets, supply ports, etc., such as the processing target supply unit 20, heat exchanger 100, first purification system 110, and the like.

According to the non-limiting embodiment described above, the chemical solution manufacturing apparatus 10 further includes a second purification system 120 that directly or indirectly communicates with the first purification system 110, and the second purification system 120 is 1. The above filtration medium 124 is included. In the exemplary embodiment shown in FIG. 1, the second purification system 120 is located downstream of the first purification system 110. However, it should be noted that the relative configuration of the first purification system 110 and the second purification system 120 is not limited to the examples shown above.

Each of the one or more filtration media 124s in the second purification system 120 may be compartmentalized and housed in one or more enclosures 122. For example, the second purification system 120 may include at least one enclosure 122 selected from a fourth enclosure 122a, a fifth enclosure 122b, a sixth enclosure 122c, and at least one enclosure. 122 contains and accommodates one or more units of the filtration medium 124 therein. In other words, the second purification system 120 may include one, two, or three enclosures 122. In another exemplary embodiment, the second purification system 120 may include a fourth enclosure 122a, a fifth enclosure 122b, a sixth enclosure 122c, as well as more enclosures 122. .. Further, there is no need for a separate enclosure 122, and one or more filtration media 124s are configured to be non-partitioned in the second purification system 120. In yet another exemplary embodiment, the second purification system 120 may include one or more filtration media 124 plus other purification modules not shown.

According to the example described above, the fourth housing 122a may contain one or more units of the fourth filtration medium 124a, and the fifth housing 122b may contain one or more units of the fifth filtration medium 124b. Often, the sixth enclosure 122c may include one or more units of the sixth filtration medium 124c, the fourth filtration medium 124a, the fifth filtration medium 124b, and the sixth filtration medium 124c having a function or performance. Different and different purification treatments may be provided, each with one or more units of filtration medium 124 (124a, 124b, 124c) housed in each selected enclosure 122 (122a, 122b, 122c) being the same or similar. Has a purification function, physicochemical properties, pore diameter and / or constituent materials, etc. For example, the second purification system 120 may include a filtration medium 124 (124a, 124b, 124c) selected from a particle removal filter, an ion exchange membrane, and an ion adsorption membrane.

Similar to the first purification system 110, the temperature control unit 190 may be configured upstream of the inlet of the housing 122 accommodating one or more ion exchange membranes or one or more ion adsorption membranes and passes through the housing 122. The temperature of the chemical solution is limited to a predetermined optimum temperature range. The principle, arrangement, and specifications of the application of the temperature control unit 190 adopted in the second purification system 120 are similar to those described in the first purification system 110 exemplified in paragraphs [0051] to [0058].

According to the exemplary embodiment shown in FIG. 1, the temperature control unit 190 may be configured on the upstream side of the entrance of the fourth housing 122a, and the fourth housing 122a may have one or more ion exchange membranes. Alternatively, the ion adsorption membrane is housed and the temperature to be treated is preferably about 80 ° F. or less by the temperature control unit 190 before the material to be treated enters the fourth housing 122a of the second purification system 120. Is adjusted to about 65 ° F or less. In another embodiment, the temperature control unit 190 is set within a temperature range of about 30-70 ° F. In yet another embodiment, the temperature control unit 190 is preferably set within a temperature range of about 41-67 ° F. In an alternative embodiment, it is more preferred that the temperature control unit 190 is set within a temperature range of about 50-65 ° F. Note that in certain embodiments, the temperature control unit 190 is avoided from being set to a temperature above 70 ° F. In some embodiments, the temperature control unit 190 is prevented from rising above 68.5 ° F. In yet another embodiment, the temperature control unit 190 is restricted from rising above 67.5 ° F. As an example, the fifth or sixth enclosure (122b or 122c) may include one or more particle removal filters having a pore size of 10 nm or less.

It should be noted that the arrangement order of the housing 122 and the filtration medium 124 exemplified in the above example is for illustrative purposes only and is not intended to be limited. In some embodiments, the temperature control unit 190 may be configured between the fourth housing 122a and the fifth housing 122b in the second purification system 120, and the temperature of the material to be processed may be determined. Before the material to be processed is filled in the fifth housing 122b , the temperature control unit 190 adjusts the temperature to a desired temperature range, and the fifth housing 112b is the ion exchange filtration medium 114b or the ion adsorption filtration medium 114b. Containing either, the fourth housing 122a may include one or more particle removal filters. Further, another temperature control unit may or may not be attached downstream of the fifth housing 122b. In the installation of another temperature control unit, another means or device capable of reintroducing thermal energy into the material to be processed, such as a pump, accommodates the fifth housing 122b and another ion exchange medium or ion adsorption medium. It is optional, provided that it is not introduced or placed with a subsequent enclosure (eg, sixth enclosure 122c ). It should be understood that the location of the temperature control unit 190 is not limited to the examples shown above.

In some exemplary embodiments, the second purification system 120 is re-processed so that the partially purified subject is returned to the second purification system 120 and processed again by the second purification system 120 . A recirculation conduit 160f for circulation may be included. Further, another temperature control unit / heat exchanger may be configured along the recirculation conduit 160f.

<Method of manufacturing chemicals>

FIG. 2 is a flow chart of processing steps in a method for producing an exemplary chemical solution according to some embodiments of the present invention.

With reference to both FIGS. 1 and 2, the method of producing a drug solution according to some embodiments comprises providing the drug solution manufacturing apparatus 10 in step 10 for producing the drug solution. According to an exemplary embodiment of the invention, the chemical solution manufacturing apparatus 10 includes at least one first purification system 110 containing one or more first filtration media 114, and the first filtration medium 114 is at least. Includes one or more ion exchange membranes and / or one or more ion adsorption membranes. In a particular embodiment, the drug solution manufacturing apparatus 10 includes at least the first purification system 110 and a second purification system 120.

Next, referring to step 30, the pretreated chemical solution or the material to be treated is sent to the first purification system 110 of the chemical solution manufacturing apparatus 10. The material to be treated contains an organic solvent containing a metal component selected from the group of metal elements consisting of iron (Fe), chromium (Cr), nickel (Ni) and lead (Pb), and the metal in the pretreated chemical solution. The content of the component is in the range of about 0.1 to 1000 mass ppt. In another embodiment, the content of the metal component contained in the pretreated chemical solution may be 200 to 1000 mass ppt. In yet another embodiment, the content of the metal component contained in the pretreated chemical solution is in the range of 500 to 1000 mass ppt.

Also referring to FIGS. 1 and 2, the method of producing a chemical solution comprises adjusting the temperature of the material to be treated to a predetermined optimum temperature range in step 40. More specifically, according to a particular embodiment of the invention, the temperature of the material to be treated is before entering the entrance of the housing 112 containing one or more ion exchange membranes or one or more ion adsorption membranes. , Adjusted to about 65 ° F or less. For example, according to the example shown in FIG. 1, the temperature of the material to be treated is adjusted to about 80 ° F. or less, preferably about 65 ° F. or less, before entering the second housing 112b, and the second The temperature of the material to be processed passing through the housing 112b is limited to a predetermined optimum temperature range of about 80 ° F. or less. In some embodiments, the temperature of the material to be treated may be adjusted within the temperature range of about 30-70 ° F. In yet another embodiment, the temperature of the material to be treated is preferably limited to a temperature range of about 41-67 ° F. In an alternative embodiment, it is more preferred that the temperature of the material to be treated is limited to a temperature range of about 50-65 ° F. According to some embodiments of the invention, the temperature of the material to be treated is restricted from rising above 70 ° F. In other embodiments, the temperature of the material to be treated is restricted from rising above 68.5 ° F. In yet another embodiment, the temperature of the material to be treated is restricted from rising above 67.5 ° F.

In step 20, the temperature control of the material to be treated is such that the temperature of the material to be treated is set to a desired predetermined temperature when it is processed by passing through a selected housing containing, for example, one or more ion exchange membranes or ion adsorption membranes. To adjust and maintain the range, attach the temperature control unit 180 to a conduit located upstream of the entrance of the selected housing, or attach the selected housing (eg, the second housing 112b in the above example). This may be achieved by surrounding with a temperature unit.

Note that the above examples are for illustrative purposes only and the order of the processing steps is not limited to the examples shown. In other exemplary embodiments, the order of the delivery step (eg, step 30) and the temperature control step (eg, step 40) may be reversed. For example, first the temperature of the material to be treated may be limited to a predetermined optimum temperature range of about 80 ° F or less, preferably about 65 ° F or less, and then the temperature-limited material to be treated is one or more ion exchange media. Alternatively, it may be sent to the chemical solution manufacturing apparatus 10 including the ion adsorption medium. As an example, the temperature of the material to be treated is about 80 ° F. by a temperature control unit / heat exchanger 170 configured along the recirculation conduit 160h before the material to be treated is returned to the first purification system 110. Hereinafter, it is preferably limited to a predetermined optimum temperature range of about 65 ° F or less. Note that the above examples are for illustrative purposes only and are not intended to be limiting. In the above exemplary embodiment, there is no other means of reintroducing heat or thermal energy into the material to be treated between the temperature control step and the delivery step. In other words, the temperature of the material to be treated is kept substantially within a predetermined optimum temperature range during the ion exchange or ion adsorption treatment.

The method for producing the drug solution may optionally include recirculating the object to be treated to the first purification system 110 and having the first purification system 110 process it. The method may also include sending the object to be treated to the second purification system 120 and treating the object one or more times with one or more second filtration media 124 in the second purification system 120.

The number of particles collected and detected from the treated chemical solution at the end of the treatment by the first purification system 110 or the combination of the first purification system 110 and the second purification system 120 and the amount of metal impurities are controlled within a predetermined range. As soon as it is done, it contains 0.1-100 mass ppt of a metallic component selected from the group of metallic elements consisting of, for example, iron (Fe), chromium (Cr), nickel (Ni), lead (Pb). A high-purity chemical is produced in step 50. Subsequently, the ultra-purity chemical is delivered to either the next stage of manufacturing or packaging 140.

[Particle removal filter]

The particle removal treatment is a step of removing particles and / or metal impurities (solid metal impurities) in the treatment target such as a chemical solution by using a particle removal filter. The particle removal filter is not particularly limited, and a well-known particle removal filter can be used.

The average pore diameter (pore diameter) of the filter is not particularly limited, but is preferably about 0.001 to 1.0 μm (1 nm to 1000 nm), preferably about 0.003 to 0.5 μm (3 nm to 500 nm), and is about 0. More preferably, it is 005 to 0.1 μm (5 nm to 100 nm). Within this range, foreign matter such as impurities or agglomerates contained in the refined product can be reliably removed while suppressing clogging of the filter. In a particular embodiment of the invention, the first purification system 110 has a minimum average pore size of 2 nm and may be in the range of 0.002 μm (2 nm) or more and about 1.0 μm (1000 nm) or less. A filter (eg, a microfiltration membrane having a pore size of 2 nm or more) may be included. When fine particles are included in the treatment target in addition to colloidal impurities containing metal atoms such as iron or aluminum, the treatment target uses a filter having an average pore diameter of at least 20 nm or 15 nm in order to remove relatively fine particles. Thereby, prior to performing the filtration, the particles are filtered by using a filter having an average pore size of at least 50 nm to remove the particles. Therefore, the filtration efficiency is improved and the particle removal performance is further improved.

In some embodiments of the invention, the second purification system 120 has a minimum pore size of 0.001 μm (1 nm) and may range from about 0.001 μm (1 nm) to about 0.015 μm (15 nm). May include a particle removal filter with. In certain embodiments, the second purification system 122 may include a UPE filter with a minimum pore size of 1 nm. In yet another embodiment, the second purification system 120 may include a nylon or MPTFE filter with a pore size of about 5 nm. Here, the average pore diameter can refer to the nominal value of the filter manufacturer.

Examples of filter materials used for particle removal include fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight). , Perfluoroalkoxy (PFA) resin, etc., or modified polytetrafluoroethylene (MPTFE). Considering the efficient removal of fine foreign substances such as impurities and / or aggregates contained in the chemical solution, the filters used for particle removal of the present invention are nylon, polypropylene (including high-density polypropylene), polyethylene, and polytetra. It is produced by at least one selected from the group consisting of fluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyimide, and polyamide-imide. A filter made of the above material can effectively remove foreign substances having high polarity that easily cause residue defects and / or particle defects, and efficiently reduce the content of metal components in the chemical solution. Can be done.

The polyimide and / or polyamide-imide may have at least one selected from the group consisting of a carboxyl group, a salt-type carboxyl group, and an -NH- bond. For solvent resistance, fluororesins, polyimides, and / or polyamide-imides are excellent.

[Ion exchange resin membrane (ion exchange membrane)]

The ion exchange resin film used in the present embodiment is not particularly limited, and a filter containing an ion exchange resin containing an appropriate ion exchange group immobilized on the resin film may be used. Examples of such ion exchange resin films include strongly acidic cation exchange resins having cation exchange groups such as chemically modified sulfonic acid groups on the resin films, such as cellulose, diatomaceous earth, nylon (amide groups). Resin), polyethylene, polypropylene, polystyrene, resin having an imide group, resin having an amide group and an imide group, fluororesin, or a particle removing film which is a film having an integral structure of a particle removing film and an ion exchange resin film. Includes a high-density polyethylene film and an ion exchange resin film. A polyalkylene membrane chemically modified with an ion exchange group is preferable. The polyalkylene contains, for example, polyethylene and polypropylene, and polypropylene is preferable. A cation exchange group is preferable as the ion exchange group. The ion exchange resin film used in the present embodiment may be a commercially available filter having a metal ion removing function. These filters are selected based on ion exchange efficiency and have an estimated pore size of the filter with a minimum of about 0.2 μm (200 nm).

[Ion adsorption membrane]

The ion adsorption membrane has a porous membrane material and has an ion exchange function. Such an ion adsorption membrane is not particularly limited as long as it has a pore diameter of 100 μm or less and has an ion exchange function. The material, type, etc. are not particularly limited. Examples of base material materials constituting the ion adsorption film include cellulose, diatomaceous earth, nylon (resin having an amide group), polyethylene, polypropylene, polystyrene and other precision filter film film materials, resin having an imide group, and amide group. It includes, but is not limited to, a resin having an imide group, a fluororesin, a high-density polyethylene resin, a film material into which an ion-exchangeable functional group has been introduced, and the like. Examples of the shape of the membrane material include a pleated type, a flat membrane type, a hollow fiber type, a porous body described in JP-A-2003-11260, and the like. As the ion exchange group introduced into the membrane material, it is preferable to use at least two combinations of a cation exchange group, a chelate exchange group, and an anion exchange group in order to optimize the elution and selectivity of the component to be removed. Since the ion adsorption membrane is porous, it is possible to remove some of the fine particles. In a particular embodiment of the invention, the ion adsorption membrane is, for example, a nylon membrane having a pore diameter of at least 0.02 μm (20 nm).

[Example]

The present invention will be described in more detail below based on the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. described in the following examples can be appropriately changed to a certain range without departing from the gist of the present invention. Therefore, the scope of the invention should not be construed as limiting by the following examples.

[Preparation of chemicals]

The chemical solution in the sample was cyclohexanone, and was prepared by subjecting the pretreated cyclohexanone (material to be treated) to an ion exchange treatment carried out by the chemical solution manufacturing apparatus 10 of the present invention.

The pretreated cyclohexanone was passed through an ion exchange medium either with or without appropriate temperature control. The temperature of the sample with proper temperature control was suppressed to about 50 ° F to 65 ° F before the ion exchange treatment. Samples without temperature control were processed by passing through the same type of ion exchange medium above 70 ° F.

<GC-MSMS>

Each sample collected at the end of the ion exchange process was injected into a GC-MSMS (Gas Chromatography Tandem Mass Spectrometry) instrument used to clearly identify the presence of unknown volatile analytes.

<OWPC>

Each sample was collected and then inserted into a wafer coating tool. After the bare wafer was coated with the sample, the wafer was transferred to a laser inspection system for inspection. By using laser light, a laser inspection system detected, counted and recorded the position and size of each particle on the wafer with a detection limit of 19 nm. In these examples, the counting target included particles having a size of 31 nm or more. The data were used to create a wafer map and provide a total on-wafer particle count (OWPC) containing all particles with sizes in the 31 nm to 1000 nm range.

<RAE>

Evaporation residues (RAE, also known as non-volatile residues (NVR)) are soluble, suspended, suspended, or particulate matter that remains after evaporation of a volatile solution. Non-volatile analysis can be used to measure the amount of fine contaminants. RAE quantification was performed in a controlled laboratory environment and included dispensing the liquid sample into a small metering vessel and heating the vessel to a predetermined temperature for a predetermined time to evaporate the organic solvent. The amount of residue was determined by weight measurement by weighing the container before and after evaporation of the organic solvent using a high-sensitivity balance.

<Evaluation result>

As shown in FIG. 3, the GC-MSMS results represent the effect of proper temperature control of the ion exchange process during the production of cyclohexanone. The results underscore the presence of unwanted, previously unknown impurities (eg, cyclohexanone dimer) associated with the production of cyclohexanone without temperature control. On the other hand, when the ion exchange process is performed under appropriate temperature control within the desired temperature range of 50 ° F to 65 ° F, detection of unwanted organic impurities produced in the sample is present, even in trace amounts. There wasn't.

<Table 1>

As shown in Table 1, the method for producing a chemical solution of the present invention has achieved the desired advantage of improving the removal of impurities and / or the reduction of unwanted by-products produced during the production of the chemical solution. Represents. The data show that the non-volatile residue content of the sample without temperature control was 2 to 10 times that of the sample with proper temperature control. As the temperature decreases, the reduction in RAE content becomes more pronounced.

<Table 2>

The results summarized in Table 2 show that the chemical solution manufacturing method is effective in reducing the number of on-wafer particles. As shown in Table 2, OWPCs with a size of 31 nm or more from the sample with appropriate temperature control were reduced by approximately 2-3 times compared to the sample without temperature control during the ion exchange process.

<Preparation of chemicals>

In the following experiment, the drug solution in the sample is cyclohexanone again, and the present invention employs the drug solution manufacturing apparatus 10 containing the pretreated cyclohexanone at least the first purification system 110 and the second purification system 120 of the present invention. It was prepared by the method for producing the drug solution of.

The placement and selection of the filtration medium 124 in the first purification system 110 (filter medium 114 in unit A) and the second purification system 120 (unit B), such as functionality, pore size, presence or absence of temperature controller, is each. Prepared for the preparation of the drug solution having the composition of the example.

<Evaluation result>

As shown in Table 3, each example was prepared by the drug solution manufacturing apparatus of the present invention, except that the chemical solution manufacturing apparatus was configured differently to treat the pretreated cyclohexanone (treatment target) of each embodiment. did. The different configurations of the chemical solution manufacturing apparatus for treating the pretreated cyclohexanone are represented as treatments A, B, C, D and E, respectively, as summarized in Table 3.

Table 3

Table 4

Table 5

The collective results summarized in Tables 1-5 and FIG. 3 show at least all that the method of producing a drug solution using the drug solution manufacturing apparatus of the present invention significantly reduces non-volatile residues and OWPC. It confirms that the desired advantage of improving the test attributes and preventing the generation of unwanted impurities during the production of the drug solution by the synergistic effect of temperature control and treatment configuration has been achieved. These data prevent and eliminate unwanted contaminants from the manufacturing methods and equipment of the invention resulting from poorly designed manufacturing equipment and / or improperly implemented manufacturing methods. It is demonstrating improvement. Therefore, the manufacturing method and manufacturing apparatus of the present invention provide a competitive advantage in producing an ultra-high-purity chemical solution, avoiding the occurrence of defects in circuit patterns and semiconductor devices, and improving the yield.

The above outlines the features of some embodiments so that those skilled in the art can better understand aspects of the present disclosure. Those skilled in the art will readily use this disclosure as a basis for designing or modifying other processes and structures to perform the same purposes as the embodiments presented herein and / or to achieve the same benefits. You should understand that you can. Those skilled in the art should also understand that such equivalent structures do not deviate from the spirit and scope of the invention and can be modified, replaced or substituted in various ways without departing from the spirit and scope of the invention. Is.