Patent Application
20250155799
The present application claims priority to and the benefit of Korean Patent Application No. 10-2023-0155625 filed in the Korean Intellectual Property Office on Nov. 10, 2023, the entire content of which is incorporated herein by reference.
Embodiments of the present disclosure described herein are related to semiconductor photoresist compositions and methods of forming patterns using the same.
EUV (extreme ultraviolet) lithography is recognized as one important technology for manufacturing a next generation semiconductor device. The EUV lithography is a pattern-forming technology using an EUV ray having a wavelength of about 13.5 nm as an exposure light source. According to the EUV lithography, it is known or believed that an extremely fine pattern (e.g., less than or equal to about 20 nm) may be formed in an exposure process during a manufacture of a semiconductor device.
The extreme ultraviolet (EUV) lithography uses compatible photoresists which can be performed at a spatial resolution of less than or equal to about 16 nm. Currently, research or efforts to address specifications of comparable chemically amplified (CA) photoresists such as resolution, photospeed, and feature roughness (or also referred to as a line edge roughness or LER) for the next generation device are being made or pursued.
An intrinsic image blurring due to an acid catalyzed reaction in the polymer-type or kind photoresists limits a resolution in small feature sizes. Such limitation is known in electron beam (e-beam) lithography. The chemically amplified (CA) photoresists are designed for high sensitivity, but because their typical elemental makeups reduce light absorbance of the photoresists at a wavelength of about 13.5 nm and thus decrease their sensitivity, the chemically amplified (CA) photoresists may have more difficulties under an EUV exposure.
In addition, the CA photoresists may have difficulties in the small feature sizes due to roughness issues, and line edge roughness (LER) of the CA photoresists experimentally turns out to be further increased, as a photospeed is decreased partially due to an essence of acid catalyst processes. Accordingly, a novel high-performance photoresist is desired or required in a semiconductor industry because of these defects and problems of the CA photoresists.
In order to overcome the aforementioned drawbacks of the chemically amplified (CA) organic photosensitive composition, an inorganic photosensitive composition has been researched or pursued. The inorganic photosensitive composition is mainly used for negative tone patterning having resistance against removal by a developer composition due to chemical modification through nonchemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbon and thus may secure sensitivity through the nonchemical amplification mechanism and in addition, is less sensitive to a stochastic effect and thus may have low line edge roughness and small number of defects.
Inorganic photoresists based on peroxopolyacids of tungsten mixed with tungsten, niobium, titanium, and/or tantalum have been reported as radiation sensitive materials for patterning (U.S. Pat. No. 5,061,599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49 (5), 298-300, 1986), the entire content of which is incorporated herein by reference.
These materials are effective for patterning large pitches for bilayer configuration for ultraviolet (deep UV), X-ray, and electron beam sources. More recently, if (e.g., when) cationic hafnium metal oxide sulfate (HfSOx) materials along with a peroxo complexing agent has been used to image a 15 nm half-pitch (HP) through projection EUV exposure, impressive performance has been obtained (US 2011-0045406; J. K. Stowers, A. Telecky, M. Kocsis, B. L. Clark, D. A. Keszler, A. Grenville, C. N. Anderson, P. P. Naulleau, Proc. SPIE, 7969, 796915, 2011), the entire content of which is incorporated herein by reference. This system exhibits the highest performance of a non-CA photoresist and has a practicable photospeed near to a requirement for an EUV photoresist. However, the hafnium metal oxide sulfate material having the peroxo complexing agent has some drawbacks. First, these materials are coated in a mixture of corrosive sulfuric acid/hydrogen peroxide and have insufficient shelf-life stability. Second, a structural change thereof for performance improvement as a composite mixture is not easy. Third, development should be performed in a TMAH (tetramethylammonium hydroxide) solution at an extremely high concentration of about 25 wt % and/or the like.
Recently, active research has been conducted as it is known or believed that molecules containing tin have excellent or suitable absorption of extreme ultraviolet rays. As for an organotin polymer among the tin materials, alkyl ligands are dissociated by light absorption or secondary electrons produced thereby, and are crosslinked with adjacent chains through oxo bonds and thus enable the negative tone patterning which may not be removed by an organic developer. That is, such organotin polymers, among other tin materials, undergo dissociation of alkyl ligands due to light absorption or secondary electrons. These dissociated ligands then crosslink with adjacent polymer chains through oxo bonds, resulting in negative tone patterning that remains resistant to removal by organic developers. Thes organotin polymers exhibit greatly improved sensitivity as well as maintaining a resolution and line edge roughness, but the patterning characteristics may still need to be additionally improved for commercial use or availability.
Aspects according to one or more embodiments are directed toward a semiconductor photoresist composition that improves problems occurring during spin coating.
Aspects according to one or more embodiments are directed toward a method of forming patterns using the semiconductor photoresist composition.
Aspects according to one or more embodiments are directed toward a semiconductor photoresist composition that addresses or solves problems of surface roughness and coating defects occurring during spin coating.
Additional aspects will be set forth in part in the description which follows, and in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the present disclosure.
According to one or more embodiments, a semiconductor photoresist composition includes an organometallic compound; and a mixed solvent including an alcohol-based compound and a non-alcohol-based compound in a weight ratio of about 1:99 to about 30:70, wherein the alcohol-based compound is included in an amount of less than or equal to about 30 wt % based on a total weight of (100 wt % of) the mixed solvent.
According to one or more embodiments, the method of forming patterns includes forming an etching-objective layer on a substrate, coating the semiconductor photoresist composition on the etching-objective layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching-objective layer using the photoresist pattern as an etching mask.
Hereinafter, referring to the drawings, embodiments of the present disclosure are described in more detail. In the following description of the present disclosure, some suitable functions or constructions will not be described in order to clarify the present disclosure.
As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. As used herein, expressions such as “at least one of”, “one of”, and “selected from”, when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, “at least one of a, b or c”, “at least one selected from a, b and c”, etc., may indicate only a, only b, only c, both (e.g., simultaneously) a and b, both (e.g., simultaneously) a and c, both (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof.
In order to clearly illustrate the present disclosure, some description and relationships may not be provided, and throughout the disclosure, the same or similar configuration elements are designated by the same reference numerals. Also, because the size and thickness of each configuration shown in the drawing are arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.
In the drawings, the thickness of layers, films, panels, regions, and/or the like, are exaggerated for clarity. In the drawings, the thickness of a part of layers or regions, and/or the like, is exaggerated for clarity. It will be understood that if (e.g., when) an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present.
As used herein, “substituted” refers to replacement of a hydrogen atom by deuterium, a halogen, a hydroxyl group, a thiol group, a cyano group, a nitro group, —NRR′ (wherein, R and R′ may each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), —SiRR′R″ (wherein, R, R′, and R″ may each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, and/or a (e.g., any suitable) combination thereof. “Unsubstituted” refers to non-replacement of a hydrogen atom by another substituent and remaining of the hydrogen atom.
As used herein, if (e.g., when) a definition is not otherwise provided, “alkyl group” refers to a linear or branched aliphatic hydrocarbon group. The alkyl group may be “saturated alkyl group” without any double bond or triple bond.
The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.
As used herein, if (e.g., when) a definition is not otherwise provided, “cycloalkyl group” refers to a monovalent cyclic aliphatic hydrocarbon group.
The cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but the present disclosure is not limited thereto.
As used herein, “aliphatic unsaturated organic group” refers to a hydrocarbon group including a bond in which the bond between the carbon and carbon atom in the molecule is a double bond, a triple bond, and/or a (e.g., any suitable) combination thereof.
The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1 propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.
As used herein, “aryl group” refers to a substituent in which all atoms in the cyclic substituent have a p-orbital and these p-orbitals are conjugated and may include a monocyclic or fused ring polycyclic functional group (i.e., rings sharing adjacent pairs of carbon atoms) functional group.
As used herein, “heteroaryl group” may refer to an aryl group including at least one heteroatom selected from among N, O, S, P, and Si. Two or more heteroaryl groups are linked by a sigma bond directly, or if (e.g., when) the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.
As used herein, unless otherwise defined, “alkenyl group” refers to an aliphatic unsaturated alkenyl group including at least one double bond as a linear or branched aliphatic hydrocarbon group.
As used herein, unless otherwise defined, “alkynyl group” refers to an aliphatic unsaturated alkynyl group including at least one triple bond as a linear or branched aliphatic hydrocarbon group.
As utilized herein, the term “substantially” and similar terms are utilized as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. Also, the term “about” and similar terms, when utilized herein in connection with a numerical value or a numerical range, are inclusive of the stated value and a value within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (e.g., the limitations of the measurement system). For example, “about” may refer to within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Also, any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
In the context of the present application and unless otherwise defined, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively. Further, the use of “may” when describing embodiments of the present invention refers to “one or more embodiments of the present invention.”
Hereinafter, a semiconductor photoresist composition according to one or more embodiments is described.
A semiconductor photoresist composition according to one or more embodiments includes an organometallic compound, and a mixed solvent including an alcohol-based compound and a non-alcohol-based compound in a weight ratio of about 1:99 to about 30:70,
The semiconductor photoresist composition should solve defect problems that occur during spin coating, such as surface roughness and coating defects, by including a mixed solvent, specifically, a mixed solvent including an alcohol-based compound.
In addition, the storage stability of the photoresist composition can be improved.
The mixed solvent included in the semiconductor photoresist composition according to one or more embodiments may include the alcohol-based compound and the non-alcohol-based compound in a weight ratio of about 5:95 to about 30:70.
As a specific example, the alcohol-based compound may be 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, propylene glycol methyl ether, 2-methyl-2-butanol, 2-butanol, and/or a (e.g., any suitable) combination thereof.
For example, the non-alcohol-based compound may be an ether-based compound, an ester-based compound, a ketone-based compound, and/or a (e.g., any suitable) combination thereof.
As a specific example, the ether-based compound may be anisole, tetrahydrofuran, and/or a (e.g., any suitable) combination thereof.
As a specific example, the ester-based compound may be n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, and/or a (e.g., any suitable) combination thereof.
As a specific example, the ketone-based compound may be methyl ethyl ketone, 2-heptanone, and/or a (e.g., any suitable) combination thereof.
The organometallic compound may be included in an amount of about 1 wt % to about 30 wt % based on a total weight of 100 wt % of the semiconductor photoresist composition.
The semiconductor photoresist composition according to one or more embodiments includes the organometallic compound within the above content (e.g., amount) range, thereby providing a semiconductor photoresist composition having excellent or suitable sensitivity.
The organometallic compound may include tin (Sn).
The organometallic compound may include at least one of an organic oxy group or an organic carbonyloxy group.
The organometallic compound may be represented by Chemical Formula 1.
In Chemical Formula 1,
For example, R2 to R4 may be selected from among —ORb and —OC(═O)Rc.
In one or more embodiments, the compound represented by Chemical Formula 1 includes —ORb or —OC(═O)Rc as a ligand, so that a pattern formed using a semiconductor photoresist composition including the same can exhibit excellent or suitable limiting resolution.
Additionally, the —ORb or —OC(═O)Rc ligand can determine the solubility of the compound represented by Chemical Formula 1 in a solvent.
The semiconductor photoresist composition according to one or more embodiments may further include a resin in addition to the aforementioned organometallic compound and mixed solvent.
The resin may be a phenol-based resin including at least one aromatic moiety selected from moieties of Group 1.
The resin may have a weight average molecular weight of about 500 to about 20,000.
The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on a total amount (weight) of 100 wt % of the semiconductor photoresist composition.
If the resin is included in the above content (e.g., amount) range, the semiconductor photoresist composition may have excellent or suitable etch resistance and heat resistance.
In one or more embodiments, the semiconductor photoresist composition is desirably composed of the aforementioned organometallic compound, mixed solvent, and resin.
However, the semiconductor photoresist composition according to the aforementioned embodiments may further include additives as needed. Examples of the additives may be a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and/or a (e.g., any suitable) combination thereof.
The surfactant may include for example an alkyl benzene sulfonate salt, an alkyl pyridinium salt, polyethylene glycol, a quaternary ammonium salt, and/or a (e.g., any suitable) combination thereof, but the present disclosure is not limited thereto.
The crosslinking agent may be for example a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acryl-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, but the present disclosure is not limited thereto. It may be a crosslinking agent having at least two crosslinking forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acryl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis (glycidoxypropyl) tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and/or the like.
The leveling agent may be used for improving coating flatness during printing and may be a commercially available suitable leveling agent.
The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, a fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and/or a (e.g., any suitable) combination thereof, but the present disclosure is not limited thereto.
The quencher may be diphenyl (p-tolyl) amine, methyl diphenyl amine, triphenyl amine, phenylenediamine, naphthylamine, diaminonaphthalene, and/or a (e.g., any suitable) combination thereof.
A use amount of the additives may be controlled or selected depending on desired or suitable properties.
In addition, the semiconductor photoresist composition may further include a silane coupling agent as an adherence enhancer in order to improve a close-contacting force with the substrate (e.g., in order to improve adherence of the semiconductor photoresist composition to the substrate). The silane coupling agent may be for example a silane compound including a carbon-carbon unsaturated bond such as vinyltrimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyl diethoxysilane; trimethoxy [3-(phenylamino) propyl] silane, and/or the like, but the present disclosure is not limited thereto.
The semiconductor photoresist composition may be formed into a pattern having a high aspect ratio without a collapse. Accordingly, in order to form a fine pattern having a width of, for example, about 5 nm to about 100 nm, for example, about 5 nm to about 80 nm, for example, about 5 nm to about 70 nm, for example, about 5 nm to about 50 nm, for example, about 5 nm to about 40 nm, for example, about 5 nm to about 30 nm, or for example, about 5 nm to about 20 nm, the semiconductor photoresist composition may be used for a photoresist process using light in a wavelength in a range of about 5 nm to about 150 nm, for example, about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 50 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm. Accordingly, the semiconductor photoresist composition according to one or more embodiments may be used to realize extreme ultraviolet lithography using an EUV light source of a wavelength of about 13.5 nm.
According to according to one or more embodiments, a method of forming patterns using the aforementioned semiconductor photoresist composition is provided. For example, the manufactured pattern may be a photoresist pattern.
The method of forming patterns according to one or more embodiments includes forming an etching-objective layer on a substrate, coating the semiconductor photoresist composition on the etching-objective layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching-objective layer using the photoresist pattern as an etching mask.
Hereinafter, a method of forming patterns using the semiconductor photoresist composition is described referring to
Referring to
Subsequently, the resist underlayer composition for forming a resist underlayer 104 is spin-coated on the surface of the washed thin film 102. However, one or more embodiments are not limited thereto, and one or more suitable coating methods, for example a spray coating, a dip coating, a knife edge coating, a printing method, for example an inkjet printing and a screen printing, and/or the like may be used.
The coating process of the resist underlayer may not be needed, i.e., may be excluded or omitted, but hereinafter, a process including a coating of the resist underlayer is described.
Then, the coated composition is dried and baked to form a resist underlayer 104 on the thin film 102. The baking may be performed at about 100° C. to about 500° C., for example, about 100° C. to about 300° C.
The resist underlayer 104 is formed between the substrate 100 and a photoresist layer 106 and thus may prevent or reduce non-uniformity and pattern formability of a photoresist line width if (e.g., when) a ray reflected from (on) the interface between the substrate 100 and the photoresist layer 106 or (on) a hardmask between layers is scattered into an unintended photoresist region. That is, the resist underlayer (104) is situated between the substrate (100) and a photoresist layer (106).
It serves to mitigate non-uniformity and improve the pattern formability of the photoresist line width. Specifically, it helps prevent unintended scattering of rays reflected at the interface between the substrate (100) and the photoresist layer (106) or at a hardmask between layers.
Referring to
More specifically, the formation of a pattern by using the semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 through spin coating, slit coating, inkjet printing, and/or the like and then, drying it to form the photoresist layer 106.
The semiconductor photoresist composition has already been described in detail and will not be described again.
Subsequently, a substrate 100 having the photoresist layer 106 is subjected to a first baking process. The first baking process may be performed at about 80° C. to about 120° C.
Referring to
For example, the exposure may use an activation radiation with light having a high energy wavelength such as EUV (extreme ultraviolet; a wavelength of about 13.5 nm), an E-Beam (an electron beam), and/or the like as well as a short wavelength such as an i-line (a wavelength of about 365 nm), a KrF excimer laser (a wavelength of about 248 nm), an ArF excimer laser (a wavelength of about 193 nm), and/or the like.
More specifically, light for the exposure according to one or more embodiments may have a short wavelength in a range of about 5 nm to about 150 nm or have a high energy wavelength, for example, EUV (extreme ultraviolet; a wavelength of 13.5 nm), an E-Beam (an electron beam), and/or the like. Specifically, in some embodiments, the exposure light may have a short wavelength within the range of approximately 5 nm to 150 nm. Additionally, it may include high-energy wavelengths such as EUV (extreme ultraviolet) with a wavelength of 13.5 nm, an E-Beam (electron beam), and/or the like.
The exposed region 106a of the photoresist layer 106 has a different solubility from the unexposed region 106b of the photoresist layer 106 by forming a polymer by a crosslinking reaction such as condensation between organometallic compounds.
Subsequently, the substrate 100 is subjected to a second baking process. The second baking process may be performed at a temperature of about 90° C. to about 200° C. The exposed region 106a of the photoresist layer 106 becomes easily indissoluble regarding a developer due to the second baking process.
In
As described above, a developer used in a method of forming patterns according to one or more embodiments may be an organic solvent. The organic solvent used in the method of forming patterns according to one or more embodiments may be for example ketones such as methylethylketone, acetone, cyclohexanone, 2-heptanone, and/or the like, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and/or the like, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and/or the like, aromatic compounds such as benzene, xylene, toluene, and/or the like, and/or a (e.g., any suitable) combination thereof.
However, the photoresist pattern according to one or more embodiments is not necessarily limited to the negative tone image but may be formed to have a positive tone image. Herein, a developer used for forming the positive tone image may be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and/or a (e.g., any suitable) combination thereof.
As described above, exposure to light having a high energy such as EUV (extreme ultraViolet; a wavelength of 13.5 nm), an E-Beam (an electron beam), and/or the like as well as light having a wavelength such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and/or the like may provide a photoresist pattern 108 having a width of a thickness of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width of a thickness of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.
In contrast, the photoresist pattern 108 may have a pitch of having a half-pitch of less than or equal to about 50 nm, for example less than or equal to about 40 nm, for example less than or equal to about 30 nm, for example less than or equal to about 20 nm, or for example less than or equal to about 15 nm, and a line width roughness of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.
Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer 104. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 also may have a width corresponding to that of the photoresist pattern 108.
Referring to
The etching of the thin film 102 may be for example dry etching using an etching gas and the etching gas may be for example CHF3, CF4, Cl2, BCl3 and/or a mixed gas thereof.
The thin film pattern 114 formed by using the photoresist pattern 108 formed through the exposure process performed by using an EUV light source may have a width corresponding to that of the photoresist pattern 108. For example, the thin film pattern 114 may have a width of about 5 nm to about 100 nm which is equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed by using the photoresist pattern 108 formed through the exposure process performed by using an EUV light source may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, and more specifically a width of less than or equal to about 20 nm, like that of the photoresist pattern 108.
Hereinafter, the present disclosure will be described in more detail through examples of the preparation of the aforementioned semiconductor photoresist composition. However, the present disclosure is technically not restricted by the following examples.
40.7 g of t-butylSnPhs and 300 g of propionic acid were added to a 250 ml 2-necked round-bottomed flask and then, refluxed by heating for 24 hours.
A compound represented by Chemical Formula 2 was obtained by removing the unreacted propionic acid under a reduced pressure therefrom.
After adding 30 mL of anhydrous pentane to 10 g of t-AmylSnCls and maintaining their temperature at 0° C., 7.4 g of diethyl amine and 6.1 g of ethanol were added thereto and then, stirred at room temperature for 1 hour. When a reaction was completed, the resultant was filtered, concentrated, and vacuum-dried, obtaining a compound represented by Chemical Formula 3.
The compounds represented by Chemical Formulas 2 and 3 obtained in Synthesis Examples 1 and 2 were dissolved at a concentration of 3 wt % in a mixed solvent with the composition shown in Table 1, and then, filtered with a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare semiconductor photoresist compositions.
Each of the photoresist compositions was spin-coated at 1500 rpm for 30seconds on a 200 mm circular silicon wafer of which the surface was deposited with HMDS, fired at 110° C. for 60 seconds (post-apply baked (PAB)), and then, allowed to stand at room temperature for 30 seconds. Then, the wafer is patterned to a size of 180 nm L/S (1/1) using a KrF scanner to form a photoresist thin film. After exposure, it is baked at 170° C. for 60 seconds and then developed with PGMEA solvent. Finally, after firing at 150° C. for 60 seconds, the line width of the pattern (line) is measured using SEM (Scanning electron microscopy).
The photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were each spin-coated on the wafer at 1500 rpm for 60seconds, baked at 110° C. for 60 seconds to form thin films. The surface roughness of the thin films was measured according to the following standards using software (ex. optical profiler) from images taken with an atomic force microscope (AFM), and/or the like, and the results are shown in Table 2.
Among surface roughness, average roughness (Rq; root mean square roughness) refers to the average square root (rms) of the square of the vertical value within the reference length of the roughness profile.
The photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were each spin-coated on the wafer at 1500 rpm for 60seconds, baked at 110° C. for 60 seconds, exposed, and then baked at 170° C. for 60seconds to manufacture patterns. At this time, after confirming the level of sensitivity (Eop/mJ) at which the pattern was formed, the samples were divided into three and stored at 5° C. (low temperature), 25° C. (room temperature), and 40° C. (high temperature). Afterwards, it was confirmed whether the initial sensitivity level was maintained at one-month intervals, and the results are shown in Table 2.
From the results in Table 2, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 3 have improved coating properties compared to Comparative Examples 1 to 6.
In addition, the storage stability of the semiconductor photoresists to which the present disclosure was applied was improved under low/room temperature/high temperature conditions.
A battery management system (BMS) device, and/or any other relevant devices or components according to embodiments of the present invention described herein may be implemented utilizing any suitable hardware, firmware (e.g. an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the device may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the device may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the present disclosure.
A person of ordinary skill in the art would appreciate, in view of the present disclosure in its entirety, would appreciate that each suitable feature of the various embodiments of the present disclosure may be combined or combined with each other, partially or entirely, and may be technically interlocked and operated in various suitable ways, and each embodiment may be implemented independently of each other or in conjunction with each other in any suitable manner unless otherwise stated or implied.
Hereinbefore, the certain embodiments of the present disclosure have been described and illustrated, however, it is apparent to a person with ordinary skill in the art that the present disclosure is not limited to one or more embodiments as described, and may be variously modified and transformed without departing from the spirit and scope of the present disclosure. Accordingly, the modified or transformed embodiments as such may not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure, and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0155625 | Nov 2023 | KR | national |
