Patent Application
20250068066
The present application claims priority to and the benefit of Korean Patent Application No. 10-2023-0110007, filed on Aug. 22, 2023, in the Korean Intellectual Property Office, the entire content of which is incorporated herein by reference.
One or more aspects of embodiments of this disclosure are directed toward a semiconductor photoresist composition and a method of forming (or providing) patterns utilizing the same.
EUV (extreme ultraviolet) lithography is considered to be important (or even essential) technology for manufacturing a next generation semiconductor device. The EUV lithography is a pattern-forming technology utilizing an EUV ray having a wavelength of 13.5 nanometer (nm) as a light exposure source. When EUV lithography is applied, an extremely fine pattern (e.g., less than or equal to 20 nm) may be formed in an exposure process during a manufacture of a semiconductor device.
The extreme ultraviolet (EUV) lithography is realized through (e.g., is performed by) development of compatible photoresists, where the development (e.g., the process of developing a photoresist) can be performed at a spatial resolution of less than or equal to 16 nm. Currently, efforts to overcome or mitigate insufficient or unsuitable specifications of chemically amplified (CA) photoresists such as resolution, photospeed, and/or feature roughness (also referred to as a line edge roughness or LER) for the next generation device are being pursued.
An intrinsic image blurring due to an acid catalyzed reaction in the polymer-type or kind photoresists may limit resolution in small feature sizes, a phenomenon that has been known to occur in electron beam (e-beam) lithography. The chemically amplified (CA) photoresists are designed for relatively high sensitivity, but because their elemental makeups may reduce light absorbance of the photoresists at a wavelength of 13.5 nm and thus decrease their sensitivity, the chemically amplified (CA) photoresists may in some ways 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 experiments tend to show line edge roughness (LER) of the CA photoresists is increased as photospeed is decreased, at least in part due to an essence (e.g., the nature) of acid catalyst processes. Accordingly, a novel relatively high-performance photoresist is required or desired in a semiconductor industry to help overcome 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. The inorganic photosensitive composition is mainly utilized 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 (e.g., sensitivity to EUV light) through the nonchemical amplification mechanism and in addition, may be less sensitive about a stochastic effect and thus may have relatively low line edge roughness and a relatively 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. (See also, as examples, U.S. Pat. No. 5,061,599; and H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986; the entire content of each of the two examples is incorporated herein by reference.) These materials may be effective or suitable for patterning large pitches for bilayer configuration as far ultraviolet (deep UV), X-ray, and/or electron beam sources.
More recently, if (e.g., when) cationic hafnium metal oxide sulfate (HfSOx) materials along with a peroxo complexing agent have been utilized to image a 15 nm half-pitch (HP) through projection EUV exposure, improved performance has been obtained (See also, as examples, US 2011-0045406; and 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 each of the two examples is incorporated herein by reference). This system exhibits a relatively high performance for a non-CA photoresist and has a practicable photospeed close to the one required (or desired) for an EUV photoresist. However, the hafnium metal oxide sulfate material having the peroxo complexing agent has a few practical drawbacks. First, these materials are coated in a mixture of corrosive sulfuric acid/hydrogen peroxide and have insufficient or unsuitable shelf-life stability. Second, a structural change thereof for performance improvement as a composite mixture is not easily achieved. Third, development should be performed in a TMAH (tetramethylammonium hydroxide) solution at an extremely high concentration of 25 wt % and/or the like.
Recently, research has been pursued to explore molecules containing tin as they may have excellent or suitable absorption of extreme ultraviolet rays. Among organotin polymer compounds, alkyl ligands may be dissociated by light absorption and/or secondary electrons produced thereby, and may be crosslinked with adjacent chains through oxo bonds thus enabling the negative tone patterning which may not be removed by an organic developer. Such organotin polymer may exhibit greatly improved sensitivity as well as maintain a suitable resolution and line edge roughness, but it is desirable to further improve patterning characteristics thereof for commercial availability.
One or more aspects of embodiments of the present disclosure are directed toward a semiconductor photoresist composition that exhibits improved contrast performance.
One or more aspects of embodiments of the present disclosure are directed toward a method of forming (or providing) patterns utilizing the semiconductor photoresist composition.
A semiconductor photoresist composition according to one or more embodiments includes an organometallic compound represented by Chemical Formula 1 and a solvent.
In Chemical Formula 1,
The method of forming (or providing) patterns according to one or more embodiments includes forming (or providing) an etching-objective layer on a substrate, coating the semiconductor photoresist composition on the etching-objective layer to form (or provide) a photoresist layer, patterning the photoresist layer to form (or provide) a photoresist pattern, and etching the etching-objective layer utilizing the photoresist pattern as an etching mask.
The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern with improved contrast performance.
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:
Hereinafter, referring to the drawings, embodiments of the present disclosure are described in more detail. In the following description of the present disclosure, functions or constructions that should be well understood by those of ordinary skill in the art will not be described for clarity of the present disclosure.
In order to clearly illustrate the present disclosure, some description and relationships are not 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 enlarged and/or 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 (e.g., without any intervening elements therebetween) or intervening elements may also be present.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element could be termed a second element without departing from the teachings of the present invention. Similarly, a second element could be termed a first element.
As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It will be further understood that the terms “includes,” “including,” “comprises,” and/or “comprising,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.
As used herein, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.
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 selected from among a, b and c”, “at least one of a, b or c”, and “at least one of a, b and/or c” 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.
As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
Further, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure”.
Spatially relative terms, such as “beneath,” “below,” “lower,” “above,” “upper,” “bottom,” “top” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” or “over” the other elements or features. Thus, the term “below” may encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.
As used herein, the terms “substantially”, “about”, and similar terms are used 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. “About” or “approximately,” as used herein, is inclusive of the stated value and means 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 (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
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.
As utilized herein, “substituted” refers to replacement of a hydrogen atom by deuterium, a halogen, a hydroxy group, a thiol group, a cyano group, a nitro group, a carbonyl 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 utilized 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 bonds or triple bonds.
The alkyl group may be a C1 to C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group, without limitation. 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, and/or a 2,2-dimethylpropyl group.
As utilized 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 C10 cycloalkyl group, for example, a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and/or a cyclohexyl group, but the present disclosure is not limited thereto.
As utilized 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 (i.e., rings sharing adjacent pairs of carbon atoms) functional group.
As utilized herein, unless otherwise defined, “alkenyl group” refers to an aliphatic unsaturated alkenyl group including at least one double bond in a linear or branched aliphatic hydrocarbon group.
As utilized herein, unless otherwise defined, “alkynyl group” refers to an aliphatic unsaturated alkynyl group including at least one triple bond in a linear or branched aliphatic hydrocarbon group.
In the chemical formulae described herein, t-Bu refers to a tert-butyl group.
Hereinafter, a semiconductor photoresist composition according to one or more embodiments is described.
The semiconductor photoresist composition according to one or more embodiments include an organometallic compound represented by Chemical Formula 1 and a solvent.
In Chemical Formula 1,
The organometallic compound of the present disclosure improves sensitivity by introducing a functional group that can suitably stabilize radical compounds generated during exposure, and maximizes or improves a difference in solubility of the exposed and unexposed regions of the photoresist layer in the developer to increase pattern formability and process margin.
The functional group capable of suitably stabilizing the radical compound may be located in a position corresponding to at least one of R2 to R4 in Chemical Formula 1, and may be a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, C(O)—Rc (wherein Rc may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group), P(O)ORdRe (wherein Rd and Re may each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group), P(O)ORfORg (wherein Rf and Rg may each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group), S(O)Rh (wherein Rh may be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2Ri (wherein Ri may be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group); and/or adjacent groups among R2 to R4 may be linked to each other to form (or provide) a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.
As an example, if at least one of R2 to R4 includes a C(O)—Rc group, then the following reaction mechanism as shown in Reaction Scheme 1 can occur, and the radicals generated after exposure may be stabilized by the carbonyl group and become more sensitive to photosensitive reactions. As a result, the difference in physical properties between the exposed and unexposed regions is maximized or increased, enabling excellent or suitable contrast performance.
For example, M may be selected from among Sn, Sb, I, Te, In, Ag, Ni, Bi, and Po.
In some embodiments, M may be Sn.
The organic tin compound according to the present disclosure may concurrently (e.g., simultaneously) include a hydrolyzable group and a photosensitive reactive group in addition to a functional group capable of stabilizing a radical compound in tin, the central metal.
For example, at least one of R2 to R4 may be a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, C(O)—Rc (wherein Rc may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), P(O)ORdRe (wherein Rd and Re may each independently be a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), P(O)ORfORg (wherein Rf and Rg may each independently be a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), S(O)Rh (wherein Rh and Rg may each independently be a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), or S(O)2Ri (wherein Ri may be a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group); or
For example, at least one of R2 to R4 may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, C(O)—Rc (wherein Rc may be hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group), C(Rr)═C(Rs)(Rt) (wherein Rr, Rs, and Rt may each independently be hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group), P(O)ORdRe (wherein Rd and Re may each independently be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group), P(O)ORfORg (wherein Rf and Rg may each independently be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group), S(O)Rh (wherein Rh may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group), or S(O)2Ri (wherein Ri may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, or a substituted or unsubstituted xylene group); and/or
For example, at least one of R2 to R4 may be selected from among the substituents listed in Group 1-1; and/or
In Group 1-1 and Group 1-2, * is a carbon which corresponding one(s) of R2 to R4 are linked to.
For example, R1 may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or La-O—Ra (wherein La may be a substituted or unsubstituted C1 to C10 alkylene group and Ra may be a substituted or unsubstituted C1 to C10 alkyl group).
In some embodiments, R1 may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, and/or a (e.g., any suitable) combination thereof, and
For example, X may be a halogen, O-Lb-C(O)—Rj (wherein Lb may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group, Rj may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof), alkylamido or dialkylamido group (e.g., —NRkRl, wherein Rk and Rl may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof), amidato group (e.g., —NRm(CORn), wherein Rm and Rn may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof), or amidinato group (e.g., —NRoC(NRp)Rq, wherein Ro, Rp, and Rq may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof).
For example, X may be a halogen or O-Lb-C(O)—Rj (wherein Lb may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group and Rj may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof).
In one or more embodiments, X may be O-Lb-C(O)—Rj (wherein Lb may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group and Rj may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a (e.g., any suitable) combination thereof).
For example, Rj may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, and/or a (e.g., any suitable) combination thereof, and
The organometallic compound may have excellent or suitable sensitivity due to its relatively high reactivity to extreme ultraviolet light at about 13.5 nm and/or to additional secondary electrons generated thereby.
The organometallic compound may be included in an amount of about 1 wt % to about 30 wt %, for example about 1 wt % to about 25 wt %, for example about 1 wt % to about 20 wt %, for example about 1 wt % to about 15 wt %, for example about 1 wt % to about 10 wt %, or, for example, about 1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition, and the present disclosure is not limited thereto. When the organometallic compound is included in the content (e.g., amount) within any of the above ranges, storage stability and etch resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.
Because the semiconductor photoresist composition according to one or more embodiments includes the organometallic compound, a semiconductor photoresist composition having excellent or suitable sensitivity and stability may be provided.
The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, and may be, for example, selected from among aromatic compounds (e.g., xylene, toluene, and/or the like), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, and/or the like), ethers (e.g., anisole, tetrahydrofuran, and/or the like), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, and/or the like), ketones (e.g., methyl ethyl ketone, 2-heptanone, and/or the like), and/or a (e.g., any suitable) mixture thereof, but the present disclosure is not limited thereto.
The semiconductor photoresist composition according to one or more embodiments may further include a resin, in addition to the organometallic compound of the present embodiments, and solvent.
The resin may be a phenolic resin including at least one aromatic moiety of Group 3.
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 (100 wt %) of the semiconductor photoresist composition.
If (e.g., when) the resin is included in the above content (e.g., amount) range, it may have excellent or suitable etch resistance and heat resistance.
The semiconductor photoresist composition according to one or more embodiments may include (e.g., consist of) the organometallic compound according to the present embodiments, solvent, and resin. However, the semiconductor photoresist composition according to one or more embodiments may further include suitable 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, and/or a polymer-based crosslinking agent, but the present disclosure is not limited thereto. The crosslinking agent may have 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, and/or methoxymethylated thiourea, and/or the like.
The leveling agent may be utilized for improving coating flatness during printing and may be any suitable (e.g., commercially available) 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.
An amount of the additives may be controlled or selected depending on desired or suitable properties.
In one or more embodiments, 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 vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tris(β-methoxyethoxy)silane; 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 relatively high aspect ratio without a collapse. Accordingly, in order to form (or provide) 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, for example, about 5 nm to about 20 nm, or for example, about 5 nm to about 10 nm, the semiconductor photoresist composition may be utilized for a photoresist process utilizing light having 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 utilized to realize extreme ultraviolet lithography utilizing an EUV light source of a wavelength of about 13.5 nm.
According to one or more embodiments, a method of forming (or providing) patterns utilizing the semiconductor photoresist composition according to the present embodiments is provided. For example, the manufactured pattern may be a photoresist pattern.
The method of forming (or providing) patterns according to one or more embodiments includes forming (or providing) an etching-objective layer on a substrate, coating the semiconductor photoresist composition on the etching-objective layer to form (or provide) a photoresist layer, patterning the photoresist layer to form (or provide) a photoresist pattern, and etching the etching-objective layer utilizing the photoresist pattern as an etching mask.
Hereinafter, a method of forming (or providing) patterns utilizing the semiconductor photoresist composition is described referring to
Referring to
Subsequently, the resist underlayer composition for providing a resist underlayer 104 is spin-coated on the surface of the washed thin film 102. However, one or more embodiments is 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 utilized.
Hereinafter, a process including a coating of the resist underlayer is described. However, in some embodiments, the coating process of the resist underlayer may not be provided (e.g., may be omitted).
Then, the coated composition is dried and baked to form (or provide) 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 in pattern formability and 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, and/or a hardmask between layers, is scattered into an unintended (or undesirable) photoresist region.
Referring to
For example, the formation of a pattern by utilizing the semiconductor photoresist composition may include coating the semiconductor resist composition on the substrate 100 having the thin film 102 coated thereon. The semiconductor photoresist composition may be coated through spin coating, slit coating, inkjet printing, and/or the like and then, may be dried to form (or provide) the photoresist layer 106.
The semiconductor photoresist composition has already been illustrated herein and will not be illustrated 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 utilize 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 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.
For example, light for the exposure according to one or more embodiments may have a wavelength in a range of about 5 nm to about 150 nm and a relatively high energy wavelength, for example, EUV (extreme ultraviolet; a wavelength of 13.5 nm), an E-Beam (an electron beam), and/or the like.
The exposed region 106b of the photoresist layer 106 has a different solubility from the unexposed region 106a of the photoresist layer 106, where the exposed region 106b forms 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 106b of the photoresist layer 106 becomes substantially indissoluble by a developer due to the second baking process.
In
As described above, a developer (e.g., a developing composition) utilized in a method of forming (or providing) patterns according to one or more embodiments may be an organic solvent. The organic solvent utilized in the method of forming (or providing) patterns according to one or more embodiments may be, for example, selected from among 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 utilized for forming (or providing) 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 relatively 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 about 5 nm to about 100 nm. For example, the photoresist pattern 108 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, about 5 nm to about 20 nm, or about 5 nm to about 10 nm.
In some embodiments, the photoresist pattern 108 may have 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, for example less than or equal to about 10 nm, and a line width roughness of less than or equal to about 5 nm, less than or equal to about 3 nm, less than or equal to about 2 nm, or less than or equal to about 1 nm.
Subsequently, the photoresist pattern 108 is utilized 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 utilizing an etching gas, and the etching gas may be for example CHF3, CF4, Cl2, BCl3 and/or a mixed gas thereof.
In the exposure process, the thin film pattern 114 formed by utilizing the photoresist pattern 108 formed through the exposure process performed with 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 5 nm to 100 nm which is equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed by utilizing the photoresist pattern 108 formed through the exposure process performed by utilizing 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 semiconductor photoresist composition according to the present embodiments. However, the present disclosure is technically not restricted by the following examples.
In a 250 mL 2-neck round-bottomed flask, Ph3SnCl (20 g, 51.9 mmol) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF) and then, cooled to 0° C. in an ice bath, and a 2-butanone-3-magnesiumbromide in THE solution (62.3 mmol) was slowly added thereto in a dropwise fashion. When the addition in a dropwise fashion was completed, the mixture was stirred at room temperature (25° C.) for 12 hours. After distillation under a reduced pressure, 50 mL of acetic acid was slowly added in a dropwise fashion thereto and then, heated under reflux for 12 hours. Subsequently, after reducing the temperature to room temperature, acetic acid was vacuum-distilled to obtain a compound represented by Chemical Formula 2.
A compound represented by Chemical Formula 3 was obtained in substantially the same manner as in Synthesis Example 1 except that a benzyl magnesium chloride in 1 M THF solution (62.3 mmol) was utilized instead of the 1 M THF solution of 2-butanone-3-magnesium bromide.
In a 250 mL 2-neck round-bottomed flask, Ph3SnCl (20 g, 51.9 mmol) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF) and then, cooled to 0° C. in an ice bath, and a 1 M THF solution (62.3 mmol) of 2-methyl-1-butene-3-magnesium bromide was slowly added thereto in a dropwise fashion. When the addition in a dropwise fashion was completed, the mixture was stirred at room temperature for 12 hours. After distillation under a reduced pressure, a product therefrom was dissolved in 50 mL of CH2Cl2, a 2 M HCl diethyl ether solution (155.7 mmol) was slowly added thereto in a dropwise fashion at −78° C. for 30 minutes and then, stirred at room temperature for 12 hours, and the solvent was concentrated and vacuum-distilled. Subsequently, after dissolving the obtained product in 50 mL of CH2Cl2, Ag-acetylacetone (103.8 mmol), and Ag-tert-butoxide (51.9 mmol) were added thereto in a dropwise fashion at 0° C. to produce a solid, and after removing the solid by filtration, a filtrate therefrom was distilled to obtain a compound represented by Chemical Formula 4.
25 mL of acetic acid was slowly added to a tert-butyltriphenyltin compound (10 g, 25.6 mmol) in a dropwise fashion at room temperature and then, heated under reflux at 110° C. for 24 hours. Subsequently, after reducing the temperature to room temperature, the acetic acid was vacuum-distilled to obtain a compound represented by Chemical Formula 5.
The compounds represented by Chemical Formulae 2 to 5 obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were respectively dissolved in 4-methyl-2-pentanol at 3 wt % and filtered through a 0.1 um PTFE syringe filter to prepare a photoresist composition.
A 4-inch diameter circular silicon wafer with a native-oxide surface was utilized as a substrate for thin film deposition. Before deposition of the resist thin film, the wafer was treated in a UV ozone cleaning system for 10 minutes, the resist composition was spin-coated on the wafer at 1500 rpm for about 30 seconds, and baked at 100° C. for 120 seconds to form (or provide) a thin film. Afterwards, the thickness of the film after coating and firing was measured with respect to an ellipsometry, wherein the thickness was about 20 nm for Examples 1 to 3 and Comparative Example 1.
The substrate, on which the resist thin film was deposited, was exposed to an E-beam with an acceleration voltage of about 100 kV to form (or provide) nanowires of about 40 nm half-pitch. The irradiated substrate was exposed at 40° C. for 30 seconds, dipped into 2-heptanone in a petri dish for 60 seconds and taken out therefrom, washed with the same solvent for 10 seconds, and finally fired at 150° C. to complete a patterned wafer. The patterned wafer was measured with respect to a thickness of each exposed region to obtain a contrast curve, from which contrast performance y (contrast) was calculated, and the results are shown in Table 1.
Referring to Table 1, if (e.g., when) the photoresist compositions of Examples 1 to 3 were applied, compared with if (e.g., when) the photoresist composition of Comparative Example 1 was applied, excellent or suitable removal capability of a metal-containing photoresist layer and excellent or suitable pattern characteristics with improved contrast performance were realized.
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 their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0110007 | Aug 2023 | KR | national |
