CN104969129B - Diluent composition and use thereof - Google Patents
Diluent composition and use thereof Download PDFInfo
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- CN104969129B CN104969129B CN201480007310.4A CN201480007310A CN104969129B CN 104969129 B CN104969129 B CN 104969129B CN 201480007310 A CN201480007310 A CN 201480007310A CN 104969129 B CN104969129 B CN 104969129B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
Abstract
The invention relates to a diluent composition and application thereof. The thinner composition of the present invention has excellent dissolving power for various photoresists and has the most appropriate volatility, so that an unnecessarily attached photoresist can be effectively removed in a short time in an edge bead removal process or the like, and can be applied to a pre-wetting process of a semiconductor substrate, and a photosensitive film can be effectively formed with a small amount of photoresist.
Description
Technical Field
The present invention relates to a thinner composition and use thereof, and more particularly, to a thinner composition that can be used in each step of a mask etching process in a semiconductor manufacturing process, and a method of forming a photosensitive film using the same.
Background
Photo lithography is a process of transferring a pre-designed pattern to a photosensitive film on a semiconductor substrate using a photo mask and then etching the substrate or an underlying film according to the transferred pattern.
In a photo mask etching process (photolithography process), a photoresist is coated on a semiconductor substrate to form a photosensitive film. And exposing the photosensitive film to light by using exposure equipment to project the pattern of the photomask, and then carrying out a developing process to manufacture the photosensitive film pattern with the required shape. Then, the substrate is etched using the photosensitive film pattern, and thereafter, the photosensitive film pattern, which is no longer required, is removed from the substrate by peeling or the like. In this process, various light sources such as G-line (G-line), I-line (I-line), KrF (KrF), ArF (ArF), ultra Violet (ultra), Electron Beam (e-beam), X-ray (X-ray), etc. are used according to the line width of the pattern to be formed. The photoresist used for forming the photosensitive film includes various resins of main components, photosensitizers, and the like, depending on the kind of light source, the properties of the photosensitive film, and the like.
Meanwhile, in the mask etching process, a thinner composition means a substance having a dissolving power to a photoresist and thus being used for removing the photoresist or as a thinner. The dissolving power of the thinner composition for photoresist depends on the chemical components of the thinner composition and the chemical structure of the photoresist. However, since the chemical structure is greatly changed depending on the kind of photoresist, commercially available thinner compositions generally have a problem that they cannot have a fixed dissolving power for various photoresists. Specifically, if the dissolving power of the thinner composition to the photoresist is insufficient, defects may be generated in an Edge Bead Removal (EBR) process for removing the photoresist unnecessarily attached to the substrate, or a pre-wetting (pre-wetting) process of the thinner composition used for Reducing photoresist consumption (RRC) coating, etc., thereby possibly causing a reduction in yield.
Therefore, it is required to develop a thinner composition having further improved dissolving power for various photoresists.
Disclosure of Invention
The present invention provides a thinner composition having further improved dissolving power for various photoresists and applicable to various processes for forming a photosensitive film.
Another object of the present invention is to provide a method of forming a photosensitive film using the thinner composition.
In accordance with an embodiment of the present invention, there is provided a diluent composition comprising 1-methoxy-2-propanol acetate (1-methoxy-2-propanol acetate) and ethylene glycol propyl ether (ethylene glycol propyl ether).
The thinner composition may include 20 to 80 wt% of 1-methoxy-2-propanol acetate, and 20 to 80 wt% of ethylene glycol propyl ether.
Also, the thinner composition may include 40 to 80 wt% of 1-methoxy-2-propanol acetate, and 20 to 60 wt% of ethylene glycol propyl ether.
Also, the ethylene glycol propyl ether may include ethylene glycol monopropyl ether (ethylene glycol monopropyl ether), ethylene glycol isopropyl ether (ethylene glycol isopropyl ether), and mixtures thereof.
The thinner composition may further include a surfactant, and the surfactant may be included in an amount of 0.001 to 0.1 parts by weight, based on 100 parts by weight of the thinner composition.
Meanwhile, according to another embodiment of the present invention, there is provided a method for forming a photosensitive film, including the steps of: coating the photoresist on the semiconductor substrate; and applying the thinner composition onto the substrate to remove at least a portion of the photoresist from the substrate.
According to another embodiment of the present invention, there is provided a method of forming a photosensitive film, including the steps of: applying the diluent composition onto a semiconductor substrate to pre-wet (pre-wetting) the substrate; and coating photoresist on the pre-wetted substrate.
The thinner composition according to the present invention has excellent dissolving power for various photoresists and has the most appropriate volatility, so that it can effectively remove an unnecessarily attached photoresist in a short time in an edge bead removal process or the like, and can be applied to a pre-wetting process of a semiconductor substrate or the like, and can effectively form a photosensitive film with a small amount of photoresist.
Detailed Description
The diluent composition and its use according to embodiments of the present invention will be described below.
Unless otherwise specifically stated, the terms are used in the context of specific embodiments only, and are not intended to limit the invention.
Also, as used herein, the singular includes the plural unless it is explicitly stated to the contrary.
Also, the terms "comprises" and "comprising," when used herein, specify the presence of stated features, regions, integers, steps, operations, elements, or components, but do not preclude the presence or addition of other specified features, regions, integers, steps, operations, elements, or components.
Also, as used herein, "ethylene glycol propyl ether" refers to ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, or a mixture of these.
Meanwhile, the inventors have confirmed during repeated studies to improve the efficiency of the mask etching process that if a composition including 1-methoxy-2-propanol acetate and ethylene glycol propyl ether is used as a thinner composition, it has the most appropriate volatility and also exhibits excellent dissolving power for various photoresists, thereby enabling an edge bead removal process, a pre-wetting process of a semiconductor substrate, and the like with more improved efficiency.
According to an embodiment of the present invention, there is provided a thinner composition comprising: 1-methoxy-2-propanol acetate; and ethylene glycol propyl ether.
Specifically, the thinner composition of an embodiment of the present invention has excellent dissolving power not only for a high-polarity photoresist applied to a process using a light source such as krypton fluoride (KrF), argon fluoride (ArF), etc., but also for a photoresist applied to a process using a light source such as G-line (G-line), I-line (I-line), etc., and can exhibit excellent dissolving power for a photoresist applied to a spin-on hard mask (spin-on hard mask) process and having no good solubility in general organic solvents.
Therefore, in a process of forming a photosensitive film using a photoresist, the thinner composition may be applied to an edge bead removal process of removing the photoresist applied to or attached to an edge or a rear surface of a substrate, or may be applied to a rework process of removing a defective photosensitive film from a front surface of a substrate. In addition, the thinner composition may be applied to a stripping process for removing a photosensitive film pattern after development and etching, and may be applied to a pre-wetting process for Reducing a photoresist consumption (RRC) coating thinner composition to form a photosensitive film having a more uniform thickness.
In general, in a process of forming a photosensitive film by a spin coating method, photoresist may be agglomerated into a spherical shape due to a centrifugal force, and edge beads may be formed on the edge or the back surface of a substrate, which may become contaminants causing defects of a semiconductor device or malfunctions of manufacturing equipment, and may become a cause of defocus (defocus) in an exposure process. However, if the thinner composition of an embodiment of the present invention is applied to the edge bead removal process, the beads attached to the edge or the back surface of the substrate can be easily removed without damaging the photosensitive film formed on the front surface of the substrate, and thus, clearer and more uniform boundary lines of the photosensitive film can be obtained at the edge portion of the substrate.
Since ethyl lactate (ethyl lactate), which has been used in existing diluent compositions, has a high viscosity and a relatively low dissolution rate, it is difficult to sufficiently improve the cleaning performance of the diluent composition. In addition, ethylene glycol monoethyl ether (ethylene glycol monoethyl ether) has excellent solubility to a photoresist, but has high volatility and flammability, and thus there may be a problem of deterioration of a coating layer when the photoresist is pre-wetted. Also, if a mixed solvent consisting of alkyl pyruvate and methyl ethyl ketone is used as the diluent composition, the solubility of the 1, 2-naphthoquinonediazide (1, 2-naphthoquinonediazide) photosensitizer, which is one of important components of the photosensitive film, may be reduced. Also, if a solvent such as methyl pyruvate, ethyl pyruvate, or the like is used as the diluent composition, a metal member in a photosensitive waste liquid storage tank connected to the photosensitive film spin coating apparatus may be corroded after a long time use. Also, if a mixed solvent of solvents having high volatility, such as propylene glycol alkyl ether propionate (propylene glycol alkyl ether propionate) and butyl acetate (butyl acetate), is used as a thinner composition to clean the back surface of the substrate, the substrate is cooled to increase the thickness deviation of the photosensitive film. Also, if a solvent having low volatility, such as a mixed solvent of ethyl lactate (ethyl lactate) and methyl ethyl ketone (methyl ethyl ketone), is used as the thinner composition, the cleaning performance of the edge of the substrate may be reduced.
In contrast, 1-methoxy-2-propanol acetate (1-methoxy-2-propanol acetate) included in the thinner composition according to an embodiment of the present invention has excellent solubility to various photoresists, and simultaneously has the most appropriate volatility, viscosity, and surface tension.
According to an example, the diluent composition may comprise 20 to 80 wt% of 1-methoxy-2-propanol acetate. According to another example, the 1-methoxy-2-propanol acetate may be contained in an amount of 40 to 80 wt%. According to still another example, the 1-methoxy-2-propanol acetate may be present in an amount of 40 to 70 wt%.
In other words, the content of 1-methoxy-2-propanol acetate in the thinner composition is preferably 20 wt% or more to exhibit excellent dissolution power for a photoresist having high polarity and a photoresist used for a spin-on hard mask process. However, if the content of 1-methoxy-2-propanol acetate is too large, the volatility of the thinner composition may increase to cause thickness deviation of the photosensitive film or edge crack after pre-wetting. Therefore, in order to avoid these phenomena, the content of 1-methoxy-2-propanol acetate in the diluent composition is preferably 80% by weight or less.
Meanwhile, ethylene glycol propyl ether (ethylene glycol propyl ether) contained in the thinner composition according to an embodiment of the present invention may exhibit excellent solubility to a photosensitive component of a photoresist, compared to other solvents, and in particular, ethylene glycol propyl ether may exhibit excellent solubility to a very poorly soluble polymer of a C-Hardmask (C-Hardmask) structure commonly contained in a photoresist for a spin-on Hardmask process. Wherein the ethylene glycol propyl ether comprises ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, or a mixture of these, and each of the components of the compound or the mixture of the compounds may exhibit substantially equal effects. In the case of the mixture, the mixing ratio of ethylene glycol monopropyl ether and ethylene glycol isopropyl ether is not particularly limited.
Also, according to an example, the diluent composition may include 20 to 80 wt% of ethylene glycol propyl ether. According to another example, the content of the ethylene glycol propyl ether may be 20 to 60 wt%. According to yet another example, the content of ethylene glycol propyl ether may be 30 to 60 wt%.
In other words, in order to obtain the effect of improving the dissolving power of the photosensitive component of the photoresist and the polymer having a pyrene structure, the content of ethylene glycol propyl ether in the diluent composition is preferably 20% by weight or more. However, if the content of the glycol propyl ether is too large, the viscosity of the thinner composition increases to cause thickness deviation of the photosensitive film or edge crack after the pre-wetting. Therefore, in order to avoid these phenomena, the content of ethylene glycol propyl ether in the diluent composition is preferably 80% by weight or less.
If the volatility of the thinner composition is too high, the substrate is rapidly cooled and the thickness deviation of the photosensitive film is significantly increased when the thinner composition is coated. Also, if the volatility of the thinner composition is too low, an excessive amount of the thinner composition may be left on the substrate when pre-wetting, so that the photosensitive film may be dissolved or defects such as deformation of the photosensitive film may be induced, and the thinner composition may remain on the substrate after removing the edge bead to become contaminants in a subsequent process.
In addition, the thinner composition according to this embodiment may further include a surfactant. The surfactant may preferably be a nonionic surfactant in view of the characteristics of the photosensitive film forming method. As the nonionic surfactant, nonionic surfactants commonly used in the art can be used, and the structure thereof is not particularly limited.
The surfactant may be included in an amount of 0.001 to 0.1 parts by weight, based on 100 parts by weight of the diluent composition. In other words, in order to obtain more excellent profile in the edge bead removal process, it is advantageous that the content of the surfactant is 0.001 parts by weight or more based on 100 parts by weight of the thinner composition. However, if the content of the surfactant is too large, foam may be seriously generated in the diluent composition, and thus the malfunction of the liquid amount sensor may be caused when the diluent composition is used. Therefore, in order to avoid this problem, the content of the surfactant is preferably 0.1 part by weight or less based on 100 parts by weight of the diluent composition.
As described above, the thinner composition of the present invention has the most appropriate volatility and simultaneously can exhibit more improved dissolution power for various photoresists, particularly photoresists having high polarity for KrF (KrF), ArF (ArF) processes, and photoresists having poor solubility in organic solvents for spin-on hardmask processes. Accordingly, the thinner composition may be applied to an Edge Bead Removal (EBR) process, a pre-wetting (pre-wetting) process for Reducing a photoresist consumption (RRC) of the coated thinner composition, to improve process efficiency.
Meanwhile, according to another embodiment of the present invention, there is provided a method for forming a photosensitive film, including applying the thinner composition on a semiconductor substrate to pre-wet the substrate; and coating photoresist on the pre-wetted substrate.
In another embodiment, a method for forming a photosensitive film includes coating a photoresist on a semiconductor substrate; and applying the thinner composition onto the substrate to remove at least a portion of the photoresist from the substrate.
In the method of forming a photosensitive film, the semiconductor substrate may be a substrate used for manufacturing an electronic device such as a memory element, an integrated circuit element, a liquid crystal display device, or the like. Various structures constituting the electronic device, for example, an insulating film, a conductive film, wires (wires), a via hole, a gate electrode (gat e), etc., may be formed on the substrate, and the top surface of the substrate may have different heights due to the structures.
The pre-wetting process is a process of applying the thinner composition as described above onto a semiconductor substrate on which a photosensitive film is to be formed, thereby improving the wettability of the substrate before applying a photoresist. In particular, since the thinner composition of the present invention exhibits more improved dissolving power for various photoresists, it can form a photosensitive film having a uniform thickness with a small amount of photoresist through the pre-wetting process. In other words, if the pre-wetting process is performed using the thinner composition as described above, a thin and uniform film can be formed by using a relatively small amount of photoresist. In addition, defective coating of the photosensitive film on the edge of the substrate can be reduced, and a height difference that may exist on the substrate can be easily overcome to reduce thickness deviation of the photosensitive film.
The pre-wetting process may be performed by a general spin coating method, for example, by applying the diluent composition on a substrate and then spinning the substrate to apply the diluent composition on the front surface of the substrate, or by applying the diluent composition on a spinning substrate to apply the diluent composition on the front surface of the substrate.
In addition, in the method of forming a photosensitive film, the photoresist depends on the line width of a pattern to be formed, the kind of light source used, and the like, and the structure thereof is not particularly limited. As reference examples, the photoresist may include a photoresist for I-line including novolak resin (novolac resin); a photoresist for krypton fluoride (KrF) containing polyhydroxystyrene (polyhydroxystyrene) in which hydrogen of hydroxyl groups is partially terminated with acetal groups (acetal groups); a photoresist for krypton fluoride (KrF) comprising polyhydroxystyrene in which hydrogen of hydroxyl group is partially terminated with tertiary-butyl carbonate group (tert-butylcarbonate group); a photoresist containing methacrylate resin for argon fluoride (ArF); bottom antireflective coatings for krypton fluoride (KrF) containing triazine resins; bottom anti-reflective coatings containing ester resins (ester resins) for argon fluoride (ArF), and the like. Also, as a reference example, the photoresist for the I-line may include a novolak resin and 2,4-dinitroquinone (2,4-dinitroquinone) as a photosensitizer. The photoresist for krypton fluoride (KrF) may include hydroxystyrene in which a part of hydrogen of hydroxyl groups is terminated with an acetal group or a tertiary-butyl carbonate group, and triphenylsulfonium salt (triphenylsulfonium salt) as a photosensitizer. The photoresist for argon fluoride (ArF) may include polymethacrylate terminated with adamantyl (adamantyl group) and/or 4-oxatricyclo (4.2.1.0(3,7)) -5-nonanone (4-oxa-tricyclo (4.2.1.0(3,7)) and triphenylsulfonium salt as a photosensitizer.
In addition, the step of coating the photoresist on the pre-wetted substrate may be performed by a spin coating method. If the photoresist is coated by spin coating, the photoresist is agglomerated into a spherical shape by centrifugal force, and an edge bead is formed on the edge or the back of the substrate. The edge bead becomes a contaminant causing defects of electronic devices or malfunctions of manufacturing equipment, and may become a cause of defocus in an exposure process.
Thus, the thinner composition of the present invention can be used to remove at least a portion of photoresist on a substrate, such as photoresist attached to the edge or backside of a substrate. The removal may be performed using a pressurized spray of the diluent composition while rotating the substrate. As described above, since the thinner composition of the present invention has excellent dissolving power for various photoresists and the most appropriate properties such as volatility, viscosity, etc., the thinner composition can precisely remove only edge balls when removing boundary lines of a photosensitive film, and these processes can be efficiently performed in a short time.
The thinner composition used in the step of removing at least a portion of the photoresist (edge bead removal process) may be the same as or different from the thinner composition used in the pre-wetting process described above. In other words, a diluent composition having different components may be used depending on the situation of each process and desired properties, etc. However, since the thinner composition of the present invention can satisfy the properties suitable for the edge bead removal process as well as the pre-wetting process, it is preferable to use a thinner composition having an equivalent range of components in terms of improving the overall process efficiency.
After removing the edge balls attached to the edge or the back surface of the substrate, a photosensitive film may be formed through a soft baking process, and after confirming the presence or absence of a defect generated on the photosensitive film using a defect detecting apparatus, a photosensitive pattern may be formed through an exposure and development process. If the photosensitive film has defects such as cracks (tearing), scumming (tailing), thickness deviation, etc., the photosensitive film formed on the front surface of the substrate is removed by performing a rework process, and in this process, the thinner composition of the present invention may also be used.
Hereinafter, preferred embodiments are provided to facilitate understanding of the present invention. However, these examples are merely illustrative of the present invention, and the present invention is not limited thereto.
Example 1
80 wt% of 1-methoxy-2-propanol acetate and 20 wt% of ethylene glycol monopropyl ether were introduced into a mixing chamber equipped with a stirrer, and the mixture was stirred at room temperature for about 50 minutes to prepare a diluent composition.
Examples 2 to 7 and comparative examples 1 to 10
A thinner composition was prepared in the same manner as in example 1, except that the ingredients shown in table 1 below were mixed at corresponding contents (wt%; however, the content unit of the surfactant was parts by weight, based on 100 parts by weight of the remaining ingredients).
[ Table 1]
| Composition (I) | A | B | C | D | E | F | G |
| Example 1 | 80 | 20 | - | - | - | - | - |
| Example 2 | 70 | 30 | - | - | - | - | - |
| Example 3 | 60 | 40 | - | - | - | - | - |
| Example 4 | 50 | 50 | - | - | - | - | - |
| Example 5 | 40 | 60 | - | - | - | - | - |
| Example 6 | 70 | 30 | - | - | - | - | 0.01 |
| Example 7 | 50 | 50 | - | - | - | - | 0.01 |
| Comparative example 1 | 50 | - | 50 | - | - | - | - |
| Comparative example 2 | 50 | - | - | 50 | - | - | - |
| Comparative example 3 | 50 | - | - | 50 | - | - | |
| Comparative example 4 | 50 | - | 30 | 20 | - | - | - |
| Comparative example 5 | - | 50 | 30 | 20 | - | - | - |
| Comparative example 6 | - | - | 30 | 20 | 50 | - | |
| Comparative example 7 | - | - | 50 | 50 | - | - | - |
| Comparative example 8 | - | - | 50 | - | - | 50 | - |
| Comparative example 9 | - | - | 50 | 30 | 20 | - | - |
| Comparative example 10 | - | - | 20 | - | 30 | 50 | - |
The components A to G in Table 1 are shown below.
[A] 1-methoxy-2-propanol acetate (1-methoxy-2-propanol acetate)
[B] Ethylene glycol monopropyl ether (ethylene glycol monopropylether)
[C] 2-Hydroxyisobutyric acid methyl ester (methyl 2-hydroxyisobutyrate)
[D] N-butyl acetate (n-buthyl acetate)
[E] Gamma-butyrolactone (gamma-butyrolactone)
[F] 3-Ethoxypropionic acid ethyl ester (ethyl 3-ethoxypropionate)
[G] Nonionic surfactant (product name: BYK-Series, manufacturer: ALTANA)
Experimental example 1
(evaluation of edge bead removal Performance according to the type of photosensitive film)
An 8 inch silicon oxide substrate was immersed in two hydrogen peroxide/sulfuric acid mixture baths for 5 minutes each, followed by rinsing with ultra pure water. Next, the substrate was spin-dried in a spin dryer (spin dryer), and thereafter, the thinner composition of example 1 was spin-coated (about 1500 to 2500rpm) on the substrate to perform a pre-wetting process of reducing photoresist consumption (RRC) coating. Next, on the prewetted substrate, each of the photoresists described in table 2 below was spin-coated (about 3 seconds at a rotation speed of about 300rpm, and thereafter, about 20 to 30 seconds at a rotation speed of about 1000 to 2000rpm to be controlled to a predetermined thickness) on the substrate to form a photosensitive film having a corresponding thickness. In addition, an edge bead test for removing unnecessary adhesion to an edge portion of a substrate was performed using the thinner compositions of examples 1 to 7 and comparative examples 1 to 10.
In the test, each diluent composition was supplied from a pressurized vessel (pressurization pressure about 1.0kgf) equipped with a pressure gauge and sprayed through an EBR nozzle (flow rate of the composition was 10 to 20 cc/min), and the spraying time of the composition was controlled by the rotation speed of the substrate as described in table 3 below.
In addition, results of evaluating the edge bead removal efficiency are shown in tables 4 and 5, in tables 4 and 5 below, "◎" indicates that EBR line uniformity (EBR line uniformity) is uniform and constant after the edge bead removal, "○" indicates that EBR line uniformity is 80% or more satisfactory after the edge bead removal, "△" indicates that EBR line uniformity is 50% or more but less than 80% satisfactory after the edge bead removal, and "x" indicates that EBR line uniformity is 20% or more but less than 50% satisfactory after the edge bead removal and tailing (tailing) occurs at the edge.
[ Table 2]
[ Table 3 ]]
[ Table 4 ]]
| PR1 | PR2 | PR3 | PR4 | PR5 | PR6 | PR7 | PR8 | |
| Example 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Example 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Example 3 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Example 4 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Example 5 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Example 6 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Example 7 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
[ Table 5]
| PR1 | PR2 | PR3 | PR4 | PR5 | PR6 | PR7 | PR8 | |
| Example 1 | ○ | ○ | △ | △ | △ | ○ | × | × |
| Example 2 | ○ | ○ | △ | ○ | △ | △ | × | × |
| Example 3 | ○ | ○ | △ | △ | △ | × | × | △ |
| Example 4 | △ | ○ | △ | △ | △ | × | × | × |
| Example 5 | ○ | △ | △ | △ | △ | △ | △ | △ |
| Example 6 | ○ | △ | △ | △ | × | △ | △ | × |
| Example 7 | ○ | △ | △ | △ | △ | △ | △ | × |
| Example 8 | ○ | ○ | ○ | △ | △ | × | × | △ |
| Example 9 | ○ | △ | △ | △ | △ | △ | × | × |
| Example 10 | △ | △ | △ | △ | △ | △ | × | × |
Experimental example 2
(evaluation of coating uniformity of Photoresist)
Whether the photosensitive film was uniformly coated on the front surface of the substrate was evaluated in the following manner.
An 8 inch silicon oxide substrate was immersed in two hydrogen peroxide/sulfuric acid mixture baths for 5 minutes each, followed by rinsing with ultra pure water. Next, the substrate was spin-dried in a spin dryer (spin dryer), and thereafter, the thinner compositions of examples 1 to 7 and comparative examples 1 to 10 were spin-coated (about 1500 to 2500rpm) on the substrate to perform a pre-wetting process of reducing photoresist consumption (RRC) coating. At this time, each thinner composition was supplied from a pressurized container (pressurization pressure about 1.0kgf) equipped with a pressure gauge and ejected through a nozzle (flow rate of the composition was 10 to 20 cc/min), and the spraying time of the composition was controlled by the rotation speed of the substrate as described in table 6 below.
Next, on the prewetted substrate, each of the photoresists described in table 2 was spin-coated (about 3 seconds at about 300rpm, and thereafter, about 20 to 30 seconds at about 1000 to 2000rpm to be controlled to a predetermined thickness) on the substrate to form a photosensitive film having a corresponding thickness.
In addition, the results of evaluating the coating uniformity of each photosensitive film are shown in tables 7 and 8, "○" indicates that the coating uniformity of the photosensitive film is uniform and constant, "△" indicates that EBR line uniformity is satisfactory at 90% or more after the edge bead removal, and "x" indicates that coating defects occur at the edge portion of the photosensitive film.
[ Table 6]
[ Table 7]
| PR1 | PR2 | PR3 | PR4 | PR5 | PR6 | PR7 | PR8 | |
| Example 1 | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ |
| Example 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 3 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 4 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 5 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 6 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 7 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
[ Table 8]
| PR1 | PR2 | PR3 | PR4 | PR5 | PR6 | PR7 | PR8 | |
| Example 1 | △ | △ | △ | × | × | △ | △ | × |
| Example 2 | △ | ○ | △ | × | △ | × | × | × |
| Example 3 | △ | △ | △ | △ | × | △ | △ | △ |
| Example 4 | △ | ○ | △ | × | △ | × | × | × |
| Example 5 | △ | ○ | △ | △ | △ | × | △ | △ |
| Example 6 | ○ | △ | × | △ | × | △ | △ | × |
| Example 7 | △ | △ | △ | × | △ | × | × | △ |
| Example 8 | △ | ○ | ○ | × | × | × | △ | × |
| Example 9 | △ | △ | △ | × | △ | × | △ | △ |
| Example 10 | △ | △ | △ | × | △ | × | △ | × |
As is confirmed from the results shown in experimental example 1 and experimental example 2, the thinner compositions of examples 1 to 7 exhibited excellent dissolving power for various photoresists, compared to the thinner composition of comparative example, so that the edge bead removal process and the pre-wetting process of the substrate can be more efficiently performed.
Specifically, the experimental results confirmed that the thinner compositions of examples 1 to 7 had a dissolving power for I-line photoresists (PR1 and PR2), for high-polarity photoresists (PR3 to PR6) for krypton fluoride (KrF) and argon fluoride (ArF), and for poorly soluble photoresists (PR7 and PR8) for spin-on reticles, compared to the thinner composition of comparative example.
Claims (4)
1. A diluent composition consisting of the following components:
40 to 80 wt% of 1-methoxy-2-propanol acetate; and
20 to 60 wt% of ethylene glycol propyl ether.
2. The diluent composition of claim 1, wherein the ethylene glycol propyl ether comprises ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, or a mixture of these.
3. A method for forming a photosensitive film includes the following steps:
applying the diluent composition of claim 1 to a semiconductor substrate to pre-wet the substrate; and
a photoresist is coated on the pre-wetted substrate.
4. A method for forming a photosensitive film includes the following steps:
coating the photoresist on the semiconductor substrate; and
applying the thinner composition of claim 1 to the substrate to remove at least a portion of the photoresist from the substrate.
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| PCT/KR2014/000716 WO2014123318A1 (en) | 2013-02-08 | 2014-01-24 | Thinner composition and use thereof |
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| CN110221522B (en) * | 2018-03-02 | 2023-01-06 | 长鑫存储技术有限公司 | Method for screening wetting solvent |
| KR102465602B1 (en) * | 2018-08-31 | 2022-11-11 | 주식회사 이엔에프테크놀로지 | Thinner composition |
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| US4587203A (en) * | 1983-05-05 | 1986-05-06 | Hughes Aircraft Company | Wet process for developing styrene polymer resists for submicron lithography |
| CN101300529A (en) * | 2005-11-18 | 2008-11-05 | 株式会社东进世美肯 | Thinner composition for removing photoresist |
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| US4535054A (en) * | 1983-05-05 | 1985-08-13 | Hughes Aircraft Company | Wet process for developing styrene polymer resists for submicron lithography |
| KR100594815B1 (en) * | 1999-12-24 | 2006-07-03 | 삼성전자주식회사 | thinner for rinsing photoresist and method of treating photoresist layer |
| KR101097908B1 (en) * | 2004-12-09 | 2011-12-23 | 주식회사 이엔에프테크놀로지 | Thinner composition and method of manufacturing the same |
| JP4554665B2 (en) * | 2006-12-25 | 2010-09-29 | 富士フイルム株式会社 | PATTERN FORMATION METHOD, POSITIVE RESIST COMPOSITION FOR MULTIPLE DEVELOPMENT USED FOR THE PATTERN FORMATION METHOD, NEGATIVE DEVELOPMENT SOLUTION USED FOR THE PATTERN FORMATION METHOD, AND NEGATIVE DEVELOPMENT RINSE SOLUTION USED FOR THE PATTERN FORMATION METHOD |
| KR101132618B1 (en) * | 2009-08-25 | 2012-04-06 | 주식회사 이엔에프테크놀로지 | Thinner composition which can reduce consumption of photoresists |
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| US4587203A (en) * | 1983-05-05 | 1986-05-06 | Hughes Aircraft Company | Wet process for developing styrene polymer resists for submicron lithography |
| CN101300529A (en) * | 2005-11-18 | 2008-11-05 | 株式会社东进世美肯 | Thinner composition for removing photoresist |
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