Semiconductor photoresist composition and pattern forming method using the same

Abstract

To provide a semiconductor photoresist composition improved in contrast performance and a pattern forming method using the same.SOLUTION: There are provided: a semiconductor photoresist composition containing an organometallic compound represented by chemical formula 1 and a solvent; and a pattern forming method using the same.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern forming 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 performing spatial resolutions below 16 nm. Currently, traditional chemically amplified (CA) photoresists struggle to meet the specifications for resolution, photospeed, and feature roughness and line edge roughness (LER) for next generation devices.

[0004] Intrinsic image blur due to acid catalyzed reactions occurring in these polymeric photoresists limits resolution at small feature sizes, a fact that has long been known in e-beam lithography. Chemically amplified (CA) photoresists, designed for high sensitivity, can experience additional difficulties under EUV exposure, in part because their typical elemental makeup reduces the absorbance of the photoresist at 13.5 nm wavelengths, thereby reducing sensitivity.

[0005] CA photoresists can also experience difficulties with roughness issues at small feature sizes, and 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 new types 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 non-chemically amplified mechanisms. Inorganic compositions contain inorganic elements with higher EUV absorption rate than hydrocarbons, so they can ensure sensitivity even in non-chemically amplified mechanisms, and are known to have less line edge roughness and fewer defects because they are less sensitive to stochastic effects.

[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 (US5061599; 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, impressive performance has been shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to image 15 nm half pitch (HP) with projection EUV exposure (US2011-0045406; 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 some practical drawbacks. First, the materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, which results in poor shelf-life stability. Second, it is a complex mixture and cannot be easily modified to improve performance. Third, it must be developed with a very high concentration of, for example, 25 wt% TMAH (tetramethylammonium hydroxide) solution.

[0009] Recently, active research has been conducted on molecules containing tin as it has been found that they have excellent absorption of extreme ultraviolet rays. 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. These organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvement in the patterning properties is required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] One embodiment of the present invention provides a composition for a semiconductor photoresist having improved contrast performance.

[0011] Another embodiment of the present invention provides a method for forming a pattern using the semiconductor photoresist composition. [Means for solving the problem]

[0012] 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.

[0013] [ka] In the above Chemical Formula 1, M is one of a tetravalent metal, a pentavalent metal, and a hexavalent metal; 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, L a -OR a (Here, L ais a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), or C(O)-R b (where R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 ~R 4 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, C(O)-R c (where R c is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR f OR g (where R f and R g are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R h (where R h is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 ~R 4At least one of the C(O)-R is a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or c (where R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR f OR g (where R f and R g are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R h (where R h is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or R 2 ~R 4 adjacent groups among X is halogen, OL b -C(O)-R j (Here, L b is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; R jis 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, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR k R l , where R k and R l 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, or a combination thereof), amidato (-NR m (COR n ), where R m and R n 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, or a combination thereof), or amidinato (-NR o C(NR p )R q , where R o , R p and R q 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, or a combination thereof; n1 and m1 each independently represent an integer from 1 to 5; p is an integer from 0 to 4.

[0014] 4≦n1+m1+p≦6.

[0015] A method for forming a pattern according to another embodiment of the present invention includes forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition on 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. Effect of the Invention

[0016] By applying the semiconductor photoresist composition according to one embodiment of the present invention, an excellent photoresist pattern having improved contrast performance can be provided. [Brief description of the drawings]

[0017] [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

[0018] Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, the description of the functions or configurations that are already known will be omitted in order to clarify the gist of the description.

[0019] In order to clearly explain the present description, parts unnecessary for the description are omitted, and the same or similar components are designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0020] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. For convenience of explanation in the drawings, the thickness of some layers and regions is exaggerated. When a layer, film, region, plate, or other part is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part therebetween.

[0021] In this description, "substituted" means that a hydrogen atom is replaced by a deuterium atom, a halogen group, a hydroxy group, a thiol group, a cyano group, a nitro group, a carbonyl group, -NRR' (wherein R and R' are each independently hydrogen, 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 hydrogen, 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). "Unsubstituted" means that the hydrogen atom is not substituted with another substituent, but rather remains as a hydrogen atom.

[0022] As used herein, unless otherwise specified, the term "alkyl group" refers to a straight or branched chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0023] The alkyl group may be 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, or an alkyl group having 1 to 5 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.

[0024] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0025] The cycloalkyl group can be a cycloalkyl group having 3 to 10 carbon atoms, for example, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. For example, the cycloalkyl group can be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0026] As used herein, an "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functionalities.

[0027] As used herein, unless otherwise defined, an "alkenyl group" refers to an aliphatic unsaturated alkenyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more double bonds.

[0028] As used herein, unless otherwise defined, an "alkynyl group" refers to an aliphatic unsaturated alkynyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more triple bonds.

[0029] In the formulae depicted herein, t-Bu refers to a tert-butyl group.

[0030] Hereinafter, a semiconductor photoresist composition according to one embodiment of the present invention will be described.

[0031] 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.

[0032] [ka] In the above Chemical Formula 1, M is one of a tetravalent metal, a pentavalent metal, and a hexavalent metal; 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, L a -OR a (Here, L a is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), or C(O)-R b (where R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 ~R 4 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, C(O)-R c (where R c is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR f OR g (where R f and R gare each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R h (where R h is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R 2 ~R 4 At least one of the C(O)-R is a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or c (where R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR f OR g (where R f and R g are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R h (where R h is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or R 2 ~R 4adjacent groups among X is halogen, OL b -C(O)-R j (Here, L b is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; R j 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, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR k R l , where R k and R l 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, or a combination thereof), amidato (-NR m (COR n ), where R m and R n 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, or a combination thereof), or amidinato (-NR o C(NR p )R q , where R o , R p and R qeach 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, or a combination thereof; n1 and m1 each independently represent an integer from 1 to 5; p is an integer from 0 to 4.

[0033] 4≦n1+m1+p≦6.

[0034] The present invention improves sensitivity by introducing a functional group capable of stabilizing a radical compound generated upon exposure, and maximizes the difference in solubility in a developer between an exposed portion and an unexposed portion of a photoresist film, thereby improving pattern formability and process margins.

[0035] The functional group capable of stabilizing a radical compound is R 2 ~R 4 and a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, C(O)-R c (where R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR f OR g (where R f and R g are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R h (where Rh is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or R 2 ~R 4 The group may be a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms formed by linking adjacent groups among the above, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0036] As an example, R 2 ~R 4 At least one of the following is C(O)-R: c When the carbonyl group is included, the mechanism is explained as in the following reaction formula 1, and the radical generated after exposure is stabilized by the carbonyl group and becomes more sensitive to the photosensitive reaction, thereby maximizing the difference in physical properties between the exposed and unexposed areas, thereby implementing excellent contrast performance.

[0037] [ka] As an example, M may be selected from Sn, Sb, I, Te, In, Ag, Ni, Bi and Po.

[0038] As a specific example, M may be Sn.

[0039] The organotin compound according to the present invention can simultaneously contain a hydrolyzable group and a photosensitive reactive group in addition to the functional group capable of stabilizing the radical compound at the central metal, tin.

[0040] As an example, the above-mentioned R 2 ~R 4 At least one of the C(O)-R is a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or c(where R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), P(O)OR d R e (where R d and R e each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), P(O)OR f OR g (where R f and R g are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), S(O)R h (where R h is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms) or S(O)R i (where R i is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or R 2 ~R 4 The adjacent groups among the above may be linked to form a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0041] As a specific example, the above-mentioned R 2 ~R 4 At least one of C(O)-R is a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, c (where R cis 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(R r )=C(R s )(R t ) (where R r , R s and R t are each independently a hydrogen atom, 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)OR d R e (where R d and R e are each independently 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)OR f OR g (where R f and R gare each independently 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)R h (where R h is 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)R i (where R i is 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 R 2 ~R 4 Adjacent groups of may be linked to form a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, or a substituted or unsubstituted cyclodecyl group.

[0042] For example, the above R 2 ~R 4 At least one of is one selected from the substituents listed in Group 1-1 below; or R 2 ~R 4 Adjacent groups among these may be linked to form one of the ring groups listed in Group 1-2 below.

[0043] [ka] In the above Group 1-1 and Group 1-2, * is R 2 ~R 4 is the carbon to which it is linked.

[0044] As an example, the above-mentioned R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or L a -OR a (Here, L a is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R a may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0045] As a specific example, the above-mentioned R 1is 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, or a combination thereof; R a can 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, or a combination thereof.

[0046] In one example, X is a halogen, OL b -C(O)-R j (Here, L b is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms; R j is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR k R l , where Rk and R l are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), amidato (-NR m (COR n ), where R m and R n are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), or amidinato (-NR o C(NR p )R q , where R o , R p and R q may each independently be hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0047] As a specific example, X is halogen or OL. b -C(O)-R j (Here, L b is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms; R jmay be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0048] In one embodiment, X is OL. b -C(O)-R j (Here, L b is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms; R j may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0049] For example, the above R j is 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, or a combination thereof; The organometallic compound may be selected from the compounds listed in Group 2 below.

[0050] [ka] The organometallic compound is highly reactive and has excellent sensitivity to extreme ultraviolet light at 13.5 nm or the additional secondary cell generated thereby.

[0051] In one embodiment, the semiconductor photoresist composition may contain the organometallic compound in an amount of 1% by weight to 30% by weight, for example, 1% by weight to 25% by weight, for example, 1% by weight to 20% by weight, for example, 1% by weight to 15% by weight, for example, 1% by weight to 10% by weight, for example, 1% by weight to 5% by weight, but is not limited thereto. When the organometallic compound is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0052] The composition for semiconductor photoresist according to one embodiment of the present invention includes the organometallic compound, so that a composition for semiconductor photoresist having excellent contrast characteristics can be provided.

[0053] The solvent contained in the semiconductor resist composition according to an embodiment is 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.

[0054] In one embodiment, the semiconductor resist composition may further include a resin in addition to the organometallic compound and the solvent.

[0055] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0056] The solvent included in the semiconductor photoresist composition according to an embodiment is 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.

[0057] In one embodiment, the semiconductor photoresist composition may further include a resin in addition to the organometallic compound and the solvent.

[0058] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 3 below.

[0059] [ka] The resin may have a weight average molecular weight of 500 to 20,000.

[0060] The resin may be included in an amount of 0.1% by weight to 50% by weight based on the total content of the composition for semiconductor photoresist.

[0061] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0062] Meanwhile, the semiconductor photoresist composition according to one embodiment preferably comprises the organometallic compound, a solvent, and a resin. However, the semiconductor photoresist composition according to the above embodiment may further include additives, if necessary. The additives may include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0063] 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.

[0064] 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. Examples of the crosslinking agent having at least two crosslinking-forming substituents include 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.

[0065] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0066] The organic acid can be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluorides, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0067] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0068] The amounts of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0069] In addition, the semiconductor photoresist composition may further contain a silane coupling agent as an additive as an adhesion enhancer to improve adhesion to a substrate (for example, to improve adhesion of the semiconductor photoresist composition to a substrate). The silane coupling agent may be, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or a carbon-carbon unsaturated bond-containing silane compound such as trimethoxy[3-(phenylamino)propyl]silane, but is not limited thereto.

[0070] The semiconductor photoresist composition may not 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 can be used in a photoresist process using light having a wavelength of, for example, 5 nm to 150 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 100 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 30 nm, for example, a photoresist process using light having 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.

[0071] According to another embodiment, there is provided a method for forming a pattern using the composition for semiconductor photoresist. For example, the pattern formed may be a photoresist pattern.

[0072] According to an embodiment, a method for forming a pattern includes forming a film to be etched on a substrate, applying the semiconductor photoresist composition on 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.

[0073] Hereinafter, a method for forming a pattern using the semiconductor photoresist composition will be described with reference to Figures 1 to 5. Figures 1 to 5 are cross-sectional views illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0074] 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.

[0075] 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, such as spray coating, dip coating, knife edge coating, and printing methods, such as inkjet printing and screen printing, may also be used.

[0076] The resist underlayer film coating step can be omitted, and the following describes the case where the resist underlayer film is coated.

[0077] 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.

[0078] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and disruption of pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hard mask is scattered into unintended photoresist regions.

[0079] 2, the 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 semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0080] 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.

[0081] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0082] 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.

[0083] Referring to FIG. 3, the photoresist film 106 is selectively exposed to light using a patterned mask 110 .

[0084] As an example, examples of light that can be used in the exposure process include light having wavelengths such as 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).

[0085] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0086] The exposed regions 106b of the photoresist film 106 have a different solubility from the unexposed regions 106a of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0087] 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 difficult to dissolve in a developer.

[0088] 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.

[0089] 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, or combinations thereof.

[0090] 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, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0091] 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.

[0092] 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.

[0093] Next, the resist underlayer film 104 is etched using the photoresist pattern as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern .

[0094] 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 into a thin film pattern 114.

[0095] The thin film 102 can be etched by dry etching using an etching gas such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0096] The thin film pattern 114 formed by 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. As an example, it may have a width of 5 nm to 100 nm, similar to 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. EXAMPLES

[0097] The present invention will be described in more detail below with reference to examples of the preparation of the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples.

[0098] (Synthesis of organometallic compounds) Synthesis Example 1: Synthesis of the compound represented by formula 2 In a 250mL two-neck round-bottom flask, Ph3SnCl (20g, 51.9mmol) was dissolved in 100mL of anhydrous tetrahydrofuran (THF), and the temperature was lowered to 0℃ using an ice bath, and then 2-butanone-3-magnesium bromide 1M THF solution (62.3mmol) was gradually added dropwise. After the addition was completed, the mixture was stirred at room temperature (25℃) for 12 hours. After distillation under reduced pressure, 50mL of acetic acid was gradually added dropwise, and the mixture was heated to reflux for 12 hours. After that, the temperature was lowered to room temperature, and the acetic acid was vacuum distilled to obtain a compound represented by the following chemical formula 2.

[0099] [ka]

[0100] Synthesis Example 2: Synthesis of the compound represented by formula 3 A compound represented by the following formula 3 was obtained in the same manner as in Synthesis Example 1, except that a 1M THF solution of benzylmagnesium chloride (62.3 mmol) was used instead of a 1M THF solution of 2-butanone-3-magnesium bromide in Synthesis Example 1.

[0101] [ka]

[0102] Synthesis Example 3: Synthesis of the compound represented by chemical formula 4 In a 250mL two-neck round-bottom flask, dissolve Ph3SnCl (20g, 51.9mmol) in 100mL of anhydrous tetrahydrofuran (THF), and then lower the temperature to 0℃ with an ice bath. Then, gradually add 2-methyl-1-butene-3-magnesium bromide 1M THF solution (62.3mmol). After the addition is complete, stir at room temperature for 12 hours. After vacuum distillation, dissolve in 50mL of CH2Cl2, gradually add 2M HCl diethyl ether solution (155.7mmol) at -78℃ for 30 minutes, and stir at room temperature for 12 hours. After that, concentrate the solvent and vacuum distill. Then, it was dissolved again in 50 mL of CH2Cl2, and Ag-acetylacetone (103.8 mmol) and Ag-tert-butoxide (51.9 mmol) were added dropwise at 0°C. The solid formed was removed by filtration, and the filtrate was distilled to obtain a compound represented by the following chemical formula 4.

[0103] [ka]

[0104] Comparative synthesis example 1 25 ml of acetic acid was slowly added dropwise to tert-butyltriphenyltin compound (10 g, 25.6 mmol) at room temperature, and the mixture was heated to reflux at 110° C. for 24 hours. The temperature was then lowered to room temperature, and the acetic acid was distilled under vacuum to obtain a compound represented by the following chemical formula 5.

[0105] [ka]

[0106] (Production of semiconductor photoresist composition) Examples 1 to 3 and Comparative Example 1 The compounds represented by Chemical Formulae 2 to 5 obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were dissolved in 4-methyl-2-pentanol at 3 wt % and filtered through a 0.1 μm PTFE syringe filter to prepare photoresist compositions.

[0107] A 4-inch diameter circular silicon wafer with a native oxide surface was used as a substrate for thin film deposition. Prior to deposition of the resist thin film, the wafer was treated with a UV ozone cleaning system for 10 minutes, and the resist composition was spin-coated onto the wafer at 1500 rpm for 30 seconds and baked at 100°C for 120 seconds to form a thin film. The thickness of the film after coating and baking was then measured by ellipsometry, and the results were ~25 nm for Examples 1 to 3 and ~20 nm for Comparative Example 1.

[0108] Evaluation: Contrast performance The substrate on which the thin resist film was deposited was exposed to an E-beam with an acceleration voltage of 100kV to form nanowires with a 40nm half-pitch. The irradiated substrate was exposed at 40℃ for 30 seconds, then immersed in a Petri dish containing 2-heptanone for 60 seconds, removed, washed with the same solvent for 10 seconds, and finally baked at 150℃ to complete a patterned wafer. The thickness of each exposed part of the patterned wafer was measured, and the contrast performance (γ(contrast) was calculated from the obtained contrast curve, and the results are shown in Table 1 below.

[0109] γ(contrast)=1 / log(D0 / D 100 ) D 100 = Exposure at which PR begins to remain at 100% D0 = exposure dose at which PR is completely removed

[0110] [Table 1]

[0111] Referring to Table 1 above, it was found that the photoresist compositions of Examples 1 to 3 had excellent removal ability for a metal-containing photoresist film and improved contrast performance, compared to the photoresist composition of Comparative Example 1, and thus achieved excellent pattern characteristics.

[0112] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and 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]

[0113] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...unexposed area, 106b...exposed area, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. An organometallic compound represented by the following chemical formula 1: A composition for semiconductor photoresist, comprising a solvent: 【Chemistry 1】 In the above Chemical Formula 1, M is one of a tetravalent metal, a pentavalent metal, and a hexavalent metal; R １ represents 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, L ａ -O-R ａ (Here, L ａ is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), or C(O)-R ｂ (Here, R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R ２ ~R ４ 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, C(O)-R ｃ (Here, R ｃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR ｄ R ｅ (Here, R ｄ and R ｅ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR ｆ OR ｇ (Here, R ｆ and R ｇ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R ｈ (Here, R ｈ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), or S(O) ２ R ｉ (Here, R ｉ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R ２ ~R ４ At least one of the C(O)-R is a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or ｃ (Here, R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR ｄ R ｅ (Here, R ｄ and R ｅ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), P(O)OR ｆ OR ｇ (Here, R ｆ and R ｇ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), S(O)R ｈ (Here, R ｈ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), or S(O) ２ R ｉ (Here, R ｉ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or R ２ ~R ４ adjacent groups among X is halogen, O-L ｂ -C(O)-R ｊ (Here, L ｂ is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; R ｊ 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, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR ｋ R ｌ , where R ｋ and R ｌ 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, or a combination thereof), amidato (-NR ｍ (C.O.R. ｎ ), where R ｍ and R ｎ 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, or a combination thereof), or amidinato (—NR ｏ C (NR ｐ ) R ｑ , where R ｏ , R ｐ and R ｑ 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, or a combination thereof; n1 and m1 are each independently an integer from 1 to 5; p is one of the integers from 0 to 4; 4≦n1+m1+p≦6.

2. 2. The semiconductor photoresist composition according to claim 1, wherein M is one selected from the group consisting of Sn, Sb, I, Te, In, Ag, Ni, Bi and Po.

3. 2. The semiconductor photoresist composition according to claim 1, wherein M is Sn.

4. The R ２ ~R ４ At least one of C(O)-R is a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, ｃ (Here, R ｃ is 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(R ｒ ) = C(R ｓ ) (R ｔ ) (where R ｒ , R ｓ and R ｔ are each independently a hydrogen atom, 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)OR ｄ R ｅ (Here, R ｄ and R ｅ are each independently 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)OR ｆ OR ｇ (Here, R ｆ and R ｇ are each independently 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)R ｈ (Here, R ｈ is 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) ２ R ｉ (Here, R ｉ is 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 R ２ ~R ４ 2. The semiconductor photoresist composition according to claim 1, wherein adjacent groups among

5. The R ２ ~R ４ At least one of is one selected from the substituents listed in Group 1-1 below; or R ２ ~R ４ The semiconductor photoresist composition according to claim 1, wherein adjacent groups of the following are linked to form one of the cyclic groups listed in Group 1-2 below: 【Chemistry 2】 In Group 1-1 and Group 1-2, ＊ is R ２ ~R ４ is the carbon to which it is linked.

6. The R １ is 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 aryl group, or unsubstituted ethenyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylene, substituted or unsubstituted benzyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or combinations thereof; R ａ is 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, or a combination thereof.

7. X is a halogen, O-L ｂ -C(O)-R ｊ (Here, L ｂ is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms; R ｊ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR ｋ R ｌ , where R ｋ and R ｌ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), amidato (-NR ｍ (C.O.R. ｎ ), where R ｍ and R ｎ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), or amidinato (—NR ｏ C (NR ｐ ) R ｑ , where R ｏ , R ｐ and R ｑ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

8. 2. The composition for semiconductor photoresist according to claim 1, wherein the organometallic compound is one selected from the compounds listed in Group 2 below: 【Chemistry 3】

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

10. 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.

11. forming a film to be etched on a substrate; applying a composition for a semiconductor photoresist according to any one of claims 1 to 10 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the layer to be etched using the photoresist pattern as an etching mask.

12. 12. The method of claim 11, wherein the forming of the photoresist pattern uses light having a wavelength of 5 nm to 150 nm.

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