CN116500864A - Composition of combined ARC and Si hard mask - Google Patents

Composition of combined ARC and Si hard mask Download PDF

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Publication number
CN116500864A
CN116500864A CN202210055708.1A CN202210055708A CN116500864A CN 116500864 A CN116500864 A CN 116500864A CN 202210055708 A CN202210055708 A CN 202210055708A CN 116500864 A CN116500864 A CN 116500864A
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bis
etch
trichlorosilane
group
monomer
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郑学刚
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Shanghai Aishensi Technology Co ltd
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Shanghai Aishensi Technology Co ltd
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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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

The novel composition comprises as a combination an antireflective coating (ARC) and a Hard Mask (HM) a siloxane copolymer formed by the cohydrolysis of: r is R 1 SiCl 3 、R 2 SiCl 3 、R 3 SiCl 3 、X 3 Si(CH 2 ) a SiX 3 、R 4 SiX 3 、Si(OR) 4 Wherein: x=cl OR, R is alkyl such as methyl OR ethyl, R 1 Is a chromophore such as phenyl, phenylmethyl, phenylethyl and phenylpropyl, R 2 Is H, R 3 Is methyl or optionally substituted C 2 ‑C 5 An alkyl group, and optionally R 4 Is a hydrophilic group such as 2- [ methoxy (polyethylene oxy) 6‑9 Propyl group]Or 2- (methyl) ethyl, wherein the mole of each monomer in the starting monomer mixture0.00 mole percent<(A)、(B)、(C)、(D)、(E)、(F)<0.95，0.00≤(D)<0.50, and the total number of moles of (a) + (B) + (C) + (D) + (E) + (F) =1.

Description

Composition of combined ARC and Si hard mask
Technical Field
The present invention relates to etch-resistant antireflective compositions, and methods of coating microelectronic devices by using such compositions.
Background
Typical four-layer photolithography:
● 1-organic Photoresist (spin coating method)
● 2-anti-reflective coating (ARC) (spin coating method)
● 3-Si-containing hard mask (for obtaining etching selectivity such as SiON) (chemical vapor deposition method)
● 4-hard mask containing C (amorphous carbon, post ACL) (chemical vapor deposition method)
● 5-device wafer
In order to reduce the cost and improve performance of electronic devices, the semiconductor industry needs to have finer features to produce smaller but more dense devices.
In order to be able to manufacture smaller devices, new and better microlithography materials and methods are needed.
Typically, to pattern semiconductor devices, a single layer of Photoresist (PR) is used over the substrate and an anti-reflective coating (ARC) layer to control the reflection of light from the underlying layer that can affect Line Edge Roughness (LER) and Critical Dimension (CD).
Prior art techniques such as us patent No. 4,010,122 to Brewer Science and us patent No. 5,693,691 teach the use of ARC in microlithographic patterning.
As resolution of photolithographic patterning increases, the need to reduce PR thickness has become an effective way to reduce the aspect ratio of the PR/ARC stack and avoid pattern collapse.
However, the etch resistance of the organic PR in the thinner PR/ARC stack (Tokyo Electron Limited, us patent No. 7,888,267) is not sufficient to transfer the pattern to the underlying layer, and therefore a new way of employing a Hard Mask (HM) layer is used.
For example, honeywell U.S. patent No. 6,506,497, taiwan Semiconductor Manufacturing Company U.S. patent No. 6,777,340, texas Inst U.S. patent No. 6,803,661 teach the use of a hard mask in a photolithography stack with better etch selectivity to transfer a pattern to the underlying PR/ARC/HM.
PR stripping and Reactive Ion Etching (RIE) are used to transfer the pattern to the underlying layer as shown in the following prior art teachings: novellus U.S. Pat. No. 8,178,443, U.S. Pat. No. 8,569,179, U.S. Pat. No. 8,664,124, U.S. Pat. No. 8,846,525, and Tokyo Electron Limited U.S. Pat. No. 9,576,816, U.S. Pat. No. 9,530,667, U.S. Pat. No. 9,607,843.
In a more efficient manner, the ARC and hard mask are combined into one layer, as indicated by the teachings of the following patents: IBM us patent No. 6,420,088, IBM us patent No. 7,077,903, IBM us patent No. 7,276,327, dow Corning us patent No. 7,756,384, tokyo Electron Limited us patent No. 7,888,267, brewer Science's us patent No. 7,939,244, samsung Industries us patent No. 8,026,035, globalFoundries us patent No. 8,492,279.
Accordingly, improvements in ARC/hard mask materials as monolayers are always welcome to address many of the integration problems that occur during semiconductor device fabrication.
Disclosure of Invention
It is an object of the present invention to provide an etch resistant antireflective composition for the ARC/HM comprising or consisting of:
siloxane copolymers prepared by cohydrolysis of a mixture of chlorosilanes and alkoxysilanes, preferably in a one pot process. The microlithography is preferably ArF microlithography with a wavelength of 193 nm. Specifically, the siloxane copolymers are formed from the cohydrolysis of the following monomers in a solvent:
(A)R 1 SiCl 3 ，
(B)R 2 SiCl 3 ，
(C)R 3 SiCl 3 ，
(D)R 4 SiX 3 ，
(E)X 3 Si(CH 2 ) a SiX 3 ，
(F)(RO) 4 Si，
Wherein:
x=cl OR an alkoxy group (OR),
r, at each occurrence, independently represents an alkyl group having 1 to 12, more preferably 1 to 6C atoms, most preferably methyl or ethyl, a=1 to 7;
R 1 at each occurrence, independently represent an antireflective chromophore such as phenyl, phenylmethyl, phenylethyl and phenylpropyl, in microlithography at wavelengths of 180-210nm, preferably 190-200nm, more preferably 193nm,
R 2 is H, is a group of the formula,
R 3 independently at each occurrence, represents methyl or optionally substituted C 2 -C 5 An alkyl group, a hydroxyl group,
R 4 at each occurrence, independently represents a hydrophilic group such as 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Or a 2- (methyl) ethyl group,
wherein the molar percent (mol%) concentration of each monomer in the starting monomer mixture is 0.00< (a), (B), (C), (E), (F) <95%,0.00 + (D) <50%, wherein the preferred mol% range of (a) is 8% < (a) <20%, (B) is 35% < (B) <45%, (C) is 20% < (C) <70%, (D) is 1% < (D) <20%, (E) is 2% < (E) <30%, (F) is 2% < (F) <30%, and the total mole number of (a) + (B) + (C) + (D) + (E) + (F) = 100%.
According to the present invention, the monomer (A) controls the values of n and K that minimize the reflectivity upon ArF exposure light; the monomer (B) contributes to better etch selectivity by increasing the mole percent Si (% Si) in the siloxane copolymer; monomer (C) also increases the% Si content of the siloxane copolymer and enhances the better solubility of the material in organic solvents; monomer (D) improves solubility and adhesion to the substrate; and monomer (E) to enhance adhesion and accelerate curing; monomer (F) is based on a tetrafunctional Q structure providing better low temperature crosslinking and thus enhancing structural stability, wherein monomer (E) is a ditrialkoxy-or ditrichloro-olefin silane, resulting in a bis-silyl-olefin structure (e.g. O 1.5 Si(CH 2 ) a SiO 1.5 A linking group, wherein a = 1-7) to obtain stability and accelerate low temperature curing; monomer (F) is a tetraalkoxysilane (e.g., having four Si-O bonds (Si-O)) producing a Q structure 4 A linker), the tetrafunctional Q structure provides better low temperature crosslinking and thus enhances structural stability.
The single layer thermally cured coating thus obtained has very low reflectivity in ArF exposure and serves as an anti-reflective coating (ARC) in microlithography for the manufacture of semiconductor devices according to the etch-resistant anti-reflective composition of the invention.
The single layer heat cured coating thus obtained is insoluble in the photoresist solvent or developer according to the etch resistant antireflective composition of the invention.
The single layer heat cured coating thus obtained is converted into a Hard Mask (HM) with good etch selectivity during photolithography and etching according to the etch-resistant antireflective composition of the invention.
Furthermore, the combination of anti-reflective coating (ARC) and Hard Mask (HM) properties that provide useful entities is referred to herein as ARC/HM.
According to a particular aspect of the invention, the composition of the ARC/HM layer material is based on a siloxane copolymer containing a bis-silyl olefin structure (e.g., O 1.5 Si(CH 2 ) a SiO 1.5 A linking group, wherein a = 1-7) to achieve stability and faster low temperature cure.
According to a particular aspect of the invention, the composition of the ARC/HM layer material is based on a siloxane copolymer that contains Si-H side groups in its structure for increasing the% Si content and accelerating the low temperature cure. The amount of Si in the final copolymer ranges from 8mol% to 46mol%, more preferably from 15mol% to 45mol%, and most preferably from 35mol% to 45mol%.
According to a particular aspect of the invention, the composition of the ARC/HM layer material has specific chromophore side groups on the siloxane backbone of the siloxane copolymer to tailor the antireflective properties of the coating.
According to a particular aspect of the invention, the composition of the ARC/HM layer material has a particular% Si on the siloxane backbone of the siloxane copolymer to tailor the etch selectivity properties of the coating. The Si-containing copolymers of the present invention increase etch resistance and improve etch selectivity to organic photoresists.
In a preferred embodiment, the composition according to the invention has the following siloxane copolymer structure:
[(OH) 3 Si(CH 2 ) a Si(OH) 2 O 0.5 ] b [(OH) 2 Si(CH 2 ) a Si(OH) 2 O] c [O(OH)Si(CH 2 ) a Si(OH)O] q [O 1.5 Si(CH 2 ) a SiO 1.5 ] e [R 1 Si(OH) 2 O 0.5 ] f [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH) 2 O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p [R 3 Si(OH) 2 O 0.5 ] v [R 3 SiO 1.5 ] w [R 3 Si(OH)O] d [R 4 Si(OH) 2 O 0.5 ] x [R 4 SiO 1.5 ] y [R 4 Si(OH)O] z [Si(OH) 3 O 0.5 ] j [Si(OH) 2 O] k [Si(OH)O 1.5 ] l [SiO 2 ] t ，
wherein 0< b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t <0.9, 0.00. Ltoreq.x, y, z <0.50, a=1-7,a is preferably in the range 1-3, and b+c+q+e+f+g+h+m+n+p+v+w+d+x+y+z+j+k+l+t=1,
R 1 chromophores such as phenyl, phenylmethyl, phenylethyl and phenylpropyl, for antireflection in microlithography at a wavelength of 193nm,
R 2 Is H for increasing the% S for better etch selectivity,
R 3 is methyl or optionally substituted C 2 -C 5 An alkyl group to obtain stability,
R 4 is a hydrophilic group such as 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Or 2- (methyl) ethyl for adhesion.
According to the etch-resistant antireflective composition of the invention, the siloxane copolymer helps control the etch selectivity of the ARC/HM coating material by controlling the amount of the H-containing trichlorosilane or trialkoxysilane to control the amount of% Si in the siloxane copolymer composition.
According to the etch-resistant antireflective composition of the invention, there are bis-silyl olefin units (e.g., O 1.5 Si(CH 2 ) a SiO 1.5 A linking group, wherein a=1-7) is formed by introducing a crosslink density into siliconThe oxyalkyl polymers enhance thermal curing by increasing silanol (Si-OH) functionality in the structure that is readily crosslinked. The amount of bis-silyl olefin units is controlled by controlling the amount of bis-trialkoxy olefin silane or bis-trichloroolefin or a combination of mixtures thereof.
According to the etching-resistant antireflective composition of the invention, silanol (Si-OH) is also derived from the T structure (e.g., RSi (OH)) in a backbone siloxane copolymer of an alkyl-or aryl-containing trichloroalkyl or trialkoxysilane 2 O 0.5 、RSiO 1.5 RSi (OH) O). The uncondensed silanol functions cause crosslinking of the coating at lower temperatures. The T structure is formed by trichlorosilane or trialkoxysilane containing alkyl or aryl.
According to a particular aspect of the invention, the composition of the ARC/HM layer material is based on a siloxane copolymer containing Q structures (e.g., (Si-O) in the backbone 4 A linking group) to achieve stability and faster low temperature cure.
It is another object of the present invention to provide a method of coating a microelectronic device comprising the steps of:
(i) The etch-resistant antireflective composition of the invention is prepared,
(ii) The formulation is prepared by dissolving the etch-resistant antireflective composition of the invention in a polar organic solvent,
(iii) The formulation is coated on a substrate, forming a coating,
(iv) The polar organic solvent is evaporated from the coating,
(v) The coating is cured to form a film.
In one aspect of the process, in step (ii), the polar organic solvent is selected from ketones such as methyl isobutyl ketone (MIBK), methyl Ethyl Ketone (MEK), and cyclohexanone; alcohols such as methanol, ethanol, propanol and isopropanol; ethers such as Tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Glycol Monomethyl Ether (PGME) and diAn alkane; esters such as ethyl acetate, butyl acetate, ethyl lactate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA). Of coating solutions The solvent in the total ARC/HM formulation may be in an amount of 90% to 99% by weight.
In one aspect of the method, in step (v), the curing is performed at a temperature in the range of about 100 ℃ to about 250 ℃.
In one aspect of the method, in step (v), the curing is performed over a period of about 1 to about 2 minutes.
In one aspect of the method, the substrate is a Si wafer, a substrate of an integrated circuit, or other microelectronic device substrate.
In one aspect of the method, in step (iii), the coating is spin coating.
In one aspect of the method, the polar organic solvent is evaporated during spin coating.
In one aspect of the method, the film has a thickness of about 10nm to about 200nm.
It is another object of the present invention to provide a method of forming a patterned device, comprising:
a) Preparing a formulation by dissolving the etch-resistant antireflective composition of the invention in a polar organic solvent and coating the formulation on a substrate of a device to form a Si-rich ARC layer;
b) Coating ArF photoresist over the Si-rich ARC layer;
c) Photo-patterning the ArF photoresist and forming a resist pattern over the Si hard mask ARC layer;
d) The exposed areas are removed by etching and a patterned device is created.
The ARC/HM silicone copolymer solution material can be spin coated and thermally cured at a temperature of 100-250 ℃ for a period of 30-60 seconds to prevent thickness loss of the photoresist solvent and developer.
Drawings
An example of the application of an ARC/hard mask coating of the present invention in semiconductor device fabrication is illustrated in fig. 1. The photolithography, patterning and etching steps are illustrated in the following figures:
fig. 1a illustrates a cross section of a coating layer of a stack of (filled black areas), (1) photoresist, (2) ARC/HM, (3) SiN or ACL, (4) dielectric layer, masked on a substrate, with the downward arrow showing ArF exposure;
FIG. 1b illustrates the patterned photoresist layer (1) exposed and developed on top of other layers;
FIG. 1c illustrates pattern transfer of photoresist (1) to ARC/HM (2) layer;
FIG. 1d illustrates the photoresist layer (1) removed from the stack, leaving behind a patterned ARC/HM (2);
FIG. 1e illustrates the transfer of the ARC/HM (2) pattern to the SiN or ACL (3) layer;
FIG. 1f illustrates ARC/HM (2) removed from the stack, leaving behind patterned SiN or ACL (3);
FIG. 1g illustrates transfer of SiN or ACL (3) patterns to the dielectric layer (4);
fig. 1h illustrates SiN or ACL (3) removed from the stack, leaving a patterned dielectric layer (4).
An example of a typical four layer photolithography is illustrated in FIG. 2, in which
Fig. 2I illustrates a cross-section of four layers of a coating of a stack of dielectric layers, siN or ACL, (5) a mask (filled black areas), (1) a photoresist, (2) an ARC, (3) a hard mask, wherein the downward arrow shows ArF exposure;
FIG. 2J illustrates the patterned photoresist layer (1) exposed and developed on top of other layers;
FIG. 2K illustrates the transfer of photoresist (1) pattern RIE to ARC (2) and hard mask layer (3);
FIG. 2L illustrates a C-hard mask etch (4);
FIG. 2M illustrates pattern transfer to the underlayer;
fig. 2N illustrates the removal of the C-hard mask from the stack, leaving behind a patterned IC (dielectric) layer.
Detailed Description
The present invention provides etch-resistant antireflective compositions, and the single layer thermally cured coatings thus obtained have very low reflectivity in ArF exposure and serve as antireflective coatings (ARCs) in microlithography for semiconductor device fabrication processes.
The present invention provides an etch-resistant antireflective composition, whereby the resulting thermally cured coating is transformed into a Hard Mask (HM) with good etch selectivity during photolithography and etching.
The present invention provides an etch-resistant antireflective composition whereby the resulting thermally cured coating is insoluble in a photoresist solvent or developer.
In an important aspect of the invention, a combination of both anti-reflective coating (ARC) and Hard Mask (HM) properties, formed after curing the ARC/HM coating, is achieved by the etch-resistant anti-reflective composition of the invention, which comprises or consists of a siloxane copolymer formed by co-hydrolysis of the following monomers in a solvent:
(A)R 1 SiCl 3 ，
(B)R 2 SiCl 3 ，
(C)R 3 SiCl 3 ，
(D)R 4 SiX 3 ，
(E)X 3 Si(CH 2 ) a SiX 3 ，
(F)(RO) 4 Si，
Wherein:
x=cl OR an alkoxy group (OR),
r, at each occurrence, independently represents an alkyl group having 1 to 12, more preferably 1 to 6C atoms, most preferably methyl or ethyl, a=1 to 7;
R 1 at each occurrence, independently represent an antireflective chromophore such as phenyl, phenylmethyl, phenylethyl and phenylpropyl, in microlithography at wavelengths of 180-210nm, preferably 190-200nm, more preferably 193nm,
R 2 is H, is a group of the formula,
R 3 independently at each occurrence, represents methyl or optionally substituted C 2 -C 5 An alkyl group having a hydroxyl group,
R 4 independently at each occurrence, represents a hydrophilic group, e.g., 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Or a 2- (methyl ester) ethyl group,
wherein the molar% concentration of each monomer in the starting monomer mixture is 0.00< (a), (B), (C), (E), (F) <95%,0.00 + (D) <50%, wherein the preferred molar% range of (a) (mol%) is 8% < (a) <20%, (B) (preferred mol% range of (B) (35% < (B) <45%, (C) (preferred mol% range of 20% < (C) <70%, (D) (preferred mol% range of (D) (1% < (D) <20%, (E) (preferred mol% range of 2% < (E) <30%, (F) (preferred mol% range of 2% < (F) <30%, and the total molar number of (a) + (B) + (C) + (D) + (E) + (F) =100%.
The monomer (A) controls the values of n and K that minimize reflectance at ArF exposure.
The monomer (B) contributes to better etching selectivity by increasing the% Si content in the siloxane copolymer.
The monomers (C) also increase the% Si content of the siloxane copolymer and the better solubility of the material in organic solvents.
Monomer (D) for better solubility and adhesion.
The monomer (E) is a ditrialkoxy-or ditrichloro-olefin silane, thereby producing a bis-silyl-olefin linkage (e.g., O) 1.5 Si(CH 2 ) a SiO 1.5 A linking group, wherein a=1-7) for the purpose of obtaining backbone stability and accelerating low temperature curing.
In addition, monomer (E) enhances adhesion and accelerates curing.
Monomer (F) is a tetraalkoxysilane (e.g., having four Si-O bonds (Si-O)) producing a Q structure 4 A linker), the tetrafunctional Q structure provides better low temperature crosslinking, thus enhancing structural stability.
In addition, the siloxane copolymer of the present invention has the following structure:
[(OH) 3 Si(CH 2 ) a Si(OH) 2 O 0.5 ] b [(OH) 2 Si(CH 2 ) a Si(OH) 2 O] c [O(OH)Si(CH 2 ) a Si(OH)O] q [O 1.5 Si(CH 2 ) a SiO 1.5 ] e [R 1 Si(OH) 2 O 0.5 ] f [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH) 2 O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p [R 3 Si(OH) 2 O 0.5 ] v [R 3 SiO 1.5 ] w [R 3 Si(OH)O] d [R 4 Si(OH) 2 O 0.5 ] x [R 4 SiO 1.5 ] y [R 4 Si(OH)O] z [Si(OH) 3 O 0.5 ] j [Si(OH) 2 O] k [Si(OH)O 1.5 ] l [SiO 2 ] t
wherein 0< b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t <0.9, 0.00. Ltoreq.x, y, z <0.50, a=1-7,a is preferably in the range 1-3, and b+c+q+e+f+g+h+m+n+p+v+w+d+x+y+z+j+k+l+t=1,
R 1 is a chromophore such as phenyl, phenylmethyl, phenylethyl or phenylpropyl for antireflection in microlithography at a wavelength of 193nm,
R 2 is H, for increasing the% S to obtain better etch selectivity,
R 3 Is methyl or optionally substituted C 2 -C 5 An alkyl group, for obtaining stability,
R 4 is a hydrophilic group such as 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Trichlorosilane or 2- (methyl ester) ethyl trichlorosilane for adhesion.
The siloxane copolymers of the invention are prepared in a single synthetic process ("one pot process") of cohydrolysis of a mixture of chlorosilane monomers and alkoxysilane monomers. The monomer may be selected from bis-trialkoxysilane or bis-trichloroolefin silane, such as 1, 1-bis-trimethoxysilylmethane, or 1, 2-bis-trimethoxysilylethane, or 1, 3-bis-trimethoxysilylpropane, or 1, 4-bis-trimethoxysilylbutane, or 1, 5-bis-trimethoxysilylpentane, or 1, 6-bis-trimethoxysilylhexane, or 1, 7-bis-trimethoxysilylheptane, or 1, 1-bis-triethoxysilylmethane, or 1, 2-bis-triethoxysilylethane, or 1, 3-bis-triethoxysilylpropane, or 1, 4-bis-triethoxysilylbutane, or 1, 5-bis-triethoxysilylpentane, or 1, 6-bis-triethoxysilaneHexane, or 1, 7-bis-triethoxysilane, or 1, 1-bis-trimethylsilylmethane, or 1, 2-bis-trimethylsilylethane, or 1, 3-bis-trimethylsilylpropane, or 1, 4-bis-trimethylsilylbutane, or 1, 5-bis-trimethylsilylpentane, or 1, 6-bis-trimethylsilylhexane, or 1, 7-bis-trimethylsilylheptane, or a combination thereof. The monomer is also selected from aryl-containing trichlorosilane such as phenyltrichlorosilane, or phenylmethyltrichlorosilane, or phenylethyltrichlorosilane, or phenylpropyl trichlorosilane, or a combination of all. The monomer is also selected from H-containing trichlorosilane or trialkoxysilanes such as trichlorosilane or trimethoxysilane or triethoxysilane or combinations thereof. The monomer is also selected from alkyl-containing trichlorosilane or trialkoxysilane such as methyltrichlorosilane, or ethyltrichlorosilane, or propyltrichlorosilane, or butyltrichlorosilane, or pentyltrichlorosilane, or methyltrimethoxysilane, or ethyltrimethoxysilane, or propyltrimethoxysilane, or butyltrimethoxysilane, or methyltriethoxysilane, or ethyltriethoxysilane, or propyltriethoxysilane, or a combination thereof. The monomers are also selected from trichlorosilane or trialkoxysilanes containing hydrophilic groups, for example 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trichlorosilane, or 2- (methyl) ethyl trichlorosilane, or a combination thereof.
Chromophores useful as side groups for the trichlorosilane or trialkoxysilane may be selected from aryl-containing moieties such as phenyl trichlorosilane, or phenyl methyl trichlorosilane, or phenyl ethyl trichlorosilane, or phenyl propyl trichlorosilane, or phenyl trimethoxysilane, or phenyl methyl trimethoxysilane, or phenyl ethyl trimethoxysilane, or phenyl propyl trimethoxysilane, or phenyl triethoxysilane, or phenyl methyl triethoxysilane, or phenyl ethyl triethoxysilane, or phenyl propyl triethoxysilane. In addition, the refractive index (n) value and extinction coefficient (k) value controlling the light reflection of the ARC/HM coating can be adjusted by controlling the amount of silane containing the corresponding chromophore used in the synthesis of the siloxane copolymer.
Another useful feature of the siloxane copolymers of the invention is the control of the etch selectivity of the ARC/HM coating material by controlling the amount of the% Si in the siloxane copolymer composition by controlling the amount of the H-containing trichlorosilane or trialkoxysilane and other trichlorosilane monomers or trialkoxysilane monomers.
Yet another useful component of the siloxane copolymers of the invention is the presence of a bis-silyl olefin structure (e.g., O) 1.5 Si(CH 2 ) a SiO 1.5 A linking group, where a = 1-7) to achieve stability and to accelerate low temperature curing and to increase silanol (Si-OH) functionality in the structure that is easily cross-linked. The number of bis-silyl olefin units is controlled by controlling the amount of bis-trialkoxysilane or bis-trichloroolefin silane, or mixtures thereof.
In yet another important aspect of the present invention, a useful component of the siloxane copolymers in the etch-resistant antireflective compositions of the invention is the presence of Q units (e.g. (Si-O) in the structure 4 A linking group) that enhances thermal cure by introducing crosslink density into the siloxane polymer and increasing silanol (Si-OH) functionality in the structure that is readily crosslinked. The number of Q units is controlled by controlling the amount of tetrachlorosilane, or tetramethoxysilane, or tetraethoxysilane, or mixtures thereof.
Silanol (Si-OH) functionality is also derived from the T structure (e.g., RSi (OH)) in a backbone siloxane copolymer of an alkyl-or aryl-containing trichlorosilane or trialkoxysilane 2 O 0.5 、RSiO 1.5 RSi (OH) O). The uncondensed silanol functions cause crosslinking of the coating at lower temperatures. The T structure is formed from: alkyl-or aryl-containing trichlorosilane or trialkoxysilane, for example methyltrichlorosilane, or ethyltrichlorosilane, or propyltrichlorosilane, or butyltrichlorosilane, or pentyltrichlorosilane, or methyltrimethoxysilane, or ethyltrimethoxysilane, or propyltrimethoxysilane, or butyltrimethoxysilane, or methyltriethoxysilane, or ethyltriethoxysilane, or propyltriethoxysilane, or phenyltrichlorosilane, or phenylmethyltrichlorosilane, or phenylethyl Trichlorosilane, phenyl propyl trichlorosilane, phenyl trimethoxysilane, phenyl methyl trimethoxysilane, phenyl ethyl trimethoxysilane, phenyl propyl trimethoxysilane, phenyl triethoxysilane, phenyl methyl triethoxysilane, phenyl ethyl triethoxysilane, or phenyl propyl triethoxysilane. The number of T structures is controlled by controlling the amount of methyltrichlorosilane, or ethyltrichlorosilane, or propyltrichlorosilane, or butyltrichlorosilane, or pentyltrichlorosilane, or methyltrimethoxysilane, or ethyltrimethoxysilane, or propyltrimethoxysilane, or butyltrimethoxysilane, or methyltriethoxysilane, or ethyltriethoxysilane, or propyltriethoxysilane, or phenyltrichlorosilane, or phenylmethyltrichlorosilane, or phenylethyltrichlorosilane, or phenylpropyltrichlorosilane, or phenylmethyltrimethoxysilane, or phenylpropyltrimethoxysilane, or phenylmethyltriethoxysilane, or phenylmethyltrimethoxysilane.
The cohydrolysis and polycondensation of the monomers of the invention can form siloxane copolymers with mixtures of T, Q and bis-silyl olefin units in random branched and cage networks of various structural sizes.
The uncondensed silanol (Si-OH) functional groups from the T, Q and disilylone structures in the siloxane copolymer tended to crosslink and form three and four Si-O-Si bonds around each silicon atom in the corresponding T, Q and disilylone structures completed during thermal curing. The stability of the ARC/HM coating in organic solvents increases with increased Si-OH polycondensation and Si-O-Si bond formation, the more fully condensed the ARC/HM coating, the more stable the coating in organic solvents. The thermally cured ARC/HM coating must be insoluble in the photoresist solvent and developer to be stable during subsequent photoresist coating and development. Optionally, a thermal cure catalyst may be used as a formulation additive to increase the rate of thermal cure of the ARC/HM coated silanol. The amount of acid such as acetic acid, hydrochloric acid, sulphonic acid, methane sulphonic acid or phosphoric acid is 100 to 1000ppm. Alternatively, the condensation catalyst may be selected from a thermal acid generator or a thermal base generator. The amount of Si-containing monomer having T, Q and bis-silyl olefin structure can control the% Si in the final composition.
The ARC/HM silicone copolymer may have a weight average molecular weight (Mw) of about 800 to about 20,000, as determined by Gel Permeation Chromatography (GPC).
The solvent in the cohydrolysis is a mixture of water and at least one organic solvent selected from the group consisting of: ketones such as methyl isobutyl ketone (MIBK), methyl Ethyl Ketone (MEK) or cyclohexanone; alcohols such as methanol, ethanol, propanol or isopropanol; ethers such as Tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Glycol Monomethyl Ether (PGME) or diAn alkane; esters such as ethyl lactate and Propylene Glycol Monomethyl Ether Acetate (PGMEA). The amount of the solvent and the water in the mixture is 5 wt% to 95 wt%.
In some embodiments, the siloxane copolymer may comprise 1 wt% to 10 wt% of the total ARC/HM formulation of the coating solution.
Spin coating may be used as a method of applying ARC/HM formulations in semiconductor device fabrication. Spin coating processes typically require pouring a small amount of ARC/HM solution as a paste (pump) onto the surface of the semiconductor device, followed by spreading the material on the surface at an acceleration of 4,000-5,000rpm to a selected final speed of 2000 to 3000rpm and holding the final speed for 10-20 seconds before the spin is completed. In this way, a uniform coating of ARC/HM material is formed as an ARC/HM layer on the surface of the semiconductor device.
The ARC/HM coating may be thermally cured by heating, e.g., a hotplate or furnace, in semiconductor device fabrication using any of the generally suitable techniques used in curing. The ARC/HM coating can be thermally cured at a temperature of 100-250 ℃ for a period of 30-60 seconds to increase the cross-linking density of the siloxane copolymer in the coating and to polycondense silanol (Si-OH) to form Si-O-Si bonds. The thermally cured siloxane copolymer will cure sufficiently to be stable in photoresist solvents such as PGMEA, PGME, gamma Butyrolactone (GBL), ethyl Lactate (EL), and the like.
After the ARC/HM coating is applied and cured, a thin photoresist layer is spin coated on the surface of the cured ARC/HM coating, followed by a photo-patterning process by photoresist exposure and development to produce a patterned photoresist structure. The next step is to transfer the patterned photoresist pattern to the ARC/HM layer using Reactive Ion Etching (RIE). The step after pattern transfer through the ARC/HM layer is an oxygen plasma etch to remove the photoresist and convert the patterned ARC/HM layer into a mostly patterned hard mask layer. This patterned hard mask will also be able to be transferred to the underlying layer using a suitable RIE etch chemistry pattern, after which the hard mask is removed and the target patterned structure is produced on the semiconductor device.
An example of the application of the ARC/HM coating of the present invention in semiconductor device fabrication is illustrated in FIG. 1, however, this is not the only use and is not intended to be limiting of the use of the present invention, and the coating of the present invention may be used in many other ways. The geometries and dimensions used in this example are presented for purposes of illustration only and are not intended to represent actual geometries and dimensions.
The substrate may be a metal such as Si, ge, al, etc., or an alloy such as SiGe, gallium arsenide, etc., or an insulator such as SiO 2 、Si 3 N 4 Etc., or doped variants or mixtures thereof. An example of a target layer to be patterned in this example is a dielectric (4) layer. Layer (3) in the stack of fig. 1a is SiN or an Amorphous Carbon Layer (ACL). The ARC/HM silicon copolymer composition of the present invention is spin coated on layer (3) at a speed of about 2000 to about 3000rpm for a period of about 10 seconds to about 20 seconds. The ARC/HM silicon copolymer composition coating is then thermally cured at a temperature of about 100deg.C to about 250deg.C for a time of about 30 seconds to about 60 seconds to increase the cross-linking density of the copolymer in the coating and to condense silanol (Si-OH) to form Si-O-Si bonds, which results in a spin-coated ARC/HM layer (2) that is insoluble in the photoresist solvent in the subsequent step of photoresist coating. ARC/HM layer (2) Has light absorption properties that are controlled by adjusting the number of chromophores in the composition and the thickness of the coating to optimize n and k to reduce light reflection. To complete the stack in fig. 1a, the photoresist was spin coated and ArF photo-patterned through an exposure mask (filled black areas) and developed to remove the exposed areas. The photolithography, patterning and etching steps are illustrated in more detail in the following figures of fig. 1 a-h:
fig. 1a illustrates a cross section of a coating layer of a stack of (filled black areas), (1) photoresist, (2) ARC/HM, (3) SiN or ACL, (4) dielectric layer, masked on a substrate, with the downward arrow showing ArF exposure.
Fig. 1b illustrates the patterned photoresist layer (1) exposed and developed on top of the other layers.
Fig. 1c illustrates the transfer of the photoresist (1) pattern to the ARC/HM layer (2) when the ARC/HM layer (2) is patterned using the photoresist pattern as an etch mask.
Fig. 1d illustrates the photoresist layer (1) removed from the stack, leaving the patterned ARC/HM layer (2) to be used as a hard mask for the underlayer on other target materials.
FIG. 1e illustrates ARC/HM layer (2) pattern transfer to underlying SiN or ACL (3).
Fig. 1f illustrates the ARC/HM layer (2) removed from the stack, leaving behind a patterned SiN or ACL (3) layer.
Fig. 1g illustrates the transfer of SiN or ACL (3) pattern to the dielectric layer (4).
Fig. 1h illustrates the SiN or ACL (3) layer removed from the stack, leaving a patterned dielectric target layer (4).
Compared with the prior art, the invention has the following advantages:
according to the etching-resistant antireflective composition of the invention, a single-layer thermosetting coating thus obtained,
has very low reflectivity in ArF exposure and serves as an anti-reflective coating (ARC) in microlithography for semiconductor device fabrication processes,
is insoluble in photoresist solvents or developers,
a Hard Mask (HM) with good etch selectivity is transformed during photolithography and etching,
the composition of the ARC/HM layer material is based on a siloxane copolymer containing Si-H side groups in its structure for increasing the% Si content and accelerating low temperature curing, the composition of the ARC/HM layer material has specific chromophore side groups on the siloxane backbone of the siloxane copolymer to adjust the anti-reflective properties of the coating,
the composition of the ARC/HM layer material has a specific% Si on the siloxane backbone of the siloxane copolymer to tailor the etch selectivity properties of the coating.
The Si-containing copolymers of the present invention increase etch resistance and improve etch selectivity to organic photoresists.
The following synthesis examples are presented to produce various compositions to illustrate the results of their synthesis and coating. These examples should not be considered limiting. The usual procedure for preparing siloxane copolymers is based on one pot cohydrolysis of the following monomers: (A) R is R 1 SiCl 3 、(B)R 2 SiCl 3 、(C)R 3 SiCl 3 、(D)R 4 SiX 3 、(E)X 3 Si(CH 2 ) a SiX 3 And (F) (RO) 4 Si, wherein: x is chloro or alkoxy, R is an ethyl group, R 1 Is phenyl, R 2 Is H, R 3 Is methyl, R 4 Is 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Or 2- (methyl) ethyl, wherein the molar% concentration of each monomer in the starting monomer mixture is 0.00<(A)、(B)、(C)、(E)、(F)<95％，0.00≤(D)<50%, and (a) + (B) + (C) + (D) + (E) + (F) total mole number=100%.
Detailed Description
Examples
Example 1
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (33.0 g,0.09 moles), phenyltrichlorosilane (5.5 g,0.026 moles), methyltrichlorosilane (12 g,0.08 moles), trichlorosilane (7.0 g,0.05 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trimethoxysilane (5.0 g,0.01 mol), tetraethoxysilane (7.0,0.03 mol) and PGMEA (200 g). The mixture is stirred and by usingThe circulation cooler/heater system controls the jacket temperature to cool to 18 ℃. A clear, homogeneous mixture of water (11.0 g,0.61 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and then rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Example 2
A500 mL jacketed glass vessel was charged with a mixture of 1,2 bis- (triethoxysilyl) ethane (36.0 g,0.10 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrichlorosilane (11 g,0.07 moles), trichlorosilane (7.0 g,0.05 moles), tetraethoxysilane (7.0,0.03 moles), and PGMEA (210 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.7 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and then rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Example 3
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (40.0 g,0.11 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrichlorosilane (10 g,0.07 moles), trichlorosilane (5.0 g,0.04 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trimethoxysilane (5.0 g,0.01 mol), tetraethoxysilane (8.0,0.04 mol) and PGMEA (200 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.7 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the completion of the water/PGMEA mixture addition, the 500mL container was heatedTo 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and then rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Example 4
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (30.0 g,0.08 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrichlorosilane (10 g,0.07 moles), trichlorosilane (5.0 g,0.04 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trimethoxysilane (5.0 g,0.01 mol), tetraethoxysilane (10.0,0.05 mol) and PGMEA (200 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.7 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Example 5
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (20.0 g,0.06 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrichlorosilane (10 g,0.07 moles), trichlorosilane (7.0 g,0.05 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trimethoxysilane (5.0 g,0.01 mol), tetraethoxysilane (20.0,0.06 mol) and PGMEA (200 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.7 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated in PGMEA4% solids content.
Example 6
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (21.0 g,0.06 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrichlorosilane (10 g,0.07 moles), trichlorosilane (10.0 g,0.07 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]A mixture of trichlorosilane (5.0 g,0.01 mol), tetraethoxysilane (7.0,0.03 mol), and PGMEA (200 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.7 moles) and PGMEA (200 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃ and rinsed with water, rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Example 7
A500 mL jacketed glass vessel was charged with 1,2 bis- (triethoxysilyl) ethane (21.0 g,0.06 moles), phenyltrichlorosilane (6.0 g,0.028 moles), methyltrimethoxysilane (10 g,0.074 moles), trichlorosilane (10.0 g,0.07 moles), 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]A mixture of trichlorosilane (5.0 g,0.01 mol), tetraethoxysilane (7.0,0.03 mol), and PGMEA (300 g). The mixture was stirred and cooled to 18 ℃ by controlling the jacket temperature using a recirculating cooler/heater system. A clear, homogeneous mixture of water (12.0 g,0.9 mol) and PGMEA (230 g) was added to the mixture in a 500mL container by a metering pump over 60 minutes. After the addition of the water/PGMEA mixture was complete, the 500mL vessel was heated to 35 ℃ and stirred for 4 hours. The resulting mixture was cooled to 20 ℃, rinsed with water and rotary evaporated to remove traces of water. The product obtained was characterized by GPC and finally formulated to a solids content of 4% in PGMEA.
Characterization and testing:
the siloxane copolymers synthesized in the above examples were characterized by Waters GPC (gel permeation chromatography) on tetrahydrofuran as carrier solvent. Column calibration was performed using polystyrene standards with molecular weights ranging from 500 to 50,000 daltons. Table 1 summarizes the GPC results of the polymers of the above examples.
The siloxane copolymer of the above examples was filtered using a 0.1 micron Teflon filter and spin coated on Si wafers using a Lebo Scientific spin coater at an acceleration of 3,000-6,000rpm and a hold time of 20-50 seconds in final speed. The coated wafer is cured with a hot plate at 200-250 c for 30-60 seconds. The yield, mw/Mn and n and K of the cured films are summarized in Table 1.
TABLE 1
Peel test study of cured films with PGMEA and TMAH, mixing was performed at 30 seconds for PGMEA and 60 seconds for TMAH. Film thickness was measured using theta metrics before and after the peel test. The results of the peel test are summarized in table 2.
TABLE 2
The results of the solubility or peel test of table 2 indicate the stability of the coating in PGMEA and TMAH. All of the above examples have less than 2% thickness loss in the corresponding PGMEA and TMAH peel test.

Claims (15)

  1. An etch resistant antireflective composition of arc/HM comprising:
    A siloxane copolymer formed from the cohydrolysis of the following monomers in a polar organic solvent:
    (A)R 1 SiCl 3 ，
    (B)R 2 SiCl 3 ，
    (C)R 3 SiCl 3 ，
    (D)R 4 SiX 3 ，
    (E)X 3 Si(CH 2 ) a SiX 3 ，
    (F)(RO) 4 Si，
    wherein:
    x=cl OR,
    r independently at each occurrence represents an alkyl group having 1 to 12, more preferably 1 to 6C atoms, a=1 to 7,
    R 1 at each occurrence, independently represent anti-reflective chromophores in microlithography at wavelengths of 180-210nm, such as phenyl, phenylmethyl, phenylethyl and phenylpropyl,
    R 2 is H, is a group of the formula,
    R 3 independently at each occurrence, represents methyl or optionally substituted C 2 -C 5 An alkyl group having a hydroxyl group,
    R 4 independently at each occurrence, represents a hydrophilic group, e.g., 2- [ methoxy (polyethylene oxy) 6-9 Propyl group]Or a 2- (methyl ester) ethyl group,
    wherein the mole percent (mole% or mol%) of each monomer in the starting monomer mixture is 0.00< (a), (B), (C), (E), (F) <95%,0.00 + (D) <50%, wherein the preferred mole% range of (a) is 8% < (a) <20%, (B) is 35% < (B) <45%, (C) is 20% < (C) <70%, (D) is 1% < (D) <20%, (E) is 2% < (E) <30%, (F) is 2% < (F) <30%, and the total mole% of (a) + (B) + (C) + (D) + (E) + (F) is = 100 mole%.
  2. 2. An etch-resistant antireflective composition according to claim 1, where the monomer (E) in the siloxane is selected from the group consisting of ditrialkoxy olefin silane or ditrichloro olefin silane, said monomer yielding a bis-silyl olefin structure (e.g. O 1.5 Si(CH 2 ) a SiO 1.5 A linking group, wherein a = 1-7), preferably the monomer (E) is selected from a ditrialkoxysilane or a ditrichloroolefinic silane, such as 1, 1-bis-trimethoxysilylmethane, or 1, 2-bis-trimethoxysilylethane, or 1, 3-bis-trimethoxysilylpropane1, 4-bis-trimethoxysilylbutane or 1, 5-bis-trimethoxysilylbutane or 1, 6-bis-trimethoxysilylmethane or 1, 7-bis-trimethoxysilylmethane or 1, 1-bis-triethoxysilylmethane or 1, 2-bis-triethoxysilylethane or 1, 3-bis-triethoxysilylpropane or 1, 4-bis-triethoxysilylbutane or 1, 5-bis-triethoxysilylpentane or 1, 6-bis-triethoxysilylhexane or 1, 7-bis-triethoxysilylheptane or 1, 1-bis-trichlolylmethane or 1, 2-bis-trichlolylmethane or 1, 3-bis-trichlolylmethane or 1, 4-bis-trichlolylmethane or 1, 5-bis-trichlolylmethane or 1, 6-bis-trichlolylmethane or 1, 7-bis-trichlolylmethane or combinations thereof.
  3. 3. The etching resistant antireflective composition according to claim 1, wherein the monomer (a) in the siloxane copolymer contributes to the Q structure in the backbone, which is (Si-O) 4 The linking group, preferably the monomer (A), is selected from phenyl trichlorosilane, or phenyl methyl trichlorosilane, or phenyl ethyl trichlorosilane, or phenyl propyl trichlorosilane, or a combination of all or other aryl-containing trichlorosilane.
  4. 4. The etch-resistant antireflective composition according to claim 1, wherein the amount of Si in the final copolymer ranges from 8mol% to 46mol%, more preferably ranges from 15mol% to 45mol%, and most preferably ranges from 35mol% to 45mol%.
  5. 5. The etch-resistant antireflective composition according to claim 1, wherein the monomer (B) is selected from the group consisting of trichlorosilane, trimethoxysilane, triethoxysilane, and combinations thereof, as well as other H-containing trichlorosilane or trialkoxysilane.
  6. 6. The etch-resistant antireflective composition of claim 1, where the monomer (C) is selected from the group consisting of methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, and combinations thereof, as well as other alkyl-containing trichlorosilane or trialkoxysilane.
  7. 7. The etching-resistant antireflective composition according to claim 1, wherein the monomer (E) is selected from trichlorosilane or trialkoxysilane containing hydrophilic group, such as 2- [ methoxy (polyethyleneoxy) 6-9 Propyl group]Trichlorosilane, or 2- (methyl) ethyl trichlorosilane, or a combination thereof.
  8. 8. The etch-resistant antireflective composition according to claim 1, wherein the solvent is a mixture of water and one or more organic solvents selected from the group consisting of: ketones such as methyl isobutyl ketone (MIBK), methyl Ethyl Ketone (MEK), and cyclohexanone; alcohols such as methanol, ethanol, propanol and isopropanol; ethers such as Tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Glycol Monomethyl Ether (PGME) and diAn alkane; esters such as ethyl lactate, propylene Glycol Monomethyl Ether Acetate (PGMEA), isopropanol, and PGME, wherein the amount of the organic solvent and/or the water in the mixture is 5 wt% to 95 wt%.
  9. 9. The etch-resistant antireflective composition according to claim 1, wherein the weight average molecular weight Mw of the siloxane copolymer is from about 800 to about 20,000, preferably from about 1,000 to 10,000.
  10. 10. The etch-resistant antireflective composition according to claim 1, wherein the siloxane copolymer has the structure:
    [(OH) 3 Si(CH 2 ) a Si(OH) 2 O 0.5 ] b [(OH) 2 Si(CH 2 ) a Si(OH) 2 O] c
    [O(OH)Si(CH 2 ) a Si(OH)O] q [O 1.5 Si(CH 2 ) a SiO 1.5 ] e [R 1 Si(OH) 2 O 0.5 ] f
    [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH) 2 O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p
    [R 3 Si(OH) 2 O 0.5 ] v [R 3 SiO 1.5 ] w [R 3 Si(OH)O] d [R 4 Si(OH) 2 O 0.5 ] x [R 4 SiO 1.5 ] y
    [R 4 Si(OH)O] z [Si(OH) 3 O 0.5 ] j [Si(OH) 2 O] k [Si(OH)O 1.5 ] l [SiO 2 ] t
    Wherein 0< b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t <0.9, 0.00.ltoreq.x, y, z <0.50, a=1-7, and b+c+q+e+f+g+h+m+n+p+v+w+d+x+y+z+j+l+t=1,
    R 1 、R 2 、R 3 、R 4 as defined in claim 1.
  11. 11. A method for coating a microelectronic device, comprising the steps of:
    (i) Preparation of the etch-resistant antireflective composition according to any one of claims 1 to 10,
    (ii) A formulation prepared by dissolving the etch-resistant antireflective composition of any one of claims 1 to 10 in a polar organic solvent,
    (iii) The formulation is coated on a substrate, forming a coating,
    (iv) The polar organic solvent is evaporated from the coating,
    (v) The coating is cured to form a film.
  12. 12. The method according to claim 11Wherein the polar organic solvent is selected from ketones such as methyl isobutyl ketone (MIBK), methyl Ethyl Ketone (MEK), and cyclohexanone; alcohols such as methanol, ethanol, propanol and isopropanol; ethers such as Tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Glycol Monomethyl Ether (PGME) and diAn alkane; esters such as ethyl acetate, butyl acetate, ethyl lactate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA), the amount of polar organic solvent ranges from 90 wt% to 99 wt% based on the total ARC/HM formulation of the coating solution.
  13. 13. The method of claim 11, wherein in step (v), the curing is performed at a temperature ranging from about 100 ℃ to about 250 ℃.
  14. 14. The method of claim 11, wherein the film has a thickness of about 10nm to about 200nm.
  15. 15. A method of forming a patterned device, comprising:
    a) Preparing a formulation by dissolving the etch-resistant antireflective composition of any one of claims 1 to 10 in a polar organic solvent and coating the formulation on a substrate of a device to form a silicon-rich etch-resistant antireflective layer;
    b) Coating ArF photoresist on the silicon-rich anti-etching anti-reflection layer;
    c) Photo-patterning the ArF photoresist and forming a resist pattern on the silicon-rich etch-resistant anti-reflective layer;
    d) The exposed areas are removed by etching and a patterned device is created.
CN202210055708.1A 2022-01-18 2022-01-18 Composition of combined ARC and Si hard mask Pending CN116500864A (en)

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CN116500864A true CN116500864A (en) 2023-07-28

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