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JP-7855055-B2 - Composition for semiconductor photoresist and method for forming patterns using the same

JP7855055B2JP 7855055 B2JP7855055 B2JP 7855055B2JP-7855055-B2

Inventors

  • 尹志賢
  • 張勝宇
  • 辛乘旭
  • 金旻惠
  • 呉慶雅

Assignees

  • 三星エスディアイ株式会社

Dates

Publication Date
20260507
Application Date
20241224
Priority Date
20240216

Claims (18)

  1. Sn-containing organometallic compounds containing at least one of an organic oxy group and an organic carbonyl oxy group ; Compounds comprising at least two ketone groups , represented by the following chemical formula 1 or chemical formula 2 ; A composition for semiconductor photoresist comprising: an aromatic ring compound substituted with OH, SH, and NR 13 R 14 (where R 13 and R 14 are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, or a C6-C20 aryl group); and a solvent. In the aforementioned chemical formula 1 and chemical formula 2, R1 to R6 are each independently hydrogen, halogen, substituted or unsubstituted C1 -C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. L1 to L3 are each independently a single bond, a carbonyl group, a substituted or unsubstituted C1-C20 alkylene group, or a combination thereof . n1 and n2 are each independently one of the integers between 0 and 2. n1 + n2 is greater than or equal to 1.
  2. The semiconductor photoresist composition according to claim 1, wherein the aromatic ring compound: the compound containing at least two ketone groups is present in a weight ratio of 1:1 to 1:10.
  3. The aromatic ring compound is a phenyl group substituted with at least one of OH , SH, and NR13R14 ; a naphthyl group substituted with at least one of OH, SH, and NR13R14 ; an anthracenyl group substituted with at least one of OH , SH, and NR13R14 ; a phenanthrene group substituted with at least one of OH, SH, and NR13R14 ; or a triphenylene group substituted with at least one of OH, SH , and NR13R14 . The semiconductor photoresist composition according to claim 1, wherein R13 and R14 are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, or a C6-C20 aryl group.
  4. The semiconductor photoresist composition according to claim 1, wherein the aromatic ring compound is substituted with at least two of OH, SH, and NR 13 R 14 (wherein R 13 and R 14 are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, or a C6-C20 aryl group).
  5. The semiconductor photoresist composition according to claim 4, wherein the aromatic ring compound is substituted with at least two OH groups.
  6. The semiconductor photoresist composition according to claim 4, wherein the aromatic ring compound is substituted with at least two SH groups.
  7. The semiconductor photoresist composition according to claim 4, wherein the aromatic ring compound is substituted with at least two NR13 R14 groups ( R13 and R14 are each independently substituted with hydrogen, a substituted or unsubstituted C1-C10 alkyl group, or a C6-C20 aryl group).
  8. The semiconductor photoresist composition according to claim 1, wherein the compound containing at least two ketone groups is at least one selected from pentane-2,4-dione, 2,3-butanedione, 3-methyl-2,4-pentanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione.
  9. The semiconductor photoresist composition according to claim 1, wherein the aromatic ring compound is at least one selected from 1,4-hydroquinone, 1,2-benzenediol, 1,3-benzenediol, benzene-1,2-dithiol, 1,4-phenylenediamine, 4-aminobenzene-1-thiol, 3-aminobenzene-1-thiol, and 2-aminobenzene-1-thiol.
  10. The semiconductor photoresist composition according to claim 1, wherein the compound containing at least two ketone groups and the aromatic ring compound are present in an amount of 0.001 to 10% by weight based on 100% by weight of the semiconductor photoresist composition.
  11. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound is present in an amount of 0.5 to 30% by weight relative to 100% by weight of the semiconductor photoresist composition.
  12. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound, the compound containing at least two ketone groups, and the aromatic ring compound are present in a weight ratio of 90:10 to 50:50.
  13. The semiconductor photoresist composition according to claim 1, further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, an inhibitor (quencher), or a combination thereof.
  14. The Sn-containing organometallic compound is represented by the following chemical formula 3, and is the semiconductor photoresist composition according to claim 1: In the aforementioned chemical formula 3, R7 is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R8 to R10 are, independently, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C30 aryl group, or a combination thereof), carboxyl groups (-O(C=O)R b , R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR c R d , where R c and R d are independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR e (C=OR f ), where R e and R f is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR g C(NR h )R i , where R g , R h and Ri are independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(C=O)R k , where k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), At least one of R8 to R10 is an alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (-O(C=O)R b , where R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or dialkylamide (-NR c R d , where R c and R d is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, or an unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR e (C=OR f ), where Re and R f are independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR g C (NR h )R i Here, R g , R h and Ri are independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and thiocarboxyl groups (-S(C=O)R k , R k is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.
  15. The semiconductor photoresist composition according to claim 14, wherein at least one of the R8 to R10 is selected from alkoxy and aryloxy (-OR a , where Ra is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and carboxyl groups (-O(C=O)R b , where R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2- C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).
  16. The R7 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof. Ra is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof. The semiconductor photoresist composition according to claim 14, wherein R b is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.
  17. The Sn-containing organometallic compound is represented by the following chemical formula 4 or chemical formula 5, the semiconductor photoresist composition according to claim 1: In the aforementioned chemical formula 4, R 11 is the C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; In the aforementioned chemical formula 5, R 12 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR l or -OC(=O)R m , The R<sub> l </sub> is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. R m is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. a1, b1, c1, and d1 are each independent integers between 1 and 20.
  18. Steps include forming an etching target film on a substrate; A step of forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 17 onto the film to be etched; A pattern formation method comprising the steps of: patterning the photoresist film to form a photoresist pattern; and etching the film to be etched using the photoresist pattern as an etching mask.

Description

This description relates to a semiconductor photoresist composition and a pattern formation method using the same. EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that utilizes EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (e.g., 20 nm or less) in the exposure process of semiconductor device manufacturing. The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can achieve spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, and feature roughness/line edge roughness (LER) for next-generation devices. The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a phenomenon long known in electron beam lithography. Chemically amplified (CA) photoresists, while designed for high sensitivity, can be partially more challenging under EUV exposure because their typical elemental makeup reduces the photoresist's absorbance at a wavelength of 13.5 nm, resulting in reduced sensitivity. CA photoresists can suffer from roughness issues at small feature sizes, and experiments have shown that line-edge roughness (LER) increases as the photospeed decreases, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry is seeking new types of high-performance photoresists. To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are primarily used for negative tone patterning, where chemical modification via a non-chemical amplification mechanism is required to prevent removal by developer compositions. Because inorganic compositions contain inorganic elements with higher EUV absorption rates compared to hydrocarbons, sensitivity can be ensured even with a non-chemical amplification mechanism. Furthermore, they are not sensitive to the stochastic effect, resulting in lower line edge roughness and fewer defects. Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and/or tantalum have been reported for use as radiation-sensitive materials for patterning (US 5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986). These materials proved effective for patterning large features in bilayer configurations as deep UV, X-ray, and electron beam sources. Furthermore, in recent years, the use of positive ionic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent for imaging 15 nm half-pitch (HP) by projection EUV lithography has shown impressive performance (US2011-0045406; 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). This system exhibits the best performance of non-CA photoresists and possesses a speed of light approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. Firstly, the material is coated with a highly corrosive sulfuric acid/hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, as a composite mixture, structural modifications for performance improvement are not readily available. Thirdly, the film must be developed using an extremely high concentration TMAH (tetramethylammonium hydroxide) solution of approximately 25 wt%. In recent years, molecules containing tin have been found to exhibit excellent absorption of extreme ultraviolet light, leading to active research. In the case of organotin polymers, one such example, the dissociation of alkyl ligands due to light absorption or the secondary electrons generated by this dissociation, followed by crosslinking via oxo bonds with surrounding chains, enables negative tone patterning that is not removed by organic developers. While such organotin polymers have demonstrated a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, further improvements to the aforementioned patterning properties are necessary for commercialization. This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition as an example. The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of already known functions or