KR102287507B1 - Hardmask composition and method of forming patterns - Google Patents

Abstract

A hard mask composition comprising a solvent and a cluster compound comprising at least one of a metal cluster compound and a metal-oxo cluster compound, and a pattern forming method using the hard mask composition.

Description

Hard mask composition and pattern formation method

It relates to a hardmask composition and a pattern forming method using the hardmask composition.

Recently, the semiconductor industry has developed from a pattern of several hundreds of nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. An effective lithographic technique is essential to realize such ultra-fine technology.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask. do.

Recently, as the size of a pattern to be formed is reduced, it is difficult to form a fine pattern having a good profile using only the above-described typical lithographic technique. Accordingly, a fine pattern may be formed by forming an auxiliary layer called a hardmask layer between the material layer to be etched and the photoresist layer.

One embodiment provides a hardmask composition capable of improving etch resistance.

Another embodiment provides a pattern forming method using the hardmask composition.

According to one embodiment, there is provided a hardmask composition including a cluster compound including at least one of a metal cluster compound and a metal-oxo cluster compound, and a solvent.

The metal may be any one selected from Al, Ga, In, Tl, Sn, Pb, Sb, Bi, and Po.

The cluster compound may include a metal-carbon bond.

The metal-carbon bond may be represented by Formula 1 below.

[Formula 1]

In Formula 1, M ¹ is a metal,

X ¹ is a substituted or unsubstituted C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C30 heterocyclic group, carbonyl group, carboxyl group, ester group, amide group, or a combination thereof;

n ¹ is an integer from 1 to 5,

* is the point of connection with other elements in the cluster compound.

The metal-oxo cluster compound may include at least one of a moiety represented by the following Chemical Formula 2 and a moiety represented by the following Chemical Formula 3.

[Formula 2] [Formula 3]

In Formula 2 or 3,

M ^{2 To} M ⁶ are each independently the same or different metals or organometals,

O is an element of oxygen,

n ² to n ⁶ are each independently an integer of 1 to 5,

* is the point of connection with other elements in the metal-oxo cluster compound.

The cluster compound may be a cationic compound.

The hard mask composition may further include an anion.

The anion is a halogen anion, hydroxide, cyanide, nitrate, bisulfite, dihydrogen phosphate, acetate, benzenesulfonate, benzenesulfite, C7 to C30 alkyl benzenesulfonate, C7 to C30 alkyl benzenesulfite or a combination thereof.

The cluster compound may have a particle diameter of 0.1 nm to 10 nm.

The cluster compound may be included in an amount of 0.1 to 30% by weight based on the total content of the hardmask composition.

The hardmask composition may further include a hardmask monomer or hardmask polymer including at least one aromatic ring.

The hard mask monomer may include a substituted or unsubstituted ring group selected from the following group 1.

[Group 1]

In group 1,

Z ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl Rene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C=O, NR ^a , oxygen (O), sulfur (S), or a combination thereof,

Z ³ to Z ¹⁸ are each independently C=O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^{c ,} or a combination thereof,

R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, a halogen-containing group , or a combination thereof.

The hard mask monomer may be represented by any one of Chemical Formulas 4 to 9 below.

[Formula 4]

In Formula 4,

A ^a is a substituted or unsubstituted aromatic ring group,

X ^a , X ^b and X ^c are each independently a monovalent group derived from a substituted or unsubstituted indole,

Y ^a , Y ^b and Y ^c are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkyl an amine group, or a substituted or unsubstituted C1 to C30 alkoxy group,

ma ^a , m ^b , m ^c , na ^a , n ^b and n ^c are each independently 0 or 1.

However, m ^a, m ^b and m ^c, at least one is 1, and m ^a is 0, n ^a is 0, and, if m ^b is 0 and n ^b is 0, when m ^c is 0, n ^c is 0.

[Formula 5]

In Formula 5,

T is triazine or a triazine derivative,

R ^d , R ^e and R ^f are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or these It is a group having one or two or more combinations of.

However, ^{at least one of R d} , R ^e and R ^f includes a substituted or unsubstituted aryl group.

[Formula 6]

In Formula 6,

A ^b , A ^c , A ^d , A ^e and A ^f are each independently a substituted or unsubstituted aromatic ring group,

X ^d and X ^e are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ^d and Y ^e are each independently -O-, -S-, -NH-, or -Se-,

M ^a and M ^b are cyano groups,

k and l are each independently 0 or 1, satisfying 1≤k+l≤2,

m ^d and n ^d is an integer satisfying 0≤m ^d ≤3, 0≤n ^d ≤3, the case of k = 1 m ^d is greater than 1 when the integer and l = 1 n ^d is an integer greater than 1,

p and q are each independently an integer of 1 or more, satisfying 1≤p+q≤(the maximum number of substituents that ^{A b can have).}

[Formula 7]

In Formula 7,

A ^g is It is an aliphatic ring group or an aromatic ring group,

A ^h to A ^j are each a phenylene group,

X ^f to X ^h are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,

M ^c is CR ^g , SiR ^h , N, P, PR ⁱ R ^j or PR ^k ;

n ^e is an integer from 1 to 4,

In M ^c , R ^g , R ^h , R ⁱ and R ^j are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

R ^k is oxygen (O) or sulfur (S).

[Formula 8]

In the formula (8),

A ^k to A ^m are each independently an aliphatic ring group or an aromatic ring group,

X ⁱ to X ^k are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,

n ^f is an integer from 3 to 5,

m ^e is an integer from 1 to 3.

[Formula 9]

In Formula 9,

A ⁿ and A ^o are each independently a substituted or unsubstituted aliphatic ring group or an aromatic ring group,

X ¹ is a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

Y ^f is a boron (B) containing group,

n ^g is an integer from 1 to 5;

The hard mask polymer may include a structural unit represented by the following Chemical Formula 10.

[Formula 10]

In the formula (10),

A ¹ is a divalent ring group including at least one substituted or unsubstituted aromatic ring,

B ¹ is a divalent organic group,

* is the connection point.

In Formula 10, A ¹ is a divalent cyclic group derived from any one of the compounds listed in Group 2 or 3, and the divalent cyclic group may be one in which at least one hydrogen atom is substituted or unsubstituted.

[Group 2]

[Group 3]

In group 2 or 3 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl;

R ⁰ and R ¹ are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkoxy group, a halogen atom, or a combination thereof.

In Formula 10, B ¹ may be represented by Formula 11 below.

[Formula 11]

In the above formula (11),

m and n are each independently an integer of 0 to 2,

Z is a divalent cyclic group derived from any one selected from the following group 4, the divalent cyclic group is a group in which at least one hydrogen atom is substituted or unsubstituted,

* is the connection point:

[Group 4]

In group 4,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl.

According to another embodiment. Forming a hardmask layer by applying a hardmask composition on a material layer and heat-treating, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to form a photoresist pattern, said There is provided a pattern forming method comprising selectively removing the hardmask layer using a photoresist pattern, exposing a portion of the material layer, and etching the exposed portion of the material layer.

It is possible to secure the etch resistance of the hard mask layer.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Hereinafter, unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group , amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C30 alkyl group, C2 to C30 alkenyl group , C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and combinations thereof.

In addition, the substituted halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group , thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group , C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C30 heterocyclic group, adjacent two groups Two substituents may be fused to form a ring. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

As used herein, the term “aryl group” refers to a group having one or more hydrocarbon aromatic moieties, and broadly refers to a form in which hydrocarbon aromatic moieties are connected by a single bond and a non-aromatic group in which hydrocarbon aromatic moieties are directly or indirectly fused. Also included are fused rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a concept including a heteroaryl group, in addition to carbon (C) in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. It means containing at least one hetero atom selected from N, O, S, P and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

More specifically, a substituted or unsubstituted aryl group and/or a substituted or unsubstituted heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted A substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted Or an unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazole Diyl, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted Or an unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted qui Nolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, A substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a pyridoindolyl group, a benzopyridooxazinyl group, a benzopyridothia Jinyl group, 9,9-dimethyl 9,10 dihydroacridinyl group, a combination thereof, or a combination thereof may be in a fused form, Not limited. In one embodiment of the present invention, the heterocyclic group or the heteroaryl group may be a pyridyl group, a carbazolyl group or a pyridoindolyl group.

In the present specification, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted divalent heterocyclic group is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group as defined above. It means that there are two linking groups, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or Unsubstituted naphthacenylene group, substituted or unsubstituted pyrenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quaterphenylene group, substituted or unsubstituted chrysenyl group Rene group, substituted or unsubstituted triphenylenylene group, substituted or unsubstituted perylenylene group, substituted or unsubstituted indenylene group, substituted or unsubstituted furanylene group, substituted or unsubstituted thiophenylene group, substituted or an unsubstituted pyrrolylene group, a substituted or unsubstituted pyrazolylene group, a substituted or unsubstituted imidazolylene group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted Thiazolylene group, substituted or unsubstituted oxadiazolylene group, substituted or unsubstituted thiadiazolylene group, substituted or unsubstituted pyridinylene group, substituted or unsubstituted pyrimidinylene group, substituted or unsubstituted pyrazinyl group Rene group, substituted or unsubstituted triazinylene group, substituted or unsubstituted benzofuranylene group, substituted or unsubstituted benzothiophenylene group, substituted or unsubstituted benzimidazolylene group, substituted or unsubstituted indolylene group , substituted or unsubstituted quinolinylene group, substituted or unsubstituted isoquinolinylene group, substituted or unsubstituted quinazolinylene group, substituted or unsubstituted quinoxalinylene group, substituted or unsubstituted naphthyridinyl Ren group, substituted or unsubstituted benzoxazinylene group, substituted or unsubstituted benzthiazinylene group, substituted or unsubstituted acridinylene group, substituted or unsubstituted phenazinylene group, substituted or unsubstituted phenothiazine An ylene group, a substituted or unsubstituted phenoxazinylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted A dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolene group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

In one embodiment of the present invention, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted divalent heterocyclic group is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group , a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted pyrimidine group, or a combination thereof.

In addition, unless otherwise defined herein, '*' indicates a connection point of a compound or a compound moiety.

In this specification, a metal is a concept including alkali metals, alkaline earth metals, transition metals, and post-transition metals, and the transition metal refers to a d-region element on the periodic table in which an electron with the highest energy level in the ground state is in d orbital. , for example, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W or Ir, but is not limited thereto. Post-transition metal refers to a metal element of the p-region element on the periodic table in which the electron of the highest energy level in the ground state is in the p orbital, for example, Al, Ga, In, Tl, Sn, Sb, Pb, Bi or Po. may be, but is not limited thereto.

in this specification. An organometal is a set of elements including a metal-carbon direct bond, and a metal element and a carbon element of a monovalent or monovalent or more monovalent organic group interact by a sigma or pi bond. For example, organometallics may contain direct single, double and/or triple bonds between the metal and carbon. Organometals can combine with other elements within a compound.

The cluster compound may include a cluster structure of a core and a substituent on an outer shell. Unless otherwise stated herein, the term 'in the cluster compound' refers to the cluster structure of the core.

Hereinafter, a hard mask composition according to an embodiment will be described.

A hardmask composition according to an embodiment includes a cluster compound including at least one of a metal cluster compound and a metal-oxo cluster compound, and a solvent.

The cluster compound may be a compound having a three-dimensional structure in which three or more atoms of the same element or a plurality of types of elements are gathered and combined into a single mass, for example, the cluster compound is a compound in which three or more elements are cyclic or It may be a compound having a three-dimensional structure that forms a non-cyclic group, and a plurality of the cyclic or non-cyclic group forms a bundle.

The cluster compound may include a cluster structure of the core and a substituent on the outer shell, for example, the substituent on the outer shell may be substituted outside the cluster structure of the core.

For example, the cluster compound may or may not have an element in the cluster structure of the core, for example, may have a polyhedral structure. For example, it may have a convex polyhedron. The polyhedron structure may be, for example, an octahedron, a decahedron, a dodecahedron, an icosahedron, or a tetrahedron, but is not limited thereto.

For example, the metal may be an alkali metal, an alkaline earth metal, a transition metal, a post-transition metal, or a combination thereof. For example, the metal may be a transition metal and/or a post-transition metal, for example, a post-transition metal. The metal may be, for example, any one selected from Al, Ga, In, Tl, Sn, Sb, Pb, Bi, and Po, but is not limited thereto.

Since the cluster compound includes the metal after the transition, it is easy to synthesize the cluster compound including the metal-carbon bond, and better etching selectivity and ease of removal can be ensured in the subsequent etching process.

For example, the metal of the cluster compound may be one or a plurality of two or more.

For example, the plurality of metals may be the same as or different from each other.

The cluster compound may have one or more substituents bonded to the metal, and the substituents may be, for example, organic groups. For example, the cluster compound may have an organic group bonded to a metal, for example, a metal-carbon bond in which a metal and carbon in the organic group are bonded.

For example, the metal-carbon bond may be represented by Formula 1 below.

[Formula 1]

In Formula 1, M ¹ is a metal,

X ¹ is a substituted or unsubstituted C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C30 heterocyclic group, carbonyl group, carboxyl group, ester group, amide group, or a combination thereof;

n ¹ is an integer from 1 to 5,

* is the point of connection with other elements in the cluster compound.

The * means a connection portion with other elements constituting the cluster structure of the core in the cluster compound, for example, the other elements may be metal elements, oxygen elements, or carbon elements, but is not limited thereto.

For example, M ¹ may be an alkali metal, an alkaline earth metal, a transition metal, a post-transition metal, or a combination thereof.

For example, M ¹ may be a transition metal and/or a post-transition metal.

For example, M ¹ may be a post-transition metal, for example, may be any one selected from Al, Ga, In, Tl, Sn, Sb, Pb, Bi, and Po, but is not limited thereto.

For example, X 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 pentyl group, or a substituted or unsubstituted hexyl group It may be a group, a substituted or unsubstituted heptyl group, a substituted or unsubstituted octyl group, a substituted or unsubstituted nonyl group, or a substituted or unsubstituted decanyl group, but is not limited thereto.

For example, n ¹ may each independently be 2 to 5, 3 to 5, 2 to 4, 3 to 4, or 4 to 5, but preferably 4 may be.

For example, the cluster compound may include one or more metal-carbon bonds.

For example, the plurality of metal-carbon bonds may be the same as or different from each other.

Since the cluster compound contains the aforementioned metal-carbon bond, it is compatible with other cluster compounds, monomers or polymers in the hardmask composition, and preferably crosslinks with the monomers or polymers in the hardmask composition.

The cluster compound may include, for example, at least one of a metal cluster compound including a bond between metal elements in the cluster compound, and a metal-oxo cluster compound including a bond between a metal element and oxygen.

The metal cluster compound may be, for example, a compound in which one or more adjacent metals combine with each other to form a three-dimensional structure. For example, at least one of the metals constituting the metal cluster compound may have an organic group, for example, a metal-carbon bond in which the metal and carbon in the organic group are bonded.

For example, the metal-oxo cluster compound may include at least one of a moiety represented by Formula 2 and a moiety represented by Formula 3 below.

[Formula 2] [Formula 3]

In Formula 2 or 3,

M ^{2 To} M ⁶ are each independently the same or different metals or organometals,

O is an element of oxygen,

n ² to n ⁶ are each independently an integer of 1 to 5,

* is the point of connection with other elements in the metal-oxo cluster compound.

The * denotes a connection portion with other elements constituting the cluster structure of the core in the metal-oxo cluster compound, for example, the other element may be a metal element, an oxygen element, or a carbon element, but is not limited thereto.

Since the cluster compound includes at least one of the moieties represented by Chemical Formulas 2 and 3, a more rigid layer may be formed, and superior etch resistance may be secured in a subsequent etching process.

For example, M ² to M ⁶ may each independently be an alkali metal, an alkaline earth metal, a transition metal, a post-transition metal, or a combination thereof.

For example, M ² to M ⁶ may be a transition metal and/or a post-transition metal.

For example, M ² to M ⁶ may be a transition metal, for example, Al, Ga, In, Tl, Sn, Sb, Pb, Bi, and Po may be any one selected from, but is not limited thereto.

For example, M ² to M ⁶ may each independently be an organometal including a direct single, double, and/or triple bond between a metal and carbon.

For example, M ² to M ⁶ may each independently be a metal represented by the above-described Chemical Formula 1-organometal including a carbon bond.

For example, in Formulas 2 and/or 3, n ² to n ⁶ may each independently be 2 to 5, 3 to 5, 2 to 4, 3 to 4, or 4 to 5, preferably 4 days. can

For example, the metal-oxo cluster compound may be represented by the following Chemical Formula A.

[Formula A]

In Formula A, M ¹ and X ¹ are the same as described above.

The cluster compound described above can be prepared by a method of synthesizing small molecules (bottom-up).

The hard mask including the cured product of the hard mask composition including the cluster compound has better etching resistance to the etching gas in the subsequent etching process than the hard mask including the cured product of the hard mask composition not including the cluster compound. can do.

The hard mask composition including the cluster compound has excellent surface properties and dispersibility, so that a surface modification process and use of a dispersant may be unnecessary, and better etch selectivity may be secured by not using a dispersant. there is.

For example, the cluster compound may be an ionic or non-ionic compound. Herein, the ionic compound means that at least a part of a positively or negatively charged moiety is present in the compound. When the cluster compound is an ionic compound, the cluster compound is more excellently dispersed in the hardmask composition, and the use of an additional dispersant is unnecessary, thereby exhibiting excellent etch resistance in a subsequent etching process.

For example, the cluster compound may be a cationic compound or an anionic compound. For example, the cluster compound may have an overall positive or negative charge, for example, the cluster compound may have a surface positive charge or a surface negative charge.

For example, the cluster compound may be a cationic compound.

For example, when the cluster compound is a cationic compound, the hardmask composition may further include an anion as a counter-ion. When the cluster compound is an anionic compound, the hardmask composition may be a counter-ion. It may further include a cation.

According to the type of the counter ion, the etching selectivity may be controlled in the subsequent etching process of the hard mask including the cured product of the hard mask composition.

For example, the counter ion may be an ion including an aromatic ring. By using an ion containing an aromatic ring, etch resistance may be more excellent in a subsequent etching process. The aromatic ring may have a substituent, and the substituent may preferably be an alkyl group. Since the ion including the aromatic ring has the alkyl group, it may be compatible with other cluster compounds, monomers or polymers in the hardmask composition, and may have better compatibility.

For example, the counter ion may include elemental sulfur, for example, a sulfonium-based ion. By using a sulfonium-based ion, the charge of the cluster compound can be stabilized by ionic bonding.

For example, the hardmask composition may further include an anion.

For example, the anion is a halogen anion, hydroxide, cyanide, nitrate, bisulfite, dihydrogen phosphate, acetate, benzenesulfonate, benzenesulfite, C7 to C30 alkyl benzenesulfonate, C7 to C30 alkyl benzenesulfite or a combination thereof.

For example, the cluster compound may have a particle diameter of 0.1 nm to 10 nm, more specifically, 0.1 nm to 7 nm, 0.2 nm to 5 nm, or 0.5 nm to 2 nm.

When the particle size of the cluster compound is within the above range, the cluster compound may be prepared by a method of synthesizing a small molecule (bottom-up), and the cluster compound prepared by the method has a uniform particle size, excellent dispersibility and compatibility last name can have

For example, the cluster compound may be included in an amount of 0.1 to 30% by weight, more specifically 0.5 to 20% by weight or 1 to 10% by weight, based on the total content of the hardmask composition.

For example, the hardmask composition may include the aforementioned hardmask cluster compound and a hardmask monomer and/or a hardmask polymer. For example, the hardmask monomer and/or the hardmask polymer may include at least one aromatic ring. can

For example, the hardmask monomer may include a cyclic group in which at least three substituted or unsubstituted benzene rings are fused in its structure. The hard mask monomer may secure etch resistance by including a cyclic group in which three or more benzene rings are fused.

The molecular weight of the hard mask monomer may be 1,500 or less, 1,300 or less, or 500 or more and 1,300 or less, but is not limited thereto. Accordingly, the film flatness of the hardmask layer prepared therefrom may be further improved.

In addition, the hard mask monomer may include, for example, a cyclic group in which 3, 4, or 5 substituted or unsubstituted benzene rings are fused, and the fused shape is not particularly limited.

The hardmask monomer may include a plurality of substituted or unsubstituted aliphatic or aromatic ring groups in its structure.

For example, the hardmask monomer may include a substituted or unsubstituted ring group selected from Group 1 below.

[Group 1]

In group 1,

Z ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl a lene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C=O, NR ^a , oxygen (O), sulfur (S), or a combination thereof, wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, or a combination thereof;

Z ³ to Z ¹⁸ are each independently C=O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^{c ,} or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, substituted or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, a halogen-containing group, or a combination thereof.

For example, the cyclic groups listed in Group 1 may be in an unsubstituted form, but may be included in the monomer as a form in which at least one hydrogen atom is substituted in these cyclic groups. In this case, the physical properties of the hard mask composition can be controlled by selecting the type and number of the substituents, and the functional groups include a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C4 alkyl ether, substituted or unsubstituted C7 to C20 arylalkylene ether, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C1 to C20 alkylborane group, and substituted or unsubstituted C6 to It may be selected from the group consisting of a C30 arylborane group, but is not limited thereto.

For example, the hard mask monomer may have a molecular weight of 1,500 or less, and various structural modifications are possible within a range including a cyclic group in which at least three substituted or unsubstituted benzene rings are fused.

For example, the hard mask monomer may be represented by any one of the following Chemical Formulas 4 to 9, but is not limited thereto.

[Formula 4]

In Formula 4,

A ^a is a substituted or unsubstituted aromatic ring group,

X ^a , X ^b and X ^c are each independently a monovalent group derived from a substituted or unsubstituted indole,

Y ^a , Y ^b and Y ^c are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkyl an amine group, or a substituted or unsubstituted C1 to C30 alkoxy group,

ma ^a , m ^b , m ^c , na ^a , n ^b and n ^c are each independently 0 or 1.

However, m ^a, m ^b and m ^c, at least one is 1, and m ^a is 0, n ^a is 0, and, if m ^b is 0 and n ^b is 0, when m ^c is 0, n ^c is 0.

[Formula 5]

In Formula 5,

T is triazine or a triazine derivative,

R ^d , R ^e and R ^f are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or these It is a group having one or two or more combinations of.

However, ^{at least one of R d} , R ^e and R ^f includes a substituted or unsubstituted aryl group.

[Formula 6]

In Formula 6,

A ^b , A ^c , A ^d , A ^e and A ^f are each independently a substituted or unsubstituted aromatic ring group,

X ^d and X ^e are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ^d and Y ^e are each independently -O-, -S-, -NH-, or -Se-,

M ^a and M ^b are cyano groups,

k and l are each independently 0 or 1, satisfying 1≤k+l≤2,

m ^d and n ^d is an integer satisfying 0≤m ^d ≤3, 0≤n ^d ≤3, the case of k = 1 m ^d is greater than 1 when the integer and l = 1 n ^d is an integer greater than 1,

p and q are each independently an integer of 1 or more, satisfying 1≤p+q≤(the maximum number of substituents that ^{A b can have).}

[Formula 7]

In Formula 7,

A ^g is It is an aliphatic ring group or an aromatic ring group,

A ^h to A ^j are each a phenylene group,

X ^f to X ^h are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,

M ^c is CR ^g , SiR ^h , N, P, PR ⁱ R ^j or PR ^k ;

n ^e is an integer from 1 to 4,

In M ^c , R ^g , R ^h , R ⁱ and R ^j are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

R ^k is oxygen (O) or sulfur (S).

[Formula 8]

In the formula (8),

A ^k to A ^m are each independently an aliphatic ring group or an aromatic ring group,

X ⁱ to X ^k are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,

n ^f is an integer from 3 to 5,

m ^e is an integer from 1 to 3.

[Formula 9]

In Formula 9,

A ⁿ and A ^o are each independently a substituted or unsubstituted aliphatic ring group or an aromatic ring group,

X ¹ is a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

Y ^f is a boron (B) containing group,

n ^g is an integer from 1 to 5;

For example, the hardmask monomer may include at least one hydroxyl group, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C10 alkyl group, a C6 to C30 aryl group, a C1 to C30 alkoxy group, or a combination thereof in the structure thereof. It may contain functional groups. In this case, not only can the solubility of the monomer be further improved so that it can be effectively formed by the spin-on coating method, but also the gap between the patterns can be filled when formed by the spin-on coating method on the lower layer having a predetermined pattern. It also has excellent peel properties and flattening properties.

The hardmask monomer may be included, for example, in an amount of about 0.1 to 50% by weight, such as about 0.5 to 40% by weight, about 1 to 30% by weight, or about 5 to 20% by weight based on the total content of the hardmask composition. By including the hardmask monomer in the above range, the thickness, surface roughness, and planarization degree of the hardmask can be adjusted.

For example, the hard mask polymer may include a structural unit represented by the following Chemical Formula 10.

[Formula 10]

In the formula (10),

A ¹ is a divalent ring group including at least one substituted or unsubstituted benzene ring,

B ¹ is a divalent organic group,

* is the connection point:

The hardmask polymer includes a cyclic group represented by ^{A 1} and a linking group represented by ^{B 1 in its structural unit.}

For example, in Formula 10, A ¹ may be a divalent cyclic group including at least two rings in its structure, for example, as a divalent cyclic group derived from any one of the compounds listed in Groups 2 and 3 below. The divalent cyclic group may be one in which at least one hydrogen atom is substituted or unsubstituted, but is not limited thereto.

[Group 2]

[Group 3]

In group 2,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl;

In group 3,

R ⁰ and R ¹ are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkoxy group, a halogen atom, a halogen-containing group, or a group thereof It is a combination.

For example, in Formula 10, B ¹ may be represented by Formula 11 below, but is not limited thereto.

[Formula 11]

In the above formula (11),

m and n are each independently an integer of 0 to 2,

Z is a divalent cyclic group derived from any one selected from the following group 4, the divalent cyclic group is a group in which at least one hydrogen atom is substituted or unsubstituted,

* is the connection point:

[Group 4]

In group 4,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl.

For example, m and n may each be 1, for example.

For example, Z is at least one such as, for example, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkoxy group, a halogen atom, a halogen-containing group, or a combination thereof. It may be substituted by a functional group of

For example, the weight average molecular weight of the polymer may be 1,000 to 200,000, 2,000 to 100,000, 3,000 to 80,000, 3,500 to 70,000, or 4,000 to 60,000, but is not limited thereto.

The hardmask polymer may be included in, for example, about 0.1 to 50% by weight, such as about 0.5 to 40% by weight, about 1 to 30% by weight, or about 5 to 20% by weight, based on the total content of the hardmask composition. By including the polymer in the above range, it is possible to control the thickness, surface roughness, and planarization degree of the hard mask.

The hardmask monomer or hardmask polymer including at least one aromatic ring described above may be used together with the aforementioned cluster compound to secure better etch resistance, chemical resistance and heat resistance in a subsequent etching process.

The solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility or dispersibility for the cluster compound, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether. , tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethyl It may include at least one selected from acetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The hard mask composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

The surfactant may be, for example, a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The crosslinking agent may be, for example, a melamine-based, substituted urea-based, or polymer-based agent. Preferably, crosslinking agents having at least two crosslinking substituents are, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

In addition, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. As a crosslinking agent with high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (eg, a benzene ring, a naphthalene ring) in the molecule can be used.

The thermal acid generator is, for example, an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and/or 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight based on 100 parts by weight of the hardmask composition. By including in the above range, solubility can be improved without changing the optical properties of the hardmask composition.

According to another embodiment, an organic film prepared using the above-described hard mask composition is provided. The organic film may be in a form cured through a heat treatment process after coating the above-described hard mask composition on a substrate, for example, and may include an organic thin film used in electronic devices such as a hard mask layer, a planarization film, a sacrificial film, and a filler. there is.

Hereinafter, a method of forming a pattern using the above-described hard mask composition will be described.

A pattern forming method according to an embodiment includes forming a material layer on a substrate, applying a hard mask composition including the cluster compound and a solvent on the material layer, and heat-treating the hard mask composition to form a hard mask layer forming a photoresist layer on the hardmask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hardmask layer using the photoresist pattern; exposing a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The material layer may be formed, for example, by a chemical vapor deposition method.

The hard mask composition is the same as described above, and may be prepared in the form of a solution and applied by a spin-on 　 coating method. At this time, the thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 50 to 200,000 Å.

The heat treatment of the hard mask composition may be performed, for example, at about 100 to 700° C. for about 10 seconds to 1 hour.

As an example, the method may further include forming a silicon-containing thin film layer on the hardmask layer. The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

For example, before the step of forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer or on the hard mask layer.

The exposing of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. In addition, a heat treatment process may be performed at about 100 to 700° C. after exposure.

The etching of the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} or a mixture thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be various, such as a metal pattern, a semiconductor pattern, an insulating pattern, and may be applied as various patterns in, for example, a semiconductor integrated circuit device.

The above-described embodiment will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

Synthesis example

Synthesis example of cluster compound

All reactions were performed under a nitrogen atmosphere. The starting material, butyltin hydroxy oxide, was purchased from Alfa Aesar and used without further purification. All other reagents were purchased from Sigma Aldrich and used without a separate purification process.

Cluster compound synthesis example 1: [(BuSn) ₁₂ O ₁₄ (OH) ₆ ][p-CH ₃ C6H ₄ SO ₃ ] ₂ synthesis of

C. Eychenne-Baron, F. Ribot and C. Sanchez, Journal of Organometallic Chemistry , 1998, 567, 137-142. Reference was made to the synthesis method in the literature. BuSnO(OH) (20g), p-toluene sulfonic acid (5.77g) and toluene (500ml) were placed in a 1L round-bottom flask, a Dean-Stark condenser was installed, and the mixture was refluxed for 48 hours. The solution removed by filtration of the unreacted material was concentrated to obtain 23 g of white powder. The obtained powder was placed in a 1,4-dioxane solution containing 0.5 wt% of water, heated to about 85° C. to dissolve, and then left at room temperature for several days to obtain 11 g of a cluster compound. (yield rate: 50%)

Cluster compound synthesis example 2: [(BuSn) ₁₂ O ₁₄ (OH) ₆ ][OH] ₂ synthesis of

C. Eychenne-Baron, F. Ribot and C. Sanchez, Journal of Organometallic Chemistry , 1998, 567, 137-142. Reference was made to the synthesis method in the literature. A mixed solution of tetraammonium hydroxide containing 65 wt% of tetraammonium hydroxide and isopropanol was added to isopropanol so that the content of the cluster compound obtained in Synthesis Example 1 became 20 wt%, and stirred vigorously. After stirring for 30 minutes, the suspension reaction mixture was left at -20°C overnight to obtain needle-like crystals. The obtained crystals were separated by filtration and dried to obtain a cluster compound. (yield rate 90%)

Cluster compound synthesis example 3: [(BuSn) ₁₂ O ₁₄ (OH) ₆ ][C ₆ H ₅ CH ₂ COO] ₂ synthesis of

The synthesis method of Advances in Patterning Materials and Processes XXXI, 90511B (4 April 2014) was referred to. In a 50ml round bottom flask, put the cluster compound (1.0g, 0.41mmol) and tetrahydrofuran (THF, 10ml) obtained in Synthesis Example 2 of the cluster compound, and phenylacetane (0.112g, 0.82mmol) containing 10wt% of phenyl A mixed solution of acetane and tetrahydrofuran was added, followed by stirring for 10 minutes. After stirring, the solvent was removed in vacuo to obtain a white cluster compound.

Hard mask monomer synthesis example

Step 1: Friedel-Craft Acylation reaction

To the flask were added 15.85 g (0.05 mol) of benzopyrene, 23.13 g (0.105 mol) of methoxy naphthoyl chloride and 214 g of dichloroethane. 14.668 g (0.11 mol) of aluminum chloride was slowly added to the solution and stirred at room temperature for 1 hour. When the reaction was completed, methanol was added and the formed precipitate was filtered and dried.

Second step: demethylation reaction

After adding the compound obtained in the first step, 36.21 g (0.18 mol) of 1-dodecanthiol, 12.55 g (0.22 mol) of potassium hydroxide, and 315 g of N,N-dimethylformamide to a flask, at 120° C. for 8 hours stirred. Then, the mixture was cooled, neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate (Ethyl Acetate), and dried.

Third step: reduction reaction

The compound obtained in the second step was dissolved in 100 mL of tetrahydrofuran in a flask, and 22.98 g (0.60 mol) of lithium aluminum hydride was added little by little and reacted. After completion of the reaction, reaction by-products were removed using a water/methanol mixture to obtain a monomer represented by Chemical Formula 1aa.

[Formula 1aa]

Hard mask polymer synthesis example

In a flask, 50.0 g (0.143 mol) of 9,9'-bis (4-hydroxyphenyl) fluorene, 23.7 g (0.143 mol) of 1,4-bis (methoxymethyl) benzene, and 50 g of propylene glycol monomethyl ether acetate were added to the flask. was added to prepare a solution. After adding 1.10 g (7.13 mmol) of diethyl sulfate to the solution, the mixture was stirred at 100° C. for 24 hours. Upon completion of polymerization, the polymer was precipitated in methanol to remove monomers and low molecular weight substances to obtain a polymer including a structural unit represented by the following Chemical Formula 1bb. The weight average molecular weight of the obtained polymer was 33,500.

[Formula 1bb]

Example

Example 1

The cluster compound (20 g) obtained in Synthesis Example 1 of the cluster compound and the polymer (80 g) obtained in the Polymer Synthesis Example were mixed with propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3). (v/v)) was dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

Example 2

The cluster compound (40 g) obtained in Synthesis Example 1 of the cluster compound and the polymer (60 g) obtained in the Polymer Synthesis Example were mixed with propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3). (v/v)) was dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

Example 3

The cluster compound (20 g) obtained in Synthesis Example 1 of the cluster compound and the monomer (80 g) obtained in the monomer synthesis example were mixed with propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3). (v/v)) was dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

Example 4

The cluster compound (20 g) obtained in Synthesis Example 2 of the cluster compound and the polymer (80 g) obtained in the Polymer Synthesis Example were mixed with propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3). (v/v)) was dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

Example 5

The cluster compound (20 g) obtained in Synthesis Example 3 of the cluster compound and the polymer (80 g) obtained in the Polymer Synthesis Example were mixed with propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3). (v/v)) was dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

comparative example

Comparative Example 1

The polymer (100 g) obtained in the polymer synthesis example was dissolved in a mixed solvent (900 g) of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v/v)). After filtration, a hard mask composition was prepared.

Comparative Example 2

Sn(OtBu)4 (Sigma-Aldrich Product No.: 494135, CAS Number 36809-75-3) (20g) and the polymer obtained in the Polymer Synthesis Example (80g) were mixed with propylene glycol monomethyl ether acetate (PGMEA). ) and cyclohexanone (7:3 (v/v)) were dissolved in a mixed solvent (900 g) and filtered to prepare a hard mask composition.

Evaluation: corrosion resistance

On a silicon wafer, the hard mask compositions (4 wt %) according to Examples 1 to 5 and Comparative Examples 1 and 2 were heat-treated at 400° C. for 120 seconds to form a thin film, and then the thickness was measured. _{Then, N 2} /O ₂ mixed gas (50mT/300W/10O ₂ /50N ₂ ) and CF _x gas (100mT/600W/42CF ₄ /600Ar/15O ₂ ) were used on the thin film to dry for 60 seconds and 120 seconds, respectively. After etching, the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated according to Equation 1 below from the thickness and etching time of the thin film before and after dry etching.

[Formula 1]

Etch rate (Å/sec) = (initial thin film thickness - thin film thickness after etching) / etch time

The results are shown in Table 1.

Bulk etch rate(Å/sec) N ₂ /O ₂ etch rate CFx etch rate Example 1 15.6 18.1 Example 2 16.2 18.8 Example 3 17.1 19.5 Example 4 17.5 22.0 Example 5 16.4 19.5 Comparative Example 1 20.6 23.8 Comparative Example 2 24.8 29.4

Referring to Table 1, it can be seen that the thin films formed from the hardmask compositions according to Examples 1 to 5 have sufficient etch resistance to the etching gas as compared to the thin films according to Comparative Examples 1 and 2, so that the etch resistance is improved.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also presented. It belongs to the scope of the invention.

Claims (17)

a cluster compound comprising at least one of a metal cluster compound and a metal-oxo cluster compound, and
A hard mask composition comprising a solvent,
The metal-oxo cluster compound is a hard mask composition comprising at least one of a moiety represented by the following Chemical Formula 2 and a moiety represented by the following Chemical Formula 3:
[Formula 2] [Formula 3]

In Formula 2 or 3,
M ^{2 To} M ⁶ are each independently the same or different metals or organometals,
O is an element of oxygen,
n ² to n ⁶ are each independently an integer of 1 to 5,
* is the point of connection with other elements in the metal-oxo cluster compound.
In claim 1,
The metal is any one selected from Al, Ga, In, Tl, Sn, Pb, Sb, Bi, and Po hard mask composition.
In claim 1,
The cluster compound is a hard mask composition comprising a metal-carbon bond.
In claim 3,
The metal-carbon bond is a hard mask composition represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1, M ¹ is a metal,
X ¹ is a substituted or unsubstituted C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C30 heterocyclic group, carbonyl group, carboxyl group, ester group, amide group, or a combination thereof;
n ¹ is an integer from 1 to 5,
* is the point of connection with other elements in the cluster compound.
delete In claim 1,
The hard mask composition wherein the cluster compound is a cationic compound.
In claim 6,
A hard mask composition further comprising an anion.
In claim 7,
The anion is a halogen anion, hydroxide, cyanide, nitrate, bisulfite, dihydrogen phosphate, acetate, benzenesulfonate, benzenesulfite, C7 to C30 alkyl benzenesulfonate, C7 to C30 alkyl benzenesulfite Or a hard mask composition that is a combination thereof.
In claim 1,
The cluster compound is a hard mask composition having a particle diameter of 0.1 nm to 10 nm.
In claim 1,
The hard mask composition comprising the cluster compound in an amount of 0.1 to 30% by weight based on the total content of the hardmask composition.
In claim 1,
A hardmask composition further comprising a hardmask monomer or hardmask polymer comprising at least one aromatic ring.
In claim 11,
The hard mask monomer is a hard mask composition comprising a substituted or unsubstituted ring group selected from the following group 1:
[Group 1]

In group 1,
Z ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl Rene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C=O, NR ^a , oxygen (O), sulfur (S), or a combination thereof,
Z ³ to Z ¹⁸ are each independently C=O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^{c ,} or a combination thereof,
R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, a halogen-containing group , or a combination thereof.
In claim 12,
The hard mask monomer is a hard mask composition represented by any one of the following Chemical Formulas 4 to 9:
[Formula 4]

In Formula 4,
A ^a is a substituted or unsubstituted aromatic ring group,
X ^a , X ^b and X ^c are each independently a monovalent group derived from a substituted or unsubstituted indole,
Y ^a , Y ^b and Y ^c are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkyl an amine group, or a substituted or unsubstituted C1 to C30 alkoxy group,
ma ^a , m ^b , m ^c , na ^a , n ^b and n ^c are each independently 0 or 1.
A stage, m ^a, and at least one of m ^b and m ^c is 1, m ^a is 0, n ^a is 0, and, if m ^b is 0 and n ^b is 0, m ^c is 0, n ^c is 0:
[Formula 5]

In Formula 5,
T is triazine or a triazine derivative,
R ^d , R ^e and R ^f are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or these It is a group having one or two or more combinations of.
provided ^{that at least one of R d} , R ^e and R ^f includes a substituted or unsubstituted aryl group:
[Formula 6]

In Formula 6,
A ^b , A ^c , A ^d , A ^e and A ^f are each independently a substituted or unsubstituted aromatic ring group,
X ^d and X ^e are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ^d and Y ^e are each independently -O-, -S-, -NH-, or -Se-,
M ^a and M ^b are cyano groups,
k and l are each independently 0 or 1, satisfying 1≤k+l≤2,
m ^d and n ^d is an integer satisfying 0≤m ^d ≤3, 0≤n ^d ≤3, the case of k = 1 m ^d is greater than 1 when the integer and l = 1 n ^d is an integer greater than 1,
p and q are each independently an integer of 1 or more, satisfying 1≤p+q≤(the maximum number of substituents that ^{A b can have):}
[Formula 7]

In Formula 7,
A ^g is It is an aliphatic ring group or an aromatic ring group,
A ^h to A ^j are each a phenylene group,
X ^f to X ^h are each independently a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,
M ^c is CR ^g , SiR ^h , N, P, PR ⁱ R ^j or PR ^k ;
n ^e is an integer from 1 to 4,
In M ^c , R ^g , R ^h , R ⁱ and R ^j are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
R ^k is oxygen (O) or sulfur (S):
[Formula 8]

In the formula (8),
A ^k to A ^m are each independently an aliphatic ring group or an aromatic ring group,
X ⁱ to X ^k are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,
n ^f is an integer from 3 to 5,
m ^e is an integer from 1 to 3:
[Formula 9]

In Formula 9,
A ⁿ and A ^o are each independently a substituted or unsubstituted aliphatic ring group or an aromatic ring group,
X ¹ is a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,
L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
Y ^f is a boron (B) containing group,
n ^g is an integer from 1 to 5;
In claim 11,
The hard mask polymer is a hard mask composition comprising a structural unit represented by the following formula (10):
[Formula 10]

In the formula (10),
A ¹ is a divalent ring group including at least one substituted or unsubstituted aromatic ring,
B ¹ is a divalent organic group,
* is the connection point.
15. In claim 14,
In Formula 10, A ¹ is a divalent cyclic group derived from any one of the compounds listed in Groups 2 or 3, wherein at least one hydrogen atom of the divalent cyclic group is unsubstituted or substituted for a hard mask composition:
[Group 2]

[Group 3]

In group 2 or 3 above,
M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl;
R ⁰ and R ¹ are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkoxy group, a halogen atom, or a combination thereof.
15. In claim 14,
In Formula 10, B ¹ is a hard mask composition represented by Formula 11 below:
[Formula 11]

In the above formula (11),
m and n are each independently an integer of 0 to 2,
Z is a divalent cyclic group derived from any one selected from the following group 4, the divalent cyclic group is a group in which at least one hydrogen atom is substituted or unsubstituted,
* is the connection point:
[Group 4]

In group 4,
M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ -, or carbonyl.
17. A method comprising: applying the hardmask composition according to any one of claims 1 to 4 and 6 to 16 on the material layer and heat-treating to form a hardmask layer;
forming a photoresist layer over the hardmask layer;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
etching the exposed portion of the material layer;
A pattern forming method comprising a.