Composition for semiconductor photoresist and method for forming pattern using the same

Abstract

To provide a semiconductor photoresist composition that exhibits superior sensitivity and offers improved stability and coatability, and a method of forming patterns using the same.SOLUTION: A semiconductor photoresist composition according to an embodiment includes an organometallic compound represented by Chemical Formula 1, and a solvent.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] This description relates to a semiconductor photoresist composition and a patterning method using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the elemental technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses 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) during the exposure step in the semiconductor device manufacturing process.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of achieving spatial resolutions below 16 nm. Conventional chemically amplified (CA) photoresists are currently being considered to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next generation devices.

[0004] A long-known fact in electron beam (e-beam) lithography is that intrinsic image blur due to acid catalyzed reactions occurring in polymeric photoresists limits resolution at small feature sizes. Chemically amplified (CA) photoresists were designed for high sensitivity, but their typical elemental makeup reduces the absorbance of the photoresist at 13.5 nm wavelengths, thereby reducing sensitivity, which can be even more problematic under EUV exposure, in part because of this.

[0005] CA photoresists can also suffer from roughness issues at small feature sizes. For example, experiments have shown that line edge roughness (LER) increases as the photospeed decreases, due in part to the nature of the acid catalyzed process. Due to the shortcomings and problems of CA photoresists, there is a demand in the semiconductor industry for a new class of high performance photoresists.

[0006] In order to overcome the disadvantages of the above-mentioned chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been researched. Inorganic photosensitive compositions are mainly used for negative tone patterning, which is resistant to removal by developer compositions due to chemical modification by a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, and are known to ensure sensitivity even with a non-chemically amplified mechanism, to be less sensitive to stochastic effects, and to have fewer line edge roughness and defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation sensitive materials (Patent Document 1: US5061599; Non-Patent Document 1: H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective in patterning large features in a bilayer configuration with deep UV, x-ray, and electron beam sources. More recently, they have shown impressive performance when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to image 15 nm half pitch (HP) with projection EUV exposure (Patent Document 2: US2011-0045406; Non-Patent Document 2: JK Towers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011). This system shows the best performance of a non-CA photoresist and has a light speed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, the materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, which results in poor shelf-life stability. Second, as a complex mixture, it is not easy to modify the structure to improve performance. Third, they must be developed with a very high concentration of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] As it is known that molecules containing tin have excellent extreme ultraviolet absorption, active research has been conducted in recent years. In the case of organotin polymers, which are one of them, alkyl ligands are dissociated by light absorption or secondary electrons generated by the absorption, and crosslinking with surrounding chains by oxo bonds allows negative tone patterning that is not removed by organic developers. Such organotin polymers have been shown to dramatically improve sensitivity while maintaining resolution and line edge roughness, but further improvement of the patterning properties is required for commercialization. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Pat. No. 5,061,599 [Patent Document 2] US Patent No. 2011-0045406 [Non-patent literature]

[0011] [Non-Patent Document 1] H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986 [Non-Patent Document 2] JKStowers,A.Telecky,M.Kocsis,BLClark,DAKeszler,A.Grenville,CNAnderson,PPNaulleau,Proc.SPIE,7969,796915,2011 Summary of the Invention [Problem to be solved by the invention]

[0012] One embodiment provides a composition for semiconductor photoresist that exhibits excellent sensitivity and improved stability.One embodiment provides a composition for semiconductor photoresist that exhibits improved coatability.

[0013] Another embodiment provides a method of forming a pattern using the semiconductor photoresist composition. [Means for solving the problem]

[0014] According to one embodiment, the composition for semiconductor photoresist includes an organometallic compound represented by the following Formula 1 and a solvent.

[0015] [ka]

[0016] In the above chemical formula 1, R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, or -R a -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n and m are each independently an integer from 1 to 6; 2≦n+m≦6, X is a ligand represented by at least one of the following formulas 1A and 1B:

[0017] [ka]

[0018] In the above Chemical Formula 1A and Chemical Formula 1B, R 2 , R 3 and R 5 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R 2 , R 3 may be bonded to each other to form a ring, R 4 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof; * is the point where it is connected to M.

[0019] The organometallic compound can be represented by the following Formula 2 or Formula 3.

[0020] [ka]

[0021] In the above Chemical Formula 2 and Chemical Formula 3, R 1is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, or -R a -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n1 and m1 each independently represent an integer from 1 to 5; 2≦n1+m1≦6, R 2 , R 3 and R 5 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R 2 , R 3 may be bonded to each other to form a ring.

[0022] R 4is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

[0023] The n+m may be an integer of 4 to 6.

[0024] The M may be Sn or Sb.

[0025] R 2 , R 3 and R 5 may each independently be a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which case, R 2 , R 3 may be bonded to each other to form a ring.

[0026] R 4may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

[0027] R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R 2 , R 3 and R 5 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, R 4 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms.

[0028] R 1 may be a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms.

[0029] R 1 may be iso-propyl, iso-butyl, iso-pentyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, sec-butyl, sec-pentyl, sec-hexyl, sec-heptyl, sec-octyl, tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, or tert-decyl.

[0030] The organometallic compound may be one selected from the compounds listed in Group 1 below.

[0031] [ka]

[0032] [ka]

[0033] The organometallic compound may be present in an amount of 1 to 30% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0034] The semiconductor photoresist composition may further include additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

[0035] According to another embodiment, a method for forming a pattern includes forming a film to be etched on a substrate, applying the semiconductor photoresist composition to the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.

[0036] The step of forming the photoresist pattern may use light having a wavelength of 5 nm to 150 nm.

[0037] The photoresist pattern may have a width of 5 nm to 100 nm. Effect of the Invention

[0038] The composition for a semiconductor photoresist according to an embodiment may provide a photoresist pattern with improved storage stability and sensitivity. [Brief description of the drawings]

[0039] [Figure 1] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 2] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 3] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Figure 4] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 5] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, a description of a function or configuration that is already known will be omitted in order to clarify the gist of the description.

[0041] In order to clearly explain the present description, parts unnecessary for the description will be omitted, and the same or similar components will be given the same reference numerals throughout the specification. In addition, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, so the present description is not necessarily limited to those shown in the drawings.

[0042] In the drawings, the thickness of various layers and regions is exaggerated to clearly show them. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, or other part is said to be "on" or "on" another part, this includes not only the case where it is "directly on" another part, but also the case where there is another part therebetween.

[0043] In this description, "substituted" means that a hydrogen atom is replaced by a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, a thiol group, -NRR' (wherein R and R' are each independently a hydrogen atom, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R" (wherein R, R', and R" are each independently a hydrogen atom, "Non-substituted" means that the hydrogen atom is substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a combination thereof. "Non-substituted" means that the hydrogen atom remains as a hydrogen atom without being substituted with another substituent.

[0044] As used herein, unless otherwise specified, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0045] The alkyl group may be, for example, an alkyl group having 1 to 10 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms 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.

[0046] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0047] The cycloalkyl group may be, for example, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 carbon atoms. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0048] As used herein, an "aryl group" refers to a substituent in which all elements of a cyclic substituent have p-orbitals and these p-orbitals form a conjugation, including monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functionalities.

[0049] As used herein, unless otherwise defined, an "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0050] As used herein, unless otherwise defined, an "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0051] In the chemical formulas described herein, t-Bu (t-butyl) refers to a tert-butyl group.

[0052] Hereinafter, a composition for semiconductor photoresist according to an embodiment will be described.

[0053] A composition for semiconductor photoresist according to one embodiment of the present invention includes an organometallic compound represented by the following Formula 1 and a solvent.

[0054] [ka]

[0055] In the above chemical formula 1, R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), or -R a -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n and m are each independently an integer from 1 to 6; 2≦n+m≦6, X is a ligand represented by at least one of the following formulas 1A and 1B:

[0056] [ka]

[0057] In the above Chemical Formula 1A and Chemical Formula 1B, R 2 , R 3 and R 5each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R 2 , R 3 may be bonded to each other to form a ring (in this case, R 2 and R 3 It is preferable that both of are not hydrogen atoms. R 4 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof; * is the point where it is connected to M.

[0058] The organometallic compound has an alpha effect, and the metal-ligand bond is strengthened by the electron donor property of N, thereby improving storage stability against moisture.

[0059] In particular, compared to a general monomolecular form coordinated to tetravalent (or pentavalent), the coordination number of Sn (or Sb) is satisfied by additional coordination bonds, resulting in a form in which Sn atoms (or Sb atoms) are structurally covered, improving water stability and preventing aggregation, and coating in an amorphous form without the use of additives during spin coating, thereby improving sensitivity and coatability.

[0060] For example, the organometallic compound may be represented by the following Formula 2 or 3.

[0061] [ka]

[0062] In the above Chemical Formula 2 and Chemical Formula 3, R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), or -R a -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n1 and m1 each independently represent an integer from 1 to 5; 2≦n1+m1≦6, R 2 , R 3 and R 5each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R 2 , R 3 may be bonded to each other to form a ring.

[0063] R 4 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (or 7 to 30 carbon atoms), a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

[0064] In the following description, the preferred ranges and the like of m and n also apply to n1 and m1.

[0065] For example, n+m (or n1+m1) may be one of integers from 3 to 6.

[0066] For example, the n+m (or the n1+m1) may be one of integers from 4 to 6. The n+m (or the n1+m1) may be 4 or 5.

[0067] As an example, n and m may be independently an integer of 1 to 3.

[0068] The M may be Sn or Sb. For example, when M is Sn, n may be 1 and m may be 3, and when M is Sb, n may be 3 and m may be 2. By coordinating a plurality of N-containing ligands having an alpha effect to a metal (m is 2 or more), the bond between the metal and the ligand is strengthened due to the electron donor property of N, and storage stability against moisture can be further improved.

[0069] R 2 , R 3 and R 5 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof. 2 , R 3 and R 5 may each independently be a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. 2 , R 3 and R 5 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0070] R 4may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (in this case, the substituent may be an aryl group having 6 to 30 carbon atoms or a phenoxy group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof. 4 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (in this case, the substituent may be an aryl group having 6 to 30 carbon atoms or a phenoxy group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

[0071] R 4 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms).

[0072] R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R 2 , R 3 and R 5each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, R 4 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms.

[0073] R 1 R 1 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0074] R 1 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms. 1 may be a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms, an unsubstituted branched alkyl group having 3 to 20 carbon atoms, an unsubstituted branched alkyl group having 3 to 12 carbon atoms, or an unsubstituted branched alkyl group having 3 to 8 carbon atoms. In this case, the substituent of the alkyl group may be an aryl group having 6 to 30 carbon atoms, such as a phenyl group.

[0075] For example, when M is Sn, the R 1 may be a methyl group, an ethyl group, a tert-butyl group, a benzyl group, a cyclopentyl group or an iso-propyl group.

[0076] For example, when M is Sb, the R 1 may be a phenyl group, an ethyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group or an iso-propyl group.

[0077] R 1may be iso-propyl, iso-butyl, iso-pentyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, sec-butyl, sec-pentyl, sec-hexyl, sec-heptyl, sec-octyl, tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, or tert-decyl.

[0078] R 5 may be a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms).

[0079] When M is Sn and X is represented by formula 1A, R 2 and R 3 may each independently be a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms), a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms (preferably a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms), or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), 2 , R 3 may be bonded to each other to form a ring, R 2 and R 3 Both of the radicals cannot be hydrogen atoms.

[0080] When M is Sn and X is represented by formula 1B, R 4may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms), a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms (for example, a benzyl group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably a substituted or unsubstituted aryl group having 6 to 24 carbon atoms), or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, in which case the substituent may be an aryl group having 6 to 30 carbon atoms or may be a phenoxy group).

[0081] When M is Sb and X is represented by formula 1A, R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms), a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms (preferably a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably a substituted or unsubstituted It may be a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms (preferably a substituted or unsubstituted heteroaryl group having 5 to 24 carbon atoms, more preferably a substituted or unsubstituted heteroaryl group having 5 to 12 carbon atoms), or a substituted or unsubstituted acyl group having 1 to 30 carbon atoms (preferably a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted acyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted acyl group having 1 to 3 carbon atoms).

[0082] When M is Sb and X is represented by formula 1B, R 4 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and more preferably a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (preferably a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, in which case the substituent may be an aryl group having 6 to 30 carbon atoms or may be a phenoxy group).

[0083] The organometallic compound can be selected from the compounds listed in Group 1 below.

[0084] [ka]

[0085] [ka]

[0086] The organometallic compound may strongly absorb extreme ultraviolet light at 13.5 nm and have excellent sensitivity to light having high energy.

[0087] In one embodiment, the organometallic compound may be included in an amount of 1 wt% to 30 wt%, for example, 1 wt% to 25 wt%, for example, 1 wt% to 20 wt%, for example, 1 wt% to 15 wt%, for example, 1 wt% to 10 wt%, for example, 1 wt% to 5 wt%, based on 100 wt% of the composition for semiconductor photoresist, but is not limited thereto. When the organometallic compound is included in an amount within the above range, the storage stability and etching resistance of the composition for semiconductor photoresist are improved, and the resolution characteristics are improved.

[0088] The composition for semiconductor photoresist according to one embodiment of the present invention contains the organometallic compound described above, so that a composition for semiconductor photoresist having excellent sensitivity and pattern formability can be provided.

[0089] The solvent included in the semiconductor photoresist composition according to an embodiment may be an organic solvent, and examples thereof include, but are not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

[0090] In one embodiment, the semiconductor photoresist composition may further comprise a resin in addition to the organometallic compound and the solvent.

[0091] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0092] [ka]

[0093] The resin may have a weight average molecular weight of 500 to 20,000.

[0094] The resin may be included in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0095] When the resin is contained in the above content range, excellent etching resistance and heat resistance can be obtained.

[0096] Meanwhile, the semiconductor photoresist composition according to an embodiment preferably comprises the organometallic compound, a solvent, and a resin. However, the semiconductor photoresist composition according to the embodiment may further include an additive, if necessary. Examples of the additive include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0097] The surfactant may be, for example, but is not limited to, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, a quaternary ammonium salt, or a combination thereof.

[0098] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Crosslinking agents having at least two crosslink-forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea, can be used.

[0099] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0100] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0101] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0102] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0103] In addition, the semiconductor photoresist composition may further use a silane coupling agent as an additive to enhance adhesion to a substrate (e.g., to enhance the adhesive strength of the semiconductor photoresist composition to a substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing carbon-carbon unsaturated bonds such as trimethoxy[3-(phenylamino)propyl]silane.

[0104] The composition for semiconductor photoresist does not or is unlikely to cause pattern collapse even when a pattern having a high aspect ratio is formed. Therefore, in order to form a fine pattern having a width of, for example, 5 nm to 100 nm, for example, a fine pattern having a width of, for example, 5 nm to 80 nm, for example, a fine pattern having a width of, for example, 5 nm to 70 nm, for example, a fine pattern having a width of, for example, 5 nm to 50 nm, for example, a fine pattern having a width of, for example, 5 nm to 40 nm, for example, a fine pattern having a width of, for example, 5 nm to 30 nm, for example, a fine pattern having a width of, for example, 5 nm to 20 nm, for example, a fine pattern having a width of, for example, 5 nm to 10 nm, the composition for semiconductor photoresist can be used in a photoresist process using light with a wavelength of, for example, 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of, for example, 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of, for example, 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of, for example, 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of, for example, 5 nm to 30 nm, for example, a photoresist process using light with a wavelength of, for example, 5 nm to 20 nm. Therefore, the semiconductor photoresist composition according to one embodiment can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm.

[0105] Meanwhile, according to another embodiment, there is provided a method for forming a pattern using the above-mentioned semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0106] A method for forming a pattern according to an embodiment includes the steps of forming a film to be etched on a substrate, applying the semiconductor photoresist composition to the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.

[0107] A method for forming a pattern using the above-mentioned semiconductor photoresist composition will be described below with reference to Figures 1 to 5. Figures 1 to 5 are cross-sectional views illustrating the method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0108] Referring to FIG. 1, first, an object to be etched is prepared. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, only the case where the object to be etched is the thin film 102 will be described. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0109] Next, a composition for forming a resist underlayer film is coated by applying a spin coating method on the surface of the cleaned thin film 102 to provide a resist underlayer film 104. However, an embodiment is not necessarily limited thereto, and various known coating methods, for example, spray coating, dip coating, knife edge coating, and printing methods, for example, inkjet printing and screen printing, may also be used.

[0110] The resist underlayer coating process may be omitted, and the following description will be made of the case where the resist underlayer is coated.

[0111] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking process can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0112] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106 to prevent radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hardmask from scattering into unintended photoresist regions, thereby preventing non-uniformity of the photoresist linewidth and disrupting pattern formability.

[0113] 2, the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the above-described semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0114] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the semiconductor photoresist composition onto the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, or the like, and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0115] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0116] Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process can be performed at a temperature of about 80°C to about 120°C.

[0117] Referring to FIG. 3, the photoresist film 106 is selectively exposed to light using a patterned mask 110 .

[0118] As an example, examples of light that can be used in the exposure process include light having short wavelengths such as (activating radiation diagram) i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0119] More specifically, the exposure light according to an embodiment may be short wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0120] The exposed regions 106b of the photoresist film 106 form polymers through a crosslinking reaction such as condensation between organometallic compounds, and thus have a different solubility from the unexposed regions 106a of the photoresist film 106.

[0121] Next, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90° C. to about 200° C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in a developer.

[0122] 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, completing the photoresist pattern 108 corresponding to the negative tone image.

[0123] As described above, the developer used in the pattern formation method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to an embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, and combinations thereof.

[0124] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, and may be formed to have a positive tone image. In this case, a developer that can be used to form a positive tone image includes a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0125] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) may have a thickness width of 5 nm to 100 nm. As an example, the photoresist pattern 108 may be formed with a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm, or 5 nm to 10 nm.

[0126] Meanwhile, the photoresist pattern 108 may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 10 nm or less, and a line width roughness of about 5 nm or less, about 3 nm or less, about 2 nm or less, or about 1 nm or less.

[0127] Next, the resist underlayer 104 is etched using the photoresist pattern 108 as an etching mask. An organic layer pattern 112 is formed by the above-mentioned etching process. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0128] 5, the photoresist pattern 108 is used as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

[0129] The thin film 102 can be etched by dry etching using an etching gas such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0130] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using an EUV light source in the previous exposure process may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, the same as the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process performed using an EUV light source may have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, may be formed to have a width of 20 nm or less.

[0131] The present invention will be described in more detail with reference to the following examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples. EXAMPLES

[0132] (Synthesis of organometallic compounds) Synthesis Example 1 10 g (25.5 mmol) of t-butyltrisdiethylamide tin was placed in a 100 mL Schlenk flask, and 10 mL of anhydrous dichloromethane was added thereto, followed by stirring at 0° C. under a nitrogen atmosphere.

[0133] A solution of 5.7 g (78 mmol) of acetone oxime dissolved in 16 mL of anhydrous dichloromethane was slowly added thereto at 0° C. The solution was stirred at room temperature for 3 hours, and then concentrated under reduced pressure to remove dichloromethane and diethylamine, thereby obtaining a compound represented by the following chemical formula 1a.

[0134] [ka]

[0135] Synthesis Example 2 10 g (25.5 mmol) of t-butyltrisdiethylamide tin was placed in a 100 mL Schlenk flask, and 10 mL of anhydrous dichloromethane was added thereto, followed by stirring at 0° C. under a nitrogen atmosphere.

[0136] A solution of 10.4 g (78 mmol) of t-butyl-N-hydroxycarbamate dissolved in 16 mL of anhydrous dichloromethane was slowly added thereto at 0° C. The solution was stirred at room temperature for 3 hours, and then concentrated under reduced pressure to remove dichloromethane and diethylamine. The solid was then recrystallized with normal hexane to obtain a compound represented by the following chemical formula 1b.

[0137] [ka]

[0138] Synthesis Example 3 A 100 mL Schlenk flask was charged with 5.8 g (78 mmol) of acetohydroxamic acid, and 16 mL of anhydrous dichloromethane was added thereto, followed by stirring at 0° C. under a nitrogen atmosphere.

[0139] A solution of 10 g (25.5 mmol) of t-butyl tris(diethylamido)tin dissolved in 10 mL of anhydrous dichloromethane was slowly added to the solution at 0° C. The solution was stirred at room temperature for 3 hours, and then concentrated under reduced pressure to remove dichloromethane and diethylamine. The solid was then recrystallized from dichloromethane / normal hexane to obtain a compound represented by the following chemical formula 1c.

[0140] [ka]

[0141] Synthesis Example 4 A solution of 1.43g (19.5mmol) of acetone oxime dissolved in 20mL of anhydrous tetrahydrofuran was cooled to 0℃ in a 100mL Schlenk flask and stirred under nitrogen. 0.45g (19.5mmol) of sodium pieces was gradually added to the solution and allowed to react. The solution was stirred at 0℃ for 30 minutes. A solution of 5g (9.75mmol) of triphenylantimony dibromide dissolved in 30mL of anhydrous toluene was gradually added to the solution.

[0142] The reaction solution was stirred in a nitrogen atmosphere at 70° C. for 12 hours. The reaction solution was cooled to room temperature and then filtered through Celite. The filtrate was concentrated under reduced pressure, and the solid was recrystallized from dichloromethane / normal hexane to obtain a compound represented by the following chemical formula 1d.

[0143] [ka]

[0144] Synthesis Example 5 In a 100mL Schlenk flask, 2.6g (19.5mmol) of t-butyl-N-hydroxycarbamate was dissolved in 20mL of anhydrous tetrahydrofuran and cooled to 0℃ and stirred under nitrogen. 0.45g (19.5mmol) of sodium pieces was gradually added to the solution and allowed to react. The solution was stirred at 0℃ for 30 minutes. 5g (9.75mmol) of triphenylantimony dibromide was gradually added to the solution in 30mL of anhydrous toluene.

[0145] The reaction solution was stirred in a nitrogen atmosphere at 70° C. for 12 hours. The reaction solution was cooled to room temperature, filtered through Celite, and the filtrate was concentrated. The solid was dissolved in dichloromethane and recrystallized by adding normal hexane to obtain a compound represented by the following chemical formula 1e.

[0146] [ka]

[0147] Comparative synthesis example 1 n-BuSnCl3 (8.5g, 30mmol) was dissolved in anhydrous pentane and the temperature was lowered to 0℃. Then, triethylamine (10.0g, 99mmol) was slowly added dropwise, followed by the addition of ethanol (4.2g, 90mmol) and stirring at room temperature for 5 hours. After the reaction was completed, the mixture was filtered, concentrated, and dried in vacuum to obtain the compound represented by the following formula 4.

[0148] [ka]

[0149] Comparative synthesis example 2 A compound represented by the following formula 5 was obtained by synthesizing in the same manner as in Comparative Synthesis Example 1, except that BnSnCl3 was used instead of n-BuSnCl3 in Comparative Synthesis Example 1.

[0150] [ka]

[0151] (Production of semiconductor photoresist composition) Examples 1 to 5, Comparative Examples 1 and 2 The compounds represented by Chemical Formula 1a to Chemical Formula 1e obtained in Synthesis Examples 1 to 5 and the compounds represented by Chemical Formula 4 and Chemical Formula 5 obtained in Comparative Synthesis Examples 1 and 2 were each dissolved in PGMEA (propylene glycol monomethyl ether acetate) at 3 wt % and filtered through a 0.1 μm PTFE syringe filter to prepare photoresist compositions.

[0152] Evaluation 1: Sensitivity and Line Edge Roughness (LER) evaluation A linear array of 50 circular pads, each 500 μm in diameter, was projected using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET) onto wafers coated with the photoresist compositions of Examples 1 to 5 and Comparative Examples 1 and 2. Pad exposure times were adjusted so that an incremental EUV dose was applied to each pad.

[0153] The resist and substrate were then exposed on a hotplate at 160°C for 120 seconds and then post-exposure baked (PEB). The baked film was then immersed in a developer (2-heptanone) for 30 seconds each, and then washed in the same developer for an additional 10 seconds to form a negative tone image, i.e., remove the unexposed coating area. The process was then terminated by a hotplate bake at 150°C for 2 minutes.

[0154] The remaining resist thickness of the exposed pad was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and graphed as a function of the exposure dose. Dg (energy level at which development is complete) was evaluated for each type of resist according to the following criteria and shown in Table 1.

[0155] *Evaluation criteria (Dg value) A: 16 mJ / cm 2 less than B: 16 mJ / cm 2 The end.

[0156] Evaluation 2: Storage stability evaluation The storage stability of the organometallic compounds used in Examples 1 to 5 and Comparative Examples 1 and 2 was evaluated according to the following criteria, and the results are shown in Table 1 below.

[0157] [Storage stability] The semiconductor photoresist compositions according to Examples 1 to 5 and Comparative Examples 1 and 2 were left at room temperature (20±5° C.) for a specific period of time, and the degree of precipitation was observed with the naked eye and evaluated according to the following storage standards.

[0158] *Evaluation criteria -○: Can be stored for more than one month -△: Can be stored for 1 week to less than 1 month -X: Can be stored for less than one week

[0159] [Table 1]

[0160] From the results in Table 1, it can be seen that the semiconductor photoresist compositions according to the Examples have superior sensitivity and significantly improved storage stability compared to the Comparative Examples.

[0161] Although specific embodiments of the present invention have been described and illustrated above, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0162] 100: Substrate 102: Thin film 104: Resist underlayer film 106: Photoresist film 106a: Unexposed area 106b: Exposed area 108: Photoresist pattern 110: Patterned mask 112: Organic film pattern 114: Thin film pattern

Claims

1. A composition for semiconductor photoresist, comprising an organometallic compound represented by the following chemical formula 1; and a solvent: 【Chemistry 1】 In the above chemical formula 1, R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, or -R ａ -O-R ｂ (Here, R ａ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n and m are each independently an integer from 1 to 6; 2≦n+m≦6, X is a ligand represented by at least one of the following formulas 1A and 1B: 【Chemistry 2】 In the above Chemical Formula 1A and Chemical Formula 1B, R ２ , R ３ and R ５ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R ２ , R ３ may be bonded to each other to form a ring, R ４ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof; * is the point where it is connected to M.

2. The composition for semiconductor photoresist according to claim 1 , wherein the organometallic compound is represented by the following Formula 2 or 3: 【Chemistry 3】 In the above Chemical Formula 2 and Chemical Formula 3, R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, or -R ａ -O-R ｂ (Here, R ａ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; M is a metal selected from Groups 2 to 16 of the Periodic Table; n1 and m1 each independently represent an integer from 1 to 5; 2≦n1+m1≦6, R ２ , R ３ and R ５ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R ２ , R ３ may be bonded to each other to form a ring, R ４ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

3. 2. The composition for semiconductor photoresist of claim 1, wherein n+m is an integer of 4 to 6.

4. 2. The semiconductor photoresist composition according to claim 1, wherein M is Sn or Sb.

5. The R ２ , R ３ and R ５ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, or a combination thereof, in which R ２ , R ３ The semiconductor photoresist composition according to claim 1 , wherein may be bonded to each other to form a ring.

6. The R ４ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a combination thereof.

7. The R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R ２ , R ３ and R ５ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, R ４ 2. The semiconductor photoresist composition according to claim 1, wherein is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms.

8. The R １ 2. The semiconductor photoresist composition according to claim 1, wherein is a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms.

9. The R １ is an isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an isononyl group, an isodecyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a sec-heptyl group, a sec-octyl group, a tert-butyl group, a tert-pentyl group, a tert-hexyl group, a tert-heptyl group, a tert-octyl group, a tert-nonyl group, or a tert-decyl group.

10. 2. The composition for semiconductor photoresist according to claim 1, wherein the organometallic compound is one selected from the compounds listed in Group 1 below: 【Chemistry 4】 【Chemistry 5】

11. 2. The composition for semiconductor photoresist according to claim 1, wherein the organometallic compound is present in an amount of 1 to 30% by weight, based on 100% by weight of the composition for semiconductor photoresist.

12. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, and combinations thereof.

13. forming a film to be etched on a substrate; applying a composition for a semiconductor photoresist according to any one of claims 1 to 12 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and The method of forming a pattern includes etching the layer to be etched using the photoresist pattern as an etching mask.

14. 14. The method of claim 13, wherein the forming of the photoresist pattern uses light having a wavelength of 5 nm to 150 nm.

15. The pattern forming method according to claim 13, wherein the photoresist pattern has a width of 5 nm to 100 nm.

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