Composition of combined ARC and Si hard mask

Abstract

The new composition comprises a siloxane copolymer as a combination of an antireflective coating (ARC) and a hard mask (HM) formed by the co-hydrolysis of the following monomers: R 1 SiCl3, R 2 SiCl3, R 3 SiCl3, X3Si(CH2) a SiX3, R 4 SiX3, Si(OR)4, wherein: X = Cl or OR, R is an alkyl group such as methyl or ethyl, R 1 is an aromatic group such as phenyl, phenylmethyl, phenylethyl and phenylpropyl, R 2 is H, R 3 is methyl or an optionally substituted C2-C5 alkyl group, and the optional R 4 is a hydrophilic group such as 2-[methoxy(polyethyleneoxy) 6‑9 propyl] or 2-(methoxycarbonyl)ethyl, wherein the mole percent of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D), (E), (F) < 0.95, 0.00 ≤ (D) < 0.50, and the total moles of (A) + (B) + (C) + (D) + (E) + (F) = 1.

Description

TECHNICAL FIELD

[0001] The present invention relates to an etch resistant anti-reflective composition, a method of coating a microelectronic device by using such a composition. BACKGROUND

[0002] Typical four layer photolithography:

[0003] • 1 - Organic photoresist (spin coating)

[0004] • 2 - Anti-reflective coating (ARC) (spin coating)

[0005] • 3 - Si containing hard mask (for etch selectivity, e.g. SiON) (chemical vapor deposition)

[0006] • 4 - C containing hard mask (amorphous carbon, post ACL) (chemical vapor deposition)

[0007] • 5 - Device wafer

[0008] To reduce the cost and improve the performance of electronic devices, the semiconductor industry needs to have finer features to produce smaller but denser devices.

[0009] To be able to manufacture smaller devices, new and better materials and methods of micro lithography are needed.

[0010] Typically, to pattern a semiconductor device, a single layer of photoresist (PR) is used on a substrate and an anti-reflective coating (ARC) layer to control light reflection from the underlying layers that can affect line edge roughness (LER) and critical dimension (CD).

[0011] Prior art such as U.S. Patent No. 4,010,122 and U.S. Patent No. 5,693,691 to Brewer Science teach the use of ARC in micro lithography patterning.

[0012] As the resolution of photolithography patterning is increased, the need to reduce PR thickness has become an effective method to lower the aspect ratio of the PR / ARC stack and avoid pattern collapse.

[0013] However, the etch resistance of the organic PR in thinner PR / ARC stacks (Tokyo Electron Limited U.S. Patent No. 7,888,267) is not sufficient to transfer the pattern to the underlying layers, therefore, a new approach using a hard mask (HM) layer is used.

[0014] For example, Honeywell US Patent No. 6,506,497, Taiwan Semiconductor Manufacturing Company US Patent No. 6,777,340, Texas Instruments US Patent No. 6,803,661 teach the use of a hard mask in a photolithography stack with better etch selectivity to transfer the pattern to the PR / ARC / HM.

[0015] PR stripping and reactive ion etching (RIE) are used to transfer the pattern to the underlying layer as shown in the teachings of the following prior art: Novellus US Patent No. 8,178,443, US Patent No. 8,569,179, US Patent No. 8,664,124, US Patent No. 8,846,525, and Tokyo Electron Limited US Patent No. 9,576,816, US Patent No. 9,530,667, US Patent No. 9,607,843.

[0016] In a more efficient way, ARC and hard mask are combined into one layer as shown in 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.

[0017] Therefore, there is always a welcome improvement in ARC / hard mask materials as a single layer to address the many integration issues that arise during semiconductor device manufacturing. SUMMARY

[0018] It is an object of the present invention to provide an etch resistant anti-reflective composition for ARC / HM comprising or consisting of:

[0019] a siloxane copolymer prepared by the co-hydrolysis of a mixture of chlorosilanes and alkoxysilanes, preferably in a one pot process. The microlithography is preferably an ArF microlithography with a wavelength of 193 nm. In particular, the siloxane copolymer is formed by the co-hydrolysis of the following monomers in a solvent:

[0020] (A) R 1 SiCl3,

[0021] (B) R 2 SiCl3,

[0022] (C) R 3 SiCl3,

[0023] (D) R 4 SiX3,

[0024] (E) X3Si(CH2) a SiX3,

[0025] (F) (RO)4Si,

[0026] wherein:

[0027] X = Cl or alkoxy (OR),

[0028] R, independently in each occurrence, represents an alkyl group having 1-12, more preferably 1-6 C atoms, most preferably methyl or ethyl, a = 1-7;

[0029] R 1 independently in each occurrence, represents an antireflection chromophore in microlithography at a wavelength of 180-210 nm, preferably 190-200 nm, more preferably 193 nm, such as phenyl, phenylmethyl, phenylethyl and phenylpropyl,

[0030] R 2 is H,

[0031] R 3 independently in each occurrence, represents methyl or optionally substituted C2-C5 alkyl,

[0032] R 4 independently in each occurrence, represents a hydrophilic group such as 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(carbomethoxy)ethyl,

[0033] wherein the molar % (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 for (A) is 8 % < (A) < 20 %, the preferred mol % range for (B) is 35 % < (B) < 45 %, the preferred mol % range for (C) is 20 % < (C) < 70 %, the preferred mol % range for (D) is 1 % < (D) < 20 %, the preferred mol % range for (E) is 2 % < (E) < 30 %, the preferred mol % range for (F) is 2 % < (F) < 30 %, and the total moles of (A) + (B) + (C) + (D) + (E) + (F) = 100 %.

[0034] According to the present invention, monomer (A) controls the n and K values that minimize reflectivity at ArF exposure light; monomer (B) helps better etch selectivity by increasing the Si mole percent (%Si) in the siloxane copolymer; monomer (C) also increases the %Si content of the siloxane copolymer and enhances better solubility of the material in organic solvents; monomer (D) improves solubility and adhesion to the substrate; and monomer (E) enhances adhesion and accelerates curing; monomer (F) is based on a tetrafunctional Q structure that provides better low temperature crosslinking and thus enhances structural stability, wherein monomer (E) is a bis-trialkoxyalkene silane or bis-trichloroalkene silane, thereby creating a bis-silylalkene structure in the main chain (e.g. O 1.5 Si(CH2) a SiO 1.5 linker, where a = 1-7) to obtain stability and faster low temperature curing; and monomer (F) is a tetraalkoxysilane that produces a Q structure (e.g. a (Si-O)4linker with four Si-O bonds), the tetrafunctional Q structure provides better low temperature crosslinking and thus enhances structural stability.

[0035] The etch resistant antireflective composition according to the present invention, the monolayer thermally cured coating thus obtained has very low reflectivity in ArF exposure and acts as an antireflective coating (ARC) in the microlithography process of the semiconductor device manufacturing method.

[0036] The etch resistant antireflective composition according to the present invention, the monolayer thermally cured coating thus obtained is insoluble in photoresist solvents or developers.

[0037] The etch resistant antireflective composition according to the present invention, the monolayer thermally cured coating thus obtained is converted into a hard mask (HM) with good etch selectivity during the photolithography and etching processes.

[0038] Further, the combination of the antireflective coating (ARC) and hard mask (HM) performance with the available entities is referred to as ARC / HM in the present invention.

[0039] According to a particular aspect of the present invention, the composition of the ARC / HM layer material is based on a siloxane copolymer that contains a bis-silylalkene structure in the main chain (e.g. O 1.5 Si(CH2) a SiO 1.5 linker, where a = 1-7) to obtain stability and faster low temperature curing.

[0040] According to a particular aspect of the present application, the composition of the ARC / HM layer material is based on a siloxane copolymer which contains Si-H pendant groups in its structure for increasing the % Si content and accelerating low temperature curing. The amount of Si in the final copolymer ranges from 8 mol% to 46 mol%, more preferably from 15 mol% to 45 mol%, and most preferably from 35 mol% to 45 mol%.

[0041] According to a particular aspect of the present application, the composition of the ARC / HM layer material has specific chromophore pendant groups on the siloxane backbone of the siloxane copolymer to tune the anti-reflective properties of the coating.

[0042] According to a particular aspect of the present application, the composition of the ARC / HM layer material has specific % Si on the siloxane backbone of the siloxane copolymer to tune the etch selectivity properties of the coating. The Si-containing copolymers of the present application increase the etch resistance and improve the etch selectivity for organic photoresists.

[0043] In a preferred embodiment, the composition according to the present application has the following siloxane copolymer structure:

[0044] [(OH)3Si(CH2) a Si(OH)2O 0.5 ] b [(OH)2Si(CH2) a Si(OH)2O] c [O(OH)Si(CH2) a Si(OH)O] q [O 1.5 Si(CH2) a SiO 1.5 ] e [R 1 Si(OH)2O 0.5 ] f [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH)2O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p [R 3 Si(OH)2O 0.5 ] v [R 3 SiO 1.5 ] w [R3 Si(OH)O] d [R 4 Si(OH)2O 0.5 ] x [R 4 SiO 1.5 ] y [R 4 Si(OH)O] z [Si(OH)3O 0.5 ] j [Si(OH)2O] k [Si(OH)O 1.5 ] l [SiO2] t ,

[0045] where 0 < b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t < 0.9, 0.00 < x, y, z < 0.50, a = 1-7, the preferred range of a is 1-3, and b + c + q + e + f + g + h + m + n + p + v + w + d + x + y + z + j + k + l + t = 1,

[0046] R 1 is a chromophore such as phenyl, phenylmethyl, phenylethyl and phenylpropyl for antireflection in 193 nm microlithography,

[0047] R 2 is H for increasing %S for better etch selectivity,

[0048] R 3 is methyl or optionally substituted C2-C5 alkyl group for stability,

[0049] R 4 is a hydrophilic group such as 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl for adhesion.

[0050] According to the etch resistant antireflective composition of the present invention, the amount of %Si in the composition of the siloxane copolymer is controlled by controlling the amount of H containing trichlorosilane or trialkoxysilane to aid in controlling the etch selectivity of the ARC / HM coating material.

[0051] According to the etch resistant antireflective composition of the present invention, the presence of disilyl olefin units (e.g. O 1.5 Si(CH2) a SiO 1.5The crosslinking is enhanced by introducing crosslinking density into the siloxane polymer and increasing the silanol (Si-OH) functionality in the structure that is susceptible to crosslinking. The number of disilylalkene units is controlled by controlling the amount of disilylalkene silane or disilylchloroalkene or mixtures thereof.

[0052] According to the etch resistant anti-reflective composition of the present invention, the silanol (Si-OH) is also formed from T structures (e.g. RSi(OH)20 0.5 , RSiO 1.5 , RSi(OH)O) in the backbone siloxane copolymer from alkyl or aryl containing trichloroalkyl or trialkoxysilane. The uncondensed silanol functionality causes crosslinking of the coating at lower temperatures. The T structures are formed from alkyl or aryl containing trichlorosilane or trialkoxysilane.

[0053] According to a particular aspect of the present invention, the composition of the ARC / HM layer material is based on a siloxane copolymer containing Q structures (e.g. (Si-O)4linkages) in the backbone for stability and faster low temperature curing.

[0054] It is another object of the present invention to provide a method of coating a microelectronic device comprising the steps of:

[0055] (i) preparing the etch resistant anti-reflective composition of the present invention,

[0056] (ii) preparing a formulation by dissolving the etch resistant anti-reflective composition of the present invention in a polar organic solvent,

[0057] (iii) applying the formulation on a substrate to form a coating,

[0058] (iv) evaporating the polar organic solvent from the coating,

[0059] (v) curing the coating to form a thin film.

[0060] In an aspect of the method, 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 dioxane; esters such as ethyl acetate, butyl acetate, ethyl lactate and propylene glycol monomethyl ether acetate (PGMEA). The solvent in the total ARC / HM formulation of the coating solution can be in an amount of 90 wt% to 99 wt%.

[0061] In an aspect of the method, in step (v), the curing is performed at a temperature range of about 100°C to about 250°C.

[0062] ​In an aspect of the method, in step (v), the curing is performed in a time period of about 1 to about 2 minutes.

[0063] In an aspect of the method, the substrate is a Si wafer, a substrate for an integrated circuit, or other microelectronic device substrate.

[0064] In an aspect of the method, in step (iii), the coating is spin coating.

[0065] In an aspect of the method, the polar organic solvent is evaporated during the spin coating process.

[0066] In an aspect of the method, the thin film has a thickness of about 10 nm to about 200 nm.

[0067] It is another object of the present application to provide a method of forming a patterned device comprising:

[0068] a) preparing a formulation by dissolving the etch resistant anti-reflective composition of the present application in a polar organic solvent and coating the formulation on a substrate of a device to form a Si-rich ARC layer;

[0069] b) coating an ArF photoresist over the Si-rich ARC layer;

[0070] c) photo patterning the ArF photoresist and forming a resist pattern over the Si hard mask ARC layer;

[0071] d) removing the exposed areas by etching and producing a patterned device.

[0072] The ARC / HM siloxane copolymer solution material can be spin coated and thermally cured at a temperature of 100-250 °C for a time period of 30-60 seconds to prevent thickness loss of photoresist solvents and developers. BRIEF DESCRIPTION OF DRAWINGS

[0073] In Figure 1 Examples of the application of the ARC / hard mask coating of the present application in semiconductor device manufacturing are illustrated in the following figures. The lithography, patterning and etching steps are illustrated in the following figures:

[0074] Figure 1 a illustrates a cross section of a coated layer of a stack of a mask (filled black area) on a substrate, (1) photoresist, (2) ARC / HM, (3) SiN or ACL, (4) dielectric layer, where the downward arrow shows the ArF exposure;

[0075] Figure 1 b illustrates the patterned photoresist layer (1) exposed and developed on top of the other layers;

[0076] Figure 1 c illustrates the photoresist (1) pattern transfer to the ARC / HM (2) layer;

[0077] Figure 1 d illustrates the photoresist layer (1) removed from the stack leaving the patterned ARC / HM (2);

[0078] Figure 1 e illustrates the pattern transfer of ARC / HM (2) to SiN or ACL (3) layer;

[0079] Figure 1 f illustrates the ARC / HM (2) removed from the stack leaving the patterned SiN or ACL (3);

[0080] Figure 1 g illustrates the SiN or ACL (3) pattern transfer to dielectric layer (4);

[0081] Figure 1 h illustrates the SiN or ACL (3) removed from the stack leaving the patterned dielectric layer (4).

[0082] In Figure 2 illustrates an example of a typical four layer photolithography process where

[0083] Figure 2 I illustrates a cross section of a coated four layer stack of mask (filled black area), (1) photoresist, (2) ARC, (3) hard mask, (4) SiN or ACL, (5) dielectric layer on a substrate, where the downward arrow shows the ArF exposure;

[0084] Figure 2 J illustrates the patterned photoresist layer (1) exposed and developed on top of the other layers;

[0085] Figure 2 K illustrates the photoresist (1) pattern RIE transfer to ARC (2) and hard mask layer (3);

[0086] Figure 2 L illustrates the C-hard mask etch (4);

[0087] Figure 2 M illustrates the pattern transfer to the bottom layer;

[0088] Figure 2 N illustrates the C-hard mask removed from the stack leaving the patterned IC (dielectric) layer.

[0089] DETAILED DESCRIPTION

[0090] The present invention provides an etch resistant antireflective composition, whereby the monolayer thermally cured coating obtained has very low reflectivity in ArF exposure and acts as an antireflective coating (ARC) in the microlithography process of the semiconductor device manufacturing process.

[0091] The present invention provides an etch-resistant antireflective composition, whereby the thermally cured coating obtained therefrom is converted into a hard mask (HM) with good etch selectivity during photolithography and etching processes.

[0092] The present invention provides an etch-resistant antireflective composition, whereby the thermally cured coating obtained therefrom is not soluble in photoresist solvents or developers.

[0093] In an important aspect of the present invention, the combination of both antireflective coating (ARC) and hard mask (HM) performance after curing the ARC / HM coating is achieved by the etch-resistant antireflective composition of the present invention, which comprises or consists of a siloxane copolymer formed by the co-hydrolysis of the following monomers in a solvent:

[0094] (A) R 1 SiCl3,

[0095] (B) R 2 SiCl3,

[0096] (C) R 3 SiCl3,

[0097] (D) R 4 SiX3,

[0098] (E) X3Si(CH2) a SiX3,

[0099] (F) (RO)4Si,

[0100] wherein:

[0101] X = Cl or alkoxy (OR),

[0102] R, independently in each occurrence, represents an alkyl group having 1-12, more preferably 1-6 C atoms, most preferably methyl or ethyl, a = 1-7;

[0103] R 1 independently in each occurrence, represents an antireflective chromophore in microlithography at a wavelength of 180-210 nm, preferably 190-200 nm, more preferably 193 nm, such as phenyl, phenylmethyl, phenylethyl and phenylpropyl,

[0104] R 2 is H,

[0105] R 3 independently in each occurrence, represents methyl or an optionally substituted C2-C5 alkyl group,

[0106] R 4independently at each occurrence represents a hydrophilic group, for example 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl,

[0107] 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 mole percent (mol%) range for (A) is 8% < (A) < 20%, the preferred mol% range for (B) is 35% < (B) < 45%, the preferred mol% range for (C) is 20% < (C) < 70%, the preferred mol% range for (D) is 1% < (D) < 20%, the preferred mol% range for (E) is 2% < (E) < 30%, the preferred mol% range for (F) is 2% < (F) < 30%, and the total moles of (A) + (B) + (C) + (D) + (E) + (F) = 100%.

[0108] Monomer (A) controls the n and K values that minimize reflectivity at ArF exposure.

[0109] Monomer (B) helps better etch selectivity by increasing the % Si content in the siloxane copolymer.

[0110] Monomer (C) also increases the % Si content of the siloxane copolymer and better solubility of the material in organic solvents.

[0111] Monomer (D) for better solubility and adhesion.

[0112] Monomer (E) is a bis-trialkoxyalkene silane or bis-trichloroalkene silane, thereby creating a bis-silylalkene linkage (e.g., O 1.5 Si(CH2) a SiO 1.5 linkage, where a = 1-7) for main chain stability and to accelerate low temperature curing.

[0113] In addition, Monomer (E) enhances adhesion and accelerates curing.

[0114] Monomer (F) is a tetraalkoxysilane that produces a Q structure (e.g., a (Si-O)4 linkage with four Si-O bonds), the tetrafunctional Q structure provides better low temperature crosslinking, thus enhancing the structural stability.

[0115] In addition, the siloxane copolymer of the present invention has the following structure:

[0116] [(OH)3Si(CH2) a Si(OH)2O 0.5 ] b [(OH)2Si(CH2) aSi(OH)2O c [O(OH)Si(CH2) a Si(OH)O] q [O 1.5 Si(CH2) a SiO 1.5 ] e [R 1 Si(OH)2O 0.5 ] f [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH)2O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p [R 3 Si(OH)2O 0.5 ] v [R 3 SiO 1.5 ] w [R 3 Si(OH)O] d [R 4 Si(OH)2O 0.5 ] x [R 4 SiO 1.5 ] y [R 4 Si(OH)O] z [Si(OH)3O 0.5 ] j [Si(OH)2O] k [Si(OH)O 1.5 ] l [SiO2] t

[0117] where 0 < b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t < 0.9, 0.00 < x, y, z < 0.50, a = 1-7, the preferred range of a is 1-3, and b + c + q + e + f + g + h + m + n + p + v + w + d + x + y + z + j + k + l + t = 1,

[0118] R 1is a chromophore, such as phenyl, phenylmethyl, phenylethyl or phenylpropyl, for antireflection in microlithography at a wavelength of 193 nm,

[0119] R 2 is H for increasing the %S for better etch selectivity,

[0120] R 3 is, methyl or an optionally substituted C2-C5 alkyl group for stability,

[0121] R 4 is a hydrophilic group such as 2-[methoxy(polyethyleneoxy) 6-9 propyl]trichlorosilane or 2-(carbomethoxy)ethyltrichlorosilane for adhesion.

[0122] The siloxane copolymers of the present invention are prepared in a single synthesis process ("one-pot process") of the co-hydrolysis of a mixture of chlorosilane monomers and alkoxysilane monomers. The monomers can be selected from the group consisting of bis-trialkoxysilane or bis-trichloroalkylsilane, such as 1,1-bis-trimethoxysilylmethane, or 1,2-bis-trimethoxysilyl ethane, 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-triethoxysilyl ethane, 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-trichlorosilylmethane, or 1,2-bis-trichlorosilyl ethane, or 1,3-bis-trichlorosilylpropane, or 1,4-bis-trichlorosilylbutane, or 1,5-bis-trichlorosilylpentane, or 1,6-bis-trichlorosilylhexane, or 1,7-bis-trichlorosilylheptane, or combinations thereof. The monomers are also selected from the group consisting of aryl-containing trichlorosilanes such as phenyltrichlorosilane, or phenylmethyltrichlorosilane, or phenylethyltrichlorosilane, or phenylpropyltrichlorosilane, or combinations of all. The monomers are also selected from the group consisting of H-containing trichlorosilanes or trialkoxysilanes such as trichlorosilane or trimethoxysilane or triethoxysilane or combinations thereof. The monomers are also selected from the group consisting of alkyl-containing trichlorosilanes or trialkoxysilanes 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 combinations thereof. The monomers are also selected from the group consisting of hydrophilic group-containing trichlorosilanes or trialkoxysilanes such as 2-[methoxy(polyethyleneoxy) 6-9 propyl]trichlorosilane, or 2-(carbomethoxy)ethyltrichlorosilane, or combinations thereof.

[0123] The chromophore that can be used as a pendant group of trichlorosilane or trialkoxysilane can 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 methyl trimethoxysilane, or phenyl ethyl trimethoxysilane, or phenyl propyl trimethoxysilane, or phenyl triethoxysilane, or phenyl methyl triethoxysilane, or phenyl methyl triethoxysilane, or phenyl ethyl triethoxysilane, or phenyl propyl triethoxysilane. In addition, the refractive index (n) values and extinction coefficient (k) values of the ARC / HM coating can be tuned by controlling the amount of silane containing the corresponding chromophore used in the synthesis of the siloxane copolymer.

[0124] Another useful feature of the siloxane copolymers of the present invention is to control the amount of % Si in the composition of the siloxane copolymer by controlling the amount of trichlorosilane or trialkoxysilane containing H and other trichlorosilane monomers or trialkoxysilane monomers to control the etch selectivity of the ARC / HM coating material.

[0125] Yet another useful component of the siloxane copolymers of the present invention is the presence of a disilylalkene structure (e.g., O 1.5 Si(CH2) a SiO 1.5 Linkage where a = 1-7) in the backbone to achieve stability and accelerated low temperature cure as well as to increase the silanol (Si-OH) functionality in the structure that is readily crosslinkable. The number of disilylalkene units is controlled by controlling the amount of bis-trialkoxysilane or bis-trichloroalkenesilane, or mixtures thereof.

[0126] In yet another important aspect of the present invention, a useful component of the siloxane copolymers in the etch resistant antireflective composition of the present invention is the presence of Q units (e.g., (Si-O)4linkage) in the structure that enhances thermal cure by introducing crosslinking density into the siloxane polymer as well as increasing the silanol (Si-OH) functionality in the structure that is readily crosslinkable. The number of Q units is controlled by controlling the amount of tetrachlorosilane, or tetramethoxysilane, or tetraethoxysilane, or mixtures thereof.

[0127] The silanol (Si-OH) functionality is also contributed by the T structure (e.g., RSi(OH)20 0.5 , RSiO 1.5, RSi(OH)O) formation. Uncondensed silanol functionality causes crosslinking of the coating at lower temperatures. T structures are formed from alkyl or aryl containing trichlorosilanes or trialkoxysilanes, 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 phenyltrichlorosilane, or phenylmethyltrichlorosilane, or phenylethyltrichlorosilane, or phenylpropyltrichlorosilane, or phenyltrimethoxysilane, or phenylmethyltrimethoxysilane, or phenylmethyltrimethoxysilane, or phenylethyltrimethoxysilane, or phenylpropyltrimethoxysilane, or phenyltriethoxysilane, or phenylmethyltriethoxysilane, or phenylmethyltriethoxysilane, or phenylethyltriethoxysilane, or phenylpropyltriethoxysilane. 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 phenyltrimethoxysilane, or phenylmethyltrimethoxysilane, or phenylmethyltrimethoxysilane, or phenylethyltrimethoxysilane, or phenylpropyltrimethoxysilane, or phenyltriethoxysilane, or phenylmethyltriethoxysilane, or phenylmethyltriethoxysilane, or phenylethyltriethoxysilane, or phenylpropyltriethoxysilane.

[0128] The cohydrolysis and polycondensation of the monomers of the present invention can form siloxane copolymers in a network of random branching and cages of various structural dimensions with mixtures of T, Q, and disilylalkene units.

[0129] Uncondensed silanol (Si-OH) functionality from T, Q, and bis-silylalkene structures in the siloxane copolymer tends to crosslink and complete the formation of three and four Si-O-Si bonds around each silicon atom in the corresponding T, Q, and bis-silylalkene structures during thermal curing. The stability of the ARC / HM coating in organic solvents increases as the Si-OH condensation and Si-O-Si bond formation increases, the more completely condensed the ARC / HM coating, the more stable the coating is in organic solvents. The thermally cured ARC / HM coating must be insoluble in photoresist solvents and developers to be stable during subsequent photoresist coating and development processes. Optionally, a thermal curing catalyst can be used as a formulation additive to increase the rate of thermal curing of the ARC / HM coated silanol. The amount of acid, such as acetic acid, hydrochloric acid, sulfonic acid, methanesulfonic acid, or phosphoric acid is 100 to 1000 ppm. Alternatively, the condensation catalyst can be selected from a thermal acid generator or a thermal base generator. The amount of Si-containing monomers with T, Q, and bis-silylalkene structures can control the %Si in the final composition.

[0130] The ARC / HM siloxane copolymer can have a weight average molecular weight (Mw) of about 800 to about 20,000, as determined by gel permeation chromatography (GPC).

[0131] The solvent in the co-hydrolysis 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 dioxane; 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% - 95 wt%.

[0132] In some embodiments, the siloxane copolymer can comprise 1 wt% to 10 wt% of the total ARC / HM formulation of the coating solution.

[0133] Spin coating can be used as a method to apply the ARC / HM formulation in semiconductor device manufacturing. The method of spin coating typically entails pouring a small amount of the ARC / HM solution as a puddle onto the surface of the semiconductor device, followed by accelerating the material to a selected final speed of 2000 to 3000 rpm at 4,000 - 5,000 rpm, and maintaining the material at the final speed for 10 - 20 seconds before completing the spin. In this way, a uniform coating of the ARC / HM material as an ARC / HM layer is formed on the surface of the semiconductor device.

[0134] ​The ARC / HM coating can be thermally cured by heating, for example, a hot plate or a hot furnace, in semiconductor device manufacturing using any generally suitable technique used in curing. The ARC / HM coating can be thermally cured at a temperature of 100-250°C for a time period of 30-60 seconds to increase the cross-linking density of the siloxane copolymer in the coating and condense silanol (Si-OH) to form Si-O-Si bonds. The thermally cured siloxane copolymer will be sufficiently cured to be stable in photoresist solvents such as PGMEA, PGME, gamma butyrolactone (GBL), ethyl lactate (EL), and the like.

[0135] After the ARC / HM coating is applied and cured, a thin photoresist layer is spun 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 the ARC / HM layer pattern transfer is oxygen plasma etching 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 pattern transfer to the underlying layers using the appropriate RIE etching chemistry followed by removal of the hard mask and production of the target patterned structure on the semiconductor device.

[0136] Figure 1 The example in the semiconductor device manufacturing of applying the ARC / HM coating of the present invention is described, however, this is not the only use and should not be used as a limiting factor of the uses of the present invention, and the coating of the present invention can be used in many other ways. The geometry and dimensions used in this example are only for illustration to better clarify the example and are not representative of the actual geometry and dimensions.

[0137] The substrate can be a metal such as Si, Ge, Al, and the like, or an alloy such as SiGe, gallium arsenide, and the like, or an insulator such as SiO2, Si3N4, and the like, or a doped variant or mixture thereof. The example of the target layer to be patterned in this example is a dielectric (4) layer. Figure 1The layer (3) in the stack of a is SiN or an amorphous carbon layer (ACL). The ARC / HM silicon copolymer composition of the present application is spin-coated on the layer (3) at a speed of about 2000 to about 3000 rpm for a period of about 10 seconds to about 20 seconds. The ARC / HM silicon copolymer composition coating is then heat cured at a temperature of about 100 °C to about 250 °C for a period of about 30 seconds to about 60 seconds to increase the cross-link density of the copolymer in the coating and condense the silanol (Si-OH) to form Si-O-Si bonds, which results in an ARC / HM layer (2) that is insoluble in photoresist solvent that is spin-coated in the subsequent step of photoresist coating. The ARC / HM layer (2) has light absorption properties that are controlled by adjusting the amount of chromophore in the composition and the thickness of the coating to optimize n and k to reduce reflection of light. To complete the stack of a, the photoresist is spin-coated and patterned by ArF light through an exposure mask (filled black area) and developed to remove the exposed areas. The stack of a-h is illustrated in more detail in the following figures in which the photoresist, ARC / HM, and SiN or ACL layers are shown as cross-sections of the coated layers on the substrate. Figure 1 To complete the stack of a, the photoresist is spin-coated and patterned by ArF light through an exposure mask (filled black area) and developed to remove the exposed areas. The stack of a-h is illustrated in more detail in the following figures in which the photoresist, ARC / HM, and SiN or ACL layers are shown as cross-sections of the coated layers on the substrate. Figure 1 The photoresist, ARC / HM, and SiN or ACL layers are shown as cross-sections of the coated layers on the substrate in the following figures in which the photoresist, ARC / HM, and SiN or ACL layers are shown as cross-sections of the coated layers on the substrate.

[0138] Figure 1 a illustrates the cross-section of the coated layers of the stack of a mask (filled black area), (1) photoresist, (2) ARC / HM, (3) SiN or ACL, (4) dielectric layer on a substrate, where the downward arrow shows ArF exposure.

[0139] Figure 1 b illustrates the patterned photoresist layer (1) exposed and developed on top of the other layers.

[0140] Figure 1 c illustrates the photoresist (1) pattern transferred to the ARC / HM layer (2) when the ARC / HM layer (2) is patterned using the photoresist pattern as an etch mask.

[0141] Figure 1 d 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 underlying layers on other target materials.

[0142] Figure 1 e illustrates the ARC / HM layer (2) pattern transferred to the underlying SiN or ACL (3).

[0143] Figure 1 f illustrates the ARC / HM layer (2) removed from the stack leaving the patterned SiN or ACL (3) layer.

[0144] Figure 1 g illustrates the SiN or ACL (3) pattern transferred to the dielectric layer (4).

[0145] Figure 1 h illustrates the SiN or ACL (3) layer removed from the stack leaving the patterned dielectric target layer (4).

[0146] The present application has the following advantages compared to the prior art:

[0147] The etch resistant antireflective composition according to the present application, the monolayer thermally cured coating obtained thereby,

[0148] having very low reflectivity in ArF exposure and acting as an antireflective coating (ARC) in the microlithography process of semiconductor device manufacturing,

[0149] being insoluble in photoresist solvents or developers,

[0150] transforming into a hard mask (HM) with good etch selectivity during the lithography and etching process,

[0151] The composition of the ARC / HM layer material is based on a siloxane copolymer which contains Si-H pendant groups in its structure for increasing the % Si content and accelerating the low temperature curing, the composition of the ARC / HM layer material has specific chromophore pendant groups on the siloxane backbone of the siloxane copolymer to tune the antireflective properties of the coating,

[0152] The composition of the ARC / HM layer material has specific % Si on the siloxane backbone of the siloxane copolymer to tune the etch selectivity properties of the coating.

[0153] The Si containing copolymer of the present application improves the etch resistance and improves the etch selectivity to organic photoresists.

[0154] The following synthesis examples to produce various compositions are presented to illustrate their synthesis and the results of the coatings. These examples should not be considered limiting. The general procedure for preparing the siloxane copolymers is based on a one-pot cohydrolysis of the following monomers: (A) R 1 SiCl3, (B) R 2 SiCl3, (C) R 3 SiCl3, (D) R 4 SiX3, (E) X3Si(CH2) a SiX3and (F) (RO)4Si, where: X is chlorine or alkoxy, R is an ethyl group, R 1 is a phenyl group, R 2 is H, R 3 is a methyl group, R 4 is 2-[methoxy(polyethyleneoxy) 6-9propyl] or 2-(methoxymethyl)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 the total moles of (A)+(B)+(C)+(D)+(E)+(F) = 100%. DETAILED DESCRIPTION

[0155] EXAMPLE

[0156] Example 1

[0157] A 500 mL jacketed glass vessel was charged with a mixture of 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 A 500 mL jacketed glass vessel was charged with a mixture of 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)

[0158] Example 2

[0159] A 500 mL jacketed glass container contained a mixture of 1,2-bis-(triethoxysilyl)ethane (36.0 g, 0.10 mol), phenyltrichlorosilane (6.0 g, 0.028 mol), methyltrichlorosilane (11 g, 0.07 mol), trichlorosilane (7.0 g, 0.05 mol), tetraethoxysilane (7.0 g, 0.03 mol), and PGMEA (210 g). The mixture was stirred and cooled to 18 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (12.0 g, 0.7 mol) and PGMEA (200 g) was added to the 500 mL container over 60 minutes using a metering pump. After the water / PGMEA mixture was added, the 500 mL container was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C, rinsed with water, and then rotary evaporated to remove trace amounts of water. The obtained product was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0160] Example 3

[0161] A 500 mL jacketed glass container contains 40.0 g (0.11 mol) of 1,2-bis-(triethoxysilyl)ethane, 6.0 g (0.028 mol) of phenyltrichlorosilane, 10 g (0.07 mol) of methyltrichlorosilane, 5.0 g (0.04 mol) of trichlorosilane, and 2-[methoxy(polyethyloxy)] 6-9 A mixture of [propyltrimethoxysilane](5.0 g, 0.01 mol), tetraethoxysilane(8.0 g, 0.04 mol), and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 18 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (12.0 g, 0.7 mol) and PGMEA (200 g) was added to the mixture in a 500 mL vessel over 60 minutes using a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL vessel was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C, washed with water, and then rotary evaporated to remove trace amounts of water. The obtained product was characterized by GPC and finally formulated to a solid content of 4% PGMEA.

[0162] Example 4

[0163] A 500 mL jacketed glass container contains 30.0 g (0.08 mol) of 1,2-bis-(triethoxysilyl)ethane, 6.0 g (0.028 mol) of phenyltrichlorosilane, 10 g (0.07 mol) of methyltrichlorosilane, 5.0 g (0.04 mol) of trichlorosilane, and 2-[methoxy(polyethyloxy)] 6-9A mixture of [propyltrimethoxysilane](5.0 g, 0.01 mol), tetraethoxysilane(10.0 g, 0.05 mol), and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 18 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (12.0 g, 0.7 mol) and PGMEA (200 g) was added to the mixture in a 500 mL vessel over 60 minutes using a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL vessel was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C, washed with water, and rotary evaporated to remove trace amounts of water. The obtained product was characterized by GPC and finally formulated to a solid content of 4% PGMEA.

[0164] Example 5

[0165] A 500 mL jacketed glass container contains 20.0 g (0.06 mol) of 1,2-bis-(triethoxysilyl)ethane, 6.0 g (0.028 mol) of phenyltrichlorosilane, 10 g (0.07 mol) of methyltrichlorosilane, 7.0 g (0.05 mol) of trichlorosilane, and 2-[methoxy(polyethyloxy)] 6-9 A mixture of [propyltrimethoxysilane](5.0 g, 0.01 mol), tetraethoxysilane (20.0 g, 0.06 mol), and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 18 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (12.0 g, 0.7 mol) and PGMEA (200 g) was added to the mixture in a 500 mL vessel over 60 minutes using a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL vessel was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C, washed with water, and rotary evaporated to remove trace amounts of water. The obtained product was characterized by GPC and finally formulated to a solid content of 4% PGMEA.

[0166] Example 6

[0167] A 500 mL jacketed glass container contains 21.0 g (0.06 mol) of 1,2-bis-(triethoxysilyl)ethane, 6.0 g (0.028 mol) of phenyltrichlorosilane, 10 g (0.07 mol) of methyltrichlorosilane, 10.0 g (0.07 mol) of trichlorosilane, and 2-[methoxy(polyethyloxy)]ethane. 6-9A mixture of phenyltrichlorosilane (5.0 g, 0.01 mole), tetraethoxysilane (7.0, 0.03 mole) and PGMEA (300 g). The mixture was stirred and cooled to 18°C by controlling the jacket temperature using a recirculating chiller / heater system. A clear homogeneous mixture of water (12.0 g, 0.9 mole) and PGMEA (230 g) was added to the mixture in a 500 mL vessel over 60 minutes by a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL vessel was heated to 35°C and stirred for 4 hours. The resulting mixture was cooled to 20°C, rinsed with water and rotary evaporated to remove trace amounts of water. The resulting product was characterized by GPC and finally formulated to 4% solids in PGMEA.

[0168] Example 7

[0169] A 500 mL jacketed glass vessel was charged with 1,2 bis-(triethoxysilyl)ethane (21.0 g, 0.06 mole), phenyltrichlorosilane (6.0 g, 0.028 mole), methyltrimethoxysilane (10 g, 0.074 mole), trichlorosilane (10.0 g, 0.07 mole), 2-[methoxy(polyethyleneoxy) 6-9 A mixture of phenyltrichlorosilane (5.0 g, 0.01 mole), tetraethoxysilane (7.0, 0.03 mole) and PGMEA (300 g). The mixture was stirred and cooled to 18°C by controlling the jacket temperature using a recirculating chiller / heater system. A clear homogeneous mixture of water (12.0 g, 0.9 mole) and PGMEA (230 g) was added to the mixture in a 500 mL vessel over 60 minutes by a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL vessel was heated to 35°C and stirred for 4 hours. The resulting mixture was cooled to 20°C, rinsed with water and rotary evaporated to remove trace amounts of water. The resulting product was characterized by GPC and finally formulated to 4% solids in PGMEA.

[0170] Characterization and Testing:

[0171] The siloxane copolymers synthesized in the above examples were characterized using a Waters GPC (gel permeation chromatography) with tetrahydrofuran as the 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 for the polymers of the above examples.

[0172] The silicone copolymers of the above examples were filtered using a 0.1 micron Teflon filter and spin coated on Si wafers using a Lebo Scientific spinner at an acceleration of 3,000-6,000 rpm and a final speed with a hold time of 20-50 seconds. The coated wafers were baked on 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.

[0173] Table 1

[0174]

[0175] The results of the stripping tests are summarized in Table 2.

[0176] Table 2

[0177]

[0178] The results of the solubility or stripping tests of Table 2 indicate the stability of the coatings in PGMEA and TMAH. All of the above examples have less than 2% thickness loss in the respective PGMEA and TMAH stripping tests.

Claims

1. An etch resistant anti-reflective composition of ARC / HM comprising: a siloxane copolymer having the following structure: [(OH)3Si(CH2) a Si(OH)2O 0.5 ] b [(OH)2Si(CH2) a Si(OH)2O] c [O(OH)Si(CH2) a Si(OH)O] q [O 1.5 Si(CH2) a SiO 1.5 ] e [R 1 Si(OH)2O 0.5 ] f [R 1 SiO 1.5 ] g [R 1 Si(OH)O] h [R 2 Si(OH)2O 0.5 ] m [R 2 SiO 1.5 ] n [R 2 Si(OH)O] p [R 3 Si(OH)2O 0.5 ] v [R 3 SiO 1.5 ] w [R 3 Si(OH)O] d [R 4 Si(OH)2O 0.5 ] x [R 4 SiO 1.5 ] y [R 4 Si(OH)O] z [Si(OH)3O 0.5 ] j [Si(OH)2O] k [Si(OH)O 1.5 ] l [SiO2] t where 0 < b, c, q, e, f, g, h, m, n, p, v, w, d, j, k, l, t < 0.9, 0.00 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 + k + l + t = 1, R 1 independently at each occurrence represents phenyl, phenylmethyl, phenylethyl and phenylpropyl, R 2 is H, R 3 independently at each occurrence represents methyl, R 4 independently represents, at each occurrence, 2-[methoxy(polyethyleneoxy) 6-9 propyl], the amount of Si in the final copolymer ranges from 35 mol% to 45 mol%, the weight average molecular weight Mw of the siloxane copolymer is from 1,000 to 10,000.

2. The etch resistant anti-reflective composition according to claim 1, wherein the solvent is water and a mixture of one or more organic solvents selected from the group consisting of ketones; alcohols; ethers; esters; wherein the amount of the organic solvent and / or the water in the mixture is from 5 wt% to 95 wt%.

3. The etch resistant anti-reflective composition according to claim 2, wherein the ketone is selected from the group consisting of methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) and cyclohexanone; the alcohol is selected from the group consisting of methanol, ethanol, propanol and isopropanol; the ether is selected from the group consisting of tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME) and di ethyl ether; and the ester is selected from the group consisting of ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), a mixture of isopropyl alcohol and propylene glycol monomethyl ether (PGME).

4. The etch resistant anti-reflective composition according to claim 1, wherein the siloxane copolymer is prepared in a single synthetic process by co-hydrolysis of a mixture of chlorosilane monomers and alkoxy silane monomers.

5. A method for coating a microelectronic device comprising the steps of: (i) preparing the etch resistant anti-reflective composition of any one of claims 1-4, (ii) preparing a formulation by dissolving the etch resistant anti-reflective composition of any one of claims 1-4 in a polar organic solvent, (iii) coating the formulation on a substrate, (iv) evaporating the polar organic solvent from the coating, (v) curing the coating to form a thin film.

6. The method according to claim 5, wherein the polar organic solvent is selected from the group consisting of ketones; alcohols; ethers; esters; the amount of the polar organic solvent is from 90 wt% to 99 wt% based on the total ARC / HM formulation of the coating solution.

7. The method according to claim 6, wherein the ketones are selected from the group consisting of methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) and cyclohexanone; the alcohols are selected from the group consisting of methanol, ethanol, propanol and isopropanol; the ethers are selected from the group consisting of tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME) and di ethyl ether; and the esters are selected from the group consisting of ethyl acetate, butyl acetate, ethyl lactate and propylene glycol monomethyl ether acetate (PGMEA).

8. The method according to claim 5, wherein in step (v) the curing is performed at a temperature range of 100 °C to 250 °C.

9. The method according to claim 5, wherein in step (v) the curing is performed for 1 to 2 minutes.

10. The method according to claim 5, wherein the substrate is a Si wafer, a substrate of an integrated circuit, or other device substrate.

11. The method according to claim 5, wherein in step (iii) the coating is spin coating.

12. The method according to claim 5, wherein the polar organic solvent is evaporated during the spin coating process.

13. The method according to claim 5, wherein the thickness of the thin film is from 10 nm to 200 nm.

14. A method of forming a patterned device comprising: a) preparing a formulation by dissolving the etch resistant anti-reflective composition of any one of claims 1-4 in a polar organic solvent and coating the formulation on a substrate of a device to form a Si-rich ARC layer; b) coating an ArF photoresist on the Si-rich ARC layer; c) photo patterning the ArF photoresist and forming a resist pattern on the Si hard mask ARC layer; d) removing the exposed areas by etching and producing a patterned device.

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