Combined hard mask and ARC in single layer compositions for KrF microlithography

Abstract

The new composition comprises a siloxane copolymer as a combination of an antireflective coating (ARC) and a hard mask (HM) formed by the cohydrolysis of the following monomers: (RO)4Si, R 1 SiCl3, R 2 SiCl3, R 3 SiCl3, and R 4 SiCl3wherein: R is an alkyl group such as a methyl or ethyl group, R 1 is an antireflective chromophore in 248 nm microlithography such as a polycyclic aryl group such as anthracene, anthrylmethyl, anthrylethyl, and anthrylpropyl, R 2 is H, R 3 is a methyl or optionally substituted C2-C5 alkyl group, and optionally R 4 is a hydrophilic group such as 2-[methoxy(polyethyleneoxy) 6‑9 propyl]trichlorosilane or 2-(methoxycarbonyl)ethyltrichlorosilane. Wherein the mole % concentration of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D) < 0.95, 0.00 ≤ (E) < 0.50, and the total mole % concentration of (A) + (B) + (C) + (D) + (E) = 1.

Description

Technical Field

[0001] This invention generally relates to etch-resistant and anti-reflective compositions for coating microelectronic devices using such compositions. In particular, this invention relates to hard masks and anti-reflective coatings (ARCs) combined in single-layer compositions for KrF microlithography. Background Technology

[0002] The typical four-layer lithography method is well-known in the art, which involves:

[0003] ·1-Organic photoresist (spin coating method)

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

[0005] ·3-Si-containing hard masks (for etching selectivity, e.g., SiON) (chemical vapor deposition)

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

[0007] ·5-Device wafers.

[0008] Replacing layers 2 and 3 with a spin-coated Si-hard mask ARC results in reduced costs for the owner and improved performance of electronic devices.

[0009] To reduce the cost and improve the performance of electronic devices, semiconductors need finer features to produce smaller, denser devices. New and improved microlithography materials and methods are required to manufacture these smaller devices.

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

[0011] Existing technologies, such as U.S. Patent Nos. 4,010,122 and 5,693,691 of Brewer Science, teach the use of ARC in microlithography patterning.

[0012] As the resolution of photolithographic patterning improves, reducing the thickness of the photolithographic polymer (PR) layer has become an effective way to reduce the aspect ratio of PR / ARC stacks and avoid pattern collapse. However, the etch resistance of organic PR in thinner PR / ARC stacks (Tokyo Electron Limited, U.S. Patent No. 7,888,267) is insufficient to transfer the pattern to the underlying layer. Therefore, a new approach using a hard mask (HM) layer has been adopted. For example, Honeywell U.S. Patent Nos. 6,506,497, 6,777,340, and Texas Inst U.S. Patent No. 6,803,661 teach the use of hard masks in photolithographic stacks of PR / ARC / HM layers, which have better etch selectivity for transferring the pattern to the underlying layer. Pattern transfer to the underlying layer is achieved using PR stripping and reactive ion etching (RIE), as shown in the teachings of the following prior art: Novellus U.S. Patent Nos. 8,178,443, 8,569,179, 8,664,124, and 8,846,525, and Tokyo Electron Limited U.S. Patent Nos. 9,576,816, 9,530,667, and 9,607,843.

[0013] In a more efficient approach, ARC and a hard mask are combined into a single layer, as illustrated by the teachings of the following patents: IBM U.S. Patent No. 6,420,088, IBM U.S. Patent No. 7,077,903, IBM U.S. Patent No. 7,276,327, Dow Corning U.S. Patent No. 7,756,384, Tokyo Electron Limited U.S. Patent No. 7,888,267, Brewer Science's U.S. Patent No. 7,939,244, Samsung Industries U.S. Patent No. 8,026,035, and GlobalFoundries U.S. Patent No. 8,492,279.

[0014] Polymers currently known in the prior art do not have the composition claimed in this invention, but use novel siloxane copolymers with unique structures to achieve enhanced stability, faster curing and better etch resistance.

[0015] Therefore, improvements to ARC / hard mask materials as single-layer materials are always welcome to address many integration challenges that arise during semiconductor device manufacturing. Summary of the Invention

[0016] One object of this invention is to provide an etch-resistant and anti-reflective composition (ARC / HM) comprising a siloxane copolymer formed by the co-hydrolysis of the following monomers in a solvent:

[0017] (A) (RO)4Si,

[0018] (B) R 1 SiCl3

[0019] (C) R 2 SiCl3

[0020] (D) R 3 SiCl3

[0021] (E) R 4 SiCl3

[0022] where:

[0023] R is independently selected, each time it appears, from C1-C4 alkyl groups, such as methyl or ethyl groups,

[0024] R 1 is a chromophore that is antireflective in 248 nm microlithography, such as polycyclic aromatic groups such as anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl,

[0025] R 2 is H,

[0026] R 3 is methyl or an optionally substituted C2-C5 alkyl group, preferably the optionally substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl,

[0027] R 4 is a hydrophilic group, such as C1-C4 alkoxy(polyethyleneoxy) 6-9 C1-C4 alkyl or (methoxycarbonyl)C1-C4 alkyl, preferably 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl,

[0028] where the molar % concentration of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D) < 0.95, 0.00 ≤ (E) < 0.50 and the total molar % concentration of (A) + (B) + (C) + (D) + (E) = 1; preferably, 0 < A < 0.80, 0.05 < B < 0.20, 0 < C < 0.50, 0 < D < 0.80 and 0 ≤ E < 0.40.

[0029] The tetraalkoxysilane produces a Q structure (such as a (Si-O)4 bond) in the main chain of the siloxane copolymer.

[0030] According to the present invention, a single-layer thermosetting coating prepared from an etch-resistant antireflective composition has a very low reflectivity in KrF exposure and serves as an antireflective coating (ARC) in the microlithography process of semiconductor device manufacturing methods.

[0031] According to the present invention, the single-layer thermosetting coating prepared from the etch-resistant and anti-reflective composition is insoluble in photoresist solvents or developer materials.

[0032] According to the present invention, a single-layer thermosetting coating prepared from an etch-resistant and anti-reflective composition is transformed into a hard mask (HM) with good etch selectivity during photolithography and etching processes.

[0033] Therefore, the combination of anti-reflective coating (ARC) and hard mask (HM) properties that provide a usable entity is referred to as ARC / HM in this disclosure.

[0034] Advantageously, compositions of ARC / HM layer materials based on siloxane copolymers contain Q structures (e.g., (Si-O)4 bonds) in the main chain to achieve stability and faster low-temperature curing.

[0035] Advantageously, the composition of the ARC / HM layer of the material has specific chromophore side groups on the siloxane backbone of the siloxane copolymer to modulate the antireflective properties of the coating.

[0036] Advantageously, the composition of the ARC / HM layer of the material has a specific mol% Si content on the siloxane backbone of the siloxane copolymer to adjust the etching selectivity of the coating, preferably with a mol% Si content of <50 mol%. The Si-containing copolymer of the present invention improves etching resistance and enhances etching selectivity against organic photoresists.

[0037] Advantageously, the etch-resistant and anti-reflective composition has the following siloxane copolymer structure:

[0038] [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[Si(OH)3O 0.5 ]r[Si(OH)2O]s[Si(OH)O 1.5 ]t[SiO2]q[R 3 Si(OH)2O 0.5 ]v[R 3 SiO1.5 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

[0039] where 0 < f, g, h, m, n, p, r, s, t, q, v, w, d < 0.9, 0.00 ≤ x, y, z < 0.50 and f + g + h + m + n + p + r + s + t + q + v + w + d + x + y + z = 1; preferably, 0.05 < f, g, h < 0.20, 0 < m, n, p < 0.50, 0 < r, s, t, q < 0.80, 0 < v, w, d < 0.80 and 0 ≤ x, y, z < 0.40;

[0040] R 1 is a chromophore that is antireflective in 248 nm microlithography, such as polycyclic aromatic groups such as anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl,

[0041] R 2 is H,

[0042] R 3 is methyl or an optionally substituted C2-C5 alkyl group, preferably the optionally substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl,

[0043] R 4 is a hydrophilic group, such as C1-C4 alkoxy(polyethyleneoxy) 6-9 C1-C4 alkyl or (methoxycarbonyl)C1-C4 alkyl, preferably 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl.

[0044] In particular, in the above siloxane copolymer structure, R 2 is H, used to increase the mol% Si to obtain better etch selectivity, R 3 is methyl or an optionally substituted C2-C5 alkyl group to obtain stability, tetraalkoxysilane produces a Q structure (such as (Si-O)4 bond) in the main chain to obtain stability, and R 4 is a hydrophilic group, such as 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl for adhesion.

[0045] Advantageously, a useful feature of the siloxane copolymer of the present invention is that the amount of mol% Si in the composition of the siloxane copolymer is controlled by controlling the amount of H-containing trichloro- or trialkoxy-silane, thereby controlling the etch selectivity of the ARC / HM coating material, preferably, the amount of mol% Si is <50 mol%.

[0046] Advantageously, another useful component of the siloxane copolymer of the present invention is the presence of Q units (e.g., (Si-O)4 bonds) in the structure, which enhances thermosetting by introducing crosslinking density into the siloxane polymer and increasing the functionality of easily crosslinkable silanols (Si-OH) in the structure. The number of Q units is controlled by controlling the amount of tetramethoxysilane or tetraethoxysilane or mixtures thereof.

[0047] The functionality of silanols (Si-OH) is also determined by the T-structures (e.g., RSi(OH)₂O) in the main-chain siloxane copolymers of alkyl or aryl trichloro- or trialkoxy-silanes. 0.5 ,RSiO 1.5 The uncondensed silanol functionality leads to crosslinking of the coating at lower temperatures. The T-structure is formed from trichloro- or trialkoxy-silanes containing alkyl or aryl groups.

[0048] ARC / HM siloxane copolymer solution materials can be spin-coated and thermo-cured at 100-250°C for 60-120 seconds to reduce solubility in photoresist solvents and developers.

[0049] Another objective of this invention is to provide a method for preparing the etch-resistant and anti-reflective composition of the present invention by co-hydrolysis of a mixture of chloro-silanes and alkoxy-silanes in a one-pot process.

[0050] Another object of this invention disclosure is to provide a method for coating microelectronic devices, comprising:

[0051] (i) Preparation of an etch-resistant and anti-reflective composition ARC / HM comprising a siloxane copolymer formed by the co-hydrolysis of the following monomers in a solvent:

[0052] (A)(RO)4Si,

[0053] (B)R 1 SiCl3

[0054] (C)R 2 SiCl3

[0055] (D)R 3 SiCl3

[0056] (E)R 4 SiCl3

[0057] Wherein:

[0058] R is independently selected from C1-C4 alkyl each time it appears, such as methyl or ethyl groups,

[0059] R 1 is a chromophore that is antireflective in 248 nm microlithography, such as polycyclic aromatic groups such as anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl,

[0060] R 2 is H,

[0061] R 3 is methyl or an optionally substituted C2-C5 alkyl group, preferably the optionally substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl,

[0062] R 4 is a hydrophilic group, such as C1-C4 alkoxy(polyethyleneoxy) 6-9 C1-C4 alkyl or (methoxycarbonyl)C1-C4 alkyl, preferably 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl,

[0063] where the molar % concentration of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D) < 0.95, 0.00 ≤ (E) < 0.50 and the total molar % concentration of (A)+(B)+(C)+(D)+(E) = 1; preferably, 0 < A < 0.80, 0.05 < B < 0.20, 0 < C < 0.50, 0 < D < 0.80 and 0 ≤ E < 0.40;

[0064] (ii) Preparing a formulation by dissolving the etch-resistant antireflective composition in a polar organic solvent;

[0065] (iii) Coating a substrate with the formulation prepared in step (ii);

[0066] (iv) Evaporating the solvent from the coating;

[0067] (v) Curing the coating to form a thin film.

[0068] Another object of the present disclosure is to provide a method for forming a patterned device, including:

[0069] a. Preparing a formulation by dissolving the etch-resistant antireflective composition of the present invention in a polar organic solvent and coating the formulation on the substrate of the device to form a Si-rich ARC layer;

[0070] b. Coating a KrF photoresist on the Si-rich ARC layer;

[0071] c. Photo-patterning of KrF photoresist and forming a resist pattern on a Si-hard mask ARC layer; and

[0072] d. Remove the exposed areas by etching to create a patterned device. Attached Figure Description

[0073] exist Figure 1 Examples of the application of the ARC / hard mask combined in the single-layer coating of this invention in semiconductor device manufacturing are illustrated below. The photolithography, patterning, and etching steps are illustrated in the following figures:

[0074] Figure 1 Example a cross-section of a coating on a substrate consisting of a mask (filled black area), (1) photoresist, (2) ARC / HM, (3) SiN or ACL, and (4) a stack of dielectric layers, where the downward arrows indicate KrF exposure;

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

[0076] Figure 1 c. Example illustrating the transfer of photoresist (1) pattern to ARC / HM (2) layer;

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

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

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

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

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

[0082] exist Figure 2 The text provides an example of a typical four-layer photolithography method in the prior art, in which...

[0083] Figure 2I illustrate the cross-section of four coating layers on a substrate: a mask (filled black area), (1) photoresist, (2) ARC, (3) hard mask, (4) SiN or ACL, and (5) dielectric layer stack, where the downward arrows show KrF exposure.

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

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

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

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

[0088] Figure 2 N illustrates the removal of the C-hard mask from a stack, leaving a patterned IC (dielectric) layer. Invention Details

[0089] One object of this invention is to provide a coating composition in which a single-layer thermosetting coating has very low reflectivity in KrF exposure and acts as an anti-reflective coating (ARC) in the microlithography process of semiconductor device fabrication methods.

[0090] Another object of this invention disclosure is to provide a coating composition wherein a thermosetting coating is converted into a hard mask (HM) with good etch selectivity during photolithography and etching processes. Another object of this invention disclosure is to provide a coating composition wherein the thermosetting coating is insoluble in photoresist solvents or developers.

[0091] Furthermore, the combination of antireflective coating (ARC) and hard mask (HM) properties formed after curing the ARC / HM coating is produced by a siloxane copolymer formed by the co-hydrolysis of the following monomers in a solvent:

[0092] (A)(RO)4Si

[0093] (B)R 1 SiCl3

[0094] (C)R 2 SiCl3

[0095] (D)R 3 SiCl3

[0096] (E)R 4 SiCl3

[0097] Wherein:

[0098] R is independently selected from C1-C4 alkyl each time it appears, such as methyl or ethyl groups,

[0099] R 1 is a chromophore that is antireflective in 248 nm microlithography, such as polycyclic aromatic groups such as anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl,

[0100] R 2 is H,

[0101] R 3 is methyl or an optionally substituted C2-C5 alkyl group, preferably the optionally substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl,

[0102] R 4 is a hydrophilic group such as C1-C4 alkoxy(polyethyleneoxy) 6-9 C1-C4 alkyl or (methoxycarbonyl)C1-C4 alkyl, preferably 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl.

[0103] Wherein the molar % concentration of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D) < 0.95, 0.00 ≤ (E) < 0.50 and the total molar % concentration of (A) + (B) + (C) + (D) + (E) = 1; preferably, 0 < A < 0.80, 0.05 < B < 0.20, 0 < C < 0.50, 0 < D < 0.80 and 0 ≤ E < 0.40.

[0104] Specifically, the value of A can be, for example, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60 or 0.70. The value of B can be, for example, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18 or 0.19. The value of C can be, for example, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40 or 0.45. The value of D can be, for example, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60 or 0.70. The value of E can be, for example, 0.00, 0.10, 0.15, 0.20, 0.25, 0.30 or 0.35.

[0105] Particularly, R is alkyl, such as methyl or ethyl groups to obtain faster curing, R 1These are antireflective chromophores used in 248nm photolithography, such as polycyclic aromatic groups like anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl, R. 2 H is used to increase mol% Si to obtain better etching selectivity, R 3 The stability is achieved by methyl or non-necessarily substituted C2-C5 alkyl groups, with tetraalkoxysilanes forming Q structures (e.g., (Si-O)4 bonds) in the main chain, and R... 4 It is a hydrophilic group, such as 2-[methoxy(polyethyloxy)] 6-9 [Propyl] or 2-(methoxycarbonyl)ethyl is used for adhesion.

[0106] Monomer (A) in siloxane copolymers contributes to the Q structure (e.g., (Si-O)4 bond) in the main chain, which is used to obtain stability and faster low-temperature curing.

[0107] The monomer (B) controls the n and k values, which optimize the reflection of light exposed to KrF and minimize reflectivity. n = refractive index, k = extinction coefficient. n and k can be measured using elliptic polarization.

[0108] Monomer (C) contributes to better etching selectivity by increasing the %Si content of the siloxane copolymer.

[0109] Monomer (D) also increases the %Si content of siloxane copolymers and improves the solubility of the material in organic solvents.

[0110] Monomer (E) is used for better solubility and adhesion.

[0111] Advantageously, the siloxane copolymer of the present invention has the following structure:

[0112] [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[Si(OH)3O 0.5 ]r[Si(OH)2O]s[Si(OH)O 1.5 ]t[SiO2]q[R 3 Si(OH)2O 0.5 ]v[R 3 SiO 1.5 ]w[R 3 Si(OH)O]d[R 4 Si(OH)2O0.5 x[R 4 SiO 1.5 y[R 4 Si(OH)O]z

[0113] where 0 < f, g, h, m, n, p, r, s, t, q, v, w, d < 0.9, 0.00 ≤ x, y, z < 0.50 and f + g + h + m + n + p + r + s + t + q + v + w + d + x + y + z = 1; preferably, 0.05 < f, g, h < 0.20, 0 < m, n, p < 0.50, 0 < r, s, t, q < 0.80, 0 < v, w, d < 0.80 and 0 ≤ x, y, z < 0.40;

[0114] R 1 is a chromophore that is antireflective in 248 nm microlithography, such as a polycyclic aromatic group such as anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl,

[0115] R 2 is H,

[0116] R 3 is methyl or an optionally substituted C2-C5 alkyl group, preferably the optionally substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl,

[0117] R 4 is a hydrophilic group, such as C1-C4 alkoxy(polyethyleneoxy) 6-9 C1-C4 alkyl or (methoxycarbonyl)C1-C4 alkyl, preferably 2-[methoxy(polyethyleneoxy) 6-9 propyl] or 2-(methoxycarbonyl)ethyl.

[0118] Specifically, f, g, and h can be independently 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, or 0.17, 0.18, or 0.19, respectively. m, n, and p can be independently 0.10, 0.20, 0.30, or 0.40, respectively. r, s, t, and q can be independently 0.10, 0.20, 0.30, 0.……

[0119] Specifically, tetraalkoxysilanes, tetramethoxy- or tetraethoxysilanes generate Q structures (e.g., (Si-O)4 bonds) in the main chain to gain stability, and Si-OH is generated for faster thermosetting. 1 These are antireflective chromophores used in 248nm photolithography, such as polycyclic aromatic groups like anthracene, anthracenemethyl, anthraceneethyl, and anthracenepropyl, R. 2 H is used to increase mol% Si to obtain better etching selectivity, R 3 It is a methyl or non-necessarily substituted C2-C5 alkyl group to obtain stability, R 4 It is a hydrophilic group, such as 2-[methoxy(polyethyloxy)] 6-9 [Propyl] or 2-(methoxycarbonyl)ethyl is used for adhesion.

[0120] The siloxane copolymers of the present invention are prepared in a single synthetic method via the co-hydrolysis of a mixture of chloro- and alkoxy-silane monomers. The monomers may be selected from tetraalkoxysilanes, such as tetraethoxysilane or tetramethoxysilane, or combinations thereof. The monomers are also selected from anthracene-containing trichlorosilanes, such as anthracene trichlorosilane, or anthracene methyl trichlorosilane, or anthracene ethyl trichlorosilane, or anthracene propyl trichlorosilane, or combinations thereof. The monomers are also selected from H-containing trichlorosilanes or trialkoxysilanes, such as trichlorosilane, trimethoxysilane, or triethoxysilane, or combinations thereof. The monomer is also selected from 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 monomer is also selected from trichlorosilanes or trialkoxysilanes containing hydrophilic groups, such as 2-[methoxy(polyethyloxy)] 6-9 [Propyl]trichlorosilane or 2-(methoxycarbonyl)ethyltrichlorosilane or combinations thereof.

[0121] The chromophores that can be used as side groups of trichlorosilanes or trialkoxysilanes can be selected from anthracene-containing trichlorosilanes, such as anthracene trichlorosilane, or anthracene methyl trichlorosilane, or anthracene ethyl trichlorosilane, or anthracene propyl trichlorosilane, or all combinations thereof, or anthracene trimethoxysilane, or anthracene methyl trimethoxysilane, or anthracene ethyl trimethoxysilane, or anthracene propyl trimethoxysilane, or anthracene triethoxysilane, or anthracene methyl triethoxysilane, or anthracene ethyl triethoxysilane, or anthracene propyl triethoxysilane. Furthermore, the refractive index (n) and extinction coefficient (k) values ​​of the ARC / HM coating can be adjusted by controlling the amount of silanes containing the corresponding chromophores used in the synthesis of the siloxane copolymer.

[0122] Another useful feature of the siloxane copolymer of the present invention is that the mol% Si content in the siloxane copolymer composition is controlled by controlling the amount of H-containing trichloro- or trialkoxy-silane and other trichloro- or trialkoxy-silane monomers, thereby controlling the etch selectivity of the ARC / HM coating material. Preferably, the mol% Si content is <50 mol%. The final copolymer has a mol% Si percentage in the range of 8 mol% to 46 mol%, more preferably 15 mol% to 45 mol%, and most preferably 35 mol% to 45 mol%.

[0123] Another useful component of the siloxane copolymer of the present invention is the presence of Q units (e.g., (Si-O)4 bonds) in the structure, which enhances thermosetting by introducing crosslinking density into the siloxane polymer and increasing the functionality of easily crosslinkable silanols (Si-OH) in the structure. The number of Q units is controlled by controlling the amount of tetramethoxysilane or tetraethoxysilane or mixtures thereof.

[0124] The functionality of silanols (Si-OH) is also determined by the T-structures (e.g., RSi(OH)₂O) in the main-chain siloxane copolymers of alkyl or aryl trichloro- or trialkoxy-silanes. 0.5 ,RSiO 1.5The formation of RSi(OH)O is achieved. The uncondensed silanol functionality leads to crosslinking of the coating at lower temperatures. The T structure is formed by: trichlorosilanes or trialkoxysilanes containing alkyl or aryl groups, 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 anthracene trichlorosilane, or anthracene methyltrichlorosilane, or anthracene ethyltrichlorosilane, or anthracene propyltrichlorosilane, or all combinations thereof, or anthracene trimethoxysilane, or anthracene methyltrimethoxysilane, or anthracene ethyltrimethoxysilane, or anthracene propyltriethoxysilane. 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 anthracenetrichlorosilane, or anthracenemethyltrichlorosilane, or anthraceneethyltrichlorosilane, or anthracenepropyltrichlorosilane, or all combinations thereof, or anthracenetrimethoxysilane, or anthracenemethyltrimethoxysilane, or anthraceneethyltrimethoxysilane, or anthracenepropyltrimethoxysilane, or anthracenetriethoxysilane, or anthracenemethyltriethoxysilane, or anthraceneethyltriethoxysilane, or anthracenepropyltriethoxysilane.

[0125] The co-hydrolysis and condensation of the monomers of the present invention can form siloxane copolymers, which are mixtures of T and Q units in randomly branched networks and cages of various structural sizes.

[0126] In siloxane copolymers, the uncondensed silanols (Si-OH) from both the T and Q structures tend to crosslink, and during thermosetting, three and four Si-O-Si bonds are formed around each silicon atom in the respective T and Q structures, respectively. The stability of the ARC / HM coating in organic solvents increases with increasing Si-OH condensation and Si-O-Si bond formation; the more complete the condensation of the ARC / HM coating, the more stable it is in organic solvents. Thermosetting ARC / HM coatings must be insoluble in photoresist solvents and developers to ensure stability during subsequent photoresist coating and development. Optionally, a thermosetting catalyst can be used as a formulation additive to increase the thermosetting rate of the silanols in the ARC / HM coating. The amount of acid, such as acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, or phosphoric acid, is 100 to 1000 ppm. Alternatively, the condensation catalyst can be selected from a hot acid generator or a hot alkali generator. The amount of Si-containing monomers with T and Q structures controls the mol% Si in the final composition.

[0127] ARC / HM siloxane copolymers can have a weight-average molecular weight (Mw) of about 800 Daltons to about 25,000 Daltons, which is determined by gel permeation chromatography (GPC).

[0128] The solvent used in the synthesis is water and at least one other solvent selected from the following organic solvents: 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 diethyl ether. Alkane; esters such as ethyl acetate, butyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate (PGMEA). The water content is 10%-95% by weight, based on the total weight of the solvent mixture, and the organic solvent content is 10%-95% by weight, based on the total weight of the solvent mixture.

[0129] The synthesis or hydrolysis of silanes can be carried out primarily in water containing some organic solvent, and is independent of the solvent-to-water ratio. The final product mixture is a siloxane ARC / HM copolymer at a concentration of 1% to 10% by weight in an organic solvent.

[0130] In some embodiments, the siloxane copolymer can be the total ARC / HM formulation of the coating solution, ranging from 1% to 10% by weight.

[0131] Spin coating can be used as a method for applying ARC / HM formulations in semiconductor device manufacturing. The spin coating method typically involves pouring a small amount of ARC / HM solution as a slurry onto the surface of the semiconductor device, followed by accelerating the spin speed from 4000-5000 rpm to a selected final speed of 2000-3000 rpm, which lays the material on the surface and maintains the final speed for 10-20 seconds before completing the spin. This forms a uniform coating of ARC / HM material as an ARC / HM layer on the surface of the semiconductor device.

[0132] The ARC / HM coating can be thermo-cured using any generally suitable technique employed in curing, by heating in semiconductor device manufacturing, such as a hot plate or oven. The ARC / HM coating can be thermo-cured at 100-250°C for 60-120 seconds to increase the crosslinking density of the siloxane copolymer in the coating and to condense silanols (Si-OH) to form Si-O-Si bonds. The thermo-cured siloxane copolymer will be fully cured to be stable in photoresist solvents such as PGMEA, PGME, γ-butyrolactone (GBL), ethyl lactate (EL), and other solvents.

[0133] After applying and curing the ARC / HM coating, a thin photoresist layer is spin-coated onto the surface of the cured ARC / HM coating. This is followed by a photolithography process that exposes and develops the photoresist to create a patterned photoresist structure. The next step involves transferring the patterned photoresist pattern to the ARC / HM layer using reactive ion etching (RIE). Following the pattern transfer through the ARC / HM layer, oxygen plasma etching removes the photoresist and transforms the patterned ARC / HM layer into a largely patterned hard mask layer. This patterned hard mask can then be further patterned to lower layers using appropriate RIE etch chemistry, after which the hard mask is removed on the semiconductor device, protecting the target patterned structure.

[0134] Figure 1 Examples of the application of the ARC / HM coating of the present invention in semiconductor device manufacturing are illustrated below. However, this is not the only application and is not a limiting factor for the use of the present invention. Many other ways of using the coating of the present invention are possible. The geometries and dimensions used in this example are for illustration only and do not represent actual geometries and dimensions. The substrate may be a metal such as Si, Ge, Al, or other, or an alloy such as SiGe, gallium arsenide, or other, or an insulator such as SiO2, Si3N4, or other, or doped variants or mixtures thereof. In this example, the target layer to be patterned is a dielectric (4) layer. Figure 1 Layer (3) in the stack is SiN or an amorphous carbon layer (ACL). The ARC / HM silicone copolymer composition of the present invention is spin-coated onto layer (3) at a speed of about 2000 to about 3000 rpm for a period of about 10 to about 20 seconds. The ARC / HM silicone copolymer composition coating is then thermo-cured at a temperature of about 100°C to about 250°C for about 60 to about 120 seconds to increase the crosslinking density of the copolymer in the coating and to condense silanols (Si-OH) to form Si-O-Si bonds, which produce an ARC / HM layer (2) that is insoluble in the photoresist solvent and spin-coated in a subsequent step of photoresist coating. The ARC / HM layer (2) has light absorption properties, which reduce light reflection by adjusting the composition with the number of chromophores and controlling the thickness to optimize n and k. To complete Figure 1 In the stacked structure of a, photoresist is spin-coated and then photo-patterned and developed using an exposure mask (filled with black areas) via ArF to remove the exposed areas. Figure 1 The following diagram from ah illustrates the photolithography, patterning, and etching steps in more detail: Figure 1Figure 1a illustrates a cross-section of a stack of coatings on a substrate consisting of a mask (filled black area), (1) photoresist, (2) ARC / HM, (3) SiN or ACL, and (4) dielectric layers, with downward arrows indicating ArF exposure. Figure 1b illustrates a patterned photoresist layer (1) exposed and developed on top of the other layers. Figure 1 c indicates that when a photoresist pattern is used as an etching mask to pattern ARC / HM(2), the photoresist (1) pattern is transferred to the ARC / HM(2) layer. Figure 1 d indicates that the photoresist (1) layer is removed from the stack, leaving the patterned ARC / HM (2) as a hard mask for use as a lower layer on other target materials. Figure 1 Figure 1e illustrates the transfer of the ARC / HM(2) pattern to the underlying SiN or ACL(3). Figure 1f illustrates the removal of the ARC / HM(2) layer from the stack, leaving the patterned SiN or ACL(3) layer. Figure 1 g indicates that the SiN or ACL (3) pattern is transferred to the dielectric layer (4). Figure 1 h indicates that the SiN or ACL (3) layer is removed from the stack, leaving a patterned dielectric target layer (4).

[0135] Compared with the prior art, the present invention has the following advantages:

[0136] According to the etch-resistant and anti-reflective composition of the present invention, the resulting monolayer thermosetting coating exhibits very low reflectivity during ArF exposure and serves as an anti-reflective coating (ARC) in the microlithography process of semiconductor device fabrication.

[0137] It is insoluble in photoresist solvents or developers.

[0138] It is transformed into a hard mask (HM) with excellent etching selectivity during photolithography and etching processes.

[0139] Furthermore, the ARC / HM layer material composition is based on a siloxane copolymer containing a Q structure (e.g., (Si-O)4 bond with four Si-O bonds) in the main chain to achieve stability and faster low-temperature curing. Tetraalkoxysilanes generate the Q structure (e.g., (Si-O)4 with four Si-O bonds), and the tetrafunctional Q structure provides crosslinking in the structure, thus enhancing structural stability; the ARC / HM layer material composition has specific chromophore side groups on the siloxane main chain of the siloxane copolymer to modulate the antireflective properties of the coating.

[0140] Furthermore, the siloxane copolymer helps control the etch selectivity of the ARC / HM coating material by controlling the mol% Si of the siloxane copolymer in the composition. Controlling the mol% Si of the siloxane copolymer in the composition by the amount of H-containing trichloro- or trialkoxy-silane components, i.e., increasing the Si-H content, ultimately results in a higher mol% Si in the etch-resistant and anti-reflective coating, leading to better etch resistance.

[0141] The following synthetic examples, which produce various compositions, are presented to illustrate their synthesis and coating results. These examples should not be considered limiting. The typical process for preparing siloxane copolymers is based on the one-pot co-hydrolysis of the following monomers: (RO)4Si, R... 1 SiCl3, R 2 SiCl3, R 3 SiCl3 and R 4 SiCl3. Where: R is an ethyl group, R 1 It is anthracene methyl, R 2 It is H, R 3 It is methyl, R 4 It is 2-[methoxy(polyethyloxy)] 6-9 [Propyl]trichlorosilane or 2-(methoxycarbonyl)ethyltrichlorosilane. The molar percentage concentration of each monomer in the starting monomer mixture is 0.00 < (A), (B), (C), (D) < 0.95, 0.00 ≤ (E) < 0.50, and the total molar percentage concentration of (A) + (B) + (C) + (D) + (E) = 1. Example

[0142] Example 1

[0143] A 500 mL jacketed glass container contains tetraethoxysilane (19.0 g, 0.09 mol), anthracene methyltrichlorosilane (4.5 g, 0.014 mol), methyltrichlorosilane (11.0 g, 0.07 mol), trichlorosilane (12.0 g, 0.089 mol), and 2-[methoxy(polyethyloxy)] 6-9 A mixture of [propyltrichlorosilane](5.0 g, 0.01 mol) and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (200 g) was added to the mixture in a 500 mL container over 60 minutes using a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL container was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a 4% solids content in PGMEA.

[0144] Example 2

[0145] A 500 mL jacketed glass container contained a mixture of tetraethoxysilane (10.0 g, 0.05 mol), anthracene methyltrichlorosilane (8.5 g, 0.026 mol), methyltrichlorosilane (18.0 g, 0.12 mol), trichlorosilane (9.0 g, 0.066 mol), and PGMEA (200 g). The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (240 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 and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0146] Example 3

[0147] A 500 mL jacketed glass container contained a mixture of tetraethoxysilane (10.0 g, 0.05 mol), anthracene methyltrichlorosilane (4.5 g, 0.14 mol), methyltrichlorosilane (25.0 g, 0.17 mol), trichlorosilane (7.0 g, 0.052 mol), 2-(methoxycarbonyl)ethyltrichlorosilane (2.0 g, 0.009 mol), and PGMEA (200 g). The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (220 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 and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0148] Example 4

[0149] A 500 mL jacketed glass container contains tetraethoxysilane (4.0 g, 0.02 mol), anthracene methyltrichlorosilane (7.0 g, 0.021 mol), methyltrichlorosilane (31.0 g, 0.21 mol), trichlorosilane (4.0 g, 0.03 mol), and 2-[methoxy(polyethyloxy)] 6-9A mixture of [propyltrichlorosilane] (4.0 g, 0.01 mol) and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (240 g) was added to the mixture in a 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 and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0150] Example 5

[0151] A 500 mL jacketed glass container contains tetraethoxysilane (4.0 g, 0.02 mol), anthracene methyltrichlorosilane (7.0 g, 0.021 mol), methyltrichlorosilane (31.0 g, 0.21 mol), trichlorosilane (4.0 g, 0.03 mol), and 2-[methoxy(polyethyloxy)] 6-9 A mixture of [propyltrichlorosilane] (4.0 g, 0.01 mol) and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (240 g) was added to the mixture in a 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 and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0152] Example 6

[0153] A 500 mL jacketed glass container contains tetraethoxysilane (6.0 g, 0.03 mol), anthracene methyltrichlorosilane (6.7 g, 0.21 mol), methyltrichlorosilane (25.0 g, 0.17 mol), trichlorosilane (8.0 g, 0.059 mol), and 2-[methoxy(polyethyloxy)] 6-9A mixture of [propyltrichlorosilane](5.0 g, 0.01 mol) and PGMEA (200 g) was prepared. The mixture was stirred and cooled to 20 °C by controlling the jacket temperature using a circulating cooler / heater system. A clear, homogeneous mixture of water (11.0 g, 0.61 mol) and PGMEA (200 g) was added to the mixture in a 500 mL container over 60 minutes using a metering pump. After the water / PGMEA mixture addition was complete, the 500 mL container was heated to 35 °C and stirred for 4 hours. The resulting mixture was cooled to 20 °C and rinsed with water. The siloxane solution was rotary evaporated to remove trace amounts of water. The resulting siloxane copolymer was characterized by GPC and finally formulated to have a solids content of 4% in PGMEA.

[0154] Characterization:

[0155] The synthesized polymers were characterized using Waters GPC (gel permeation chromatography) with tetrahydrofuran as the support 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 from the above examples.

[0156] Table 1

[0157]

[0158] The siloxane copolymers of the above embodiments were filtered using a 0.1-micron Teflon filter and spin-coated onto Si wafers using a Lebo Scientific spin coater at an acceleration of 3,000-6,000 rpm and a holding time of 20-50 seconds at the final speed. The coated wafers were cured on a hot plate at 200-250°C for 60-120 seconds. The n and k of the cured films are summarized in Table 1. Peel tests were conducted on the cured films using PGMEA and TMAH, with a holding time of 30 seconds for PGMEA slurry and 60 seconds for TMAH slurry. Film thickness was measured using The Metris before and after the peel test. The results of the peel test are summarized in Table 2.

[0159] Table 2

[0160]

[0161] The results of the solubility or peel tests in Table 2 show that the coatings from all the above embodiments have a thickness loss of less than 2% in the corresponding PGMEA and TMAH peel tests.

[0162] Regarding Tables 1 and 2 above, (Ant-Meth)(Cl) is the abbreviation for the hydrolysis product of anthracene methyltrichlorosilane, "T(H)(Cl)" is the abbreviation for the hydrolysis product of HSiCl3 trichlorosilane, "T(Me)(Cl)" is the abbreviation for the hydrolysis product of MeSiCl3 (methyltrichlorosilane), "Q(TEOS)" is the abbreviation for the hydrolysis product of tetraethoxysilane, and "T(PEO)(Cl)" is the abbreviation for 2-[methoxy(polyethyloxy)] 6-9 "Propyl" is an abbreviation for the hydrolysis product of trichlorosilane, and "T(Carbo)(Cl)" is an abbreviation for the hydrolysis product of 2-(methoxycarbonyl)ethyltrichlorosilane.

[0163] Advantageously, the n and k values ​​of the present invention can be optimized for the thicknesses of both the photoresist and HM / ARC to minimize the standing wave intensity and reduce the difference in optical constants between the photoresist and HM / ARC substrates. The optimal thickness combination of the photoresist and HM / ARC provides better manufacturing tolerance.

[0164] Advantageously, Table 2 shows the favorable % thickness loss, and those who need or expect to utilize the reduced thickness loss tested by TMAH and PGMEA to protect HM / ARC from the effects of photoresist and developer solvents.

Claims

1. An etch-resistant and anti-reflective composition ARC / HM comprising a siloxane copolymer formed by the co-hydrolysis of the following monomers in a solvent: (A)(RO)4Si, (B)R 1 SiCl3 (C)R 2 SiCl3 (D)R 3 SiCl3 (E)R 4 SiCl3 in: R is independently selected from C1-C4 alkyl groups each time it appears. R 1 It is an antireflective chromophore used in 248 nm photolithography, wherein the chromophore is selected from polycyclic aromatic hydrocarbon groups, specifically anthracenemethyl, anthraceneethyl, and anthracenepropyl. R 2 It's H. R 3 It is a methyl or non-necessarily substituted C2-C5 alkyl group, wherein the non-necessarily substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl. R 4 It is a hydrophilic group, wherein the hydrophilic group is selected from 2-[methoxy(polyethyloxy)] 6-9 [Propyl] or 2-(methoxycarbonyl)ethyl, The molar percentage concentration of each monomer in the starting monomer mixture is 0 mol% < (A), (B), (C), (D) < 95 mol%, 0 mol%. (E) < 50 mol% and the total mol% concentration of (A) + (B) + (C) + (D) + (E) = 100 mol%. The siloxane copolymer has the following structure: [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 [Si(OH)3O 0.5 ]r [Si(OH)2O]s [Si(OH)O 1.5 ]t [SiO2]q [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 where 0 < f, g, h, m, n, p, r, s, t, q, v, w, d < 0.9, 0.00 x, y, z < 0.50 and f + g + h + m + n + p + r + s + t + q + v + w + d + x + y + z = 1.

2. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein R is independently selected from methyl or ethyl groups each time it appears.

3. The etch-resistant antireflective composition ARC / HM claimed in claim 1, wherein 0 mol% < A < 80 mol%, 5 mol% < B < 20 mol%, 0 mol% < C < 50 mol%, 0 mol% < D < 80 mol% and 0 mol% < E < 40 mol%.

4. The etch-resistant antireflective composition ARC / HM according to claim 1, wherein 0.05 < f, g, h < 0.20, 0 < m, n, p < 0.50, 0 < r, s, t, q < 0.80, 0 < v, w, d < 0.80 and 0 < x, y, z < 0.

40.

5. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the monomer (A) is selected from tetraethoxysilane, tetramethoxysilane, or a combination of both.

6. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the monomer (B) is selected from anthracene-containing trichlorosilanes or trialkoxysilanes, wherein the anthracene-containing trichlorosilanes or trialkoxysilanes are selected from the following: anthracene methyltrichlorosilane, or anthracene ethyltrichlorosilane, or anthracene propyltrichlorosilane, or all combinations thereof, or anthracene methyltrimethoxysilane, or anthracene ethyltrimethoxysilane, or anthracene propyltrimethoxysilane, or anthracene methyltriethoxysilane, or anthracene ethyltriethoxysilane, or anthracene propyltriethoxysilane, or all combinations thereof.

7. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the monomer (C) is selected from trichlorosilane, or trimethoxysilane, or triethoxysilane, or a combination thereof.

8. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the monomer (D) is selected from 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.

9. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the monomer (E) is selected from trichlorosilanes or trialkoxysilanes containing hydrophilic groups, wherein the trichlorosilanes or trialkoxysilanes containing hydrophilic groups are selected from 2-[methoxy(polyethyloxy)] 6-9 [Propyl]trichlorosilane or 2-(methoxycarbonyl)ethyltrichlorosilane or combinations thereof.

10. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the siloxane copolymer has a weight-average molecular weight Mw of 800 Daltons to 25,000 Daltons.

11. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 1, wherein the solvent is water and at least one polar solvent, the water content being 10% to 95% by weight, based on the total weight of the solvent mixture, and the polar solvent content being 10% to 95% by weight, based on the total weight of the solvent mixture.

12. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 11, wherein the polar solvent is a polar organic solvent.

13. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 12, wherein the polar organic solvent is selected from ketones, alcohols, ethers, and esters.

14. The etch-resistant and anti-reflective composition ARC / HM claimed in claim 13, wherein the ketone is selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclohexanone; the alcohol is selected from methanol, ethanol, propanol, and isopropanol; and the ether is selected from tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME), and diethyl ether. Alkane; and esters are selected from ethyl acetate, butyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate (PGMEA).

15. A method for preparing the etch-resistant and antireflective composition of any one of claims 1-14 by co-hydrolysis of a mixture of chloro-silane and alkoxy-silane in a one-pot process.

16. A method for coating microelectronic devices, comprising: (i) Preparation of an etch-resistant and anti-reflective composition ARC / HM, comprising a siloxane copolymer formed by co-hydrolysis of the following monomers in a solvent: (A)(RO)4Si, (B)R 1 SiCl3 (C)R 2 SiCl3 (D)R 3 SiCl3 (E)R 4 SiCl3 in: R is independently selected from C1-C4 alkyl groups each time it appears. R 1 It is an antireflective chromophore used in 248 nm photolithography, wherein the chromophore is selected from polycyclic aromatic hydrocarbon groups, specifically anthracenemethyl, anthraceneethyl, and anthracenepropyl. R 2 It's H. R 3 It is a methyl or non-necessarily substituted C2-C5 alkyl group, wherein the non-necessarily substituted groups on the C2-C5 alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl. R 4 It is a hydrophilic group, wherein the hydrophilic group is selected from 2-[methoxy(polyethyloxy)] 6-9 [Propyl] or 2-(methoxycarbonyl)ethyl, The molar percentage concentration of each monomer in the starting monomer mixture is 0 mol% < (A), (B), (C), (D) < 95 mol%, 0 mol%. (E) < 50 mol% and the total mol% concentration of (A) + (B) + (C) + (D) + (E) = 100 mol%. The siloxane copolymer has the following structure: [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 [Si(OH)3O 0.5 ]r [Si(OH)2O]s [Si(OH)O 1.5 ]t [SiO2]q [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 where 0 < f, g, h, m, n, p, r, s, t, q, v, w, d < 0.9, 0.00 x, y, z < 0.50 and f + g + h + m + n + p + r + s + t + q + v + w + d + x + y + z = 1; (ii) Preparation of a formulation by dissolving an etch-resistant and anti-reflective composition in a polar organic solvent; (iii) Coat the substrate with the formulation prepared in step (ii); (iv) Evaporate solvent from coating; (v) Curing the coating to form a thin film.

17. The method claimed in claim 16, wherein R is independently selected from methyl or ethyl groups each time it appears.

18. The method according to claim 16, wherein 0 mol% < A < 80 mol%, 5 mol% < B < 20 mol%, 0 mol% < C < 50 mol%, 0 mol% < D < 80 mol% and 0 mol% < E < 40 mol%.

19. The method claimed in claim 16, wherein the monomer (A) is selected from tetraethoxysilane, or tetramethoxysilane, or a combination of both.

20. The method claimed in claim 16, wherein the monomer (B) is selected from anthracene-containing trichlorosilanes or trialkoxysilanes, wherein the anthracene-containing trichlorosilane or trialkoxysilane is selected from anthracene methyltrichlorosilane, or anthracene ethyltrichlorosilane, or anthracene propyltrichlorosilane, or all combinations thereof, or anthracene methyltrimethoxysilane, or anthracene ethyltrimethoxysilane, or anthracene propyltrimethoxysilane, or anthracene methyltriethoxysilane, or anthracene ethyltriethoxysilane, or anthracene propyltriethoxysilane, or all combinations thereof.

21. The method claimed in claim 16, wherein the monomer (C) is selected from trichlorosilane, or trimethoxysilane, or triethoxysilane, or a combination thereof.

22. The method claimed in claim 16, wherein the monomer (D) is selected from 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.

23. The method claimed in claim 16, wherein the monomer (E) is selected from trichlorosilanes or trialkoxysilanes containing hydrophilic groups, wherein the trichlorosilanes or trialkoxysilanes containing hydrophilic groups are selected from 2-[methoxy(polyethyloxy)] 6-9 [Propyl]trichlorosilane or 2-(methoxycarbonyl)ethyltrichlorosilane or combinations thereof.

24. The method claimed in claim 16, wherein the polar organic solvent used in step (ii) is selected from ketones, alcohols, ethers, and esters; and the solvent in the total ARC / HM formulation of the coating solution is in an amount of 90% to 99% by weight.

25. The method claimed in claim 24, wherein the ketone is selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclohexanone; the alcohol is selected from methanol, ethanol, propanol, and isopropanol; and the ether is selected from tetrahydrofuran (THF), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME), and diethyl ether. Alkane; and esters are selected from ethyl acetate, butyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate (PGMEA).

26. The method claimed in claim 16, wherein the substrate is a Si wafer, an integrated circuit substrate, or other microelectronic device substrate.

27. The method claimed in claim 16, wherein the copolymer solution is spin-coated onto the substrate.

28. The method claimed in claim 16, wherein the solvent is evaporated during spin coating.

29. The method claimed in claim 16, wherein the coating is cured by heating at 100°C to 250°C for 60 to 120 seconds.

30. The method claimed in claim 16, wherein the thickness of the coating is from 10 nm to 200 nm.

31. A method for forming a patterned device, comprising: a. A formulation is prepared by dissolving the etch-resistant and anti-reflective composition of any one of claims 1-14 in a polar organic solvent and coating the formulation onto a substrate of a device to form a Si-rich ARC layer; b. Coat the Si-rich ARC layer with KrF photoresist; c. Photo-patterning of KrF photoresist and forming a resist pattern on a Si-hard mask ARC layer; d. Remove the exposed areas by etching to create a patterned device.

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