CN109478015A - Organic layer constituent and pattern forming method - Google Patents
Organic layer constituent and pattern forming method Download PDFInfo
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- CN109478015A CN109478015A CN201680087729.4A CN201680087729A CN109478015A CN 109478015 A CN109478015 A CN 109478015A CN 201680087729 A CN201680087729 A CN 201680087729A CN 109478015 A CN109478015 A CN 109478015A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- 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
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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
- H01L21/02104—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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- 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
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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
- 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
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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 present invention discloses a kind of organic layer constituent and the pattern forming method using organic layer constituent, and organic layer constituent includes: polymer includes the structural unit indicated by chemical formula 1；Additive includes at least one of the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, the acetenyl, azido or the itrile group that are substituted or are unsubstituted in the structure as the cycle compound containing aromatics；And solvent.Chemical formula 1 in the description defined in it is identical.
Description
Technical field
The present invention discloses a kind of organic layer constituent and the pattern forming method using the organic layer constituent.
Background technique
Recently, according to the miniaturization of electronic device (micromation (miniaturation)) and complexity (complexity)
And the high product body design carried out has accelerated the development of more advanced material and its related process, and therefore, uses traditional photoresist
The lithography of agent also needs novel pattern material and technology.
In patterning process, the organic layer for being referred to as curtain layer of hard hood (hardmask layer) can be formed as hard centre
Layer is to be transferred to downwards enough depth on substrate without collapsing it for the fine pattern of photoresist.
Curtain layer of hard hood plays the effect of middle layer to shift the fine pattern of photoresist by selective etch processing procedure
To material layer.Therefore, curtain layer of hard hood needs the feature such as heat resistance, elching resistant to be resistant to multiple etching processing procedure.
On the other hand, proposed that spin coating (spin-on coating) method substitutes chemical vapor deposition (chemical recently
Vapor deposition, CVD) method forms curtain layer of hard hood.Between spin coating method can not only execute easily and can also improve
Gap fills (gap-fill) feature and planarizing features.
Generally, due to which heat resistance and elching resistant and spin coating feature have trade-off relationship, it is therefore desirable to a kind of satisfaction
The organic layer material of all features.
Summary of the invention
Technical problem
One embodiment of the invention provides a kind of having for elching resistant that can be coated in a manner of spin coating and have raising
Machine layer constituent.
Another embodiment of the present invention provides a kind of pattern forming methods using the organic layer constituent.
Technical solution
According to an embodiment, a kind of organic layer constituent includes: polymer includes the structural unit indicated by chemical formula 1；
Additive, in the structure as the cycle compound containing aromatics comprising be substituted or be unsubstituted amido, be substituted or without taking
At least one of the vinyl in generation, the acetenyl for being substituted or being unsubstituted, azido or itrile group；And solvent.
[chemical formula 1]
In chemical formula 1,
A is the base containing aromatic ring for being substituted or being unsubstituted, is substituted or is unsubstituted base containing heteroaromatic rings or
A combination thereof,
B is divalent organic base, and
The functional group for the part (moiety) that at least one of A and B included can be indicated by chemical formula 2 replaces:
[chemical formula 2]
Wherein, in chemical formula 2,
Z is hydrogen, hydroxyl, C1 to the C10 alkyl for being substituted or being unsubstituted or the C6 to C30 for being substituted or being unsubstituted virtue
Base, and
It * is tie point.
The functional group comprising the part indicated by chemical formula 2 can be indicated by chemical formula 2 '.
[chemical formula 2 ']
In chemical formula 2 ',
W is O, S, NRaOr CRbRc, wherein RaTo RcIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted,
Halogen atom, halogen-containing base or combinations thereof,
Z is hydrogen, hydroxyl, C1 to the C10 alkyl for being substituted or being unsubstituted or the C6 to C30 for being substituted or being unsubstituted virtue
Base,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
Additive can be indicated by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
K, m and n independently is 0 or 1, and the sum of k, m and n are 2 or 3,
As k+m+n=3, X be-CH- or nitrogen (N),
As k+m+n=2, X is direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2)-,
Wherein q and t independently 1 to 5 integer, and RwFor be substituted or be unsubstituted C1 to C20 alkyl, be substituted or without taking
C6 to the C30 aryl in generation, C3 to the C30 cycloalkenyl for being substituted or being unsubstituted, C1 to the C20 alkyl for being substituted or being unsubstituted
Amido, C1 to the C20 miscellaneous alkyl for being substituted or being unsubstituted, is substituted C7 to the C20 aryl alkyl for being substituted or being unsubstituted
Or be unsubstituted C2 to C30 Heterocyclylalkyl, be substituted or be unsubstituted C2 to C30 heteroaryl, be substituted or be unsubstituted
C1 to C4 alkylether radicals, be substituted or be unsubstituted C7 to C20 aryl alkylene ether, the C1 that is substituted or is unsubstituted
To C30 halogenated alkyl, it is substituted or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R, R' and R " independently is containing the base containing aromatic ring for being substituted or being unsubstituted, and wherein R, R' or R " include warp
Amido, the vinyl for being substituted or being unsubstituted, the acetenyl, the azido that are substituted or are unsubstituted for replacing or being unsubstituted
Or at least one of itrile group.
Additive can be indicated 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,
X1For-CH- or nitrogen (N),
X2For direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2Wherein q and t is independent by)-,
The integer that ground is 1 to 5, RwFor C1 to the C20 alkyl for being substituted or being unsubstituted, the C6 to C30 for being substituted or being unsubstituted virtue
Base, C3 to the C30 cycloalkenyl for being substituted or being unsubstituted, C1 to the C20 alkyl amine group for being substituted or being unsubstituted, be substituted or
C7 to the C20 aryl alkyl that is unsubstituted, C1 to the C20 miscellaneous alkyl that is substituted or is unsubstituted are substituted or are unsubstituted
C2 to C30 Heterocyclylalkyl, C2 to the C30 heteroaryl that is substituted or is unsubstituted, C1 to the C4 alkyl for being substituted or being unsubstituted
Ether, C7 to the C20 aryl alkylene ether for being substituted or being unsubstituted, C1 to the C30 alkyl halide for being substituted or being unsubstituted
Base is substituted or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R1To R5It independently is the base containing aromatic ring, the base containing aromatic ring includes at least one in the base indicated by chemical formula 6
Person.
[chemical formula 6]
In chemical formula 6,
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C10 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Plain atom, halogen-containing base or combinations thereof,
Y is the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, is substituted or is unsubstituted
Acetenyl, azido, itrile group or combinations thereof,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
In chemical formula 4 and chemical formula 5, R1To R5Independently indicated by chemical formula 7.
[chemical formula 7]
In chemical formula 7,
R1aTo R13aIt independently is hydrogen, hydroxyl, C1 to the C10 alkyl that is substituted or is unsubstituted or is indicated by chemical formula 6
Base, wherein R1aTo R13aAt least one of for the base that is indicated by chemical formula 6,
T1And T2It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 for independently being hydrogen, being substituted or being unsubstituted
To C10 alkyl, halogen atom, halogen-containing base or combinations thereof,
C and d independently 0 to 5 integer, and
It * is tie point.
In chemical formula 1, A can be the part (moiety) for being substituted or being unsubstituted selected from group 1 and group 2.
[group 1]
[group 2]
In group 2,
Z1And Z2It independently is NRd, O, S, Te or Se,
Z3And Z4For N, and
RdAnd ReIt independently is hydrogen, hydroxyl, methoxyl group, ethyoxyl, halogen atom, halogen-containing base, is substituted or without taking
1 to the C30 alkyl in generation is substituted or C6 to the C30 aryl being unsubstituted or combinations thereof.
In chemical formula 1, A may include at least one aromatic ring for being substituted or being unsubstituted or be substituted or be unsubstituted
Heteroaromatic rings.
B can be indicated by one of chemical formula Z1 to chemical formula Z4.
[chemical formula Z1]
[chemical formula Z2]
[chemical formula Z3]
[chemical formula Z4]
In chemical formula Z1 into chemical formula Z4,
E and f independently is 0 or 1,
The integer that g is 1 to 5,
Y1To Y4It independently is one of the part for being substituted or being unsubstituted selected from group 3, and
It * is tie point.
[group 3]
In group 3,
M, M' and M " independently is C1 to C10 alkylidene, O, S, the SO for being substituted or being unsubstituted2、CRfRg、NRhOr carbonyl
Base, wherein RfTo RhIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted, halogen atom, halogen-containing base or its
Combination,
L1For be substituted or be unsubstituted C6 to C50 arlydene, containing the C1 to C10 for being substituted or being unsubstituted containing epoxy
Base (alkylene oxide-containing group) of alkane or combinations thereof,
R is integer of 0 to 10,
S is integer of 0 to 10, and
The integer that k is 0 to 3.
Polymer can also include the structural unit indicated by chemical formula 8.
[chemical formula 8]
·-X0-L0-·
In chemical formula 8,
X0For the base containing aromatic ring for being substituted or being unsubstituted, the base containing heteroaromatic rings for being substituted or being unsubstituted or
A combination thereof,
L0For divalent organic base, and
It * is tie point.
In chemical formula 8, the X0It can be the part for being substituted or being unsubstituted selected from group 1 and group 2.
[group 1]
[group 2]
In group 2,
Z1And Z2It independently is NRd, O, S, Te or Se,
Z3And Z4For N,
RdAnd ReIt independently is hydrogen, hydroxyl, methoxyl group, ethyoxyl, halogen atom, halogen-containing base, is substituted or without taking
1 to the C30 alkyl in generation is substituted or C6 to the C30 aryl being unsubstituted or combinations thereof.
Polymer may include at least one oxygen atom in structural unit.
Chemical formula 2 can be indicated by chemical formula 2 '.
[chemical formula 2 ']
In chemical formula 2 ',
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C20 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Plain atom, halogen-containing base or combinations thereof,
A is 0 or 1, and
It * is tie point.
Additive can be indicated by one of chemical formula Y1 to chemical formula Y4.
[chemical formula Y1]
[chemical formula Y2]
[chemical formula Y3]
[chemical formula Y4]
In chemical formula Y1 into chemical formula Y4,
T3And T4It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 for independently being hydrogen, being substituted or being unsubstituted
To C10 alkyl, halogen atom, halogen-containing base or combinations thereof,
RxTo RyIt independently is hydrogen, halogen atom, halogen-containing base or C1 to the C20 alkyl for being substituted or being unsubstituted, and
R33To R55It independently is the base indicated by chemical formula 6.
[chemical formula 6]
In chemical formula 6,
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C10 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Plain atom, halogen-containing base or combinations thereof,
Y is the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, is substituted or is unsubstituted
Acetenyl, azido, itrile group or combinations thereof,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
Additive can have 150 to 50,000 molecular weight.
Polymer can have 500 to 200,000 weight average molecular weight.
In terms of the total amount of organic layer constituent, the amount of additive is 5 weight % to 50 weight %.
According to another embodiment, a kind of pattern forming method includes: that material layer is provided on substrate, by organic layer constituent
It is applied in material layer, organic layer constituent is heat-treated to form curtain layer of hard hood, formed on curtain layer of hard hood siliceous
Thin layer, forms photoresist layer on siliceous thin layer, and photoresist pattern is exposed and be developed to photoresist layer, uses
Photoresist pattern removes siliceous thin layer and curtain layer of hard hood selectively to expose a part of the material layer and right
The part that is exposed of material layer is etched.
Organic layer constituent can be applied using rotating coating.
It is described heat treatment may include at 50 to 250 DEG C carry out first heat treatment and first heat treatment after 200 to
The second heat treatment is carried out at 500 DEG C.
The method can further include the formation bottom antireflective coating (bottom before forming photoresist layer
Antireflective coating, BARC).
Invention effect
The present invention provide it is a kind of because comprising predetermined polymer and due to predetermined additive be coated with spin coating method it is same
When the elching resistant with raising organic layer constituent.There is the film density improved by the organic layer that organic layer constituent manufactures
And film flatness.
Detailed description of the invention
Fig. 1 is the view for illustrating a kind of method for assessing planarizing features (scale feature).
Fig. 2 is the view for illustrating a kind of method for assessing the thickness uniformity (Thickness Uniformity) feature
Figure.
Specific embodiment
Exemplary embodiment of the invention will be described in detail following, and can be by technical staff in the related technology easily
Ground executes.However, it is many different forms that the present invention is implementable, and it should not be construed as limited to exemplary reality as described herein
Apply example.
In the present specification, when in addition not providing definition, term " being substituted " can be referred to one and take through selected from the following
Replace for base with the hydrogen of alternative compounds: halogen atom (F, Br, Cl or I), hydroxyl, alkoxy, nitro, cyano, amido, nitrine
Base, amidino groups, diazanyl, hydrazone group, carbonyl, amine formyl, mercapto, ester group, carboxyl or its salt, sulfonic group or its salt, phosphoric acid or its
Salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 aryl alkyl, C1 to C30 alkane
Oxygroup, C1 to C20 miscellaneous alkyl, C2 to C20 heteroaryl, C3 to C20 heteroaryl alkyl, C3 to C30 naphthenic base, C3 to C15 cyclenes
Base, C6 to C15 cycloalkynyl radical, C2 to C30 Heterocyclylalkyl and combinations thereof.
In the present specification, when in addition not providing definition, " miscellaneous " one that refers to includes 1 to 3 in N, O, S and P
A hetero atom.
Hereinafter, illustrating the organic layer constituent according to an embodiment.
Include according to the organic layer constituent of an embodiment: polymer includes the structural unit indicated by chemical formula 1；Add
Add agent, in the structure as the compound containing aromatic ring comprising be substituted or be unsubstituted amido, be substituted or without taking
At least one of the vinyl in generation, the acetenyl for being substituted or being unsubstituted, azido or itrile group；And solvent.
[chemical formula 1]
In chemical formula 1,
A is the base containing aromatic ring for being substituted or being unsubstituted, is substituted or is unsubstituted base containing heteroaromatic rings or
A combination thereof,
B is divalent organic base, and
At least one of A and B can the included part indicated by chemical formula 2 functional group replace:
[chemical formula 2]
Wherein, in chemical formula 2,
Z is hydrogen, hydroxyl, C1 to the C10 alkyl for being substituted or being unsubstituted or the C6 to C30 for being substituted or being unsubstituted virtue
Base, and
It * is tie point.
Organic layer constituent includes the polymer with predetermined structure and the additive with predetermined structure.Firstly, illustrating
Polymer.
Polymer includes one or more of the structural unit indicated by chemical formula 1, and chemical formula 1 wraps in structural unit
Containing the part containing aromatic ring indicated by A and the linker part indicated by B.
For example, A can be the base containing aromatic ring for being substituted or being unsubstituted, and may include for example selected from group 1
The part for being substituted or being unsubstituted, but it is not limited only to this.
[group 1]
Again for example, A can be the base containing heteroaromatic rings for being substituted or being unsubstituted, and may include for example selected from group
2 part for being substituted or being unsubstituted, but it is not limited only to this.
[group 2]
In group 2,
Z1And Z2It independently is NRd, O, S, Te or Se,
Z3And Z4For N, and
RdAnd ReIt independently is hydrogen, hydroxyl, methoxyl group, ethyoxyl, halogen atom, halogen-containing base, is substituted or without taking
1 to the C30 alkyl in generation is substituted or C6 to the C30 aryl being unsubstituted or combinations thereof.
Again for example, A can be that the base for being substituted or being unsubstituted containing aromatic ring contains with what is be substituted or be unsubstituted
The combination of the base of heteroaromatic rings.For example, in chemical formula 1, A may include that two or more is substituted or is unsubstituted
Phenyl ring, such as two phenyl ring for being substituted or being unsubstituted to six.Herein, phenyl ring can replace through at least one hydroxyl.
In chemical formula 1, the B for being designated as linker can be divalent organic linear base, the organic cyclic group of divalent or combinations thereof.
For example, B can be indicated by one of chemical formula Z1 to chemical formula Z4, but be not limited only to this.
[chemical formula Z1]
[chemical formula Z2]
[chemical formula Z3]
[chemical formula Z4]
In chemical formula Z1 into chemical formula Z4,
E and f independently is 0 or 1,
The integer that g is 1 to 5,
Y1To Y4It independently is one of the part for being substituted or being unsubstituted selected from group 3, and
* it is tie point:
[group 3]
In group 3,
M, M' and M " independently is C1 to C10 alkylidene, O, S, the SO for being substituted or being unsubstituted2、CRfRg、NRhOr carbonyl
Base, wherein RfTo RhIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted, halogen atom, halogen-containing base or its
Combination,
L1For be substituted or be unsubstituted C6 to C50 arlydene, containing the C1 to C10 for being substituted or being unsubstituted containing epoxy
Base of alkane or combinations thereof,
R is integer of 0 to 10,
The integer that s is 3 to 10, and
K is integer of 1 to 3.
On the other hand, in chemical formula 1, at least one of A and B can take via the base containing acetylene that chemical formula 2 indicates
Generation.For example, it can be replaced through the base containing acetylene by the A base containing aromatic ring indicated or the base containing heteroaromatic rings, be indicated by B
Linker can replace through the substitution of the base containing acetylene or part A and part B through the base containing acetylene.Herein, substituted number
Mesh is not particularly limited.
For example, the functional group comprising the part indicated by chemical formula 2 can be the base indicated by chemical formula 2 ', but not
It is only limitted to this.
[chemical formula 2 ']
In chemical formula 2 ',
W is O, S, NRaOr CRbRc, wherein RaTo RcIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted,
Halogen atom, halogen-containing base or combinations thereof,
Z is hydrogen, hydroxyl, C1 to the C10 alkyl for being substituted or being unsubstituted or the C6 to C30 for being substituted or being unsubstituted virtue
Base,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
For example, the functional group comprising the part indicated by chemical formula 2 can be indicated by chemical formula 2 ", but be not limited only to
This.
[chemical formula 2 "]
In chemical formula 2 ",
W is O, S, NRaOr CRbRc, wherein RaTo RcIndependently be hydrogen, C1 to the C20 alkyl that is substituted or is unsubstituted,
Halogen atom, halogen-containing base or combinations thereof,
A is 0 or 1, and
It * is tie point.
For example, polymer may include at least one oxygen atom in its structure.
Therefore polymer, comprising the base containing aromatic ring that is indicated by A or containing the base of heteroaromatic rings, and may be used in structural unit
Guarantee elching resistant, and in addition, polymer includes by the B organic group indicated and therefore certifiable flexible
(flexibility).In addition, the elching resistant of polymer can be further improved, be introduced into because of at least one acetylene A or
B, and therefore ring structure can be formed when solidifying the polymer.Therefore, the organic layer formed by using polymer is shown
Excellent film density.In addition, the organic layer formed by using polymer can guarantee the thickness uniformity (uniformity).
Polymer can further include the structural unit for example indicated by chemical formula 8.
[chemical formula 8]
·-X0-L0-·
In chemical formula 8,
X0For the base containing aromatic ring for being substituted or being unsubstituted, the base containing heteroaromatic rings for being substituted or being unsubstituted or
A combination thereof,
L0For divalent organic base, and
It * is tie point.
In chemical formula 8, X can be the part for being substituted or being unsubstituted selected from group 1 and group 2, and L0With changing
B in formula 1 as linker is identical.It is substantially different from the structural unit indicated by chemical formula 1, it is indicated by chemical formula 8
Structural unit does not include acetylene functional group.
Hereinafter, illustrating the additive of organic layer constituent.
Additive is used as the compound containing aromatic ring as described above, it includes the amido for being substituted or being unsubstituted, through taking
Generation or at least one of the vinyl being unsubstituted, the acetenyl, azido or the itrile group that are substituted or are unsubstituted.
For example, additive can be indicated by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
K, m and n independently is 0 or 1, and the sum of k, m and n are 2 or 3,
As k+m+n=3, X be-CH- or nitrogen (N),
As k+m+n=2, X is direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2)-,
Wherein q and t independently 1 to 5 integer, and RwFor be substituted or be unsubstituted C1 to C20 alkyl, be substituted or without taking
C6 to the C30 aryl in generation, C3 to the C30 cycloalkenyl for being substituted or being unsubstituted, C1 to the C20 alkyl for being substituted or being unsubstituted
Amido, C1 to the C20 miscellaneous alkyl for being substituted or being unsubstituted, is substituted C7 to the C20 aryl alkyl for being substituted or being unsubstituted
Or be unsubstituted C2 to C30 Heterocyclylalkyl, be substituted or be unsubstituted C2 to C30 heteroaryl, be substituted or be unsubstituted
C1 to C4 alkylether radicals, be substituted or be unsubstituted C7 to C20 aryl alkylene ether, the C1 that is substituted or is unsubstituted
To C30 halogenated alkyl, it is substituted or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R, R' and R " independently is containing the base containing aromatic ring for being substituted or being unsubstituted, and wherein R, R' or R " include through taking
Generation or be unsubstituted amido, be substituted or be unsubstituted vinyl, be substituted or be unsubstituted acetenyl, azido or
At least one of itrile group.For example, R, R' or R " can be for for example through one of following or both substituents: be substituted or
The amido that is unsubstituted, the vinyl for being substituted or being unsubstituted, acetenyl, azido or the nitrile for being substituted or being unsubstituted
Base.
The additive indicated by chemical formula 3 has wherein two or three bases containing aromatic ring in core represented by X
It is connected to mutual structure.When the additive tool indicated by chemical formula 3 is there are three when substituent group, core is carbon or nitrogen, and works as and add
Add agent tool there are two when substituent group, core is direct key, carbon, oxygen, sulphur or-S (O2)-。
For example, when additive have wherein three bases containing aromatic ring are connected to mutual structure in the core when,
Additive can indicate by chemical formula 4, and when that there is base of the two of them containing aromatic ring to be connected in the core is mutual for additive
When structure, additive can be indicated by chemical formula 3.
[chemical formula 4]
[chemical formula 5]
R4-X2-R5
In chemical formula 4 and chemical formula 5,
X1For-CH- or nitrogen (N),
X2For direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2Wherein q and t is independent by)-,
The integer that ground is 1 to 5, RwFor C1 to the C20 alkyl for being substituted or being unsubstituted, the C6 to C30 for being substituted or being unsubstituted virtue
Base, C3 to the C30 cycloalkenyl for being substituted or being unsubstituted, C1 to the C20 alkyl amine group for being substituted or being unsubstituted, be substituted or
C7 to the C20 aryl alkyl that is unsubstituted, C1 to the C20 miscellaneous alkyl that is substituted or is unsubstituted are substituted or are unsubstituted
C2 to C30 Heterocyclylalkyl, C2 to the C30 heteroaryl that is substituted or is unsubstituted, C1 to the C4 alkyl for being substituted or being unsubstituted
Ether, C7 to the C20 aryl alkylene ether for being substituted or being unsubstituted, C1 to the C30 alkyl halide for being substituted or being unsubstituted
Base is substituted or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R1To R5It independently is the base containing aromatic ring, the base containing aromatic ring includes in the base indicated by chemical formula 6 in the structure
At least one.
[chemical formula 6]
In chemical formula 6,
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C10 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Plain atom, halogen-containing base or combinations thereof,
Y is the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, is substituted or is unsubstituted
Acetenyl, azido, itrile group or combinations thereof,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
For example, in chemical formula 4 and chemical formula 5, R1To R5It is independently indicated, but is not limited only to by chemical formula 7
This.
[chemical formula 7]
In chemical formula 7,
R1aTo R13aIt independently is hydrogen, hydroxyl, C1 to the C10 alkyl that is substituted or is unsubstituted or is indicated by chemical formula 6
Base, wherein R1aTo R13aAt least one of for the base that is indicated by chemical formula 6,
T1And T2It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 for independently being hydrogen, being substituted or being unsubstituted
To C10 alkyl, halogen atom, halogen-containing base or combinations thereof,
C and d independently 0 to 5 integer, and
It * is tie point.
For example, additive can be indicated by one of chemical formula Y1 to chemical formula Y4, but be not limited only to this.
[chemical formula Y1]
[chemical formula Y2]
[chemical formula Y3]
[chemical formula Y4]
In chemical formula Y1 into chemical formula Y4,
T3And T4It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 for independently being hydrogen, being substituted or being unsubstituted
To C10 alkyl, halogen atom, halogen-containing base or combinations thereof,
RxTo RyIt independently is hydrogen, halogen atom, halogen-containing base or C1 to the C20 alkyl for being substituted or being unsubstituted, and
R33To R55It independently is the base indicated by chemical formula 6.
For example, additive may include at least one oxygen atom or nitrogen-atoms in its structure, and may include such as one
A to three oxygen atoms or a nitrogen-atoms, but it is not limited only to this.
Additive can be used for example as crosslinking agent.
In this way, organic layer constituent includes the additive of the polymer comprising acetylene and the compound containing aromatic ring, it is described
Additive includes the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, is substituted or is unsubstituted
At least one of acetenyl, azido or itrile group.
In this way, when using polymer and additive simultaneously, the acetylene functional group that is introduced into polymer be introduced into
Amine, acetylene, nitrine into additive etc. react and form ring during curing, and therefore the carbon content in polymer can phase
To increase.Therefore, elching resistant can be improved, and therefore etching selectivity can be also improved.As a result, by using described
Organic layer constituent and the organic layer formed shows excellent film density and pattern Forming ability.
For example, polymer can have about 500 to 200,000 weight average molecular weight.It is in when polymer has
When weight average molecular weight in range, can solubility by adjusting carbon content and in a solvent and by having comprising polymer
Machine layer constituent (for example, hard cover screen constituent) optimizes.For example, additive can have about 150 to 50,000 molecule
Amount.
Solvent can for there is enough soluble or dispersion force any solvent for polymer, and can for for example selected from
Under at least one: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, butyl, three (second two
Alcohol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolacton, N, N- diformazan
Base formamide, N, N dimethyl acetamide, methylpyrrole pyridine ketone (methylpyrrolidone), N-methyl 2-pyrrolidone N
(methylpyrrolidinone), acetylacetone,2,4-pentanedione and 3- ethoxyl ethyl propionate.
In terms of the total amount of organic layer constituent, the polymer of the amount of about 0.1 to about 50 weight % may be present.When comprising described
When polymer in range, can thickness, surface roughness and planarization to organic layer control.
In terms of the total amount of organic layer constituent, the amount of about 0.1 to 50 weight %, for example, about 5 to 50 weight % may be present
Additive.When comprising additive in the range, the original flat of organic layer can be improved.
Organic layer constituent can further include following additive: interfacial agent, crosslinking agent, thermal acid generator, plasticiser etc..
The interfacial agent may include such as alkylbenzene sulfonate, Fixanol, polyethylene glycol or quarternary ammonium salt,
But it is not limited only to this.
Crosslinking agent can be such as melamine series, substituted urea system or polymer system crosslinking agent.Preferably, it can be for extremely
Few two are cross-linked to form the crosslinking agents of substituent group, for example, such as methoxymethylated glycoluril, butoxymethyl glycoluril,
Methoxymethylated melamine, butoxymethyl melamine, methoxymethylated benzoguanamine, butoxymethyl benzene
And the chemical combination such as guanamines, methoxymethylated urea, butoxymethyl urea, methoxymethylated thiocarbamide or butoxymethyl thiocarbamide
Object.
Crosslinking agent can be the crosslinking agent with high-fire resistance.Crosslinking agent with high-fire resistance can be to contain in the molecule
There is the compound of the cross-linking substituents of aromatic ring (for example, phenyl ring or naphthalene nucleus).
Thermal acid generator can be such as acid compound, such as p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, pyridine are to toluene sulphur
Acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid etc. or/and 2,4,4,6- tetrabromo hexamethylene two
Ketenes, styrax tosylate, 2- nitrobenzyl tosylate, other organic sulfonic acid Arrcostabs etc., but not only limit
In this.
In terms of the organic layer constituent of 100 parts by weight, the addition of the amount of about 0.001 parts by weight to 40 parts by weight may be present
Agent.In the range, solubility can be improved and the optical characteristics of organic layer constituent will not change.
According to another embodiment, a kind of organic layer manufactured using organic layer constituent is provided.Organic layer can for example pass through
Organic layer constituent is coated on substrate and it is heat-treated to be solidified to form, and may include for example being filled for electronics
Curtain layer of hard hood, planarization layer, sacrificial layer, filler for setting etc..
Hereinafter, illustrating a kind of pattern forming method by using organic layer constituent.
Include: that material layer is provided on substrate according to a kind of pattern forming method of one embodiment, will include polymer
And the organic layer constituent of solvent is applied in material layer, is heat-treated organic layer constituent to form curtain layer of hard hood,
Siliceous thin layer is formed on curtain layer of hard hood, forms photoresist layer on siliceous thin layer, photoresist layer is exposed and is developed
To form photoresist pattern, siliceous thin layer and curtain layer of hard hood are removed selectively using photoresist pattern with exposed material layer
A part, and to material layer be exposed part be etched.
Substrate can be such as Silicon Wafer, glass substrate or polymeric substrates.
Material layer is to finally carry out patterned material, for example, such as the metal layers such as aluminium layer and layers of copper, such as silicon
Semiconductor layers or the insulating layers such as silicon oxide layer and silicon nitride layer such as layer.Material layer can be for example, by chemical vapor deposition
(CVD) the methods of processing procedure is formed.
Organic layer constituent is same as described above, and can be applied in the form of a solution by spin coating.Herein, organic layer forms
The thickness of object is not particularly limited, but can be for for example, about 50 to about(angstrom).
Heat treatment about 10 seconds to 1 hour can be executed to organic layer constituent for example at about 100 to 500 DEG C.
For example, the heat treatment may include being heat-treated and described first the first time executed at 50 to 250 DEG C
Second of the heat treatment executed after heat treatment and at 200 to 500 DEG C.
Siliceous thin layer can be formed by such as SiCN, SiOC, SiON, SiOCN, SiC, SiN and/or its homologue.
The method, which can further include, to be to be formed before photoresist layer on siliceous thin layer, forms bottom antireflective coating
(bottom anti-reflective coating, BARC).
Such as ArF, KrF or EUV can be used to execute exposure to photoresist layer.It after exposition, can be at about 100 to 500 DEG C
It is lower to execute heat treatment.
Etch process can be executed to the part that is exposed of material layer by using the dry etch process of etching gas, and lost
Carving gas can be such as CHF3、CF4、Cl2、BCl3And its mixed gas, but it is unrestricted.
Etched material layer can be formed multiple patterns, and multiple patterns can be metal pattern, semiconductor pattern, insulation
Pattern etc., such as the various patterns of conductor integrated circuit device.
Specific embodiment
Hereinafter, the present invention is described in more detail in reference example.However, those examples are exemplary, and the present invention is simultaneously
It is non-to be only limitted to this.
Macroscopic single crystal
It polymerize example 1
Resin polymerization
Naphthalen-1-ol (naphthalene -1- alcohol) (14.2g), polyformaldehyde (6g), p-methyl benzenesulfonic acid water have been put into flask
Object (1.9g) and propylene glycol methyl ether acetate (PGMEA) (33g) are closed, and has carried out stirring at 80 DEG C to execute polymerization instead
It answers.When weight average molecular weight reaches 2,000 to 3,500 range, by being examined during reaction with GPC to molecular weight
It looks into and completes reaction.After polymerization reaction is completed, reactant is slowly cooled to room temperature, is added to 100g hexane thereto
It to extract propylene glycol methyl ether acetate, and is then removed by using distilled water and methanol, to obtain comprising by changing
The polymer (weight average molecular weight (Mw)=3,000) for the structural unit that formula 1a ' is indicated.
[chemical formula 1a ']
Acetylation (Acetylation_) reaction
It will be comprising being dissolved in DMF (40mL) by the polymer (10g) of the chemical formula 1a ' structural unit indicated in flask
In, and the solution is stirred in ice water.After stirring 10 minutes, NaH (1g) has slowly been added dropwise thereto,
The mixture is stirred 30 minutes, and it (is 80% (80%in in toluene that propargyl bromide has been added dropwise thereto
tolutene))(5.5g).After reacting completion, it is added to EtOAc (100mL) thereto with diluting reaction solution, and use water
The reaction solution has been washed several times to remove DMF.After removing completely DMF, remaining EtOAc is removed to obtain
Obtain polymer 1a.
It polymerize example 2
Resin polymerization
Make naphthalen-1-ol (naphthalene -1- alcohol) (10g), 1,3-bis in resin polymerization method identical with synthesis example 1
(4- (methoxymethyl) phenoxy) benzene (bis- (4- (methoxy) phenoxy group) benzene of 1,3-) (24.3g), the third two
Alcohol methyl ether acetate (PGMEA) (64g) and dithyl sulfate (diethylsulfate) (0.3g) carry out at 100 DEG C
Reaction, to obtain comprising the polymer (weight average molecular weight (Mw)=3,500) by the chemical formula 1b ' structural unit indicated.
[chemical formula 1b ']
Acetylation (Acetylation_) reaction
For acetylation identical with synthesis example 1, use comprising the polymer by the chemical formula 1b ' structural unit indicated
(10g), DMF (50mL), NaH (0.6g) and propargyl bromide (being 80% (80%in tolutene) in toluene) (2.6g), come
Obtain polymer 1b.
It polymerize example 3
Resin polymerization
Pyrene-1,6-diol (pyrene -1,6- glycol) (23g), 1,4-bis has been put into flask
(methoxymethyl) benzene (bis- (methoxy) benzene of 1,4-) (25g), propylene glycol methyl ether acetate (PGMEA)
(48g) and dithyl sulfate (diethylsulfate) (0.7g), and stirring has been carried out at 100 DEG C to execute polymerization reaction.
When weight average molecular weight reaches 2,000 to 3,500 range, reaction is completed.After polymerization reaction is completed, it will react
Object is slowly cooled to room temperature and has then been added it in 20g distilled water and 200g methanol, and is carried out to the mixture
Strong stirring and make its static later.From after its removal supernatant, deposit therein 40g propylene glycol has been dissolved in
In methyl ether acetate (PGMEA), and strong stirring is carried out to the solution by using 160g methanol and 160g water, and
Then make its static (first time).Then, and the supernatant obtained from it is removed, and deposit therein is dissolved in
In 40g propylene glycol methyl ether acetate (PGMEA) (for the second time).First time processing procedure and second of processing procedure are referred to as a purifying system
Journey, and this purifying manufacturing process is performed three times.Purified polymer 40g propylene glycol methyl ether acetate has been dissolved in
(PGMEA) in, and remaining methanol and distilled water in solution are removed under reduced pressure, to obtain comprising being indicated by chemical formula 1c '
Structural unit polymer (weight average molecular weight (Mw)=2,600).
[chemical formula 1c ']
Acetylation (Acetylation_) reaction
Include the polymer by the chemical formula 1c ' structural unit indicated by using 1 according to method identical with synthesis example 1
(10g), DMF (40mL), NaH (0.6g) and propargyl bromide (being 80% (80%in tolutene) in toluene) (2.2g) obtain
Obtained polymer 1c.
It polymerize example 4
Resin polymerization
According to resin polymerization method identical with synthesis example 1 by using 4,4'- (9H- Fluorene -9,9- diyl) diphenol (4,
4'- (9H-fluorene-9,9-diyl) diphenol) (14g), bis- (methoxy) benzene (1,3-bis of 1,4-
(methoxymethyl) benzene) (6.6g), propylene glycol methyl ether acetate (PGMEA) (20g) and dithyl sulfate
(diethylsulfate) (0.25g) is obtained at 100 DEG C comprising the polymer by the chemical formula 1d ' structural unit indicated
(weight average molecular weight (Mw)=3,700).
[chemical formula 1d ']
Acetylation (Acetylation_) reaction
According to acetylation process identical with synthesis example 1 by using the structural unit comprising being indicated by chemical formula 1d '
Polymer (9g), DMF (45mL), NaH (0.9g) and propargyl bromide (being 80% (80%in tolutene) in toluene)
(3.5g) obtains polymer 1d.
It polymerize example 5
Resin polymerization
According to resin polymerization method identical with synthesis example 1 by using 6,6'- (9H-fluorene-9,9-diyl)
Dinaphthalen-2-ol (6,6'- (9H- Fluorene -9,9- diyl) dinaphthyl -2- alcohol) (18g), bis- (methoxy) benzene of 1,3-
(1,3-bis (methoxymethyl) benzene) (6.6g), propylene glycol methyl ether acetate (PGMEA) (25g) and sulfuric acid two
Ethyl ester (diethylsulfate) (0.2g) is obtained at 110 DEG C comprising the polymerization by the chemical formula 1e ' structural unit indicated
Object (weight average molecular weight (Mw)=3,800).
[chemical formula 1e ']
Acetylation (Acetylation_) reaction
Via with 1 identical acetylation polymerizeing by using the structural unit comprising being indicated by chemical formula 1e ' of synthesis example
Object (25g), DMF (45mL), NaH (0.7g) and propargyl bromide (being 80% (80%in tolutene) in toluene) (2.5g)
Obtain polymer 1e.
It polymerize example 6
According to resin polymerization method identical with synthesis example 1 by using 4,4'- (9H-fluorene-9,9-diyl)
Dibenzene-1,2-dioll (4,4'- (9H- Fluorene -9,9- diyl) hexichol -1,2- glycol) (38g), 5-hydroxy-1-
Naphthaldehyde (5- hydroxyl-1-naphthalene Formaldehyde) (17g), propylene glycol methyl ether acetate (PGMEA) (129g) and sulfuric acid two
Ethyl ester (diethylsulfate) (0.3g) obtain comprising by the chemical formula 1f ' structural unit indicated polymer (Mw:3,
200)。
[chemical formula 1f ']
Acetylation (Acetylation_) reaction
According to acetylation process identical with synthesis example 1 by using the structural unit comprising being indicated by chemical formula 1f '
Polymer (10g), DMF (50mL), NaH (1.9g) and propargyl bromide (being 80% (80%in tolutene) in toluene)
(5.1g) obtains polymer 1f.
It polymerize example 7
Resin polymerization
According to synthetic method identical with synthesis example 1 by using 5,5'- (9H-fluorene-9,9-diyl)
Dibenzene-l, 2,3-triol (5,5'- (9H- Fluorene -9,9- diyl) hexichol -1,2,3- triol) (20g), 4,4'-oxybis
((methoxymethyl) benzene) (4,4'- oxygroup is bis- ((methoxy) benzene)) (26g), 1H-indol (1H- indoles)
(6g), propylene glycol methyl ether acetate (PGMEA) (123g) and dithyl sulfate (diethylsulfate) (0.5g) are 100
It is obtained at DEG C comprising the polymer (Mw:3,300) by the chemical formula 1g ' structural unit indicated.
[chemical formula 1g ']
Acetylation (Acetylation_) reaction
For acetylation identical with synthesis example 1, use comprising the polymer by the chemical formula 1g ' structural unit indicated
(10g), DMF (50mL), NaH (1.3g) and propargyl bromide (being 80% (80%in tolutene) in toluene) (3.7g),
To obtain polymer 1g.
It polymerize example 8
Resin polymerization
According to method identical with synthesis example 1 by using naphthalen-1-ol (- 1 alcohol of naphthalene) (7.2g), 1H-indol
(1H- indoles) (5.9g), 4-hydroxy-1-naphthaldehyde (4- hydroxyl-1-naphthalene Formaldehyde) (17g), propylene glycol monomethyl ether
Acetic acid esters (PGMEA) (129g) and dithyl sulfate (diethylsulfate) (0.3g) have been synthesized comprising by chemical formula 1h ' table
The polymer (Mw:3,700) of the structural unit shown.
[chemical formula 1h ']
Acetylation (Acetylation_) reaction
It has been used according to acetylation process identical with synthesis example 1 comprising by the poly- of the chemical formula 1h ' structural unit indicated
Object (12g), DMF (55mL), NaH (1g) and propargyl bromide (being 80% (80%in tolutene) in toluene) (3.4g) are closed,
To obtain polymer 1h.
It polymerize example 9
Resin polymerization
Carbazole (16g), 5-hydroxy-1-naphthaldehyde (5- hydroxyl -1- have been put into flask at 100 DEG C
Naphthaldehyde) (17g), p-methyl benzenesulfonic acid hydrate (p-Toluenesulfonic acid monohydrate) (1.9g) and 1,4-
Dioxanes (32g) is simultaneously stirred.When the weight average molecular weight of the sample taken out in auto polymerization reactant per hour reaches
When 2000 to 3000 range, reaction is completed.After reacting completion, it is added to 100 thereto and restrains oneself alkane to extract Isosorbide-5-Nitrae-
Dioxanes is added to methanol thereto and obtains deposit, has filtered the deposit obtained from it, and remove by using methanol
Wherein remaining monomer, to obtain the polymer (weight average molecular weight (Mw)=2,600) indicated by chemical formula 1i '.
[chemical formula 1i ']
Acetylation (Acetylation_) reaction
According to acetylation process identical with synthesis example 1 by using the polymer of the structural unit comprising chemical formula 1i '
(10g), DMF (55mL), NaH (0.65g) and 1.7 grams of propargyl bromides (being 80% (80%in tolutene) in toluene) are obtained
Obtained polymer 1i.
It polymerize example 10
According to synthetic method identical with synthesis example 9 by using 1H-indol-5-ol (1H- indoles -5- in flask
Alcohol) (13g), 9- Fluorene (9-Fluorenone) (18g), p-methyl benzenesulfonic acid hydrate (p-Toluenesulfonic acid
Monohydrate) (9.5g) and 1,4- dioxanes (91g) are obtained comprising the polymerization by the chemical formula 1j ' structural unit indicated
Object (Mw:2,900).
[chemical formula 1j ']
Acetylation (Acetylation_) reaction
It has been used according to acetylation process identical with synthesis example 1 comprising by the poly- of the chemical formula 1j ' structural unit indicated
Close object (10g), DMF (50mL), NaH (0.7g) and propargyl bromide (being 80% (80%in tolutene) in toluene)
(1.8g), to obtain polymer 1j.
Compare polymerization example 1
Naphthalen-1-ol (naphthalene -1- has been used at 100 DEG C according to resin polymerization method identical with synthesis example 1
Alcohol) (14g), 1,4-bis (methoxymethyl) benzene (bis- (methoxy) benzene of 1,4-) (17g), propylene glycol list first
Ether acetic acid ester (PGMEA) (64g) and dithyl sulfate (diethylsulfate) (0.3g) include by chemical formula 1k to obtain
The polymer 1k (weight average molecular weight (Mw)=3,000) of the structural unit of expression.
[chemical formula 1k]
The synthesis of additive
Synthesis example 1
4,4'- (4,4'- (propane-2,2-diyl) bis (4,1- has been put into 500ml round-bottomed flask
Phenylene)) bis (oxy) dianiline (4,4'- (4,4'- (propane -2,2- diyl) is bis- (4,1- phenylene)) bis- (oxygen
Base) hexichol) (10), water (60ml) and broken (crushed) ice (15g), and stirred 10 minutes with stirring rod (stir bar),
And conc.HCl (HCl of concentration) (20ml) is slowly added dropwise thereto.Then, pass through dropping funel (dropping
Funnel the NaNO2 being dissolved in water (15mL)) has been added dropwise thereto of about 10 minutes.It is stirred 20 minutes by the mixture
Later, the KI being dissolved in water (15ml) has been slowly added dropwise by dropping funel (dropping funnel) thereto.By institute
After the mixture of acquisition stirs 30 minutes 1 hour, when completing the reaction and testing via TLC to reaction
Afterwards, gains have been filtered, and will be dissolved in EA from its solid obtained, and then washed with NaHSO3 and water.
Then, the solvent of organic layer is removed to obtain the additive that 8g is indicated by chemical formula 2a.
[chemical formula 2a]
Synthesis example 2
According to method identical with synthesis example 1 by using 4,4'- (biphenyl-4,4'-diylbis (oxy))
Dianiline (4,4'- (xenyl -4,4'- diyl is bis- (oxygroup)) diphenylamines) (9g), NaN02 (4g), NaN3 (4.7g) and
Conc.HCl (HCl of concentration) (15ml) obtains the additive indicated by chemical formula 2b.
[chemical formula 2b]
Synthesis example 3
According to method identical with synthesis example 1 by using 4,4'- (biphenyl-4,4'-diylbis (oxy))
Dianiline (4,4'- (xenyl -4,4'- diyl is bis- (oxygroup)) diphenylamines) (9g), NaN02 (4g), NaN3 (4.7g) and
Conc.HCl (HCl of concentration) (15ml) obtains the additive indicated by chemical formula 2c.
[chemical formula 2c]
Synthesis example 4
According to method identical with 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) is bis- (4,1- phenylene)) bis- (oxygen
Base) diphenylamines) (10g), NaN02 (4g), KI (12.1g) and conc.HCl (HCl of concentration) (20ml) obtain among solid
Object (7.7g).Intermediary obtained (5.7g) is dissolved in tetrahydrofuran (40mL), and slow thereto at -40 DEG C
2.9M ipro-MgBr (9mL) has been added dropwise.After 30 minutes, it has been slowly added dropwise thereto through dry DMF (10mL), and in room temperature
It is lower to have stirred the mixture 2 hours.After ethyl acetate (100mL) is added dropwise into reaction solution, it will be obtained from it with water
The gains obtained have washed several times.Then, EtOAc is removed to obtain the polymer indicated by chemical formula 2d '.
[chemical formula 2d ']
Compound 2d ' (4.3g) obtained is dissolved in tetrahydrofuran (50mL), and to described molten in ice water
Liquid is stirred.It has been slowly added dropwise lithium aluminium hydride (0.75g), and has stirred mixture obtained thereto in ice water
2 hours.When react complete after, be sequentially slowly added dropwise thereto 10% NaOH aqueous solution (0.75g), H2O (1.5 grams),
And 10% NaOH (2.3g).Mixture obtained has been sufficiently stirred at room temperature and has been filtered, has reduced under stress
Through filtering solution to remove tetrahydrofuran (THF) and be dissolved in EtOAc (100mL), and then it has been washed with water several
It is secondary.After removing completely organic solvent from it, intermediary 2d " is obtained.Intermediary 2d " has been dissolved in DMF (20mL),
The solution has been stirred 10 minutes, and 60% NaH (1g) has been slowly added dropwise thereto.It is stirred the mixture in ice water
30 minutes, and it (is 80% (80%in tolutene)) (4mL) in toluene that propargyl bromide has been added dropwise thereto.When having reacted
At later, being added to EtOAc (100mL) thereto with diluting reaction solution, and will be washed several times through diluting reaction solution
To remove DMF.After DMF is removed completely, remove wherein remaining EtOAc to obtain the addition indicated by chemical formula 2d
Agent (4.5g).
[chemical formula 2d]
Synthesis example 5
According to method identical with synthesis example 1 by using 4,4'- (l, 3-phenylenebis (oxy)) dianiline
(4,4'- (1,3- phenylene is bis- (oxygroup)) diphenylamines) (210g), NaN02 (5.7g), NaCN (4.7g) and conc.HCl (concentration
HCl) (15ml) obtain the additive indicated by chemical formula 2e.
[chemical formula 2e]
Synthesis example 6
Additive (the name of product: 2,2-bis [4- (4-aminophenoxy)-that the preparation used is indicated by chemical formula 2f
Phenyl] propanen (2,2- bis- [4- (4- amido phenoxy group)-phenyl] propane), manufactured by TCI company).
[chemical formula 2f]
The preparation of hard cover screen constituent
Example 1 is to example 14 and comparative example 1 to comparative example 2
By the way that polymer and additive are dissolved in propylene glycol methyl ether acetate (propylene glycol
Monomethyl ether acetate, PGMEA) in solvent and filters the solution and be prepared for hard cover screen constituent.
Polymer and additive have been used in the consisting of object shown in table 1.
[table 1]
| Polymer | Additive | |
| 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 | - |
Assessment 1: planarizing features
On patterned silicon wafer (groove width: 10 μm (micron), trench depth: 100nm (nanometer)), rotation is applied respectively
Each constituent shown in cloth table 1, and baking has been carried out to form film, and by using vertical scanning formula electron microscope
(vertical scanning electron microscope, V-SEM) equipment examines the cross section of the film
It looks into.
Solid content in hard cover screen constituent is adjusted, to be to carry out heat treatment 120 for the first time at 180 DEG C
Second and formed on bare silicon wafer after carrying out second heat treatment at 400 DEG C 120 seconds(angstrom) thick film.It revolves respectively
Turn to be coated with each hard cover screen constituent, and then, be then heat-treated at 180 DEG C first 120 seconds and secondly hot at 400 DEG C
It has handled 120 seconds.
The thickness difference of resist bottom in the porose area of throughput measuring tool and the resist bottom in non-porous another area
(that is, scale) and have evaluated planarizing features.Fig. 1 is cuing open any pattern being applied in the Silicon Wafer with coating fluid amplification
View.The thickness of arrow meaning corresponds to scale in Fig. 1.
Planarizing features are more excellent, smaller with the thickness difference (scale) in non-patterned area in patterned area, and therefore, compared with
Small value indicates excellent planarizing features.As a result it is shown in Table 2.
[table 2]
| Scale (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 |
Reference table 2, compared to respectively by the film formed according to the hard cover screen constituent of comparative example 1 and comparative example 2, difference
Excellent planarizing features are shown by the film formed according to the hard cover screen constituent of example 1 to example 7.
Assessment 2: the thickness uniformity (Thickness Uniformity)
Rotary coating is distinguished on 12 inches of Silicon Wafers according to example 7 to example 14 and comparative example 1 and comparative example 3
Hard cover screen constituent, and then the film formed by hard cover screen constituent has been heat-treated at 180 DEG C 120 seconds first and its
It is secondary to be heat-treated at 400 DEG C 120 seconds.Adjustment has been carried out to be formed after second of heat treatment to the solid content of film(angstrom) thick film.
It is calculated and using 19 points as shown in Figure 2 and measuring each thickness at 19 points according to calculation equation 2
The thickness uniformity.Thickness has been measured by using K-MAC equipment.As a result it is shown in Table 3.
[calculation equation 2]
Uniformity (uniformity) (%)=(maximum gauge-at 19 points of film is at 19 points of film
Minimum thickness)/(average thickness at 19 points of film) X 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% |
Reference table 3, compared to the film by being formed according to the hard cover screen constituent of comparative example 1 and comparative example 3, by according to reality
The film that the hard cover screen constituent of example 7 to example 14 is formed shows excellent the thickness uniformity.
Assessment 3: coating property
Rotary coating is distinguished on Silicon Wafer according to example 1 to example 8 and the hard cover screen of comparative example 2 and comparative example 3
Constituent, and be then heat-treated 120 seconds and be secondly heat-treated at 400 DEG C 120 seconds thin to be formed at 180 DEG C first
Film.The solid content of hard cover screen constituent is adjusted, to be formed after second of heat treatment(angstrom) thickness
Film.
It is checked with surface of the electron microscope to film.As a result it is shown in Table 4.
[table 4]
| Coating property | |
| Example 1 | Well |
| Example 2 | Well |
| Example 3 | Well |
| Example 4 | Well |
| Example 5 | Well |
| Example 6 | Well |
| Example 7 | Well |
| Example 8 | Well |
| Comparative example 2 | It is inferior |
| Comparative example 3 | It is inferior |
As shown in table 4, compared to respectively by the film formed according to the hard cover screen constituent of comparative example 2 and comparative example 3,
Excellent coating property is shown by the film formed according to the hard cover screen constituent of example 1 to example 8 respectively.
Although the present invention has combined and has been presently considered as practical exemplary embodiment and is illustrated, it should be appreciated that the present invention is not
It is limited to revealed embodiment, but being intended to cover on the contrary includes the various profits in the spirit and scope of appended claims
Decorations and equivalent.
Claims (20)
1. a kind of organic layer constituent, includes:
Polymer includes the structural unit indicated by chemical formula 1；
Additive, in the structure as the cycle compound containing aromatics comprising be substituted or be unsubstituted amido, be substituted or not
At least one of the vinyl being substituted, the acetenyl, azido or the itrile group that are substituted or are unsubstituted；And
Solvent:
[chemical formula 1]
Wherein, in chemical formula 1,
A is the base containing aromatic ring for being substituted or being unsubstituted, be substituted or be unsubstituted containing the base of heteroaromatic rings or its group
It closes,
B is divalent organic base, and
The functional group of the included part indicated by chemical formula 2 at least one of A and B replaces:
[chemical formula 2]
Wherein, in chemical formula 2,
Z is hydrogen, hydroxyl, is substituted or C1 to the C10 alkyl being unsubstituted or C6 to the C30 aryl for being substituted or being unsubstituted,
And
It * is tie point.
2. organic layer constituent according to claim 1, wherein including the official of the part indicated by chemical formula 2
Energy base is indicated by chemical formula 2 ':
[chemical formula 2 ']
Wherein, in chemical formula 2 ',
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C10 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Atom, halogen-containing base or combinations thereof,
Z is hydrogen, hydroxyl, is substituted or C1 to the C10 alkyl being unsubstituted or C6 to the C30 aryl for being substituted or being unsubstituted,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
3. organic layer constituent according to claim 1, wherein the additive is indicated by chemical formula 3:
[chemical formula 3]
Wherein, in chemical formula 3,
K, m and n independently is 0 or 1, and the sum of k, m and n are 2 or 3,
As k+m+n=3, X be-CH- or nitrogen (N),
As k+m+n=2, X is direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2)-, wherein q
And t is independently 1 to 5 integer, and RwFor be substituted or be unsubstituted C1 to C20 alkyl, be substituted or be unsubstituted
C6 to C30 aryl, C3 to the C30 cycloalkenyl that is substituted or is unsubstituted, C1 to the C20 alkylamine for being substituted or being unsubstituted
Base, C7 to the C20 aryl alkyl for being substituted or being unsubstituted, C1 to the C20 miscellaneous alkyl for being substituted or being unsubstituted, be substituted or
C2 to the C30 Heterocyclylalkyl that is unsubstituted, C2 to the C30 heteroaryl that is substituted or is unsubstituted are substituted or are unsubstituted
C1 to C4 alkylether radicals, C7 to the C20 aryl alkylene ether that is substituted or is unsubstituted, the C1 for being substituted or being unsubstituted extremely
C30 halogenated alkyl is substituted or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R, R' and R " independently is containing the base containing aromatic ring for being substituted or being unsubstituted, and wherein R, R' or R " include to be substituted
Or amido, the vinyl for being substituted or being unsubstituted, the acetenyl, azido or the nitrile that are substituted or are unsubstituted being unsubstituted
At least one of base.
4. organic layer constituent according to claim 3, wherein the additive is indicated by chemical formula 4 or chemical formula 5:
[chemical formula 4]
[chemical formula 5]
Wherein, in chemical formula 4 and chemical formula 5,
X1For-CH- or nitrogen (N),
X2For direct key ,-(CqH2q)-、-(CtRw 2tOxygen)-, (O), sulphur (S) ,-NH- or-S (O2Wherein q and t independently are 1 to)-,
To 5 integer, RwFor C1 to the C20 alkyl for being substituted or being unsubstituted, C6 to the C30 aryl for being substituted or being unsubstituted, warp
Replace or be unsubstituted C3 to C30 cycloalkenyl, be substituted or be unsubstituted C1 to C20 alkyl amine group, be substituted or without
Substituted C7 to C20 aryl alkyl, C1 to the C20 miscellaneous alkyl for being substituted or being unsubstituted, the C2 for being substituted or being unsubstituted are extremely
C30 Heterocyclylalkyl, C2 to the C30 heteroaryl for being substituted or being unsubstituted, C1 to the C4 alkylether radicals for being substituted or being unsubstituted,
C7 to the C20 aryl alkylene ether for being substituted or being unsubstituted, C1 to the C30 halogenated alkyl, the warp that are substituted or are unsubstituted
Replace or C2 to the C20 alkenyl being unsubstituted or combinations thereof, and
R1To R5It independently is the base containing aromatic ring, the base containing aromatic ring includes at least one in the base indicated by chemical formula 6
Person:
[chemical formula 6]
Wherein, in chemical formula 6,
W is O, S, NRaOr CRbRc, wherein RaTo RcIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted, halogen it is former
Sub, halogen-containing base or combinations thereof,
Y is the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, the acetylene for being substituted or being unsubstituted
Base, azido, itrile group or combinations thereof,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
5. organic layer constituent according to claim 4, wherein in chemical formula 4 and chemical formula 5, R1To R5Independently by
Chemical formula 7 indicates:
[chemical formula 7]
Wherein, in chemical formula 7,
R1aTo R13aIt independently is hydrogen, hydroxyl, C1 to the C10 alkyl that is substituted or is unsubstituted or described is indicated by chemical formula 6
Base, wherein R1aTo R13aAt least one of for the base indicated by chemical formula 6,
T1And T2It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 to C10 for independently being hydrogen, being substituted or being unsubstituted
Alkyl, halogen atom, halogen-containing base or combinations thereof,
C and d independently 0 to 5 integer, and
It * is tie point.
6. organic layer constituent according to claim 1, wherein A is the warp selected from group 1 and group 2 in chemical formula 1
The part for replacing or being unsubstituted:
[group 1]
[group 2]
Wherein, in group 2,
Z1And Z2It independently is NRd, O, S, Te or Se,
Z3And Z4For N, and
RdAnd ReIt independently is hydrogen, hydroxyl, methoxyl group, ethyoxyl, halogen atom, halogen-containing base, is substituted or is unsubstituted
1 to C30 alkyl, it is substituted or C6 to the C30 aryl being unsubstituted or combinations thereof.
7. organic layer constituent according to claim 1, wherein in chemical formula 1, A includes that at least one is substituted or not
The aromatic ring being substituted or the heteroaromatic rings for being substituted or being unsubstituted.
8. organic layer constituent according to claim 1, wherein B is indicated by one of chemical formula Z1 to chemical formula Z4:
[chemical formula Z1]
[chemical formula Z2]
[chemical formula Z3]
[chemical formula Z4]
Wherein, in chemical formula Z1 into chemical formula Z4,
E and f independently is 0 or 1,
The integer that g is 1 to 5,
Y1To Y4It independently is one of the part for being substituted or being unsubstituted selected from group 3, and
* it is tie point:
[group 3]
Wherein, in group 3,
M, M' and M " independently is C1 to C10 alkylidene, O, S, the SO for being substituted or being unsubstituted2、CRfRg、NRhOr carbonyl,
Middle RfTo RhIt independently is hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted, halogen atom, halogen-containing base or combinations thereof,
L1For be substituted or be unsubstituted C6 to C50 arlydene, containing the C1 to C10 for being substituted or being unsubstituted containing alkylene oxide
Base or combinations thereof,
R is integer of 0 to 10,
S is integer of 0 to 10, and
The integer that k is 0 to 3.
9. organic layer constituent according to claim 1, wherein the polymer also includes the structure indicated by chemical formula 8
Unit:
[chemical formula 8]
Wherein, in chemical formula 8,
X0For be substituted or be unsubstituted the base containing aromatic ring, be substituted or be unsubstituted containing the base of heteroaromatic rings or its group
It closes,
L0For divalent organic base, and
It * is tie point.
10. organic layer constituent according to claim 9, wherein in chemical formula 8, X0For selected from group 1 and group 2
The part for being substituted or being unsubstituted:
[group 1]
[group 2]
Wherein, in group 2,
Z1And Z2It independently is NRd, O, S, Te or Se,
Z3And Z4For N, and
RdAnd ReIt independently is hydrogen, hydroxyl, methoxyl group, ethyoxyl, halogen atom, halogen-containing base, is substituted or is unsubstituted
1 to C10 alkyl, it is substituted or C6 to the C30 aryl being unsubstituted or combinations thereof.
11. organic layer constituent according to claim 1, wherein the polymer is in the structural unit comprising at least
One oxygen atom.
12. organic layer constituent according to claim 1, wherein chemical formula 2 is indicated by chemical formula 2 ':
[chemical formula 2 ']
Wherein, in chemical formula 2 ',
W is O, S, NRaOr CRbRc, wherein RaTo RcC1 to C20 alkyl, the halogen for independently being hydrogen, being substituted or being unsubstituted
Atom, halogen-containing base or combinations thereof,
A is 0 or 1, and
It * is tie point.
13. organic layer constituent according to claim 1, wherein the additive is by chemical formula Y1 into chemical formula Y4
One indicates:
[chemical formula Y1]
[chemical formula Y2]
[chemical formula Y3]
[chemical formula Y4]
Wherein, in chemical formula Y1 into chemical formula Y4,
T3And T4It independently is O, S, NRaOr CRbRc, wherein RaTo RcThe C1 to C10 for independently being hydrogen, being substituted or being unsubstituted
Alkyl, halogen atom, halogen-containing base or combinations thereof,
RxTo RyIt independently is hydrogen, halogen atom, halogen-containing base or C1 to the C20 alkyl for being substituted or being unsubstituted, and
R33To R55It independently is the base indicated by chemical formula 6:
[chemical formula 6]
Wherein, in chemical formula 6,
W is O, S, NRaOr CRbRc, wherein RaTo RcIndependently be hydrogen, C1 to the C10 alkyl that is substituted or is unsubstituted, halogen it is former
Sub, halogen-containing base or combinations thereof,
Y is the amido for being substituted or being unsubstituted, the vinyl for being substituted or being unsubstituted, the acetylene for being substituted or being unsubstituted
Base, azido, itrile group or combinations thereof,
A is 0 or 1,
B is the integer in 0 to 10 range, and
It * is tie point.
14. organic layer constituent according to claim 1, wherein the additive has 150 to 50,000 molecular weight.
15. organic layer constituent according to claim 1, wherein the polymer is flat with 500 to 200,000 weight
Average molecular weight.
16. organic layer constituent according to claim 1, wherein in terms of the total amount of the organic layer constituent, it is described to add
The amount for adding agent is 5 weight % to 50 weight %.
17. a kind of pattern forming method, including
Material layer is provided on substrate,
By the organic layer constituent as described in any one of claims 1 to 16 be applied to as described in material layer,
The organic layer constituent is heat-treated to form curtain layer of hard hood,
Siliceous thin layer is formed on the curtain layer of hard hood,
Photoresist layer is formed on the siliceous thin layer,
The photoresist layer is exposed and is developed to photoresist pattern,
It is described to expose that the siliceous thin layer and the curtain layer of hard hood are selectively removed using the photoresist pattern
A part of material layer, and
The part that is exposed of the material layer is etched.
18. pattern forming method according to claim 17, wherein the organic layer constituent is to utilize rotary coating side
Method applies.
19. pattern forming method according to claim 17, wherein the heat treatment includes executing at 50 to 250 DEG C
Second of the heat treatment executed after being heat-treated and being heat-treated described first for the first time and at about 200 to 500 DEG C.
20. pattern forming method according to claim 17, wherein the pattern forming method further includes described in the formation
Bottom antireflective coating (BARC) is formed before photoresist layer.
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| EP1832619A4 (en) * | 2004-12-28 | 2009-04-29 | Sumitomo Bakelite Co | Benzoxazole resin precursor, polybenzoxazole resin, resin film, and semiconductor device |
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| JP4877101B2 (en) * | 2007-07-02 | 2012-02-15 | Ｊｓｒ株式会社 | Resist underlayer film forming composition and pattern forming method |
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