CN109478015B - Organic layer composition and pattern forming method - Google Patents
Organic layer composition and pattern forming method Download PDFInfo
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- CN109478015B CN109478015B CN201680087729.4A CN201680087729A CN109478015B CN 109478015 B CN109478015 B CN 109478015B CN 201680087729 A CN201680087729 A CN 201680087729A CN 109478015 B CN109478015 B CN 109478015B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H01—ELECTRIC ELEMENTS
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
Abstract
The invention discloses an organic layer composition and a pattern forming method using the same, the organic layer composition comprises: a polymer comprising a structural unit represented by chemical formula 1; an additive comprising at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group in a structure as an aromatic ring-containing compound; and a solvent. Chemical formula 1 is the same as defined in the specification. The present invention provides an organic layer composition having improved etching resistance while being coated by a spin coating method due to the inclusion of a predetermined polymer and a predetermined additive. The organic layer manufactured from the organic layer composition has improved film density and film flatness.
Description
Technical Field
The invention discloses an organic layer composition and a pattern forming method using the same.
Background
Recently, highly integrated designs based on miniaturization and complexity of electronic devices have accelerated the development of more advanced materials and associated processes, and thus, photolithography using conventional photoresists also requires new patterning materials and techniques.
In the patterning process, an organic layer called a hard mask layer (hardmask layer) may be formed as a hard interlayer to transfer a fine pattern of photoresist down to a sufficient depth on a substrate without collapsing it.
The hard mask layer functions as an intermediate layer to transfer a fine pattern of photoresist to the material layer by a selective etching process. Therefore, the hard mask layer requires characteristics such as heat resistance, etching resistance, etc. in order to withstand multiple etching processes.
On the other hand, a spin-on coating (spin-on coating) method has been recently proposed to form the hard mask layer instead of a Chemical Vapor Deposition (CVD) method. The spin-coating method is not only easily performed but also improves gap-fill (gap-fill) characteristics and planarization characteristics.
In general, since heat resistance and etching resistance have a trade-off relationship with spin-coating characteristics, an organic layer material satisfying all the characteristics is required.
Disclosure of Invention
Technical problem
An embodiment of the present invention provides an organic layer composition that can be coated by spin coating and has improved etch resistance.
Another embodiment of the present invention provides a pattern forming method using the organic layer composition.
Technical scheme
According to one embodiment, an organic layer composition includes: a polymer comprising a structural unit represented by chemical formula 1; an additive comprising at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group in a structure as an aromatic ring-containing compound; and a solvent.
[ chemical formula 1]
In the chemical formula 1, the first and second,
a is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
b is a divalent organic radical, and
at least one of a and B may be substituted with a functional group including a moiety (moiety) represented by chemical formula 2:
[ chemical formula 2]
Wherein, in chemical formula 2,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl, and
is a connection point.
The functional group including the moiety represented by chemical formula 2 may be represented by chemical formula 2'.
[ chemical formula 2' ]
In the chemical formula 2', the reaction mixture is,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
The additive may be represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the first and second,
k. m and n are independently 0 or 1, and the sum of k, m and n is 2 or 3,
when k + m + N is 3, X is-CH-or nitrogen (N),
when k + m + n is 2, X is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen (O), sulfur (S), -NH-, or-S (O)2) -, wherein q and t are independently integers of 1 to 5, and RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, and
r, R 'and R "are independently a substituted or unsubstituted aromatic ring-containing group, wherein R, R', or R" comprises at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group.
The additive may be represented by chemical formula 4 or chemical formula 5.
[ chemical formula 4]
[ chemical formula 5]
R4-X2-R5
In chemical formula 4 and chemical formula 5,
X1is-CH-or nitrogen (N),
X2is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen (O), sulfur (S), -NH-, or-S (O)2) -, where q and t are independently integers from 1 to 5, RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, and
R1to R5Independently an aromatic ring-containing group comprising at least one of the groups represented by chemical formula 6.
[ chemical formula 6]
In the chemical formula 6, the first and second,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
In chemical formulas 4 and 5, R1To R5Independently represented by chemical formula 7.
[ chemical formula 7]
In the chemical formula 7, the first and second,
R1ato R13aIndependently hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a group represented by formula 6, wherein R is1aTo R13aAt least one of which is a group represented by chemical formula 6,
T1and T2Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
c and d are independently an integer of 0 to 5, and
is a connection point.
In chemical formula 1, a may be a substituted or unsubstituted moiety (moiey) selected from group 1 and group 2.
[ group 1]
[ group 2]
In the group 2, the first group is a group,
Z1and Z2Independently is NRdO, S, Te or Se, and the use of the selenium,
Z3and Z4Is N, and
Rdand ReIndependently hydrogen, hydroxy, methoxy, ethoxy, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
In chemical formula 1, a may include at least one substituted or unsubstituted aromatic ring or substituted or unsubstituted heteroaromatic ring.
B may be represented by one of chemical formula Z1 to chemical formula Z4.
[ chemical formula Z1]
[ chemical formula Z2]
[ chemical formula Z3]
[ chemical formula Z4]
In chemical formulae Z1 to Z4,
e and f are independently 0 or 1,
g is an integer of 1 to 5,
Y1to Y4Is independently one of a substituted or unsubstituted moiety selected from group 3, and
is a connection point.
[ group 3]
In the group 3, the group is,
m, M 'and M' are independently substituted or unsubstituted C1 to C10 alkylene, O, S, SO2、CRfRg、NRhOr a carbonyl group, wherein RfTo RhIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
L1is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,
r is an integer of 0 to 10,
s is an integer of 0 to 10, and
k is an integer of 0 to 3.
The polymer may further include a structural unit represented by chemical formula 8.
[ chemical formula 8]
·-X0-L0-·
In the chemical formula 8, the first and second,
X0is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
L0is a divalent organic radical, and
is a connection point.
In chemical formula 8, the X0May be a substituted or unsubstituted moiety selected from group 1 and group 2.
[ group 1]
[ group 2]
In the group 2, the first group is a group,
Z1and Z2Independently is NRdO, S, Te or Se, and the use of the selenium,
Z3and Z4The content of the N is N,
Rdand ReIndependently hydrogen, hydroxy, methoxy, ethoxy, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
The polymer may comprise at least one oxygen atom in the structural unit.
Chemical formula 2 may be represented by chemical formula 2'.
[ chemical formula 2' ]
In the chemical formula 2', the reaction mixture is,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
The additive may be represented by one of chemical formula Y1 to chemical formula Y4.
[ chemical formula Y1]
[ chemical formula Y2]
[ chemical formula Y3]
[ chemical formula Y4]
In the chemical formulae Y1 to Y4,
T3and T4Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Rxto RyIndependently is hydrogen, a halogen atom, a halogen-containing group or a substituted or unsubstituted C1 to C20 alkyl group, and
R33to R55Independently a group represented by chemical formula 6.
[ chemical formula 6]
In the chemical formula 6, the first and second,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, haloAn elemental atom, a halogen-containing group, or a combination thereof,
y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
The additive may have a molecular weight of 150 to 50,000.
The polymer may have a weight average molecular weight of 500 to 200,000.
The amount of the additive is 5 to 50 wt% based on the total amount of the organic layer composition.
According to another embodiment, a pattern forming method includes: the method includes providing a material layer on a substrate, applying an organic layer composition on the material layer, thermally treating the organic layer composition to form a hard mask layer, forming a silicon-containing thin layer on the hard mask layer, forming a photoresist layer on the silicon-containing thin layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.
The organic layer composition may be applied using a spin coating method.
The heat treatment may include performing a first heat treatment at 50 to 250 ℃ and performing a second heat treatment at 200 to 500 ℃ after the first heat treatment.
The method may further include forming a bottom anti-reflective coating (BARC) layer before forming the photoresist layer.
Effect of the invention
The present invention provides an organic layer composition having improved etching resistance while being coated by a spin coating method, due to the inclusion of a predetermined polymer and a predetermined additive. The organic layer manufactured from the organic layer composition has improved film density and film flatness.
Drawings
Fig. 1 is a view for explaining a method of evaluating a planarization feature (step feature).
Fig. 2 is a view for explaining a method of evaluating a Thickness Uniformity (Thickness Uniformity) characteristic.
Detailed Description
Exemplary embodiments of the present invention will be described in detail below, and can be easily performed by those skilled in the relevant art. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein.
In this specification, when a definition is not otherwise provided, the term "substituted" may refer to one substituted with a substituent selected from: halogen atoms (F, Br, Cl, or I), hydroxyl groups, alkoxy groups, nitro groups, cyano groups, amine groups, azide groups, amidino groups, hydrazine groups, hydrazone groups, carbonyl groups, carbamoyl groups, thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl groups, C6 to C30 aryl groups, C7 to C30 arylalkyl groups, C1 to C30 alkoxy groups, C1 to C20 heteroalkyl groups, C2 to C20 heteroaryl groups, C3 to C20 heteroarylalkyl groups, C3 to C30 cycloalkyl groups, C3 to C15 cycloalkenyl groups, C6 to C15 cycloalkynyl groups, C2 to C30 heterocycloalkyl groups, and combinations thereof.
In this specification, when a definition is not otherwise provided, "hetero" refers to one including 1 to 3 hetero atoms selected from N, O, S and P.
Hereinafter, an organic layer composition according to an embodiment is described.
An organic layer composition according to an embodiment includes: a polymer comprising a structural unit represented by chemical formula 1; an additive comprising at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group in a structure as an aromatic ring-containing compound; and a solvent.
[ chemical formula 1]
In the chemical formula 1, the first and second,
a is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
b is a divalent organic radical, and
at least one of a and B may be substituted with a functional group including a moiety represented by chemical formula 2:
[ chemical formula 2]
Wherein, in chemical formula 2,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl, and
is a connection point.
The organic layer composition includes a polymer having a predetermined structure and an additive having a predetermined structure. First, the polymer is explained.
The polymer includes one or more of the structural units represented by chemical formula 1, and chemical formula 1 includes an aromatic ring-containing moiety represented by a and a linker moiety represented by B in the structural units.
For example, a may be a substituted or unsubstituted aromatic ring-containing group, and may include, for example, a substituted or unsubstituted moiety selected from group 1, but is not limited thereto.
[ group 1]
As another example, a may be a substituted or unsubstituted heteroaromatic ring containing group and may include, for example, but is not limited to, a substituted or unsubstituted moiety selected from group 2.
[ group 2]
In the group 2, the first group is a group,
Z1and Z2Independently is NRdO, S, Te, or Se, in a single crystal,
Z3and Z4Is N, and
Rdand ReIndependently hydrogen, hydroxy, methoxy, ethoxy, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
By way of further example, a may be a combination of a substituted or unsubstituted aromatic ring-containing group and a substituted or unsubstituted heteroaromatic ring-containing group. For example, in chemical formula 1, a may include two or more substituted or unsubstituted benzene rings, for example, two to six substituted or unsubstituted benzene rings. Herein, the benzene ring may be substituted with at least one hydroxyl group.
In chemical formula 1, B indicated as a linking group may be a divalent organic linear group, a divalent organic cyclic group, or a combination thereof. For example, B may be represented by one of formula Z1 to formula Z4, but is not limited thereto.
[ chemical formula Z1]
[ chemical formula Z2]
[ chemical formula Z3]
[ chemical formula Z4]
In chemical formulae Z1 to Z4,
e and f are independently 0 or 1,
g is an integer of 1 to 5,
Y1to Y4Is independently one of a substituted or unsubstituted moiety selected from group 3, and
is a connection point:
[ group 3]
In the group 3, the group is,
m, M 'and M' are independently substituted or unsubstituted C1 to C10 alkylene, O, S, SO2、CRfRg、NRhOr carbonyl group, wherein RfTo RhIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
L1is a substituted or unsubstituted C6 to C50 arylene, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
r is an integer of 0 to 10,
s is an integer of 3 to 10, and
k is an integer of 1 to 3.
On the other hand, in chemical formula 1, at least one of a and B may be substituted with an acetylene-containing group represented by chemical formula 2. For example, the aromatic ring-containing group or heteroaromatic ring-containing group represented by a may be substituted with an acetylene-containing group, the linking group represented by B may be substituted with an acetylene-containing group, or the a portion and the B portion may be substituted with an acetylene-containing group. Herein, the number of substitution is not particularly limited.
For example, the functional group including the moiety represented by chemical formula 2 may be a group represented by chemical formula 2', but is not limited thereto.
[ chemical formula 2' ]
In the chemical formula 2', the reaction mixture is,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
For example, the functional group including the moiety represented by chemical formula 2 may be represented by chemical formula 2 ″, but is not limited thereto.
[ chemical formula 2 "]
In the chemical formula 2 ″, the,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
a is 0 or 1, and
is a connection point.
For example, the polymer may include at least one oxygen atom in its structure.
The polymer contains an aromatic ring-containing group or a heteroaromatic ring-containing group represented by a in the structural unit and thus can secure etching resistance, and further, the polymer contains an organic group represented by B and thus can secure flexibility (flexibility). In addition, the etch resistance of the polymer may be further improved because at least one acetylene is introduced to a or B and thus a ring structure may be formed upon curing the polymer. Therefore, the organic layer formed by using the polymer shows excellent film density. In addition, the organic layer formed by using the polymer can secure thickness uniformity (uniformity).
The polymer may further include a structural unit represented by, for example, chemical formula 8.
[ chemical formula 8]
·-X0-L0-·
In the chemical formula 8, the first and second,
X0is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
L0is a divalent organic radical, and
is a connection point.
In chemical formula 8, X0Can be a substituted or unsubstituted moiety selected from group 1 and group 2, and L0The same as B as the linker in chemical formula 1. The structural unit represented by chemical formula 8 does not include an acetylene functional group, unlike the structural unit represented by chemical formula 1 essentially.
Hereinafter, additives of the organic layer composition are described.
The additive is as described above as an aromatic ring-containing compound that includes at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group.
For example, the additive may be represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the first and second,
k. m and n are independently 0 or 1, and the sum of k, m and n is 2 or 3,
when k + m + N is 3, X is-CH-or nitrogen (N),
when k + m + n is 2, X is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen (O), sulfur (S), -NH-, or-S (O)2) -, wherein q and t are independently integers of 1 to 5, and RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, and
r, R 'and R "are independently a substituted or unsubstituted aromatic ring-containing group, wherein R, R' or R" comprises at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group. For example, R, R' or R "may be substituted, for example, with one or both of: a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group or a nitrile group.
The additive represented by chemical formula 3 has a structure in which two or three aromatic ring-containing groups are linked to each other in the core represented by X. When the additive represented by chemical formula 3 has three substituents, the core is carbon or nitrogen, and when the additive has two substituents, the core is a direct bond, carbon, oxygen, sulfur or — S (O)2)-。
For example, when the additive has a structure in which three aromatic ring-containing groups are connected to each other in the core, the additive may be represented by chemical formula 4, and when the additive has a structure in which two aromatic ring-containing groups are connected to each other in the core, the additive may be represented by chemical formula 5.
[ chemical formula 4]
[ chemical formula 5]
R4-X2-R5
In chemical formula 4 and chemical formula 5,
X1is-CH-or nitrogen (N),
X2is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen (O), sulfur (S), -NH-, or-S (O)2) -, where q and t are independently integers from 1 to 5, RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, and
R1to R5Independently an aromatic ring-containing group including at least one of the groups represented by chemical formula 6 in the structure.
[ chemical formula 6]
In the chemical formula 6, the first and second,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
For example, in chemical formulas 4 and 5, R1To R5Independently, but not limited to, chemical formula 7.
[ chemical formula 7]
In the chemical formula 7, the first and second,
R1ato R13aIndependently hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a group represented by formula 6, wherein R is1aTo R13aAt least one of which is a group represented by chemical formula 6,
T1and T2Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
c and d are independently an integer of 0 to 5, and
is a connection point.
For example, the additive may be represented by one of the formulas Y1 to Y4, but is not limited thereto.
[ chemical formula Y1]
[ chemical formula Y2]
[ chemical formula Y3]
[ chemical formula Y4]
In the chemical formulae Y1 to Y4,
T3and T4Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Rxto RyIndependently is hydrogen, a halogen atom, a halogen-containing group or a substituted or unsubstituted C1 to C20 alkyl group, and
R33to R55Independently a group represented by chemical formula 6.
For example, the additive may include at least one oxygen atom or nitrogen atom in its structure, and may include, for example, one to three oxygen atoms or one nitrogen atom, but is not limited thereto.
The additives can be used, for example, as crosslinking agents.
As such, the organic layer composition comprises an additive comprising a polymer of acetylene and an aromatic ring-containing compound, the additive comprising at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group.
As such, when the polymer and the additive are used simultaneously, the acetylene functional group introduced into the polymer reacts with the amine, acetylene, azide, etc. introduced into the additive and forms a ring during curing, and thus the carbon content in the polymer may be relatively increased. Therefore, the etching resistance can be improved, and thus the etching selectivity can also be improved. As a result, the organic layer formed by using the organic layer composition shows excellent film density and patterning ability.
For example, the polymer may have a weight average molecular weight of about 500 to 200,000. Organic layer compositions comprising polymers (e.g., hard mask compositions) can be optimized by adjusting the carbon content and solubility in solvents when the polymers have weight average molecular weights within a range. For example, the additive may have a molecular weight of about 150 to 50,000.
The solvent may be any solvent having sufficient solubility or dispersibility for the polymer, and may be, for example, at least one selected from the group consisting of: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol monobutyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, methylpyrrolidone (methylpyrrolidinone), acetylacetone, and ethyl 3-ethoxypropionate.
The polymer may be present in an amount of about 0.1 to about 50 wt.%, based on the total amount of the organic layer composition. When the polymer is included in the range, the thickness, surface roughness, and planarization of the organic layer may be controlled.
Additives may be present in an amount of about 0.1 to 50 wt%, for example about 5 to 50 wt%, based on the total amount of the organic layer composition. When the additive is included in the range, initial planarization of the organic layer may be improved.
The organic layer composition may further include the following additives: surfactants, cross-linking agents, thermal acid generators, plasticizers, and the like.
The surfactant may include, for example, an alkyl benzene sulfonate, an alkyl pyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
The crosslinking agent may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Preferably, it may be a crosslinking agent having at least two crosslink forming substituents, for example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or butoxymethylated thiourea.
The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound containing a crosslinking substituent containing an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule.
The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, etc., or/and 2,4,4, 6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other alkyl organosulfonates, etc., but is not limited thereto.
The additive may be present in an amount of about 0.001 parts by weight to 40 parts by weight, based on 100 parts by weight of the organic layer composition. Within the range, the solubility can be improved without changing the optical characteristics of the organic layer composition.
According to another embodiment, an organic layer manufactured using the organic layer composition is provided. The organic layer may be formed, for example, by coating an organic layer composition on a substrate and heat-treating it to cure, and may include, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc. for an electronic device.
Hereinafter, a pattern forming method by using the organic layer composition is described.
A pattern forming method according to an embodiment includes: the method includes providing a material layer on a substrate, applying an organic layer composition including a polymer and a solvent on the material layer, thermally treating the organic layer composition to form a hard mask layer, forming a silicon-containing thin layer on the hard mask layer, forming a photoresist layer on the silicon-containing thin layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.
The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.
The material layer is a material to be finally patterned, for example, a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as a silicon oxide layer and a silicon nitride layer. The material layer may be formed by a method such as a Chemical Vapor Deposition (CVD) process.
The organic layer composition is the same as described above, and may be applied in the form of a solution by spin coating. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about
To about
(angstroms).
The heat treatment may be performed on the organic layer composition, for example, at about 100 to 500 ℃ for about 10 seconds to 1 hour.
For example, the heat treatment may include a first heat treatment performed at 5 ℃ 0 to 250 ℃ and a second heat treatment performed after the first heat treatment and at 200 ℃ to 500 ℃.
The silicon-containing thin layer may be formed of, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiN, and/or the like.
The method may further comprise forming a bottom anti-reflective coating (BARC) layer prior to forming a photoresist layer over the silicon-containing thin layer.
The exposure may be performed on the photoresist layer using, for example, ArF, KrF, or EUV. After the exposure, a heat treatment may be performed at about 100 to 500 ℃.
An etching process may be performed on the exposed portions of the material layer by a dry etching process using an etching gas, which may be, for example, CHF3、CF4、Cl2、BCl3And mixed gases thereof, but not limited.
The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulating patterns, etc., such as various patterns of semiconductor integrated circuit devices.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are exemplary, and the present invention is not limited thereto.
Polymer synthesis
Polymerization example 1
Polymerization of resins
In a flask, naphthalene-1-ol (14.2g), polyoxymethylene (6g), p-toluene sulfonic acid hydrate (1.9g), and Propylene Glycol Monomethyl Ether Acetate (PGMEA) (33g) were placed and stirred at 80 ℃ to perform polymerization. When the weight average molecular weight reaches a range of 2,000 to 3,500, the reaction is completed by checking the molecular weight by Gel Permeation Chromatography (GPC) during the reaction. When the polymerization reaction was completed, the reactant was slowly cooled to room temperature, 100g of hexane was added thereto to extract propylene glycol monomethyl ether acetate, and then removed by using distilled water and methanol, to obtain a polymer comprising the structural unit represented by chemical formula 1 a' (weight average molecular weight (Mw) ═ 3,000).
[ chemical formula 1 a' ]
Acetylation (Acetylation) reaction
A polymer (10g) containing the structural unit represented by chemical formula 1 a' was dissolved in Dimethylformamide (DMF) (40mL) in a flask, and the solution was stirred in ice water. After stirring for 10 minutes, NaH (1g) was slowly added dropwise thereto, the mixture was stirred for 30 minutes, and propargyl bromide (80% in toluene) (5.5g) was added dropwise thereto. When the reaction was completed, ethyl acetate (EtOAc) (100mL) was added thereto to dilute the reaction solution, and the reaction solution was washed several times with water to remove DMF. When the DMF was completely removed, the remaining EtOAc was removed to obtain polymer 1 a.
Polymerization example 2
Polymerization of resins
Naphthalene-1-ol (naphthalen-1-ol) (10g), 1,3-bis (4- (methoxymethyl) phenoxy) benzene (24.3g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (64g), and diethyl sulfate (diethyl sulfate) (0.3g) were reacted at 100 ℃ in the same resin polymerization method as in polymerization example 1 to obtain a polymer comprising a structural unit represented by chemical formula 1 b' (weight average molecular weight (Mw) ═ 3,500).
[ chemical formula 1 b' ]
Acetylation (Acetylation) reaction
For the same acetylation as in polymerization example 1, a polymer (10g) containing a structural unit represented by chemical formula 1 b', DMF (50mL), NaH (0.6g), and propargyl bromide (80% in toluene) (2.6g) were used to obtain a polymer 1 b.
Polymerization example 3
Polymerization of resins
Pyrene-1,6-diol (pyrene-1, 6-diol) (23g), 1,4-bis (methoxymethyl) benzene (1,4-bis (methoxymethyl) benzene) (25g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (48g) and diethyl sulfate (diethyl sulfate) (0.7g) were placed in a flask, and stirred at 100 ℃ to perform polymerization. When the weight average molecular weight reaches the range of 2,000 to 3,500, the reaction is completed. When the polymerization reaction was completed, the reaction was slowly cooled to room temperature and then added to 20g of distilled water and 200g of methanol, and the mixture was strongly stirred and then allowed to stand. After the supernatant liquid was removed therefrom, the deposit therein was dissolved in 40g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and the solution was strongly stirred by using 160g of methanol and 160g of water, and then allowed to stand (first time). Then, the supernatant obtained therefrom was removed again, and the deposit therein was dissolved in 40g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) (second time). The first and second processes are referred to as a purification process, and the purification process is performed three times. The purified polymer was dissolved in 40g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and the remaining methanol and distilled water in the solution were removed under reduced pressure to obtain a polymer comprising a structural unit represented by chemical formula 1 c' (weight average molecular weight (Mw) ═ 2,600).
[ chemical formula 1 c' ]
Acetylation (Acetylation) reaction
Polymer 1c was obtained according to the same method as polymerization example 1 by using 1 polymer (10g) containing a structural unit represented by chemical formula 1 c', DMF (40mL), NaH (0.6g), and propargyl bromide (80% in tolumen) in toluene) (2.2 g).
Polymerization example 4
Polymerization of resins
A polymer comprising a structural unit represented by chemical formula 1d ' was obtained at 100 ℃ by using 4,4' - (9H-fluorene-9,9-diyl) diphenol (4,4' - (9H-fluoroene-9, 9-diyl) diphenol) (14g), 1,4-bis (methoxymethyl) benzene (1,4-bis (methoxymethyl) benzene) (6.6g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (20g) and diethyl sulfate (diethyl sulfate) (0.25g) according to the same resin polymerization method as polymerization example 1 (weight average molecular weight (Mw) ═ 3,700).
[ chemical formula 1 d' ]
Acetylation (Acetylation) reaction
Polymer 1d was obtained according to the same acetylation method as in polymerization example 1 by using a polymer (9g) containing a structural unit represented by chemical formula 1 d', DMF (45mL), NaH (0.9g), and propargyl bromide (80% in tolumen) in toluene) (3.5 g).
Polymerization example 5
Polymerization of resins
A polymer comprising a structural unit represented by chemical formula 1e ' was obtained at 110 ℃ by using 6,6' - (9H-fluoroene-9, 9-diyl) dinaphthalalen-2-ol (6,6' - (9H-fluorene-9,9-diyl) dinaphthalen-2-ol) (18g), 1,3-bis (methoxymethyl) benzene (1,3-bis (methoxymethyl) benzene) (6.6g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (25g), and diethyl sulfate (diethylsulfate) (0.2g) according to the same resin polymerization method as in polymerization example 1 (weight average molecular weight (Mw) ═ 3,800).
[ chemical formula 1 e' ]
Acetylation (Acetylation) reaction
Polymer 1e was obtained by using a polymer (25g) containing a structural unit represented by chemical formula 1 e', DMF (45mL), NaH (0.7g) and propargyl bromide (80% in toluene) (2.5g) via the same acetylation as in polymerization example 1.
Polymerization example 6
A polymer (Mw: 3,200) comprising a structural unit represented by the formula 1f ' was obtained according to the same resin polymerization method as in polymerization example 1 by using 4,4' - (9H-fluoroene-9, 9-diyl) dibenzene-1,2-diol (4,4' - (9H-fluorene-9,9-diyl) diphenyl-1, 2-diol) (38g), 5-hydroxy-1-naphthaldehyde (5-hydroxy-1-naphthaldehyde) (17g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (129g), and diethyl sulfate (diethyl sulfate) (0.3 g).
[ chemical formula 1 f' ]
Acetylation (Acetylation) reaction
Polymer 1f was obtained according to the same acetylation method as in polymeric example 1 by using a polymer (10g) containing a structural unit represented by chemical formula 1 f', DMF (50mL), NaH (1.9g), and propargyl bromide (80% in tolumen) in toluene) (5.1 g).
Polymerization example 7
Polymerization of resins
A polymer (Mw: 3,300) comprising a structural unit represented by the chemical formula 1g 'was obtained at 100 ℃ by using 5,5' - (9H-fluorone-9, 9-diyl) dibenzene-l,2,3-triol (20g), 4'-oxybis ((methoxymethyl) benzene) (4,4' -oxybis ((methoxymethyl) benzene)) (26g), 1H-indol (1H-indole) (6g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (123g), and diethyl sulfate (diethylsulfultate) (0.5g) according to the same synthesis method as in polymerization example 1.
[ chemical formula 1 g' ]
Acetylation (Acetylation) reaction
For the same acetylation as in polymerization example 1, a polymer (10g) containing a structural unit represented by chemical formula 1 g', DMF (50mL), NaH (1.3g), and propargyl bromide (80% in toluene) (3.7g) were used to obtain 1g of a polymer.
Polymerization example 8
Polymerization of resins
A polymer (Mw: 3,700) comprising a structural unit represented by the chemical formula 1H' was synthesized by using naphthalen-1-ol (naphthalen-1-ol) (7.2g), 1H-indol (1H-indole) (5.9g), 4-hydroxy-1-naphthaldehyde (4-hydroxy-1-naphthaldehyde) (17g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (129g) and diethyl sulfate (0.3g) according to the same method as in polymerization example 1.
[ chemical formula 1 h' ]
Acetylation (Acetylation) reaction
Polymer 1h was obtained according to the same acetylation method as polymerization example 1 using polymer (12g) containing a structural unit represented by chemical formula 1 h', DMF (55mL), NaH (1g) and propargyl bromide (80% in toluene) (3.4 g).
Polymerization example 9
Polymerization of resins
Carbazole (16g), 5-hydroxy-1-naphthaldehyde (17g), p-Toluenesulfonic acid hydrate (1.9g), and 1, 4-dioxane (32g) were placed in a flask at 100 ℃ and stirred. The reaction was completed when the weight average molecular weight of the sample taken out from the polymerization reaction per hour reached the range of 2000 to 3000. After the completion of the reaction, 100g of hexane was added thereto to extract 1, 4-dioxane, methanol was added thereto to obtain a precipitate, the precipitate obtained therefrom was filtered, and the remaining monomers therein were removed by using methanol to obtain a polymer represented by chemical formula 1 i' (weight average molecular weight (Mw) ═ 2,600).
[ chemical formula 1 i' ]
Acetylation (Acetylation) reaction
Polymer 1i was obtained according to the same acetylation method as in polymerization example 1 by using a polymer (10g) containing the structural unit of chemical formula 1 i', DMF (55mL), NaH (0.65g), and 1.7 g of propargyl bromide (80% in tolumen) in toluene).
Polymerization example 10
A polymer (Mw: 2,900) comprising a structural unit represented by the chemical formula 1 j' was obtained according to the same synthesis method as in polymerization example 9 by using 1H-indol-5-ol (1H-indol-5-ol) (13g), 9-fluorene (9-fluorone) (18g), p-Toluenesulfonic acid hydrate (p-Toluenesulfonic acid monohydrate) (9.5g) and 1, 4-dioxane (91g) in a flask.
[ chemical formula 1 j' ]
Acetylation (Acetylation) reaction
Polymer 1j was obtained according to the same acetylation method as in polymerization example 1 using polymer (10g) containing a structural unit represented by chemical formula 1 j', DMF (50mL), NaH (0.7g), and propargyl bromide (80% in tolumen) in toluene) (1.8 g).
Comparative polymerization example 1
Using naphthalene-1-ol (naphthalene-1-ol) (14g), 1,4-bis (methoymethyl) benzene (1,4-bis (methoxymethyl) benzene) (17g), Propylene Glycol Monomethyl Ether Acetate (PGMEA) (64g), and diethyl sulfate (diethyl sulfate) (0.3g) at 100 ℃, polymer 1k (weight average molecular weight (Mw) ═ 3,000) including a structural unit represented by chemical formula 1k was obtained according to the same resin polymerization method as in polymerization example 1.
[ chemical formula 1k ]
Synthesis of additives
Synthesis example 1
In a 500ml round bottom flask were placed 4,4'- (4,4' - (propane-2,2-diyl) bis (4,1-phenylene)) bis (oxy) dianiline (4,4'- (4,4' - (propane-2,2-diyl) bis (4,1-phenylene)) bis (oxy) diphenyl) (10), water (60ml) and crushed (crusted) ice (15g), and stirred with a stir bar (stir) for 10 minutes, and there was slowly added dropwise conc. HCl (concentrated HCl) (20 ml). Then, NaNO dissolved in water (15mL) was added dropwise thereto through a dropping funnel (dropping funnel)2For about 10 minutes. After the mixture was stirred for 20 minutes, KI dissolved in water (15ml) was slowly added dropwise thereto through a dropping funnel (dropping funnel). The mixture obtained was stirred for 1 hourAfter 30 minutes, when the reaction was completed by checking it through Thin Layer Chromatography (TLC), the resultant was filtered, and a solid obtained therefrom was dissolved in Ethyl Acetate (EA), and then NaHSO was used3And water was washed. Then, the solvent of the organic layer was removed to obtain 8g of the additive represented by chemical formula 2 a.
[ chemical formula 2a ]
Synthesis example 2
According to the same method as that of Synthesis example 1, 4'- (biphenyl-4,4' -diylbis (oxy)) dianiline (4,4'- (biphenyl-4,4' -diylbis (oxy)) diphenylamine) (9g), NaNO2(4g)、NaN3(4.7g) and conc. HCl (concentrated HCl) (15ml) the additive represented by chemical formula 2b was obtained.
[ chemical formula 2b ]
Synthesis example 3
According to the same method as that of Synthesis example 1, 4'- (biphenyl-4,4' -diylbis (oxy)) dianiline (4,4'- (biphenyl-4,4' -diylbis (oxy)) diphenylamine) (9g), NaNO2(4g)、NaN3(4.7g) and conc. HCl (concentrated HCl) (15ml) the additive represented by chemical formula 2c was obtained.
[ chemical formula 2c ]
Synthesis example 4
According to the same method as in Synthesis example 1, by using 4,4'- (4,4' - (propane-2,2-diyl) bis (4, l-phenylene)) bis (oxy) dianiline (4,4'- (4,4' - (propane-2,2-diyl) bis (4,1-phenylene)) bis (oxy) diphenylamine) (10g),NaNO2(4g) KI (12.1g) and conc.HCl (concentrated HCl) (20ml) gave a solid intermediate (7.7 g). The obtained intermediate (5.7g) was dissolved in tetrahydrofuran (40mL) and 2.9M ipro-MgBr (9mL) was slowly added dropwise thereto at-40 ℃. After 30 minutes, dried DMF (10mL) was slowly added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. After ethyl acetate (100mL) was added dropwise to the reaction solution, the resultant obtained therefrom was washed several times with water. Then, EtOAc was removed to obtain the polymer represented by formula 2 d'.
[ chemical formula 2 d' ]
The obtained compound 2 d' (4.3g) was dissolved in tetrahydrofuran (50mL), and the solution was stirred in ice water. Lithium aluminum hydride (0.75g) was slowly added dropwise thereto, and the obtained mixture was stirred in ice water for 2 hours. After completion of the reaction, 10% aqueous NaOH solution (0.75g), H was slowly added dropwise thereto in this order2O (1.5 g), and 10% NaOH (2.3 g). The resulting mixture was stirred well at room temperature and filtered, the filtered solution was reduced under pressure to remove Tetrahydrofuran (THF) and dissolved in EtOAc (100mL), and then washed several times with water. After complete removal of the organic solvent therefrom, intermediate 2d "was obtained. Intermediate 2d "was dissolved in DMF (20mL), the solution was stirred for 10 minutes, and 60% NaH (1g) was slowly added dropwise thereto. The mixture was stirred in ice water for 30 minutes and propargyl bromide (80% in tolumen in toluene) (4mL) was added dropwise thereto. When the reaction was complete, EtOAc (100mL) was added to dilute the reaction solution, and the diluted reaction solution was washed several times to remove DMF. When DMF was completely removed, EtOAc remaining therein was removed to obtain an additive represented by formula 2d (4.5 g).
[ chemical formula 2d ]
Synthesis example 5
According to the same method as that of Synthesis example 1, 4'- (l,3-phenylenebis (oxy)) dianiline (4,4' - (1, 3-phenylenebis (oxy)) diphenylamine) (210g), NaNO2(5.7g), NaCN (4.7g) and conc. HCl (concentrated HCl) (15ml) the additive represented by chemical formula 2e was obtained.
[ chemical formula 2e ]
Synthesis example 6
Preparation of the additive represented by chemical formula 2f (product name: 2,2-bis [4- (4-aminophenoxy) -phenyl ] propanen (2, 2-bis [4- (4-aminophenoxy) -phenyl ] propane), manufactured by TCI corporation) was used.
[ chemical formula 2f ]
Preparation of hard mask composition
Examples 1 to 14 and comparative examples 1 to 3
The hard mask composition is prepared by dissolving the polymer and additives in Propylene Glycol Monomethyl Ether Acetate (PGMEA) solvent and filtering the solution.
The following compositions shown in table 1 used polymers and additives.
[ Table 1]
| Polymer and method of making same | Additive agent | |
| Example 1 | Polymer 1a | Chemical formula 2a |
| Example 2 | Polymer 1b | Chemical formula 2a |
| Example 3 | Polymer 1c | Chemical formula 2a |
| Example 4 | Polymer 1d | Chemical formula 2b |
| Example 5 | Polymer 1e | Chemical formula 2b |
| Example 6 | Polymer 1f | Chemical formula 2a |
| Example 7 | Polymer 1g | Chemical formula 2a |
| Example 8 | Polymer 1h | Chemical formula 2c |
| Example 9 | Polymer 1i | Chemical formula 2a |
| Example 10 | Polymer 1j | Chemical formula 2e |
| Example 11 | Polymer 1d | Chemical formula 2f |
| Example 12 | Polymer 1f | Chemical formula 2b |
| Example 13 | Polymer 1g | Chemical formula 2c |
| Example 14 | Polymer 1i | Chemical formula 2d |
| Comparative example 1 | Polymer 1k | - |
| Comparative example 2 | Polymer 1a | - |
| Comparative example 3 | Polymer 1b | - |
Evaluation 1: planarization features
Each composition shown in table 1 was spin-coated on a patterned silicon wafer (trench width: 10 μm (micrometer), trench depth: 100nm (nanometer)), respectively, and baked to form a thin film, and a cross section of the thin film was examined by using a vertical scanning electron microscope (V-SEM) apparatus.
The hard mask composition is adjusted to have a solid content for forming on a bare wafer after a first heat treatment at 180 ℃ for 120 seconds and a second heat treatment at 400 ℃ for 120 seconds
(angstrom) thick films. Each hard mask composition was spin coated separately and then subsequently heat treated first at 180 ℃ for 120 seconds and then at 400 ℃ for 120 seconds.
The planarization characteristics were evaluated by measuring the difference in thickness (i.e., step difference) of the bottom layer of resist in the region with holes and the bottom layer of resist in the other region without holes. Fig. 1 is an enlarged cross-sectional view of any pattern in a silicon wafer coated with a coating liquid. The thickness indicated by the arrow in fig. 1 corresponds to the step.
The more excellent the planarization characteristics, the smaller the thickness difference (step difference) in the patterned region and the non-patterned region, and thus, a smaller value indicates excellent planarization characteristics. The results are shown in Table 2.
[ Table 2]
| Step (nm) | |
| Example 1 | 26nm |
| Example 2 | 13nm |
| Example 3 | 25nm |
| Example 4 | 18nm |
| Example 5 | 27nm |
| Example 6 | 28nm |
| Example 7 | 16nm |
| Comparative example 1 | 33nm |
| Comparative example 2 | 39nm |
Referring to table 2, the thin films formed of the hard mask compositions according to examples 1 to 7, respectively, show superior planarization characteristics compared to the thin films formed of the hard mask compositions according to comparative examples 1 and 2, respectively.
Evaluation 2: thickness Uniformity (Thickness Uniformity)
The hard mask compositions according to examples 7 to 14 and comparative examples 1 and 3 were spin-coated on a 12-inch silicon wafer, respectively, and then the thin film formed from the hard mask composition was heat-treated at 180 ℃ for 120 seconds first and 4 seconds secondHeat treatment was carried out at 00 ℃ for 120 seconds. The solid content of the film is adjusted to be formed after the second heat treatment
(angstrom) thick films.
The thickness uniformity was calculated according to the calculation equation 2 by taking 19 points and measuring each thickness at the 19 points as shown in fig. 2. The thickness was measured by using a K-MAC device. The results are shown in Table 3.
[ calculation equation 2]
Uniformity (%) (maximum thickness at 19 points of the film-minimum thickness at 19 points of the film)/(average thickness at 19 points of the film) × 100
[ Table 3]
| Uniformity (%) | |
| Example 7 | <2％ |
| Example 8 | <2％ |
| Example 9 | <2％ |
| Example 10 | <2％ |
| Example 11 | <2％ |
| Example 12 | <2％ |
| Example 13 | <2％ |
| Example 14 | <2％ |
| Comparative example 1 | 7％ |
| Comparative example 3 | 6％ |
Referring to table 3, the thin films formed from the hard mask compositions according to examples 7 to 14 show superior thickness uniformity compared to the thin films formed from the hard mask compositions according to comparative examples 1 and 3.
Evaluation 3: coating Properties
The hard mask compositions according to examples 1 to 8 and comparative examples 2 and 3 were spin-coated on a silicon wafer, respectively, and then heat-treated at 180 ℃ for 120 seconds first and 400 ℃ for 120 seconds second first to form a thin film. The solid content of the hard mask composition is adjusted to form after the second heat treatment
(angstrom) thick films.
The surface of the film was examined by an electron microscope. The results are shown in Table 4.
[ Table 4]
| Coating Properties | |
| Example 1 | Good effect |
| Example 2 | Good effect |
| Example 3 | Good effect |
| Example 4 | Good effect |
| Example 5 | Good effect |
| Example 6 | Good effect |
| Example 7 | Good effect |
| Example 8 | Good effect |
| Comparative example 2 | Poor quality |
| Comparative example 3 | Poor quality |
As shown in table 4, the thin films formed of the hard mask compositions according to examples 1 to 8, respectively, showed superior coating properties compared to the thin films formed of the hard mask compositions according to comparative examples 2 and 3, respectively.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (15)
1. An organic layer composition comprising:
a polymer comprising a structural unit represented by chemical formula 1;
an additive represented by chemical formula 3; and
solvent:
[ chemical formula 1]
Wherein, in chemical formula 1,
a is a substituted or unsubstituted moiety selected from group 1 and group 2,
[ group 1]
[ group 2]
Wherein, in group 2,
Z1and Z2Independently is NRdO, S, Te, or Se, in a single crystal,
Z3and Z4Is N, and
Rdand ReIndependently hydrogen, hydroxy, methoxy, ethoxy, a halogen containing group, a substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstitutedA substituted C6 to C30 aryl group, or a combination thereof;
b is represented by one of chemical formula Z1 to chemical formula Z4:
[ chemical formula Z1]
[ chemical formula Z2]
[ chemical formula Z3]
[ chemical formula Z4]
Wherein, in the chemical formula Z1 to the chemical formula Z4,
e and f are independently 0 or 1,
g is an integer of 1 to 5,
Y1to Y4Is independently one of a substituted or unsubstituted moiety selected from group 3, and
is a connection point:
[ group 3]
Wherein, in group 3,
m, M ', and M' are independently substituted or unsubstituted C1 to C10 alkylene, O, S, SO2、CRfRg、NRhOr a carbonyl group, wherein RfTo RhIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl groups, halogen-containing groups, or combinations thereof,
L1is a substituted or unsubstituted C6 to C50 arylene, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
r is an integer of 0 to 10,
s is an integer of 0 to 10, and
k is an integer of 0 to 3;
at least one of a and B is substituted with a functional group comprising a moiety represented by formula 2':
[ chemical formula 2' ]
Wherein, in chemical formula 2',
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen containing group, or combinations thereof,
z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C30 aryl,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point;
[ chemical formula 3]
Wherein, in chemical formula 3,
k. m and n are independently 0 or 1, and the sum of k, m, and n is 2 or 3,
when k + m + n =3, X is-CH-or nitrogen,
when k + m + n =2, X is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen, sulfur, -NH-, or-S (O)2) -, wherein q and t are independently integers of 1 to 5, and RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, and
r, R 'and R' are independently substituted or unsubstituted aromatic ring-containing groups, wherein R, R 'or R' comprises at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, and a nitrile group.
2. The organic layer composition of claim 1, wherein the additive is represented by chemical formula 4 or chemical formula 5:
[ chemical formula 4]
[ chemical formula 5]
Wherein, in chemical formula 4 and chemical formula 5,
X1is-CH-or nitrogen, and is,
X2is a direct bond, - (C)qH2q)-、-(CtRw 2t) -, oxygen, sulfur, -NH-, or-S (O)2) -, where q and t are independently integers from 1 to 5, RwIs a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstitutedUnsubstituted C3 to C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C7 to C20 arylalkyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl, substituted or unsubstituted C2 to C20 alkenyl, or a combination thereof, and
R1to R5Independently an aromatic ring-containing group comprising at least one of the groups represented by chemical formula 6:
[ chemical formula 6]
Wherein, in chemical formula 6,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen containing group, or combinations thereof,
y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
3. The organic layer composition of claim 2, wherein R is represented by chemical formula 4 and chemical formula 51To R5Independently represented by chemical formula 7:
[ chemical formula 7]
Wherein, in chemical formula 7,
R1ato R13aIndependently hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or the group represented by chemical formula 6, wherein R is1aTo R13aAt least one of which is the group represented by chemical formula 6,
T1and T2Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen containing group, or combinations thereof,
c and d are independently an integer of 0 to 5, and
is a connection point.
4. The organic layer composition of claim 1, wherein in chemical formula 1, a comprises at least one substituted or unsubstituted aromatic ring or substituted or unsubstituted heteroaromatic ring.
5. The organic layer composition of claim 1, wherein the polymer further comprises a structural unit represented by chemical formula 8:
[ chemical formula 8]
Wherein, in chemical formula 8,
X0is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
L0is a divalent organic radical, and
is a connection point.
6. The organic layer composition of claim 5, wherein in chemical formula 8, X0Is a substituted or unsubstituted moiety selected from group 1 and group 2:
[ group 1]
[ group 2]
Wherein, in group 2,
Z1and Z2Independently is NRdO, S, Te or Se, and the use of the selenium,
Z3and Z4Is N, and
Rdand ReIndependently hydrogen, hydroxy, methoxy, ethoxy, a halogen-containing group, a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof.
7. The organic layer composition of claim 1, wherein the polymer comprises at least one oxygen atom in the structural unit.
8. The organic layer composition of claim 1, wherein the additive is represented by one of formula Y1 to formula Y4:
[ chemical formula Y1]
[ chemical formula Y2]
[ chemical formula Y3]
[ chemical formula Y4]
Wherein, in the chemical formulae Y1 to Y4,
T3and T4Independently O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen containing group, or combinations thereof,
Rxto RyIndependently is hydrogen, a halogen-containing radical or a substituted or unsubstituted C1 to C20 alkyl radical, and
R33to R55Independently a group represented by chemical formula 6:
[ chemical formula 6]
Wherein, in chemical formula 6,
w is O, S, NRaOr CRbRcWherein R isaTo RcIndependently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen containing group, or combinations thereof,
y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1, and a is,
b is an integer ranging from 0 to 10, and
is a connection point.
9. The organic layer composition of claim 1, wherein the additive has a molecular weight of 150 to 50,000.
10. The organic layer composition of claim 1, wherein the polymer has a weight average molecular weight of 500 to 200,000.
11. The organic layer composition of claim 1, wherein the additive is present in an amount of 5 to 50 wt%, based on the total amount of the organic layer composition.
12. A pattern forming method comprising:
a layer of material is provided on a substrate,
applying the organic layer composition of any one of claims 1 to 11 on the material layer,
heat-treating the organic layer composition to form a hard mask layer,
forming a thin layer comprising silicon on the hard mask layer,
forming a photoresist layer on the silicon-containing thin layer,
exposing and developing the photoresist layer to form a photoresist pattern,
selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer, and
the exposed portion of the material layer is etched.
13. The pattern forming method according to claim 12, wherein the organic layer composition is applied using a spin coating method.
14. The pattern forming method according to claim 12, wherein the heat treatment includes a first heat treatment performed at 50 ℃ to 250 ℃ and a second heat treatment performed after the first heat treatment and at 200 ℃ to 500 ℃.
15. The pattern forming method according to claim 12, wherein the pattern forming method further comprises forming a bottom anti-reflective coating layer before forming the photoresist layer.
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