U.S. patent application number 14/545909 was filed with the patent office on 2016-01-07 for hardmask composition and method of forming pattern using the hardmask composition.
The applicant listed for this patent is Samsung Electronics Co., Ltd.. Invention is credited to Sangwon Kim, Seongjun Park, Hyeonjin Shin.
Application Number | 20160005625 14/545909 |
Document ID | / |
Family ID | 55017511 |
Filed Date | 2016-01-07 |
United States Patent
Application |
20160005625 |
Kind Code |
A1 |
Shin; Hyeonjin ; et
al. |
January 7, 2016 |
Hardmask composition and method of forming pattern using the
hardmask composition
Abstract
A hardmask composition includes a first material including one
of an aromatic ring-containing monomer and a polymer containing a
repeating unit including an aromatic ring-containing monomer, a
second material including at least one of a hexagonal boron nitride
and a precursor thereof, a chalcogenide-based material and a
precursor thereof, and a two-dimensional carbon nanostructure and a
precursor thereof, the two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen, and a
solvent.
Inventors: |
Shin; Hyeonjin; (Suwon-si,
KR) ; Kim; Sangwon; (Seoul, KR) ; Park;
Seongjun; (Seoul, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Samsung Electronics Co., Ltd. |
Suwon-si |
|
KR |
|
|
Family ID: |
55017511 |
Appl. No.: |
14/545909 |
Filed: |
July 6, 2015 |
Current U.S.
Class: |
438/703 ;
524/104; 524/404; 524/406; 524/611 |
Current CPC
Class: |
C08K 2003/3009 20130101;
G03F 7/11 20130101; G03F 7/40 20130101; H01L 21/47573 20130101;
C08G 83/001 20130101; C08K 3/30 20130101; C08K 2003/385 20130101;
C08K 3/38 20130101; G03F 7/094 20130101; H01L 21/47 20130101; H01L
21/0271 20130101 |
International
Class: |
H01L 21/47 20060101
H01L021/47; C08K 3/38 20060101 C08K003/38; C08K 3/30 20060101
C08K003/30; H01L 21/4757 20060101 H01L021/4757 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 4, 2014 |
KR |
10-2014-0083905 |
Claims
1. A hardmask composition comprising: a first material including
one of an aromatic ring-containing monomer and a polymer containing
a repeating unit including an aromatic ring-containing monomer; a
second material including at least one of a hexagonal boron nitride
and a precursor thereof, a chalcogenide-based material and a
precursor thereof, and a two-dimensional carbon nanostructure and a
precursor thereof, the two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen; and a
solvent.
2. The hardmask composition of claim 1, wherein the first material
is bonded to the second material by a chemical bond.
3. The hardmask composition of claim 2, wherein the chemical bond
is a covalent bond.
4. The hardmask composition of claim 3, wherein the covalent bond
is one of an ester group (--C(.dbd.O)O--), an ether group (--O--),
a thioether group (--S--), a carbonyl group (--C).dbd.O)O--), and
an amide group (--C(.dbd.O)NH--).
5. The hardmask composition of claim 1, wherein a content of the
second material is about 0.1 part to about 99.9 parts by weight
based on 100 parts by weight of the total weight of the first
material and the second material.
6. The hardmask composition of claim 1, wherein the aromatic
ring-containing monomer is at least one of a monomer represented by
Formula 1 and a monomer represented by Formula 2: ##STR00020##
wherein, in Formula 1, R is a mono-substituted or multi-substituted
substituent including one of a hydrogen atom, a halogen atom, a
hydroxyl group, an isocyanate group, a glycidyloxy group, a
carboxyl group, an aldehyde group, an amino group, a siloxane
group, an epoxy group, an imino group, an urethane group, an ester
group, an epoxy group, an amide group, an imide group, an acryl
group, a methacryl group, a nitro group, --HSO.sub.3, an
unsubstituted or substituted C.sub.1-C.sub.30 saturated organic
group, and an unsubstituted or substituted C.sub.1-C.sub.30
unsaturated organic group, A-L-A' [Formula 2] wherein, in Formula
2, each of A and A' are identical to or different from each other
and are independently a monovalent organic group derived from one
including one of the monomers represented by Formula 1, and L is
one of a single bond, a substituted or unsubstituted
C.sub.1-C.sub.30 alkylene group, a substituted or unsubstituted
C.sub.2-C.sub.30 alkenylene group, a substituted or unsubstituted
C.sub.2-C.sub.30 alkynylene group, a substituted or unsubstituted
C.sub.7-C.sub.30 arylene alkylene group, a substituted or
unsubstituted C.sub.6-C.sub.30 arylene group, a substituted or
unsubstituted C.sub.2-C.sub.30 heteroarylene group, a substituted
or unsubstituted C.sub.2-C.sub.30 heteroarylene alkylene group, a
substituted or unsubstituted C.sub.1-C.sub.30 alkyleneoxy group, a
substituted or unsubstituted C.sub.7-C.sub.30 arylenealkyleneoxy
group, a substituted or unsubstituted C.sub.6-C.sub.30 aryleneoxy
group, a substituted or unsubstituted C.sub.2-C.sub.30
heteroaryleneoxy group, a substituted or unsubstituted
C.sub.2-C.sub.30 heteroarylenealkyleneoxy group, --C(.dbd.O)--, and
--SO.sub.2.
7. The hardmask composition of claim 1, wherein the first material
is at least one of a compound represented by Formula 3 and a
compound represented by Formula 4: ##STR00021## wherein, in Formula
3, R is a mono-substituted or multi-substituted substituent
including one of a hydrogen atom, a halogen atom, a hydroxyl group,
an isocyanate group, a glycidyloxy group, a carboxyl group, an
aldehyde group, an amino group, a siloxane group, an epoxy group,
an imino group, an urethane group, an ester group, an epoxy group,
an amide group, an imide group, an acryl group, a methacryl group,
an unsubstituted or substituted C.sub.1-C.sub.30 saturated organic
group, and an unsubstituted or substituted C.sub.1-C.sub.30
unsaturated organic group, ##STR00022## wherein, in Formula 4, R is
as defined in the description in Formula 3, and L is one of a
single bond, a substituted or unsubstituted C.sub.1-C.sub.30
alkylene group, a substituted or unsubstituted C.sub.2-C.sub.30
alkenylene group, a substituted or unsubstituted C.sub.2-C.sub.30
alkynylene group, a substituted or unsubstituted C.sub.7-C.sub.30
arylene alkylene group, a substituted or unsubstituted
C.sub.6-C.sub.30 arylene group, a substituted or unsubstituted
C.sub.2-C.sub.30 heteroarylene group, a substituted or
unsubstituted C.sub.2-C.sub.30 heteroarylene alkylene group, a
substituted or unsubstituted C.sub.1-C.sub.30 alkyleneoxy group, a
substituted or unsubstituted C.sub.7-C.sub.30 arylenealkyleneoxy
group, a substituted or unsubstituted C.sub.6-C.sub.30 aryleneoxy
group, a substituted or unsubstituted C.sub.2-C.sub.30
heteroaryleneoxy group, a substituted or unsubstituted
C.sub.2-C.sub.30 heteroarylenealkyleneoxy group, --C(.dbd.O)--, and
--SO.sub.2.
8. The hardmask composition of claim 1, wherein the
chalcogenide-based material includes at least one metal element
including one of molybdenum (Mo), tungsten (W), niobium (Nb),
vanadium (V), tantalum (Ta), titanium (Ti), zirconium (Zr), hafnium
(Hf), technetium (Tc), rhenium (Re), copper (Cu), gallium (Ga),
indium (In), tin (Sn), germanium (Ge), and lead (Pb), and at least
one chalcogenide element including one of sulfur (S), selenium
(Se), and tellurium (Te).
9. The hardmask composition of claim 1, wherein the
chalcogenide-based material is at least one of molybdenum sulfide
(MoS.sub.2), tungsten sulfide (WS.sub.2), molybdenum selenide
(MoSe.sub.2), molybdenum telluride (MoTe.sub.2), tungsten selenide
(WSe.sub.2), and tungsten telluride (WTe.sub.2).
10. The hardmask composition of claim 1, wherein the first material
and the second material include at least one of a hydroxyl group, a
carboxyl group, an amino group, --Si(R.sub.1)(R.sub.2)(R.sub.3)
(where, R.sub.1, R.sub.2, and R.sub.3 are each independently a
hydrogen atom, a hydroxyl group, a C.sub.1-C.sub.30 alkyl group, a
C.sub.1-C.sub.30 alkoxy group, a C.sub.6-C.sub.30 aryl group, a
C.sub.6-C.sub.30 aryloxy group, or a halogen atom), a thiol group
(--SH), --Cl, --C(.dbd.O)Cl, --SCH.sub.3, a halogen atom, an
isocyanate group, a glycidyloxy group, an aldehyde group, an epoxy
group, an imino group, an urethane group, an ester group, an amide
group, an imide group, an acryl-group, a methacryl group,
--(CH.sub.2).sub.nCOOH (where, n is an integer of 1 to 10),
--CONH.sub.2, an unsubstituted or substituted C.sub.1-C.sub.30
saturated organic group, and an unsubstituted or substituted
C.sub.1-C.sub.30 unsaturated organic group.
11. The hardmask composition of claim 1, wherein the precursor of
the two-dimensional carbon nanostructure includes one of expanded
graphite obtained from exfoliated graphite and a product obtained
by oxidizing acid-treated graphite.
12. The hardmask composition of claim 1, wherein the
two-dimensional carbon nanostructure and the precursor thereof has
an intensity ratio of a D mode peak to a G mode peak of about 2 or
lower, and the two-dimensional carbon nanostructure and the
precursor thereof has an intensity ratio of a 2D mode peak to a G
mode peak of about 0.01 or higher as obtained from Raman
spectroscopy analysis.
13. The hardmask composition of claim 1, wherein the
two-dimensional carbon nanostructure includes a two-dimensional
layered structure having a (002) crystal face peak observed with a
diffraction angle within a range of about 20.degree. to about
27.degree., and the two-dimensional carbon nanostructure has a
d-spacing in a range of about 0.3 to about 0.5 nm as the result of
X-ray diffraction analysis.
14. The hardmask composition of claim 1, wherein the solvent is at
least one of water, methanol, isopropanol, ethanol,
N,N-dimethylformamide, N-methylpyrrolidone, dichloroethane,
dichlorobenzene, N,N-dimethylsulfoxide, xylene, aniline, propylene
glycol, propylene glycol diacetate, methoxypropanediol,
diethyleneglycol, gamma-butyrolactone, acetylacetone,
cyclohexanone, propylene glycol monomethyl ether acetate,
.gamma.-butyrolactone, dichloroethane, O-dichlorobenzene,
nitromethane, tetrahydrofuran, nitromethane, dimethyl sulfoxide,
nitrobenzene, butyl nitrite, methylcellosolve, ethylcellosolve,
diethylether, diethyleneglycolmethylether,
diethyleneglycolethylether, dipropyleneglycolmethylether, toluene,
xylene, hexane, methylethylketone, methylisoketone,
hydroxymethylcellulose, and heptanes.
15. A method of forming a pattern, the method comprising: forming a
layer on a substrate; forming a hardmask by providing a hardmask
composition on the layer, the hardmask composition including, a
first material including one of an aromatic ring-containing monomer
and a polymer containing a repeating unit including an aromatic
ring-containing monomer; a second material including at least one
of a hexagonal boron nitride and a precursor thereof, a
chalcogenide-based material and a precursor thereof, and a
two-dimensional carbon nanostructure and a precursor thereof, the
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen; and a solvent; forming a photoresist
layer on the hardmask; forming a hardmask pattern on the layer by
etching the hardmask using the photoresist layer as an etching
mask, the hardmask pattern including a composite, the composite
including, the polymer containing the repeating unit including the
aromatic ring-containing monomer, and the at least one of the
hexagonal boron nitride, the chalcogenide-based material, and the
two-dimensional carbon nanostructure connected to the polymer by a
chemical bond; and etching the layer using the hardmask pattern as
an etching mask.
16. The method of claim 15, wherein the forming a hardmask includes
coating a top surface of the layer with the hardmask composition
including the two-dimensional carbon nanostructure containing about
0.01 atom % to about 40 atom % of oxygen.
17. The method of claim 16, wherein the coating includes
heat-treating the coated layer during or after the coating.
18. The method of claim 15, wherein the forming a hardmask
includes: providing the hardmask composition including the
precursor of the two-dimensional carbon nanostructure; coating a
top surface of the layer with the hardmask composition, and
oxidizing or reducing the coated layer.
19. The method of claim 18, wherein the reducing the coated layer
includes one of chemical reduction, reduction by heat-treatment,
and electrochemical reduction, and the oxidizing the coated layer
includes using at least one of an acid, an oxidizing agent, UV,
ozone, IR, heat-treatment, and plasma.
20. The method of claim 16, wherein the forming the hardmask
pattern forms the hardmask pattern including the two-dimensional
carbon nanostructure by stacking two-dimensional nanocrystalline
carbon.
21. The hardmask composition of claim 1, wherein the first material
is one of the compounds represented by Formulae 6c to 6e:
##STR00023##
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of Korean Patent
Application No. 10-2014-0083905, filed on Jul. 4, 2014, in the
Korean Intellectual Property Office, the disclosure of which is
incorporated herein in its entirety by reference.
BACKGROUND
[0002] 1. Field
[0003] Example embodiments relate to a hardmask composition and a
method of forming a pattern using the hardmask composition.
[0004] 2. Description of the Related Art
[0005] The semiconductor industry has developed an ultra-fine
technique for providing a pattern of several to several tens of
nanometer size. Such an ultrafine technique benefits from effective
lithographic techniques. A typical lithographic technique includes
providing a material layer on a semiconductor substrate, coating a
photoresist layer on the material layer, exposing and developing
the same to provide a photoresist pattern, and etching the material
layer using the photoresist pattern as a mask.
[0006] According to minimizing of the pattern to be formed, it may
be difficult to provide a fine pattern having a desirable profile
by only the typical lithographic technique described above.
Accordingly, a layer, called "a hardmask", may be formed between
the material layer for the etching and the photoresist layer to
provide a fine pattern. The hardmask serves as an interlayer that
transfers the fine pattern of the photoresist to the material layer
through a selective etching process. Thus, the hardmask layer needs
to have chemical resistance, thermal resistance, and etching
resistance in order to tolerate various types of etching
processes.
[0007] As semiconductor devices have become highly integrated, a
height of a material layer is maintained the same or has relatively
increased, although a line-width of the material layer has
gradually narrowed. Thus, an aspect ratio of the material layer has
increased. Since an etching process needs to be performed under
such conditions, the heights of a photoresist layer and a hardmask
pattern also need to be increased. However, increasing the heights
of a photoresist layer and a hardmask pattern is limited. In
addition, the hardmask pattern may be damaged during the etching
process for obtaining a material layer with a narrow line-width,
and thus electrical characteristics of devices may deteriorate.
[0008] In this regard, methods have been suggested to use a single
layer or multiple layers, in which a plurality of layers are
stacked, of a conductive or insulative material such as a
polysilicon layer, a tungsten layer, and a nitride layer. However,
the single layer or the multiple layers requires a high deposition
temperature, and thus physical properties of the material layer may
be modified. Therefore, a novel hardmask material is needed.
SUMMARY
[0009] Example embodiments provide a hardmask composition with
improved etching resistance.
[0010] Example embodiments also provide a method of forming a
pattern using the hardmask composition.
[0011] Additional aspects will be set forth in part in the
description which follows and, in part, will be apparent from the
description, or may be learned by practice of example
embodiments.
[0012] According to example embodiments, a hardmask composition
includes a first material including one of an aromatic
ring-containing monomer and a polymer containing a repeating unit
including an aromatic ring-containing monomer, a second material
including at least one of a hexagonal boron nitride and a precursor
thereof, a chalcogenide-based material and a precursor thereof, and
a two-dimensional carbon nanostructure and a precursor thereof, the
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen, and a solvent.
[0013] According to example embodiments, a method of forming a
pattern includes forming a layer on a substrate, forming a hardmask
by providing a hardmask composition on the layer, the hardmask
composition including a first material including one of an aromatic
ring-containing monomer and a polymer containing a repeating unit
including an aromatic ring-containing monomer, a second material
including at least one of a hexagonal boron nitride and a precursor
thereof, a chalcogenide-based material and a precursor thereof, and
a two-dimensional carbon nanostructure and a precursor thereof, the
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen, and a solvent, forming a photoresist
layer on the hardmask, forming a hardmask pattern on the layer by
etching the hardmask using the photoresist layer as an etching
mask, the hardmask pattern including a composite, the composite
including the polymer containing the repeating unit including the
aromatic ring-containing monomer, and the at least one of the
hexagonal boron nitride, the chalcogenide-based material, and the
two-dimensional carbon nanostructure connected to the polymer by a
chemical bond, and etching the layer using the hardmask pattern as
an etching mask.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] These and/or other aspects will become apparent and more
readily appreciated from the following description of the
embodiments, taken in conjunction with the accompanying drawings in
which:
[0015] FIGS. 1A to 1E illustrate a method of forming a pattern
using a hardmask composition according to example embodiments;
[0016] FIGS. 2A to 2D illustrate a method of forming a pattern
using a hardmask composition according to example embodiments;
[0017] FIG. 3 illustrates results of X-ray diffraction analysis
performed on functionalized hexagonal boron nitrides prepared in
Preparation Example 1, Preparation Example 1a, Preparation Example
1b, and Preparation Example 2;
[0018] FIG. 4 is a Raman spectrum of tungsten sulfide (WS2);
and
[0019] FIG. 5 is Raman spectrum of tungsten sulfide, to which a
hydroxyl group is bonded, as prepared in Preparation Example
10.
DETAILED DESCRIPTION
[0020] Reference will now be made in detail to example embodiments,
examples of which are illustrated in the accompanying drawings,
wherein like reference numerals refer to like elements throughout.
In this regard, example embodiments may have different forms and
should not be construed as being limited to the descriptions set
forth herein. Accordingly, the example embodiments are merely
described below, by referring to the figures, to explain aspects of
the present description. As used herein, the term "and/or" includes
any and all combinations of one or more of the associated listed
items. Expressions such as "at least one of," when preceding a list
of elements, modify the entire list of elements and do not modify
the individual elements of the list.
[0021] It will be understood that when an element or layer is
referred to as being "on," "connected to" or "coupled to" another
element or layer, it can be directly on, connected or coupled to
the other element or layer or intervening elements or layers may be
present. In contrast, when an element is referred to as being
"directly on," "directly connected to" or "directly coupled to"
another element or layer, there are no intervening elements or
layers present. Like numerals refer to like elements throughout. As
used herein, the term "and/or" includes any and all combinations of
one or more of the associated listed items.
[0022] It will be understood that, although the terms first,
second, third, fourth etc. may be used herein to describe various
elements, components, regions, layers and/or sections, these
elements, components, regions, layers and/or sections should not be
limited by these terms. These terms are only used to distinguish
one element, component, region, layer or section from another
region, layer or section. Thus, a first element, component, region,
layer or section discussed below could be termed a second element,
component, region, layer or section without departing from the
teachings of the present inventive concepts.
[0023] Spatially relative terms, such as "beneath," "below,"
"lower," "above," "upper" and the like, may be used herein for ease
of description to describe one element or feature's relationship to
another element(s) or feature(s) as illustrated in the figures. It
will be understood that the spatially relative terms are intended
to encompass different orientations of the device in use or
operation in addition to the orientation depicted in the figures.
For example, if the device in the figures is turned over, elements
described as "below" or "beneath" other elements or features would
then be oriented "above" the other elements or features. Thus, the
example term "below" can encompass both an orientation of above and
below. The device may be otherwise oriented (rotated 90 degrees or
at other orientations) and the spatially relative descriptors used
herein interpreted accordingly.
[0024] The terminology used herein is for the purpose of describing
particular example embodiments only and is not intended to be
limiting of the present inventive concepts. As used herein, the
singular forms "a," "an" and "the" are intended to include the
plural forms as well, unless the context clearly indicates
otherwise. It will be further understood that the terms
"comprises", "includes", "including" and/or "comprising," when used
in this specification, specify the presence of stated features,
integers, steps, operations, elements, and/or components, but do
not preclude the presence or addition of one or more other
features, integers, steps, operations, elements, components, and/or
groups thereof.
[0025] Example embodiments are described herein with reference to
cross-sectional illustrations that are schematic illustrations of
idealized example embodiments (and intermediate structures). As
such, variations from the shapes of the illustrations as a result,
for example, of manufacturing techniques and/or tolerances, are to
be expected. Thus, example embodiments should not be construed as
limited to the particular shapes of regions illustrated herein but
are to include deviations in shapes that result, for example, from
manufacturing. For example, an implanted region illustrated as a
rectangle will, typically, have rounded or curved features and/or a
gradient of implant concentration at its edges rather than a binary
change from implanted to non-implanted region. Likewise, a buried
region formed by implantation may result in some implantation in
the region between the buried region and the surface through which
the implantation takes place. Thus, the regions illustrated in the
figures are schematic in nature and their shapes are not intended
to illustrate the actual shape of a region of a device and are not
intended to limit the scope of the present inventive concepts.
[0026] Unless otherwise defined, all terms (including technical and
scientific terms) used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which the
inventive concepts belong. It will be further understood that
terms, such as those defined in commonly used dictionaries, should
be interpreted as having a meaning that is consistent with their
meaning in the context of the relevant art and will not be
interpreted in an idealized or overly formal sense unless expressly
so defined herein.
[0027] Hereinafter, a hardmask composition according to example
embodiments and a method of forming a pattern using the hardmask
composition will be described in detail.
[0028] According to example embodiments, a hardmask composition
includes i) a first material including one of an aromatic
ring-containing monomer and a polymer containing a repeating unit
including an aromatic ring-containing monomer, ii) a second
material including one of a hexagonal boron nitride, a
chalcogenide-based material, a two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen, and
their precursors, and iii) a solvent.
[0029] The first material may be bound to the second material by a
chemical bond. In this regard, the first material and the second
material bound by a chemical bond have a complex structure.
[0030] The first material and the second material having the
functional group described above may be connected by a chemical
bond through a chemical reaction.
[0031] The chemical bond may be, for example, a covalent bond.
Here, an example of the covalent bond may include at least one of
an ester group (--C(.dbd.O)O--), an ether group (--O--), a
thioether group (--S--), a carbonyl group (--C).dbd.O)O--), and an
amide group (--C(.dbd.O)NH--).
[0032] The first material and the second material may include at
least one of a hydroxyl group, a carboxyl group, an amino group,
--Si(R.sub.1)(R.sub.2)(R.sub.3) (where, R.sub.1, R.sub.2, and
R.sub.3 are each independently a hydrogen atom, a hydroxyl group, a
C.sub.1-C.sub.30 alkyl group, a C.sub.1-C.sub.30 alkoxy group, a
C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30 aryloxy group, or a
halogen atom), a thiol group (--SH), --Cl, --C(.dbd.O)Cl,
--SCH.sub.3, a glycidyloxy group, a halogen atom, an isocyanate
group, an aldehyde group, an epoxy group, an imino group, an
urethane group, an ester group, an amide group, an imide group, an
acryl group, a methacryl group, a nitro group, --HSO.sub.3,
--(CH.sub.2).sub.nCOOH (where, n is an integer of 1 to 10),
--CONH.sub.2, a substituted or unsubstituted C.sub.1-C.sub.30
saturated organic group, and a substituted or unsubstituted
C.sub.1-C.sub.30 unsaturated organic group.
[0033] In example embodiments, the C.sub.1-C.sub.30 saturated
organic group and the C.sub.1-C.sub.30 unsaturated organic group
may have a hydroxyl group, a carboxyl group, an amino group,
--Si(R.sub.1)(R.sub.2)(R.sub.3) (where, each of R.sub.1, R.sub.2,
and R.sub.3 are independently one of a hydrogen atom, a hydroxyl
group, a C.sub.1-C.sub.30 alkyl group, a C.sub.1-C.sub.30 alkoxy
group, a C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30 aryloxy
group, or a halogen atom), a thiol group (--SH), --Cl,
--C(.dbd.O)Cl, --SCH.sub.3, a glycidyloxy group, a halogen atom, an
isocyanate group an aldehyde group, an epoxy group, an imino group,
an urethane group, an ester group, an amide group, an imide group,
an acryl group, a methacryl group, a nitro group, --HSO.sub.3,
--(CH.sub.2).sub.nCOOH (where, n is an integer of 1 to 10),
--CONH.sub.2, and a photosensitive functional group.
[0034] The aromatic ring-containing monomer is at least one of a
monomer represented by Formula 1 and a monomer represented by
Formula 2:
##STR00001##
[0035] In Formula 1, R is a mono-substituted or a multi-substituted
substituent that is at least one of a hydrogen atom, a halogen
atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a
carboxyl group, an aldehyde group, an amino group, a siloxane
group, an epoxy group, an imino group, an urethane group, an ester
group, an epoxy group, an amide group, an imide group, an acryl
group, a methacryl group, a nitro group, --HSO.sub.3, a substituted
or unsubstituted C.sub.1-C.sub.30 saturated organic group, and a
substituted or unsubstituted C.sub.1-C.sub.30 unsaturated organic
group.
[0036] R may be a general photosensitive functional group as well
as the groups listed above.
[0037] The C.sub.1-C.sub.30 saturated organic group and the
C.sub.1-C.sub.30 unsaturated organic group may have a
photosensitive functional group. Here, examples of the
photosensitive functional group may be an epoxy group, an amide
group, an imide group, an urethane group, and an aldehyde
group.
[0038] Examples of the C.sub.1-C.sub.30 saturated organic group and
the C.sub.1-C.sub.30 unsaturated organic group may be a substituted
or unsubstituted C.sub.1-C.sub.30 alkyl group, a substituted or
unsubstituted C.sub.1-C.sub.30 alkoxy group, a substituted or
unsubstituted C.sub.2-C.sub.30 alkenyl group, a substituted or
unsubstituted C.sub.2-C.sub.30 alkynyl group, a substituted or
unsubstituted C.sub.6-C.sub.30 aryl group, a substituted or
unsubstituted C.sub.6-C.sub.30 aryloxy group, a substituted or
unsubstituted C.sub.2-C.sub.30 heteroaryl group, a substituted or
unsubstituted C.sub.2-C.sub.30 heteroaryloxy group, a substituted
or unsubstituted C.sub.4-C.sub.30 carbon-ring group, a substituted
or unsubstituted C.sub.4-C.sub.30 carbon-ring oxy group, and a
substituted or unsubstituted C.sub.2-C.sub.30 hetero-ring
group.
[0039] In Formula 1, a binding site of R is not limited. Also, the
number of R in Formula 1 is one for convenience of description, but
R may be substituted to at any site where every substitution is
possible.
A-L-A' [Formula 2]
[0040] In Formula 2, each of A and A' are identical to or different
from each other and are independently a monovalent organic group
derived from one of the monomers represented by Formula 1; and
[0041] L is a linker single bond including one of a substituted or
unsubstituted C.sub.1-C.sub.30 alkylene group, a substituted or
unsubstituted C.sub.2-C.sub.30 alkenylene group, a substituted or
unsubstituted C.sub.2-C.sub.30 alkynylene group, a substituted or
unsubstituted C.sub.7-C.sub.30 arylenealkylene group, a substituted
or unsubstituted C.sub.6-C.sub.30 arylene group, a substituted or
unsubstituted C.sub.2-C.sub.30 heteroarylene group, a substituted
or unsubstituted C.sub.2-C.sub.50 heteroarylenealkylene group, a
substituted or unsubstituted C.sub.1-C.sub.30 alkyleneoxy group, a
substituted or unsubstituted C.sub.7-C.sub.30 arylenealkyleneoxy
group, a substituted or unsubstituted C.sub.6-C.sub.30 aryleneoxy
group, a substituted or unsubstituted C.sub.2-C.sub.30
heteroaryleneoxy group, a substituted or unsubstituted
C.sub.2-C.sub.30 heteroarylenealkyleneoxy group, --C(.dbd.O)--, and
--SO.sub.2.
[0042] In L, the substituted C.sub.1-C.sub.30 alkylene group,
substituted C.sub.2-C.sub.30 alkenylene group, substituted
C.sub.2-C.sub.30 alkynylene group, substituted C.sub.7-C.sub.30
arylenealkylene group, substituted C.sub.6-C.sub.30 arylene group,
substituted C.sub.2-C.sub.30 heteroarylene group, substituted
C.sub.2-C.sub.30 heteroarylenealkylene group, substituted
C.sub.1-C.sub.30 alkyleneoxy group, substituted C.sub.7-C.sub.30
arylenealkyleneoxy group, substituted C.sub.6-C.sub.30 aryleneoxy
group, substituted C.sub.2-C.sub.30 heteroaryleneoxy group, and
substituted C.sub.2-C.sub.30 heteroarylenealkyleneoxy group may be
substituted with i) a photosensitive functional group or ii) at
least one substituent including one of a halogen atom, a hydroxyl
group, an isocyanate group, a glycidyloxy group, a carboxyl group,
an aldehyde group, an amino group, a siloxane group, an epoxy
group, an imino group, an urethane group, an ester group, an epoxy
group, an amide group, an imide group, an acryl group, a methacryl
group, a nitro group, and --HSO.sub.3.
[0043] The first material is at least one of a compound represented
by Formula 3 and a compound represented by Formula 4:
##STR00002##
[0044] In Formula 3, R is as defined in the description of Formula
1.
##STR00003##
[0045] In Formula 4, R is as defined in the description of Formula
1; and
[0046] L is as defined in the description of Formula 2.
[0047] In Formulae 3 and 4 above, a binding site of R is not
limited, and the number of R in Formulae 3 and 4 above is one for
convenience of description, but R may be substituted to at any site
where every substitution is possible.
[0048] A weight average molecular weight of the polymer containing
a repeating unit including an aromatic ring-containing monomer is
about 300 to about 30,000. When a polymer having a weight average
molecular weight within this range is used, a thin film may be
easily formed, and a transparent hardmask may be manufactured.
[0049] In example embodiments, the first material is a compound
represented by Formula 5:
##STR00004##
[0050] In Formula 5, A is a substituted or unsubstituted C.sub.6 to
C.sub.30 arylene group;
[0051] L is a single bond or a substituted or unsubstituted C.sub.1
to C.sub.6 alkylene group; and
[0052] n is an integer of 1 to 5.
[0053] The arylene group is one of the groups of Group 1:
##STR00005##
[0054] In example embodiments, the compound of Formula 5 may be
represented by Formulae 6a to 6c:
##STR00006##
[0055] In Formula 6a, or 6b, each of L.sup.1 to L.sup.4 are
independently one of a single bond and a substituted or
unsubstituted C.sub.1 to C.sub.6 alkylene group.
[0056] The first material is one of the compounds represented by
Formulae 6c to 6e:
##STR00007##
[0057] The first material may be a co-polymer represented by
Formula 7:
##STR00008##
[0058] In Formula 7, R.sub.1 is a C.sub.1-C.sub.10 substituted or
unsubstituted alkylene group; each of R.sub.2, R.sub.3, R.sub.7,
and R.sub.8 are independently one of a hydrogen atom, a hydroxyl
group, a C.sub.1-C.sub.10 linear or branched alkyl group, a
C.sub.4-C.sub.10 cycloalkyl group, a C.sub.1-C.sub.10 alkoxy group,
and a C.sub.6-C.sub.30 aryl group; each of R.sub.4, R.sub.5, and
R.sub.6 are independently one of a hydrogen atom, a hydroxyl group,
a C.sub.1-C.sub.10 alkylether group, and a C.sub.8-C.sub.2
phenyldialkylene ether group; R.sub.9 is one of an C.sub.1-C.sub.10
alkylene group, a C.sub.8-C.sub.20 phenyldialkylene group, and a
C.sub.7-C.sub.20 hydroxyphenylalkylene group; each of x and y are
independently a mole fraction of two repeating units in part A
which is about 0 to about 1, where x+y=1; n is an integer of 1 to
200; and m is an integer of 1 to 200.
[0059] The first material is a polymer represented by Formula 7a,
Formula 7b, or Formula 7c:
##STR00009##
[0060] In Formula 7a, x is 0.2, and y is 0.8.
##STR00010##
[0061] In Formula 7b, x is 0.2, y is 0.8, n=90, and m=10.
##STR00011##
[0062] In Formula 7c, x is 0.2, y is 0.8, n=90, and m=10.
[0063] The first material may be a copolymer represented by Formula
8 or Formula 9:
##STR00012##
[0064] In Formulae 8 and 9, m, n and l are each independently an
integer of 1 to 190; R.sub.1 is one of a hydrogen (--H), a hydroxyl
group (--OH), a C1-C10 alkyl group, a C6-C10 aryl group, allyl
group, and a halogen atom; R.sub.2 is one of a group represented by
Formula 9A, a phenyl, a chrysene, a pyrene, a fluoroanthene, an
anthrone, a benzophenone, a thioxanthone, an anthracene, and their
derivatives; R.sub.3 is a conjugated diene; and R is an unsaturated
dienophile.
##STR00013##
[0065] In Formula 9A, R.sub.3 is 1,3-butadienyl group or a
1,6-cyclopentadienylmethyl, and R.sub.4 is a vinyl group or a
cyclopentenylmethyl group.
[0066] In example embodiments, the copolymer may be a polymer
represented by one of Formulae 10 to 12:
##STR00014##
[0067] In Formula 10, m and n are each independently an integer of
1 to 190, for example, m+n=21, A
[0068] The weight average molecular weight (Mw) of the polymer is
about 10,000, and a polydispersity of the polymer is about 2.1.
##STR00015##
[0069] In Formula 11, m and n are each independently an integer of
1 to 190, for example, m+n=21,
The weight average molecular weight of the polymer is about 11,000,
and a polydispersity of the polymer is about 2.1.
##STR00016##
[0070] In Formula 11, m, n and l are each independently an integer
of 1 to 190, for example, l+m+n=21; and n+m:l=2:1.
[0071] The weight average molecular weight of the copolymer is
about 10,000; a polydispersity of the polymer is about 1.9,
##STR00017##
[0072] In Formula 13, n is an integer of 1 to 190, for example, n
is an integer of about 20, The molecular average molecular weight
(Mw) of the polymer is about 10,000; a polydispersity of the
polymer is 2.0.
[0073] In the hardmask composition according to example
embodiments, an example of the second material may be at least one
of a hexagonal boron nitride and its precursor, a
chalcogenide-based material and its precursor, and a
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen and its precursor.
[0074] The chalcogenide-based material is a compound including at
least one of Group 16 (chalcogenide) elements and one or more
electropositive elements. For example, the chalcogenide-based
material includes one or more metal elements including one of
molybdenum (Mo), tungsten (W), niobium (Nb), vanadium (V), tantalum
(Ta), titanium (Ti), zirconium (Zr), hafnium (Hf), technetium (Tc),
rhenium (Re), copper (Cu), gallium (Ga), indium (In), tin (Sn),
germanium (Ge), and lead (Pb) and one chalcogenide element
including one of sulfur (S), selenium (Se), and tellurium (Te).
[0075] The chalcogenide-based material is one of molybdenum sulfide
(MoS.sub.2), tungsten sulfide (WS.sub.2), molybdenum selenide
(MoSe.sub.2), molybdenum telluride (MoTe.sub.2), tungsten selenide
(WSe.sub.2), and tungsten telluride (WTe.sub.2). In example
embodiments, the chalcogenide-based material may be molybdenum
sulfide (MoS.sub.2).
[0076] The metal chalcogenide-based material has a structure
including two chalcogenide atomic layers one of which is disposed
above and the other below a metal atom as a unit structure and thus
has semiconductor characteristics.
[0077] The chalcogenide-based material may be obtained using a
vapor deposition method or ultrasonic waves.
[0078] The vapor deposition method may be performed by sputtering a
chalcogenide-based source or by annealing process through
heat-treatment while providing sulfur to a metal oxide. Here, an
example of the metal oxide may be a molybdenum oxide or a tungsten
oxide, and an example of the chalcogenide-based material may be a
molybdenum sulfide or a tungsten sulfide. Alternatively, the vapor
deposition method may be performed by annealing process through
heat-treatment while providing sulfur to a precursor, such as
(NH.sub.4).sub.2MoS.sub.4.
[0079] In example embodiments, the annealing process may be
performed at a temperature in a range of about 300.degree. C. to
about 2,000.degree. C. Then, a further annealing process may be
performed, through additional heat-treatment.
[0080] According to the method using ultrasonic waves, the
chalcogenide-based material is obtained by performing an
intercalation process of an alkali metal on a bulk plate source;
preparing a layered structure, in which nanolevel-thin metal
chalcogenide sheets are stacked in layers, using an ultrasound
method; separating or detaching the layered structure to form a
single layer or multiple layers of a metal chalcogenide solution.
Here, a dispersant may be used to increase a concentration of the
metal chalcogenide solution.
[0081] For example, a thickness of the metal chalcogenide sheet
according to example embodiments may be in a range of about 0.67 nm
to about 200 nm. The hexagonal boron nitride may have a layered
structure including one layer to three hundred layers, for example,
one layer to 10 layers. For example, the hexagonal boron nitride
may be stable in a single layer.
[0082] The hexagonal boron nitride has a flat hexagonal crystal
structure, the vertices of which are occupied alternatively by
boron and nitrogen atoms. A layered structure of the hexagonal
boron nitride is a structure in which a boron atom and a nitrogen
atom neighboring each other are overlapped due to their polarities,
where the structure is also referred to as "an AB stacking". Here,
the hexagonal boron nitride may have a layered structure, in which
nanolevel-thin sheets are stacked in layers, and the layered
structure may be separated or detached to form a single layer or
multiple layers of a hexagonal boron nitride sheet.
[0083] The hexagonal boron nitride is inactive in an oxidation
atmosphere, and the separated or exfoliated hexagonal boron nitride
sheet has improved thermal characteristics and electric insulation
properties.
[0084] A method of forming a hexagonal boron nitride in a form of a
thin sheet may include performing a chemical vapor deposition
method on a metal surface or a method using ultrasonic waves.
[0085] When the chemical vapor deposition method performed on a
metal surface is used, a two-dimensional hexagonal boron nitride
nanostructure may be formed on the metal surface and may be formed
at a desired location using a transfer method.
[0086] When the method using ultrasonic waves is used, multiple
layers of the hexagonal boron nitride are obtained by dispersing a
hexagonal boron nitride single crystal in an organic solvent, such
as 1,2-dichloroethane, N-methylpyrrolidone, or isopropylalcohol,
and treating the multiple layers with ultrasonic waves. A
dispersant may be used to disperse a hexagonal boron nitride single
crystal in an organic solvent.
[0087] As used herein, the term "hexagonal boron nitride" denotes a
compound of an arbitrary solid form or crystallite size. A typical
form of the hexagonal boron nitride includes a powder or a single
crystal but is not limited thereto. A typical crystallite size of
the hexagonal boron nitride is several nanometers to several tens
of micrometers, and when the hexagonal boron nitride is a single
crystal, the crystallite size of the hexagonal boron nitride is up
to several millimeters.
[0088] The commercially available hexagonal boron nitride powder
may be purchased and used as it is. Alternatively, the hexagonal
boron nitride powder may be prepared by performing mechanical
pulverization by directly milling the hexagonal boron nitride in a
ball mill or treating the hexagonal boron nitride with ultrasonic
waves in a solvent. Also, at least one organic functional group
including one of a hydroxyl group, an amino group, an amide group,
a carboxyl group, a sulfonic acid, --HSO.sub.3, a nitro group
(--NO.sub.2), --CH.sub.2COOH, and --CHNH.sub.2 may be added to the
hexagonal boron nitride. Here, a method of adding the organic
functional group to the hexagonal boron nitride may be performed in
almost the same manner as used in the method of adding a functional
group to the two-dimensional carbon nanostructure. For example,
introducing a functional group to the hexagonal boron nitride may
be performed by supplying a raw material gas, which provides a
functional group, to a bulk hexagonal boron nitride contained in a
reactor, e.g., an autoclave. Here, a temperature of the reactor may
be, for example, in a range of about 80.degree. C. to about
300.degree. C., and the raw material gas may be at least one of
H.sub.2O.sub.2, NH.sub.3, N.sub.2H.sub.4, oleum, and a mixture of
sulfuric acid and nitric acid. An amount of introducing the raw
material gas to the hexagonal boron nitride may be about 1 part by
weight to 100 parts by weight based on 1 part by weight of the
hexagonal boron nitride.
[0089] A thickness of the hexagonal boron nitride sheet according
to example embodiments may be, for example, in a range of about
0.34 nm to about 100 nm. The hexagonal boron nitride may have a
layered structure including one layer to three hundred layers, for
example, one layer to 10 layers. For example, in general, the
hexagonal boron nitride may be stable in a single layer.
[0090] In the hardmask composition according to example
embodiments, a two-dimensional material that may form a chemical
bond with the polymer including an aromatic ring-containing monomer
includes at least one of a two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen and a
precursor of the two-dimensional carbon nanostructure.
[0091] As used herein, the term "two-dimensional carbon
nanostructure" refers to a sheet structure of a single atomic layer
formed by a carbon structure that forms polycyclic aromatic
molecules in which a plurality of carbon atoms are covalently bound
to one another and aligned into a planar shape, a network structure
in which a plurality of carbon structures each having a plate shape
of a small piece of film are interconnected and aligned into a
planar shape, or a combination thereof. The covalently bound carbon
atoms form repeating units that comprise 6-membered rings but may
also form 5-membered rings and/or 7-membered rings. The carbon
structure may be formed by stacking a plurality of layers including
several sheet structures and/or network structures, and an average
thickness of the carbon structure may be about 100 nm or less, for
example, about 10 nm or less, or in a range of about 0.01 nm to
about 10 nm.
[0092] The two-dimensional carbon nanostructure according to
example embodiments may include oxygen atoms in addition to carbon
atoms rather than being a complete C.dbd.C/C--C conjugated
structure. Also, the two-dimensional carbon nanostructure may have
a carboxyl group, a hydroxyl group, an epoxy group, or a carbonyl
group at its end. Also, the two-dimensional carbon nanostructure
and its precursor may include at least one functional group
including one of a hydroxyl group, a carboxyl group, an amino
group, --Si(R.sub.1)(R.sub.2)(R.sub.3) (where, each of R.sub.1,
R.sub.2, and R.sub.3 are independently one of a hydrogen atom, a
hydroxyl group, a C.sub.1-C.sub.30 alkyl group, a C.sub.1-C.sub.30
alkoxy group, a C.sub.6-C.sub.30 aryl group, a C.sub.6-C.sub.30
aryloxy group, or a halogen atom), a thiol group (--SH), --Cl,
--C(.dbd.O)Cl, --SCH.sub.3, a glycidyloxy group, a halogen atom,
--(CH.sub.2).sub.nCOOH (where, n is an integer of 1 to 10),
--CONH.sub.2, an isocyanate group, an aldehyde group, an epoxy
group, an imino group, an urethane group, an ester group, an amide
group, an imide group, an acryl group, a methacryl group, a nitro
group, --HSO.sub.3, a C.sub.1-C.sub.30 saturated organic group
having a photosensitive functional group, and a C.sub.1-C.sub.30
unsaturated organic group having a photosensitive functional group
in order to be bonded with the first material through a chemical
bond.
[0093] In example embodiments, examples of a method of introducing
the functional group to the two-dimensional carbon nanostructure
and its precursor may include an oxidation process using at least
one of a strong acid and an oxidizing agent, an electrochemical
modification method, and a surface modification reaction using a
modifier.
[0094] The strong acid may be at least one of nitric acid and
sulfuric acid, and the oxidizing agent may be one of
H.sub.2O.sub.2, KMnO.sub.4, and KClO.sub.4. For example, the
oxidation process may be performed by treating the reactants with
ultrasonic waves via a stirring process at room temperature.
[0095] Examples of the modifier may include potassium hydroxide,
alkylchloride, H.sub.2S, ammonia, chlorine (Cl.sub.2), COCl.sub.2
(solid), CO (gas), and CH.sub.3SH (gas).
[0096] A general introduction method may be used as well as the
method of introducing the functional group to the two-dimensional
carbon nanostructure and its precursor. An oxygen content of the
two-dimensional carbon nanostructure may be, for example, in a
range of about 6 atom % to about 20 atom %, for example, about 10
atom % to about 15 atom %. In the two-dimensional carbon
nanostructure, the oxygen content may be confirmed by, for example,
an X-ray Photoelectron Spectroscopy (XPS) analysis.
[0097] When an oxygen content is less than 0.01 atom % in the
two-dimensional carbon nanostructure, a bond with an aromatic ring
compound may not be formed, and when an oxygen content is higher
than 40 atom %, degassing may occur during an etching process.
[0098] The two-dimensional carbon nanostructure has an oxygen
content within the ranges described above, and thus may have
hydrophilic property so that a bonding strength to another layer
may improve. Also, a dispersing property of the two-dimensional
carbon nanostructure in a solvent may improve, and thus the
hardmask composition may be easily prepared. In addition, due to
the high bond-dissociation energy of a functional group including
an oxygen atom, etching resistance to an etching gas may
improve.
[0099] The two-dimensional carbon nanostructure according to
example embodiments may have peaks observed at about 1340 cm.sup.-1
to about 1350 cm.sup.-1, about 1580 cm.sup.-1, and about 2700
cm.sup.-1 in Raman spectrum analysis. The peaks provide information
of a thickness, a crystallinity, and a charge doping status of the
two-dimensional carbon nanostructure. The peak observed at about
1580 cm.sup.-1 is a "G mode" peak, which is generated by a
vibration mode corresponding to stretching of a carbon-carbon bond.
Energy of the "G mode" is determined by a density of excess charge
doped in the two-dimensional carbon nanostructure. Also, the peak
observed at about 2700 cm.sup.-1 is a "2D mode" peak that is useful
in the evaluation of a thickness of the two-dimensional carbon
nanostructure. The peak observed at about 1340 cm.sup.-1 to about
1350 cm.sup.-1 was a "D mode" peak, which appears when an sp.sup.2
crystal structure has defects and is mainly observed when many
defects are found around edges of a sample or in the sample itself.
Also, a ratio of a D peak intensity to a G peak intensity (an DIG
intensity ratio) provides information of a degree of disorder of
crystals of the two-dimensional carbon nanostructure.
[0100] An intensity ratio (I.sub.D/I.sub.G) of a D mode peak to a G
mode peak obtained from Raman spectroscopy analysis of the
two-dimensional carbon nanostructure is 2 or lower. For example,
the intensity ratio (I.sub.D/I.sub.G) is within a range of about
0.001 to about 2.0. An intensity ratio (I.sub.D/I.sub.G) of a D
mode peak to a G mode peak obtained from Raman spectroscopy
analysis of the two-dimensional carbon nanostructure precursor is 2
or lower. For example, the intensity ratio (I.sub.D/I.sub.G) is
within a range of about 0.001 to about 2.0.
[0101] An intensity ratio (I.sub.2D/I.sub.G) of a 2D mode peak to a
G mode peak obtained from Raman spectroscopy analysis of the
two-dimensional carbon nanostructure is 0.01 or higher. For
example, the intensity ratio (I.sub.2D/I.sub.G) is within a range
of about 0.01 to about 1.0, or about 0.05 to about 0.5.
[0102] An intensity ratio (I.sub.2D/I.sub.G) of a 2D mode peak to a
G mode peak obtained from Raman spectroscopy analysis of the
two-dimensional carbon nanostructure precursor is 0.01 or higher.
For example, the intensity ratio (I.sub.2D/I.sub.G) is within a
range of about 0.01 to about 1.0, or about 0.05 to about 0.5.
[0103] When the intensity ratio of a D mode peak to a G mode peak
and the intensity ratio of a 2D mode peak to a G mode peak are
within the ranges above, the two-dimensional carbon nanostructure
may have a high crystallinity and a small defect, and thus a
bonding energy increases so that a hardmask prepared using the
two-dimensional carbon nanostructure may have improved etching
resistance.
[0104] X-ray diffraction analysis using CuK.alpha. is performed on
the two-dimensional carbon nanostructure, and as the result of the
X-ray analysis, the two-dimensional carbon nanostructure may
include a two-dimensional layered structure having a (002) crystal
face peak. The (002) crystal face peak is observed with a
diffraction angle within a range of about 20.degree. to about
27.degree..
[0105] A d-spacing of the two-dimensional carbon nanostructure
obtained from the X-ray diffraction analysis is in a range of about
0.3 to about 0.7, for example, about 0.334 to about 0.478. In
addition, an average particle diameter of the crystals obtained
from the X-ray diffraction analysis is about 1 nm or greater, or
for example, in a range of about 23.7 .ANG. to about 43.9 .ANG..
When the d-spacing is within is range, the hardmask composition may
have improved etching resistance.
[0106] The two-dimensional carbon nanostructure is formed as a
single layer of two-dimensional nanocrystalline carbon or it is
formed by stacking multiple layers of two-dimensional
nanocrystalline carbon.
[0107] The two-dimensional carbon nanostructure according to
example embodiments has a higher content of sp.sup.2 carbon than
that of sp.sup.3 carbon and a high content of oxygen compared to a
conventional amorphous carbon layer. An sp.sup.2 carbon bond (that
is, a bond of an aromatic structure) has a higher bonding energy
than that of an sp.sup.3 carbon bond.
[0108] The sp.sup.3 structure is a 3-dimensional bonding structure
of diamond having a tetrahedral shape, and the sp.sup.2 structure
is a two-dimensional bonding structure of graphite in which a
carbon to hydrogen ratio (a C/H ratio) increases and thus may
secure resistance to dry etching.
[0109] In the two-dimensional carbon nanostructure, an sp.sup.2
carbon fraction is equal to or a multiple of an sp.sup.3 carbon
fraction. For example, an sp.sup.2 carbon fraction is a multiple of
an sp.sup.3 carbon fraction by about 1.0 to about 10, or by about
1.88 to 3.42.
[0110] An amount of the sp.sup.2 carbon atom bonding structure is
about 30 atom % or more, for example, about 39.7 atom % to about
62.5 atom %, in the C1s XPS analysis. Due to the mixing ratio, bond
breakage of the two-dimensional carbon nanostructure may be
difficult since carbon-carbon bond energy is high. Thus, when a
hardmask composition including the two-dimensional carbon
nanostructure is used, etching resistance characteristics during
the etching process may improve. Also, a bond strength between the
hardmask and adjacent layers may increase.
[0111] A hardmask obtained using conventional amorphous carbon
mainly includes a sp.sup.2-centered carbon atom binding structure
and thus may have improved etching resistance and low transparency.
Therefore, when the hardmasks are aligned, problems may occur, and
particles may be generated during a deposition process, and thus a
hardmask manufactured using a diamond-like carbon having a
sp.sup.3-carbon atom binding structure has been developed. However,
the hardmask has low etching resistance and thus has a limit in
process application.
[0112] The two-dimensional carbon nanostructure according to
example embodiments has improved transparency and etching
resistance.
[0113] The two-dimensional carbon nanostructure according to
example embodiments has crystallinity in a C-axis (a vertical
direction of the layer) and an average particle diameter of about 1
nm or higher as in the result of XRD analysis. An average particle
diameter of the crystals may be, for example, in a range of about
1.0 .ANG. to about 1000 .ANG., or about 23.7 .ANG. to about 43.9
.ANG.. When an average particle diameter of the crystals is within
this range, the hardmask may have improved etching resistance.
[0114] In the hardmask composition, a content of the second
material may be about 0.01 part to about 99.99 parts by weight, for
example, about 0.01 part to about 40.00 parts by weight for a
hardmask composition with respect to which a transparent property
is emphasized, and, for example, about 60 parts to about 99.99
parts by weight for a hardmask composition having an improved
etching resistant property, based on 100 parts by weight of the
total weight of the first material and the second material. When a
content of the second material is within these ranges, the hardmask
composition may have an improved coating property and film-forming
property, and a hardmask formed using the hardmask composition may
have an improved etching resistant property, improved bonding
strength with respect to a neighboring layer, and improved film
stability.
[0115] In the hardmask composition according to example
embodiments, any solvent capable of dissolving or dispersing the
first material and the second material may be used. For example,
the solvent may be at least one of water, an alcohol-based solvent,
and an organic solvent.
[0116] Examples of the alcohol-based solvent may include methanol,
ethanol, and isopropanol, and examples of the organic solvent may
include N,N-dimethylformamide, N-methylpyrrolidone, dichloroethane,
dichlorobenzene, N,N-dimethylsulfoxide, xylene, aniline, propylene
glycol, propylene glycol diacetate, methoxypropanediol,
diethyleneglycol, gamma-butyrolactone, acetylacetone,
cyclohexanone, propylene glycol monomethyl ether acetate,
.gamma.-butyrolactone, dichloroethane, O-dichlorobenzene,
nitromethane, tetrahydrofuran, nitromethane, dimethyl sulfoxide,
nitrobenzene, butyl nitrite, methylcellosolve, ethylcellosolve,
diethylether, diethyleneglycolmethylether,
diethyleneglycolethylether, dipropyleneglycolmethylether, toluene,
xylene, hexane, methylethylketone, methylisoketone,
hydroxymethylcellulose, and heptane.
[0117] An amount of the solvent may be about 100 parts to about
100,000 parts by weight based on 100 parts by weight of the total
weight of the first material and the second material. When an
amount of the solvent is within this range, the hardmask
composition may have an appropriate viscosity and thus may more
easily form a layer.
[0118] The two-dimensional carbon nanostructure precursor may be,
for example, i) expanded graphite obtained from exfoliated graphite
or ii) an oxidation product of acid-treated graphite.
[0119] In the hardmask composition according to example
embodiments, as described above, the first material may be bonded
to the second material through, a chemical bond. Examples of the
chemical bond may be as follows:
[0120] i) The first material and the second material are bonded by
an ester bond due to esterification of the first material, which is
an aromatic ring-containing monomer having a carboxyl group, and
the second material, which is a two-dimensional carbon
nanostructure having a hydroxyl group.
[0121] ii) The first material and the second material are bonded by
an amide bond due to reaction of the first material, which is an
aromatic ring-containing monomer having a carboxyl group, and the
second material, which is a two-dimensional carbon nanostructure
having an amino group.
[0122] iii) The first material and the second material are bonded
by a siloxane bond (--Si--O--) due to dehydration condensation of
the first material, which is an aromatic ring-containing monomer
having --Si(OCH.sub.3).sub.2OH, and the second material, which is a
two-dimensional carbon nanostructure having a hydroxyl group.
[0123] iv) The first material and the second material are bonded by
a siloxane bond (--Si--O--) due to hydrolysis and dehydration
condensation of the first material, which is an aromatic
ring-containing monomer having --Si(CH.sub.3).sub.2OH, and the
second material, which is a two-dimensional carbon nanostructure
having a hydroxyl group.
[0124] A hardmask prepared using the hardmask composition according
to example embodiments is an anti-reflection layer within a deep UV
(DUV) wavelength region, e.g., ArF (about 193 nm) and KrF (about
248 nm). The hardmask has a refractive index and absorbance within
appropriate ranges, and thus a reflective property between a resist
and a lower layer may be reduced. When a patter is formed using the
hardmask composition, the hardmask composition may have a high
etching selection ratio and sufficient resistance to multi-etching
and thus may provide an improved lithographic structure in terms of
pattern profile or margins.
[0125] Hereinafter, a method of preparing a hardmask using the
hardmask composition according to example embodiments will be
described in detail.
[0126] The hardmask composition according to example embodiments
includes i) a first material including one of an aromatic
ring-containing monomer and a polymer containing a repeating unit
including an aromatic ring-containing monomer; ii) a second
material including one of a hexagonal boron nitride, a
chalcogenide-based material, a two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen, and
their precursors; and iii) a solvent.
[0127] The hardmask composition is prepared by dissolving the first
material in the solvent to prepare a first material containing
mixture, and then mixing the first material containing mixture with
a mixture in which the second material is dispersed or
dissolved.
[0128] Examples of the solvent may include solvents, e.g.,
1,2-dichlorobenzene, 1,2-dichloroethane, dimethylformamide,
N-methylpyrrolidone, and ethanol, and water.
[0129] The dispersion may be easily performed by simply mixing with
a mechanical stirrer:
[0130] A hardmask including a polymer containing a repeating unit
including an aromatic ring-containing monomer and at least one of a
hexagonal boron nitride, a chalcogenide-based material, a
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen, and their precursors, where the at
least one of a hexagonal boron nitride, a chalcogenide-based
material, a two-dimensional carbon nanostructure containing about
0.01 atom % to about 40 atom % of oxygen, and their precursors is
connected with the polymer by a chemical bond, is prepared by
coating the hardmask composition including the first material, the
second material, and the solvent on a top surface of a to-be-etched
layer.
[0131] During or after the process of coating the to-be-etched
layer with the hardmask composition, a heat-treating process may be
performed. Conditions for the heat-treating process may vary
depending on a material of the to-be-etched layer, but a
temperature of the heat-treating process may be from room
temperature (about 25.degree. C.) to about 1500.degree. C.
[0132] The heat-treating process is performed in an inert gas
atmosphere or in vacuum.
[0133] A heating source of the heat-treating process may be
induction heating, radiant heat, lasers, infrared rays, microwaves,
plasma, ultraviolet rays, or surface plasmon heating.
[0134] The inert gas atmosphere may be prepared by mixing a
nitrogen gas and/or an argon gas.
[0135] After the heat-treating process, the solvent may be removed.
The resultant from which the solvent is removed may be baked at a
temperature of about 100.degree. C. to about 400.degree. C., and
then another heat-treating process may be performed on the baked
resultant at a temperature of about 400.degree. C. to about
1,000.degree. C.
[0136] When the temperatures of the heat-treating process and the
baking process are within these ranges above, the hardmasks with
improved etching resistance may be prepared.
[0137] A temperature increasing rate in the heat-treating process
and the baking process is about 1.degree. C./min to about
1000.degree. C./min. When a temperature increasing rate is within
this range, the deposited layer may not be damaged due to a rapid
temperature change, and thus a process efficiency may be
improved.
[0138] When the hardmask composition includes the precursor of the
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen, a hardmask may be prepared in a
manner described as follows.
[0139] The two-dimensional carbon nanostructure precursor may be i)
a two-dimensional carbon nanostructure having less than 0.01 atom %
of oxygen or ii) an oxygen free two-dimensional carbon
nanostructure.
[0140] The two-dimensional carbon nanostructure precursor according
to example embodiments may be, for example, expanded graphite
obtained from exfoliated graphite. When expanded graphite is used
as the two-dimensional carbon nanostructure precursor, self
agglomeration of carbon layers constituting the two-dimensional
carbon nanostructure is suppressed, and thus the two-dimensional
carbon nanostructure may be evenly dispersed in the hardmask
composition without adding an additive such as a dispersing agent
or a surfactant so that the hardmask thus prepared may have
improved etching resistance, and a process for removing unnecessary
hardmask patterns after forming a to-be-etched layer pattern may be
easy, where a residue such as a carbon residue may not be produced
in the process.
[0141] In example embodiments, a two-dimensional carbon
nanostructure precursor may have a structure that is formed of
carbon layers obtained by performing a liquid exfoliating process
using a solvent on expanded graphite.
[0142] The carbon layers may include different number of layers,
for example, one layer to three hundred layers. For example, the
carbon layers may include one layer to sixty layers, one layer to
fifteen layers, or one layer to ten layers.
[0143] A hardmask may be prepared by coating with the to-be-etched
layer with the hardmask composition including the two-dimensional
carbon nanostructure precursor and a solvent and then oxidizing or
reducing the coated product.
[0144] A hardmask may be manufactured by coating the to-be-etched
layer with the hardmask composition including the first material,
the second material, which is a precursor of the two-dimensional
carbon nanostructure, and the solvent; and oxidizing or reducing
the coated resultant.
[0145] In example embodiments, before the oxidizing or reducing of
the coated resultant, the coated resultant may be heat-treated for
a reaction of the first material and the second material.
[0146] In example embodiments, a heat-treating process for a
reaction between the first material and the second material may be
further performed in addition to the oxidizing or reducing of the
coated resultant.
[0147] When the two-dimensional carbon nanostructure precursor is a
two-dimensional carbon nanostructure containing more than 40 atom %
of oxygen, the to-be-etched layer may be coated with the hardmask
composition, and then the coated resultant may be reduced to form a
hardmask. The two-dimensional carbon nanostructure containing more
than 40 atom % of oxygen may contain, for example, about 60 atom %
to about 80 atom % of oxygen.
[0148] When the two-dimensional carbon nanostructure precursor
contains less than 0.01 atom % of oxygen, the to-be-etched layer
may be coated with the hardmask composition, and then the coated
resultant may be oxidized to prepare a hardmask.
[0149] The reducing process may be performed by chemical reduction,
heat-treatment reduction, or electrochemical reduction.
[0150] The chemical reduction is performed using a reducing agent.
Also, the reduction caused by heat-treatment may be performed by
heat-treatment at a temperature of about 100.degree. C. to about
1500.degree. C.
[0151] Non-limiting examples of the reducing agent may include at
least one of hydrazine, sodium borohydride, dimethylhydrazine,
sulfuric acid, hydrochloric acid, hydrogen iodide, hydrogen
bromide, hydrogen sulfide, hydroquinone, hydrogen, and acetic
acid.
[0152] The oxidizing process may be performed using at least one of
an acid, an oxidizing agent, UV, ozone, IR, heat-treatment, and
plasma.
[0153] Examples of the acid may include sulfuric acid, nitric acid,
acetic acid, phosphoric acid, hydrofluoric acid, perchloric acid,
trifluoroacetic acid, hydrochloric acid, m-chlorobenzoic acid, and
a mixture thereof. Also, examples of the oxidizing agent may
include potassium permanganate, potassium perchlorate, ammonium
persulfate, and a mixture thereof.
[0154] Hereinafter, a process of preparing a hardmask using the
two-dimensional carbon nanostructure precursor according to example
embodiments or a two-dimensional carbon nanostructure obtained
therefrom will be described in detail.
[0155] First, an interlayer insertion material may be intercalated
into graphite to obtain exfoliated graphite; expanded graphite,
which is a two-dimensional carbon nanostructure, may be obtained
from the exfoliated graphite; and thus a composition including the
two-dimensional carbon nanostructure precursor may be obtained. The
first material is added to the composition.
[0156] The expanded graphite may be obtained in the process of
applying ultrasonic waves or microwaves to the exfoliated graphite
or milling the exfoliated graphite. Here, the process of milling
the exfoliated graphite may be performed using a ball mill or a
mono-planar mill.
[0157] Optionally, a liquid exfoliating process including
dispersion in a solvent may be performed on the expanded graphite.
When the liquid exfoliating process is performed on the expanded
graphite; a two-dimensional carbon nanostructure precursor
including one layer to several tens layers of carbon layer may be
obtained.
[0158] The interlayer insertion material may be at least one of
sulfuric acid, chromic acid, and ions, e.g., potassium or sodium or
an ion-containing compound.
[0159] Examples of the solvent in the liquid exfoliating process
may be 1,2-dichlorobenzene, 1,2-dichloroethane, dimethylformamide,
N-methylpyrrolidone, ethanol, and water. Also, ultrasonic waves may
be used for the dispersion in the liquid exfoliating process. For
example, the dispersion process in the solvent may be performed for
about 0.5 hour to about 30 hours.
[0160] In example embodiments, when the expanded graphite is
obtained by applying ultrasonic waves to the exfoliated graphite, a
frequency of the ultrasonic waves may be in a range of about 20 KHz
to about 60 KHz.
[0161] In example embodiments, when the expanded graphite is
obtained by applying microwaves to the exfoliated graphite, an
output of the microwaves may be about 50 W to about 1500 W, and a
frequency of the microwaves may be in a range of about 2.45 KHz to
about 60 KHz. A period of time for applying the microwaves may vary
depending on the frequency of the microwaves but may be, for
example, about 10 minutes to about 30 minutes.
[0162] Examples of graphite used as a starting material may include
natural graphite, kish graphite, synthetic graphite, expandable
graphite or expanded graphite, and a mixture thereof.
[0163] The hardmask composition thus obtained may be used to form a
two-dimensional carbon nanostructure layer, and then, according to
a process of oxidizing the layer, a hardmask including a
two-dimensional carbon nanostructure having an oxygen content of
about 0.01 atom % to about 40 atom % may be obtained. The
two-dimensional carbon nanostructure layer obtained in this manner
may have no defect, and a hardmask including the two-dimensional
carbon nanostructure layer may have improved etching
resistance.
[0164] Second, the graphite may be acid-treated. For example, an
acid or an oxidizing agent may be added to the graphite, heated to
allow the reaction, and cooled to room temperature (about
25.degree. C.) to obtain a mixture containing a two-dimensional
carbon nanostructure precursor. An oxidizing agent is added to the
precursor-containing mixture to perform an oxidizing process, and
thus a two-dimensional carbon nanostructure having about 0.01 atom
% to about 40 atom % of oxygen may be obtained.
[0165] The two-dimensional carbon nanostructure precursor may
include less than about 0.01 atom % of oxygen or may not contain
oxygen.
[0166] The oxidizing agent, a concentration of an acid solution,
and a treating time in the oxidizing process may be adjusted to
control the oxygen content.
[0167] Examples of the acid and the oxidizing agent are as
described above. An amount of the oxidizing agent may be, for
example, about 0.00001 part to about 30 parts by weight based on
100 parts by weight of the graphite.
[0168] Third, in the second preparation process, the
two-dimensional carbon nanostructure precursor is oxidized to the
maximum to obtain a composition containing a two-dimensional carbon
nanostructure precursor having more than 40 atom % of oxygen, and a
two-dimensional carbon nanostructure precursor layer is formed
using the composition. For example, an oxygen content in the
two-dimensional carbon nanostructure precursor may be about 50 atom
% to about 60 atom %. The layer thus formed may be reduced, and
thus a hardmask containing a two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen may be
prepared.
[0169] The oxidizing process in the preparation process may be
performed using at least one of acid, an oxidizing agent, UV
(ultraviolet), ozone, IR (infrared), heat-treatment, and plasma.
Here, the acid and the oxidizing agent may be as described
above.
[0170] Heat-treatment may be performed during or after the process
of coating the to-be-etched layer with the hardmask composition.
Here, a temperature of the heat-treatment differs depending on a
purpose of the heat-treatment but may be, for example, in a range
of about 100.degree. C. to about 1500.degree. C.
[0171] Hereinafter, in example embodiments, a method of forming a
pattern using a hardmask composition will be described by referring
to FIGS. 1A to 1E.
[0172] Referring to FIG. 1A, a to-be-etched layer 11 is formed on a
substrate 10. A hardmask composition according to example
embodiments is provided on the to-be-etched layer 11 to form a
hardmask 12.
[0173] A process of providing the hardmask composition is performed
by one method including one of spin coating, air spraying,
electrospraying, dip coating, spray coating, doctor blade coating,
and bar coating.
[0174] In example embodiments, the hardmask composition may be
provided using a spin-on coating method. Here, the hardmask
composition may coat the substrate 10 at a thickness of, for
example, in a range of about 10 nm to about 10,000 nm, or, about 10
nm to about 1,000 nm, but the thickness of the hard composition is
not limited thereto.
[0175] A substrate 10 is not particularly limited, and the
substrate may be at least one including one of, for example, a Si
substrate; a glass substrate; a GaN substrate; a silica substrate;
a substrate including at least one of nickel (Ni), cobalt (Co),
iron (Fe), platinum (Pt), palladium (Pd), gold (Au), aluminum (AI),
chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo),
rhodium (Rh), iridium (Ir), tantalum (Ta), titanium (Ti), tungsten
(W), uranium (U), vanadium (V), and zirconium (Zr); and a polymer
substrate.
[0176] A photoresist layer 13 is formed on the hardmask 12.
[0177] As shown in FIG. 1B, a photoresist pattern 13a is formed by
exposing and developing the photoresist layer 13 using a common
method in the art.
[0178] The process of exposing the photoresist layer 13 may be
performed using, for example, ArF, KrF, or EUV. Also, after the
exposing process, a heat-treating process at a temperature in a
range of about 200.degree. C. to about 500.degree. C. may be
performed on the exposed photoresist layer 13.
[0179] In the developing process, a developing solution such as an
aqueous solution of tetramethylammonium hydroxide (TMAH) may be
used.
[0180] Thereafter, the hardmask 12 may be etched using the
photoresist pattern 13a as an etching mask to form a hardmask
pattern 12a on the to-be-etched layer 11 (FIG. 1C).
[0181] A thickness of the hardmask pattern 12a may be in a range of
about 10 nm to about 10,000 nm. When the thickness of the hardmask
pattern 12a is within this range, the layer may have improved
etching resistance as well as improved homogenousness.
[0182] For example, the etching process may be performed using a
dry etching method using an etching gas. Examples of the etching
gas include at least one of CF.sub.4, CHF.sub.3, SF.sub.6,
Cl.sub.2, BCl.sub.3, and O.sub.2.
[0183] In example embodiments, when a mixture gas of C.sub.4F.sub.8
and CHF.sub.3 is used as the etching gas, a mixing ratio of
C.sub.4F.sub.8 and CHF.sub.3 may be in a range of about 1:10 to
about 10:1 at a volume ratio.
[0184] The to-be-etched layer 11 may be formed as a plurality of
patterns. The plurality of patterns may vary, for example, a metal
pattern, a semiconductor pattern, and an insulator pattern. For
example, the plurality of patterns may be various patterns applied
to a semiconductor integrated circuit device.
[0185] The to-be-etched layer 11 may contain a material that is to
be finally patterned. The material of the to-be-etched layer 11 may
be, for example, a metal such as aluminum or copper, a
semiconductor such as silicon, or an insulator such as silicon
oxide or silicon nitride. The to-be-etched layer 11 may be formed
using various methods such as sputtering, electronic beam
deposition, chemical vapor deposition, and physical vapor
deposition. For example, the to-be-etched layer 11 may be formed
using a chemical vapor deposition method.
[0186] As shown in FIGS. 1D to 1E, the to-be-etched layer 11 may be
etched using the hardmask pattern 12a as an etching mask to later
form a to-be-etched layer pattern 11a having a desired fine
pattern.
[0187] The hardmask according to example embodiments may be used as
a stopper in the manufacture of a semiconductor device by being
inserted between other layers.
[0188] Hereinafter, in example embodiments, a method of forming a
pattern using a hardmask composition will be described by referring
to FIGS. 2A to 2D.
[0189] Referring to FIG. 2A, a to-be-etched layer 21 is formed on a
substrate 20.
[0190] The substrate 20 may be a silicon substrate.
[0191] The to-be-etched layer 21 may be formed as, for example, a
silicon oxide layer, a silicon nitride layer, a silicon nitroxide
layer, a silicon carbide (SiC) layer, or a derivative layer
thereof.
[0192] Thereafter, a hardmask composition may be provided on the
to-be-etched layer 21 to form a hardmask 22.
[0193] An anti-reflection layer 30 is formed on the hardmask 22.
Here, the anti-reflection layer 30 may include an inorganic
anti-reflection layer, an organic anti-reflection layer, or a
combination thereof. FIGS. 2A to 2C illustrate cases where the
anti-reflection layer 30 includes an inorganic anti-reflection
layer 32 and an organic anti-reflection layer 34.
[0194] The inorganic anti-reflection layer 32 may be, for example,
a SiON layer, and the organic anti-reflection layer 34 may be a
polymer layer commonly used in the art having an appropriate
refraction index and a high absorption coefficient on a photoresist
with respect to a wavelength of light.
[0195] A thickness of the anti-reflection layer 30 may be, for
example, in a range of about 100 nm to about 500 nm.
[0196] A photoresist layer 23 is formed on the anti-reflection
layer 30.
[0197] The photoresist layer 23 is exposed and developed in a
common manner to form a photoresist pattern 23a. Then, the
anti-reflection layer 30 and the hardmask 22 are sequentially
etched using the photoresist pattern 23a as an etching mask to form
a hardmask pattern 22a on the to-be-etched layer 21. The reflection
inhibition pattern 30a includes an inorganic reflection inhibition
pattern 32a and an organic reflection inhibition pattern 34a.
[0198] FIG. 2B illustrates that the photoresist pattern 23a and a
reflection inhibition pattern 30a remain after forming the hardmask
pattern 22a. However, in example embodiments, a portion of or the
whole photoresist pattern 23a and the reflection inhibition pattern
30a may be removed during the etching process for forming the
hardmask pattern 22a.
[0199] FIG. 2C illustrates that only the photoresist pattern 23a is
removed.
[0200] The to-be-etched layer 21 is etched using the hardmask
pattern 22a as an etching mask to form a desired layer pattern,
which is a to-be-etched layer pattern 21a (FIG. 2D).
[0201] As described above, the hardmask pattern 22a is removed
after forming the to-be-etched layer pattern 21. In the preparation
of the hardmask pattern according to example embodiments, the
hardmask pattern 22a may be more easily removed using a common
method in the art, and almost no residue remains after removing the
hardmask pattern 22a.
[0202] The removing process of the hardmask pattern 22a may be
performed by, but not limited to, O.sub.2 ashing and wet stripping.
For example, the wet stripping may be performed using alcohol,
acetone, or a mixture of nitric acid and sulfuric acid.
[0203] The hardmask formed as described above includes a composite.
The composite includes i) a polymer containing a repeating unit
including an aromatic ring-containing monomer and ii) at least one
of a hexagonal boron nitride, a chalcogenide-based material, and a
two-dimensional carbon nanostructure containing about 0.01 atom %
to about 40 atom % of oxygen, where the at least one of the
hexagonal boron nitride, the chalcogenide-based material, and the
two-dimensional carbon nanostructure is connected to the polymer by
a chemical bond.
[0204] The two-dimensional material is a structure that is formed
by stacking a two-dimensional nanocrystalline material in a
direction of a z-axis. The two-dimensional material may have a
thickness of about 100 nm or less and a length and a width in a
range of about 500 nm to about 50 .mu.m. Also, an aspect ratio (a
ratio of the longest diameter to the shortest diameter) of the
two-dimensional material, such as the two-dimensional carbon
nanostructure, is at least 50.
[0205] The hardmask includes a two-dimensional carbon nanostructure
containing about 0.01 atom % to about 40 atom % of oxygen, and the
amount of sp.sup.2 carbon structures is higher than the amount of
sp.sup.3 carbon structures in the hardmask. Thus, the hardmask may
secure sufficient resistance to dry etching.
[0206] When the hardmask composition according to example
embodiments is used, a transparent property of a thin layer may be
maintained, and thus an additional align mask is not needed. When a
monomer and a polymer are used, a coating property of the hardmask
composition may be improved compared to that of a thin layer of
inorganic flakes, and thus formation of a thin layer and thickness
control may be simplified and a uniform thickness may be formed.
Compared to a polymer or amorphous carbon of the related art, a
hardmask having improved etching resistance and mechanical strength
which may be easily removed after an etching process may be
manufactured. When the hardmask is used, efficiency of a
semiconductor process may be improved.
[0207] According to example embodiments, a pattern formed using a
hardmask composition may be used in the manufacture and design of
an integrated circuit device according to a preparation process of
a semiconductor device. For example, the pattern may be used in the
formation of a patterned material layer structure such as metal
lining, holes for contact or bias, insulation sections (for
example: a Damascene Trench (DT) or shallow trench isolation
(STI)), or a trench for a capacitor structure.
[0208] Hereinafter are definitions of substituents used in the
chemical formulae.
[0209] The term "alkyl" used in a chemical formula refers to a
fully saturated branched or unbranched (or straight chain or
linear) hydrocarbon group.
[0210] Examples of the "alkyl" include methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl,
neopentyl, iso-amyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl,
2,3-dimethyl pentyl, and n-heptyl.
[0211] At least one hydrogen atom in the "alkyl" may be substituted
with a halogen atom, a C.sub.1-C.sub.20 alkyl group (e.g.:
CCF.sub.3, CHCF.sub.2, CH.sub.2F, or CCl.sub.3) substituted with a
halogen atom, a C.sub.1-C.sub.20 alkoxy group, a C.sub.2-C.sub.20
alkoxyalkyl group, a hydroxyl group, a nitro group, a cyano group,
an amino group, an amidino group, a hydrazine group, a hydrazone
group, a carboxylic acid or a salt thereof, a sulfonyl group, a
sulfamoyl group, a sulfonic acid or a salt thereof, a phosphoric
acid or a salt thereof, or a C.sub.1-C.sub.20 alkyl group, a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
C.sub.1-C.sub.20 heteroalkyl group, a C.sub.6-C.sub.20 aryl group,
a C.sub.6-C.sub.20 arylalkyl group, a C.sub.6-C.sub.20 heteroaryl
group, a C.sub.7-C.sub.20 heteroarylalkyl group, a C.sub.6-C.sub.20
heteroaryloxy group, a C.sub.6-C.sub.20 heteroaryloxyalkyl group,
or a C.sub.6-C.sub.20 heteroarylalkyl group
[0212] The term "halogen atom" includes fluorine, bromine,
chlorine, and iodine.
[0213] The term "alkoxy" used in a chemical formula refers to
alkyl-O--, and the alkyl group is as described above. Examples of
the alkoxy include methoxy, ethoxy, propoxy, 2-propoxy, butoxy,
tert-butoxy, pentyloxy, hexyloxy, cyclopropoxy, and cyclohexyloxy.
In the alkoxy group, at least one hydrogen atom may be substituted
with the same substituent groups as described above in connection
with the alkyl group.
[0214] The term "alkenyl" used in a chemical formula refers to a
branched or non-branched hydrocarbon having at least one
carbon-carbon double bond. Examples of the alkenyl group include
vinyl, allyl, butenyl, isopropenyl, and isobutenyl, and at least
one hydrogen atom of the alkenyl group may be substituted with the
same substituent groups as described above in connection with the
alkyl group.
[0215] The term "alkynyl" used in a chemical formula refers to a
branched or non-branched hydrocarbon having at least one
carbon-carbon triple bond. Examples of the alkynyl group include
ethynyl, butynyl, isobutynyl, and isopropynyl. At least one
hydrogen atom of the alkynyl group may be substituted with the same
substituent groups as described above in connection with the alkyl
group.
[0216] The term "aryl" used in a chemical formula refers to an
aromatic hydrocarbon that may be used alone or in a combination and
includes at least one ring.
[0217] The term "aryl" includes a group, wherein aromatic rings are
fused in one or more cycloalkyl rings.
[0218] Examples of the aryl may be phenyl, naphthyl, and
tetrahydronaphthyl.
[0219] Also, at least one hydrogen atom in the aryl group may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0220] The term "arylalkyl" used in a chemical formula refers to an
alkyl group substituted with an aryl group. Examples of the
arylakyl include benzyl and phenyl-CH.sub.2CH.sub.2.
[0221] The term "aryloxy" used in a chemical formula refers to
O-aryl, and examples of the aryloxy group include phenoxy. At least
one hydrogen atom in the aryl group may be substituted with the
same substituent groups as described above in connection with the
alkyl group.
[0222] The term "heteroaryl" used in a chemical formula refers to a
monocyclic or bicyclic organic compound including at least one
heteroatom including one of N, O, P, and S, and the remaining ring
atoms are C. For example, the heteroaryl group may include 1 to 5
heteroatoms and may include 5 to 10 ring members, wherein S or N
may be oxidized to various oxidation states.
[0223] Examples of a monocyclic heteroaryl group include thienyl,
puryl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl,
1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl,
1,3,4-oxadiazoly, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl,
1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl,
isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl,
oxazol-5-yl, isooxazol-3-yl, isooxazol-4-yl, isooxazol-5-yl,
1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,3-triazol-4-yl,
1,2,3-triazol-5-yl, tetrazolyl, pyrid-2-yl, pyrid-3-yl,
2-pyrazin-2-yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl,
4-pyrimidin-2-yl, or 5-pyrimidin-2-yl.
[0224] The term "heteroaryl" used in a chemical formula refers to a
heteroaromatic ring that is fused in one or more of aryl,
cyclyaliphatic, or heterocycle.
[0225] Examples of a bicyclic heteroaryl group include indolyl,
isoindolyl, indazolyl, indolizinyl, purinyl, quinolizinyl,
quinolinyl, and isoquinolinyl.
[0226] At least one hydrogen atom in the heteroaryl group may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0227] The term "heteroarylalkyl" refers to an alkyl group
substituted with heteroaryl.
[0228] The term "heteroaryloxy" refers to an O-heteroaryl moiety.
At least one hydrogen atom in the heteroaryloxy group may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0229] The term "heteroaryloxyalkyl" denotes an alkyl group
substituted with heteroaryloxy. At least one hydrogen atom in the
heteroaryloxyalkyl group may be substituted with the same
substituent groups as described above in connection with the alkyl
group.
[0230] The term "carbon ring" used in a chemical formula refers to
a saturated or partially unsaturated non-aromatic monocyclic,
bicyclic, or tricyclic hydrocarbon group.
[0231] Examples of the monocyclic hydrocarbon group include
cyclopentyl, cyclopentenyl, cyclohexyl, and cyclohexenyl.
[0232] Examples of the bicyclic hydrocarbon group include
bicyclo[2.1.1]hexyl.
[0233] Examples of the tricyclic hydrocarbon include adamantly.
[0234] At least one hydrogen atom in the "carbon ring" may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0235] The term "a hetero-ring group" used in a chemical formula
refers to a ring group composed of 5 to 10 atoms containing a
heteroatom, such as nitrogen, sulfur, phosphor, or oxygen. In
particular, an example of the hetero-ring group is pyridyl, and at
least one hydrogen atom in the "hetero-ring group" may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0236] The term "hetero-ring-oxy" refers to an O-hetero-ring, and
at least one hydrogen atom in the "hetero-ring-oxy" group may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0237] The term "sulfonyl" denotes R''--SO.sub.2, wherein, R'' is a
hydrogen atom, alkyl, aryl, heteroaryl, aryl-alkyl,
heteroaryl-alkyl, alkoxy, aryloxy, cycloalkyl group, or a
hetero-ring group.
[0238] The term "sulfamoyl" denotes H.sub.2NS(O.sub.2)--,
alkyl-NHS(O.sub.2)--, (alkyl).sub.2NS(O.sub.2)-aryl-NHS(O.sub.2)--,
alkyl-(aryl)-NS(O.sub.2)--, (aryl).sub.2NS(O).sub.2,
heteroaryl-NHS(O.sub.2)--, (aryl-alkyl)-NHS(O.sub.2)--, or
(heteroaryl-alkyl)-NHS(O.sub.2)--.
[0239] At least one hydrogen atom in the "sulfamoyl group" may be
substituted with the same substituent groups as described above in
connection with the alkyl group.
[0240] The term "amino group" includes a nitrogen atom that is
covalently bonded to at least one carbon atom or heteroatom. The
amino group includes --NH.sub.2 and substituted moieties.
[0241] Also, examples of the amino group include an alkylamino
group, in which a nitrogen atom is bonded to at least one
additional alkyl group, and an aryl amino group or a diarylamino
group, in which a nitrogen atom is bonded to at least one or two
independently selected aryl groups.
[0242] The terms "alkylene", "alkenylene", "alkynylene", "arylene",
and "heteroarylene" are, each respectively, as defined in "alkyl",
"alkenyl", "alkynyl", "aryl", and "heteroaryl", except that
monovalent groups of the "alkyl", "alkenyl", "alkynyl", "aryl", and
"heteroaryl" are replaced with divalent groups.
[0243] A least one hydrogen atom in the "alkyl", "alkenyl",
"alkynyl", "aryl", and "heteroaryl" may be substituted with the
same substituent groups as described above in connection with the
alkyl group.
[0244] Hereinafter, the present disclosure will be described in
further detail with reference to the following examples. These
examples are for illustrative purposes only and are not intended to
limit the scope of the present inventive concepts.
Preparation Example 1
Preparation of Hexagonal Boron Nitride to which Hydroxyl (--OH)
Functional Group is Bonded
[0245] 100 mg of a bulk of a hexagonal boron nitride (h-BN)
(available from Industrial Supply, Inc.) and 10 ml of a 30 wt %
H.sub.2O.sub.2 solution were placed in an autoclave, and a
temperature of the autoclave was increased to 100.degree. C., and
the mixture was allowed to react for about 12 hours or more. When
the reaction was completed, the resultant was filtered, and thus a
hexagonal boron nitride (h-BN), to which a hydroxyl group (--OH)
was bonded, was obtained from the H.sub.2O.sub.2 solution.
Preparation Example 1a
Preparation of Hexagonal Boron Nitride to which Nitro Group
(NO.sub.2) and --HSO.sub.3 Functional Group are Bonded
[0246] A hexagonal boron nitride (h-BN), to which a nitro group
(NO.sub.2) and --HSO.sub.3 functional group were bonded, was
obtained in the same manner as in Preparation Example 1, except
that 10 ml of a mixture of a nitric acid and a sulfuric acid at a
weight ratio of 1:3 was used instead of 10 ml of the 30 wt %
H.sub.2O.sub.2 solution.
Preparation Example 1b
Preparation of Hexagonal Boron Nitride to which --HSO.sub.3
Functional Group is Bonded
[0247] A hexagonal boron nitride (h-BN), to which --HSO.sub.3
functional group was bonded, was obtained in the same manner as in
Preparation Example 1, except that 10 ml of oleum was used instead
of 10 ml of the 30 wt % H.sub.2O.sub.2 solution.
Preparation Example 2
Preparation of Hexagonal Boron Nitride to which --NH.sub.2
Functional Group is Bonded
[0248] 100 mg of h-BN and 10 ml of a hydrazine (N.sub.2H.sub.4)
solution was placed in an autoclave, and a temperature was
increased to 100.degree. C., and the mixture was allowed to react
for about 12 hours or more. When the reaction was completed, the
resultant was filtered, and thus a hexagonal boron nitride (h-BN),
to which --NH.sub.2 was bonded, was obtained from the
N.sub.2H.sub.4 solution.
Preparation Example 2a
Preparation of Hexagonal Boron Nitride to which --NH.sub.2
Functional Group is Bonded
[0249] 100 mg of h-BN was loaded in a microwave plasma chamber, 10
sccm of NH.sub.3 was flowed thereto, 200 W of power was applied
thereto, and then the resultant was treated at room temperature
(about 25.degree. C.) for 10 minutes. When the reaction was
completed, a h-BN, to which --NH.sub.2 was bonded, was
obtained.
Preparation Example 3
Preparation of Hexagonal Boron Nitride to which --(CH.sub.2)_COOH
is Bonded
[0250] 100 mg of h-BN was dispersed in THF in a flask, 100 ml of
glutaric acid acyl peroxide
(HOOC--(CH.sub.2).sub.3--C.dbd.OO--OO.dbd.C--(CH.sub.2).sub.3--COOH)
was injected thereto, and the resultant was heated for 12 hours at
a temperature of 80.degree. C. During the reaction, CO.sub.2 was
removed, and the resultant was filtered to obtain a h-BN, to which
--(CH.sub.2).sub.3COOH was bonded.
Preparation Example 4
Preparation of Hexagonal Boron Nitride to which --CONH.sub.2 is
Bonded
[0251] 100 mg of the h-BN having --(CH.sub.2)COOH as prepared in
Preparation Example 3 was added to a flask and then dispersed in
THF. 1 ml of thionyl chloride (SOCl.sub.2) was added thereto at a
temperature of 0.degree. C., the temperature was increased to room
temperature (about 25.degree. C.), and then the mixture was allowed
to react for 2 hours. The resultant was filtered to obtain a h-BN,
to which a --COCl functional group was bonded. Then, the h-BN thus
obtained was dispersed again in THF, 10 ml of NH.sub.3 gas was
bubbled in the solution, the mixture was allowed to react at room
temperature for 12 hours, and the resultant was filtered to obtain
a h-BN, to which a CONH.sub.2 functional group was bonded.
Preparation Example 5
Preparation of Two-Dimensional Carbon Structure
[0252] 1 g of a graphite powder and 8.5 g of sodium chlorate
(NaClO.sub.4) were added to 20 ml of a fuming nitric acid
(HNO.sub.3) to prepare a mixture, and the mixture was stirred at
room temperature (about 25.degree. C.) for 24 hours. When the
reaction was completed, the resultant was filtered to obtain a
powder, and the powder was washed several times with deionized (DI)
water. In this manner, a two-dimensional carbon nanostructure
having an oxygen content of about 27.4% was obtained. The
two-dimensional carbon nanostructure contained a functional group
including oxygen, such as a hydroxyl group, an epoxy group, a
carboxyl group, or a carbonyl group.
Preparation Example 6
Preparation of Two-Dimensional Carbon Structure
[0253] A two-dimensional carbon nanostructure having an oxygen
content of about 21.0% was prepared in the same manner as in
Preparation Example 5, except that a reaction time of the mixture
at room temperature was changed from 24 hours to 60 minutes.
Preparation Example 7
Preparation of Two-Dimensional Carbon Structure
[0254] A two-dimensional carbon nanostructure having an oxygen
content of about 13.3% was prepared in the same manner as in
Preparation Example 5, except that a reaction time of the mixture
at room temperature was changed from 24 hours to 5 minutes.
Preparation Example 8
Preparation of Molybdenum Sulfide to which a Hydroxyl Group is
Bonded
[0255] 1 g of a molybdenum sulfide powder (Sigma Aldrich) was added
to 10 ml of NMP, and then 5 ml of butyllithium (n-BuLi) was
injected thereto in a nitrogen atmosphere. The mixture was stirred
at room temperature for 2 days, and then the reaction mixture was
filtered to obtain a molybdenum sulfide powder.
[0256] 100 mg of the molybdenum sulfide powder and 10 ml of a 30 wt
% H.sub.2O.sub.2 solution were placed in an autoclave, and a
temperature of the autoclave was increased to 100.degree. C., and
the mixture was allowed to react for about 12 hours or more. When
the reaction was completed, the resultant was filtered to prepare a
molybdenum sulfide powder, to which a hydroxyl group was
bonded.
Preparation Example 9
Preparation of Molybdenum Sulfide (MoS.sub.2) to which a Hydroxyl
Group is Bonded
[0257] 100 mg of (NH.sub.4).sub.2MoS.sub.4 and 1 ml of mercapto
ethanol (HS--C.sub.2H.sub.4--OH) were dissolved in 10 ml of
dimethylformamide (DMF), and the solution was placed in an
autoclave.
[0258] A temperature in the autoclave was increased to about
200.degree. C., and the solution was allowed to react for 12 hours
or more. When the reaction was completed, the resultant was
filtered, and thus MoS.sub.2, to which a hydroxyl group is bonded,
was obtained.
Preparation Example 10
Preparation of Tungsten Sulfide (WS.sub.2) to which a Hydroxyl
Group is Bonded
[0259] Tungsten sulfide (WS.sub.2), to which a hydroxyl group was
bonded, was obtained in the same manner as in Preparation Example
8, except that 1 g of a tungsten sulfide powder was used instead of
1 g of a molybdenum sulfide powder.
Example 1
[0260] 0.08 g of the two-dimensional carbon nanostructure prepared
in Preparation Example 7 and 0.02 g of an aromatic ring-containing
monomer represented by Formula 6e were dispersed in 10 ml of NMP to
prepare a hardmask composition. While spray-coating a silicon
substrate, on which a silicon oxide was formed, with the hardmask
composition, the substrate was heat-treated at a temperature of
200.degree. C. Subsequently, the resultant was baked at a
temperature of 400.degree. C. for 10 minutes, and thus a hardmask
having a thickness of about 200 nm and containing a two-dimensional
carbon nanostructure was prepared.
##STR00018##
[0261] The hardmask was coated with an ArF photoresist at a
thickness of about 1700 .ANG. and then pre-baked at a temperature
of about 110.degree. C. for about 60 seconds. The resultant was
then exposed to light using a light exposing instrument available
from ASML (XT: 1400, NA 0.93) and post-baked at a temperature of
about 110.degree. C. for about 60 seconds. Next, the photoresist
was developed using an aqueous solution of 2.38 wt % tetramethyl
ammonium hydroxide (TMAH) to form a photoresist pattern.
[0262] Dry etching was performed using the photoresist pattern, as
a mask, and a CF.sub.4/CHF.sub.3 mixture gas. The etching
conditions included 20 mT of a chamber pressure, 1800 W of a RT
power, a 4/10 volume ratio of C.sub.4Fa.sub.8/CHF.sub.3, and an
etching time of about 120 seconds.
[0263] O.sub.2 ashing and wet stripping were performed on a post
hardmask and an organic material remaining after performing the dry
etching to obtain a desired silicon substrate having a silicon
oxide layer pattern as a final pattern.
Example 2
[0264] A silicon substrate having a silicon oxide layer pattern was
prepared in the same manner as in Example 1, except that 0.05 g of
the two-dimensional carbon nanostructure and 0.05 g of the aromatic
ring-containing monomer of Formula 6e were used.
Example 3
[0265] A silicon substrate having a silicon oxide layer pattern was
prepared in the same manner as in Example 1, except that 0.02 g of
the two-dimensional carbon nanostructure and 0.08 g of the aromatic
ring-containing monomer of Formula 6e were used.
Example 4
[0266] A silicon substrate having a silicon oxide layer pattern was
prepared in the same manner as in Example 2, except that the
hexagonal boron nitride prepared in Preparation Example 1 was used
instead of the precursor of the two-dimensional carbon
nanostructure.
Examples 5 and 6
[0267] A silicon substrate having a silicon oxide layer pattern was
prepared in the same manner as in Example 2, except that molybdenum
sulfides, which were chalcogenide-based materials prepared in
Preparation Examples 8 and 9, were each used instead of the
two-dimensional carbon nanostructure.
Comparative Example 1
[0268] A silicon substrate having a silicon oxide layer pattern was
prepared using a hardmask including high-temperature amorphous
carbon.
[0269] A carbon source (C.sub.3H.sub.6) was vapor-deposited on the
silicon oxide layer formed on the silicon substrate to form a
hardmask including high-temperature amorphous carbon.
[0270] The vapor deposition was performed using a chemical vapor
deposition method under conditions including a temperature of about
550.degree. C., a pressure in a range of about 0.01 mTorr to about
1 mTorr, and an ion energy in a range of about 50 eV to about 250
eV.
[0271] The hardmask was coated with an ArF photoresist at a
thickness of about 1700 .ANG. and then pre-baked at a temperature
of about 110.degree. C. for about 60 seconds. The resultant was
then exposed to light using a light exposing instrument available
from ASML (XT: 1400, NA 0.93) and post-baked at a temperature of
about 110.degree. C. for about 60 seconds. Next, the photoresist
was developed using an aqueous solution of 2.38 wt % TMAH to form a
photoresist pattern.
[0272] Dry etching was performed using the photoresist pattern, as
a mask, and a CF.sub.4/CHF.sub.3 mixture gas. The etching
conditions included 20 mT of a chamber pressure, 1800 W of a RT
power, a 4/10 volume ratio of C.sub.4F.sub.8/CHF.sub.3, and an
etching time of about 120 seconds.
[0273] O.sub.2 ashing and wet stripping were performed on the
hardmask and an organic material remaining after performing the dry
etching to obtain a desired silicon substrate having a silicon
oxide layer pattern as a final pattern.
Comparative Example 2
[0274] A silicon substrate having a silicon oxide layer pattern was
prepared using a hardmask including low-temperature amorphous
carbon in the same manner as in Comparative Example 1, except that
a temperature of a deposition condition for the carbon source
(C.sub.3H.sub.6) was changed to 300.degree. C. to obtain
low-temperature amorphous carbon.
Comparative Example 3
[0275] A monomer represented by Formula 6d was dissolved in a
mixture solvent of propylene glycol monomethyl ether acetate
(PGMEA), methylpyrrolidone, and gamma-butyrolactone (at a volume
mixing ratio of 40:20:40), and the solution was filtered to prepare
a hardmask composition.
##STR00019##
[0276] A silicon substrate having a silicon oxide layer pattern was
coated with the hardmask composition obtained in the manner
described above using a spin-on coating method, and then the
resultant was heat-treated at a temperature of about 400.degree. C.
for about 120 seconds to form a hardmask including spin-on-carbon
(SOC).
[0277] The hardmask was coated with an ArF photoresist at a
thickness of about 1700 .ANG. and then pre-baked at a temperature
of about 110.degree. C. for about 60 seconds. The resultant was
then exposed to light using a light exposing instrument available
from ASML (XT: 1400, NA 0.93) and post-baked at a temperature of
about 110.degree. C. for about 60 seconds. Next, the photoresist
was developed using an aqueous solution of 2.38 wt % TMAH to form a
photoresist pattern.
[0278] Dry etching was performed using the photoresist pattern as a
mask and a CF.sub.4/CHF.sub.3 mixture gas. The etching conditions
included 20 mT of a chamber pressure, 1800 W of a RF power, a 4/10
volume ratio of C.sub.4Fa/CHF.sub.3, and an etching time of about
120 seconds.
[0279] O.sub.2 ashing and wet stripping were performed on the
hardmask and an organic material remaining after performing the dry
etching to obtain a desired silicon substrate having a silicon
oxide layer pattern as a final pattern.
Evaluation Example 1
X-Ray Diffraction (XRD) Analysis Measurement
1) Preparation Example 1
[0280] XRD analysis was performed on the functionalized hexagonal
boron nitrides prepared in Preparation Example 1, Preparation
Example 1a, Preparation Example 1b, and Preparation Example 2. For
the XRD analysis, a 12 KW XRD diffractometer available from BRUKER
AXS was used, and the analysis-conditions included measurement at a
rate of about 4.degree. per minute within a range of about
5.degree. to about 80.degree..
[0281] The analysis results are shown in FIG. 3. In FIG. 3, a) is
related to a bulk hexagonal boron nitride, which is a starting
material, and b) is related to a boron nitride to which a OH
functional group is bonded as prepared in Preparation Example
1.
[0282] Referring to FIG. 3, the boron nitride to which a OH
functional group is bonded as prepared in Preparation Example 1 had
a (002) crystal face peak which appeared broad and weak compared to
that of the bulk hexagonal boron nitride (a parent h-BN), which was
a starting material. Also, (100), (101), and (102) crystal face
peaks were observed within a range where 26 is from about
40.degree. to about 50.degree.. In this regard, it may be known
that structure ordering of the hexagonal boron nitride was reduced.
Also, the functionalized hexagonal boron nitrides prepared in
Preparation Example 1a, Preparation Example 1b, and Preparation
Example 2 had the same XRD analysis pattern with that of b) in FIG.
3.
[0283] From the XRD analysis results of the functionalized
hexagonal boron nitrides prepared in Preparation Example 1,
Preparation Example 1a, Preparation Example 1b, and Preparation
Example 2, 2.theta.s of a (002) face, d-spacings (d.sub.002), and
average particle diameters (La) of crystals were obtained and are
shown in Table 1.
[0284] The d-spacings were calculated using Bragg's law defined in
Equation 1 below, and the average particle diameters of the
crystals were calculated using the Scherrer equation defined in
Equation 2.
d.sub.002=.lamda./2 sin .theta. [Equation 1]
La=(0.9.lamda.)/(.beta.cos .theta.) [Equation 2]
[0285] In Equations 1 and 2, .lamda. is an X-ray wavelength (1.54
.ANG.) and .beta. is a full width at half maximum (FWHM) at a
Bragg's angle.
TABLE-US-00001 TABLE 1 Average particle D-spacing diameter (La) of
2.theta.(.degree.) (d.sub.002) (nm) crystals (nm) Preparation
Example 1 26.4 0.337 5.6 Parent h-BN 26.8 0.332 23.8 Preparation
Example 1a 26.0 0.342 6.4 Preparation Example 1b 25.7 0.346 6.6
Preparation Example 2 26.5 0.336 8.2
[0286] Referring to Table 1, it may be known that the
functionalized hexagonal boron nitrides prepared in Preparation
Example 1, Preparation Example 1a, Preparation Example 1b, and
Preparation Example 2 have a structure that is similar to 28 with
respect to a (002) face of the parent h-BN, which is a starting
material.
2) Preparation Examples 5 to 7
[0287] The two-dimensional carbon nanostructure precursors prepared
in Preparation Examples 5 to 7 were XRD analyzed. When performing
the XRD analysis, a 12 KW XRD diffractometer available from BRUKER
AXS was used, and the analysis conditions included measurement at a
rate of about 4.degree. per minute within a range of about
5.degree. to about 80.degree..
[0288] From the XRD analysis results of the two-dimensional carbon
nanostructures prepared in Preparation Examples 5 to 7, d-spacings
(d.sub.002) and average particle diameters (La) with respect to the
(002) face of the crystals were obtained and are shown in Table
2.
[0289] The d-spacings were calculated using Bragg's law defined in
Equation 1 below, and the average particle diameters of the
crystals were calculated by using the Scherrer equation defined in
Equation 2.
TABLE-US-00002 TABLE 2 D-spacing Average particle diameter (La)
(d.sub.002) (nm) of crystals (nm) Preparation Example 5 0.722 1.7
Preparation Example 6 0.762 1.6 Preparation Example 7 0.324
22.6
Evaluation Example 2
Raman Spectrum Analysis
1) Preparation Examples 5 to 7 and Comparative Example 1
[0290] Raman spectroscopy analysis was performed on the
two-dimensional carbon nanostructures prepared in Preparation
Examples 5 to 7 and the high-temperature amorphous carbon prepared
in Comparative Example 1. The Raman spectroscopy analysis was
performed using the Raman instrument, RM-1000 Invia (514 nm,
Ar.sup.+ion laser), available from Renishaw. Here, a D peak, a G
peak, and a 2D peak respectively are peaks at about 1340 cm.sup.-1
to about 1350 cm.sup.-1, at about 1580 cm.sup.-1, and at about 2700
cm.sup.-1.
[0291] Intensity ratios of a D mode peak to a G mode peak
(I.sub.D/I.sub.G) of the two-dimensional carbon nanostructures
prepared in Preparation Examples 5 to 7, a high-temperature
amorphous carbon prepared in Comparative Example 1, and a
low-temperature amorphous carbon prepared in Comparative Example 2
were obtained and are shown in Table 3.
TABLE-US-00003 I.sub.D/I.sub.G Preparation Example 5 0.87
Preparation Example 6 0.86 Preparation Example 7 0.90 Comparative
Example 1 0.85
2) Preparation Example 8
[0292] Raman spectroscopy analysis was performed on the tungsten
sulfide, to which a hydroxyl group is bonded, prepared in
Preparation Example 10.
[0293] The Raman spectroscopy analysis was performed using the
Raman instrument, RM-1000 Invia (514 nm, Ar.sup.+ion laser),
available from Renishaw. Also, the result of the Raman spectroscopy
analysis performed on the tungsten sulfide, to which a hydroxyl
group is bonded, prepared in Preparation Example 10 is shown in
FIG. 5, and the Raman spectroscopy analysis of a tungsten sulfide,
which is a starting material, is shown in FIG. 4 for the comparison
with FIG. 5.
[0294] Referring to FIG. 4, an E.sup.1.sub.2g mode peak and an
A.sub.1g mode peak are each observed at Raman shits of about 355
cm.sup.-1 and about 420 cm.sup.-1, and it may be known that the
hydroxyl group is bonded to the tungsten sulfide from the peak in
the region A.
Evaluation Example 3
XPS Analysis
[0295] XPS spectroscopy was performed on the two-dimensional carbon
nanostructures prepared in Preparation Examples 5 to 9 and the
amorphous carbon prepared in Comparative Example 1 using a Quantum
2000 (Physical Electronics).
[0296] The analysis results are shown in Table 4.
TABLE-US-00004 TABLE 4 XPS Oxygen content C/O atom ratio (atom %)
Preparation Example 5 2.65 27.4% Preparation Example 6 3.76 21.0%
Preparation Example 7 6.50 13.3% Comparative Example 1 15.78 --
Evaluation Example 4
Etching Resistance
[0297] Etching resistance was evaluated by calculating an etching
rate of the hardmask when the dry etching is performed using each
of the hardmasks prepared in Examples 1 to 5 and Comparative
Example 3.
[0298] The results of the etching rate evaluation are shown in
Table 5.
TABLE-US-00005 TABLE 5 Etching rate (.ANG./sec) Example 1 9 Example
2 14 Example 3 19 Example 4 13 Example 5 13 Comparative Example 3
23.0
[0299] As shown in Table 5, it may be known that etching resistance
is better in the case of the hardmask prepared in Examples 1 to 5
compared to the hardmasks prepared in Comparative Example 3.
Evaluation Example 5
Pattern Shape Analysis
[0300] Etching was performed using each of the hardmasks prepared
in Examples 1 to 5 and Comparative Examples 1 to 3, and then a
cross-section of the silicon substrate having a silicon oxide layer
pattern was observed using FE-SEM, and the results are shown in
Table 6.
TABLE-US-00006 TABLE 6 Shape of pattern after Shape of pattern
after hardmask etching silicon oxide etching Example 1 Vertical
Vertical Example 2 Vertical Vertical Example 3 Vertical Vertical
Example 4 Vertical Vertical Example 5 Vertical Vertical Comparative
Example 1 Arched Tapered Comparative Example 2 Arched Tapered
Comparative Example 3 Arched Tapered
[0301] As shown in Table 6, the silicon oxide layer pattern shapes
having each of the hardmasks prepared in Examples 1 to 5 are
vertical, unlike that of the hardmask prepared in Comparative
Examples 1 to 3.
[0302] As described above, a hardmask including a hardmask
composition according to example embodiments has improved etching
resistance and mechanical strength, and the hardmask may be more
easily removed after an etching process. When the hardmask is used,
efficiency of a semiconductor process may be improved.
[0303] It should be understood that example embodiments described
herein should be considered in a descriptive sense only and not for
purposes of limitation.
[0304] Descriptions of features or aspects within each embodiment
should typically be considered as available for other similar
features or aspects in other embodiments.
[0305] While example embodiments have been described with reference
to the figures, it will be understood by those of ordinary skill in
the art that various changes in form and details may be made
therein without departing from the spirit and scope of the
following claims.
* * * * *