Silicon-containing coating composition and use thereof

Abstract

Novel functional poly (organosiloxane) resin compositions, methods of making novel poly (organosiloxane) coating compositions, and coated substrates having improved properties, suitable for, for example, optical applications to achieve predetermined refractive indexes, absorption coefficients, and other properties. Particular embodiments include silicon precursors whose substituents comprise a butterfly-shaped fused aromatic structure wherein the dihedral angle of the half-plane defined by the aromatic ring to which the intermediate N and S atoms are linked is less than 165 DEG and the C-S-C bond angle of the folded thiazine ring, particularly 1, 4-thiazine, is less than 110 DEG. In one embodiment, the silicon precursor has a substituent comprising an optionally substituted thiazine ring.

Description

TECHNICAL FIELD

[0001] The present invention relates to silicone resin compositions. In particular, the present invention relates to silicone polymer compositions for coating optical substrates. The present invention also relates to poly(organosiloxane) or polysilsesquioxane resin coatings for optical applications to achieve predetermined refractive index, absorption coefficient or other coating properties. The present invention also relates to the use of said compositions in semiconductor devices. BACKGROUND

[0002] Numerous microelectronic and optoelectronic applications require transparent coatings whose optical properties, mainly the refractive index and the absorption coefficient, need to be optimized in the device itself or in the device manufacturing process. Such devices and manufacturing processes often use multilayer coatings, which are stacked layer by layer and then optionally finished with a layer of plastic or glass. In practical applications, the goal is often to maximize or improve the performance of the device or its manufacturing process to minimize the reflection at the interfaces between the stacked coatings. Reflection usually occurs when the individual coatings have different refractive indices. Thus, for example, CMOS image sensors require materials with variable refractive indices to allow light to enter the photodiodes with minimal reflection losses, thereby improving image quality. Also, it is important that the refractive index of the coatings be able to maximize the light output of optoelectronic devices, such as handheld displays, to improve optical clarity and image resolution.

[0003] Advanced photolithography techniques for manufacturing state-of-the-art electronic devices are one specific example where reflection control is crucial. Photolithography processes use special coatings during the imaging process to minimize back reflection and interference phenomena of single-wavelength photons. The semiconductor industry's growing demand for smaller feature sizes has driven the development of equipment that uses deep ultraviolet light with wavelengths of 248 and 193 nanometers. This photolithography equipment can freely achieve feature sizes as small as 50 nanometers.

[0004] Manufacturing devices with micro-sized features presents new challenges, as various errors can occur in the resulting pattern due to optical interference caused by light reflection off the underlying layers of the semiconductor wafer. In addition, variations in the thickness of the photoresist due to the underlying topography also cause errors in the resulting pattern.

[0005] Commercially available ARC materials contain inorganic and organic materials. Inorganic ARC materials are superior to organic materials because multiple desired properties, such as etch selectivity, filling and planarization of the substrate surface topography, and anti-reflective function in a single layer coating, can be achieved simultaneously using inorganic ARC materials.

[0006] US 2007 / 0148586 Al relates to a hard mask composition for photoresist underlayer films, wherein the hard mask composition comprises a siloxane which can contain aryl groups. US 2010 / 167203 Al discloses a photoresist underlayer composition comprising an organosilane polymer which can optionally contain aryl groups. US 2005 / 0042538 Al relates to an antireflective hard mask composition comprising a carbosilane polymer which can contain a chromophore moiety.

[0007] However, there is still a need to develop new materials which can be used for a variety of different applications. SUMMARY

[0008] It is an object of the present invention to provide poly(organosiloxane) or polysilsesquioxane resin compositions comprising organosilicon compounds.

[0009] It is a further object of the present invention to provide a method of making functional poly(organosiloxane) or polysilsesquioxane resin coating compositions comprising such resins.

[0010] It is a third object of the present invention to provide coating substrates comprising poly(organosiloxane) or polysilsesquioxane resins.

[0011] It is a fourth object of the present invention to provide silicon precursors which can be used for poly(organosiloxane) or polysilsesquioxane resins.

[0012] It is a fifth object of the present invention to provide underlayer coatings comprising poly(organosiloxane) or polysilsesquioxane resins.

[0013] It is a sixth object of the present invention to provide substrates comprising coatings with improved properties.

[0014] The present invention relates to the use of a novel silicon precursor having a substituent comprising an aromatic structure, in one embodiment the substituent comprises a fused ring, and preferably assumes a folded conformation in space. In one embodiment, the aromatic structure comprises a fused ring, in particular one or two side aromatic rings fused to a sulfur and nitrogen containing heterocycle, such as a six-membered thiazine ring. Thus, in one embodiment, the silicon precursor has a substituent comprising a thiazine ring having an aromatic ring, such as a benzene ring, on one side or preferably on both sides, thereby forming, for example, a benzothiazine structure or a dibenzothiazine structure, in particular a dibenzo-1,4-thiazine structure. The fused ring structure can be substituted or unsubstituted, in particular bearing substituents on the aromatic benzene residue.

[0015] In space, the fused ring structure preferably assumes a butterfly shape, wherein the dihedral angle between the planes defined by the aromatic rings connected by the central N and S atoms generally assumes an angle of <165°, while the C-S-C bond angle of the folded thiazine, in particular the 1,4-thiazine ring, is less than 110°, based on the literature (Acta Cryst. (1976). B32, 5-10).

[0016] Surprisingly, we have found that poly(organosiloxane) or polysilsesquioxane resin compositions containing novel silicon precursors having substituents with aromatic structures containing sulfur and nitrogen atoms, as well as solutions and coating compositions comprising them, enable a variety of valuable properties.

[0017] Thus, the present application provides the use of the silicon precursors in organic-inorganic hybrid poly(organosiloxane) or polysilsesquioxane polymers to achieve optical properties.

[0018] Furthermore, the present application also provides the use of the precursors as components of bottom coatings in photolithography to adjust the refractive index and absorption coefficient at a given photolithography wavelength.

[0019] In an embodiment, the bottom layer comprises or consists of an alkoxy silane-based aromatic butterfly compound, wherein the dihedral angle between the two benzene rings is less than 165°, the C-S-C bond angle of the sulfur and nitrogen atoms is less than 110°, and is used as a refractive index enhancer or a surface property modifier, wherein the surface properties include, for example, hydrophobicity.

[0020] In an embodiment, the polymers comprising the monomers of the present application can be used in organic-inorganic ARCs in deep UV photolithography, wherein the monomers have substituents with aromatic structures containing sulfur and nitrogen atoms.

[0021] The present application also provides a method of using the resins of the present application containing novel silicon precursors, in an embodiment the silicon precursors assume a butterfly shape, the dihedral angle between the two benzene rings is less than 165°, and contain an aromatic structure with a C-S-C bond angle of less than 110° containing sulfur and nitrogen atoms. First, an organic bottom layer is coated and cured, then a poly(organosiloxane) or polysilsesquioxane resin is coated and cured, and finally a photoresist material is coated, baked, exposed, and developed. Wherein the obtained photoresist pattern is transferred to the poly(organosiloxane) or polysilsesquioxane resin, which is then transferred again to the organic bottom layer and the substrate using a selective dry etching process step.

[0022] More specifically, the main features of the present application are those described in the characterizing part of the independent claims.

[0023] The present application has significant advantages.

[0024] It has been discovered that resins containing novel silicon precursors of the present type, such as butterfly-shaped silicon precursors, having a dihedral angle between two phenyl rings of less than 165°, and containing an aromatic structure containing sulfur and nitrogen atoms, with a C-S-C bond angle of less than 110°, can have numerical properties useful for silicon-based coatings.

[0025] In general, the resins provided by embodiments of the present application exhibit high refractive indices at visible wavelengths, while retaining excellent mechanical properties and limited absorption, making them useful for imaging and display applications.

[0026] Similarly, the resins provided by embodiments of the present application, such as those containing a novel butterfly-shaped silicon precursor having a substituent containing an aromatic structure containing both sulfur and nitrogen atoms, are capable of simultaneously forming coatings with desirable optical, mechanical, and compositional properties, making them useful for optical lithography applications.

[0027] In addition, the resins provided by embodiments of the present application, containing novel silicon precursors having substituents containing aromatic structures containing both sulfur and nitrogen atoms, are capable of simultaneously producing coatings with desirable optical, mechanical, and compositional properties, while also having beneficial properties for pattern profile in optical lithography applications.

[0028] Solutions according to embodiments of the present application contain poly(organosiloxane) or polysilsesquioxane resins containing novel silicon precursors having aromatic structure substituents containing both sulfur and nitrogen atoms. Such solutions can be used to spin-on films on semiconductor or other substrates, and can be used directly to optimize light guidance, or applied in semiconductor manufacturing processes to adjust coating optical properties, thereby enabling superior reflectivity control.

[0029] In some embodiments, the solutions of these embodiments also aid in the curing process or the pattern shape of photoresists coated, exposed, and developed on the coating.

[0030] Thus, the present solutions can be used to cast coatings on semiconductor substrates to form coatings with predetermined optical properties, such as refractive index and absorption coefficient.

[0031] In some embodiments, the precursors of the present application can be used as additives in photoresist underlayer coatings to simultaneously adjust refractive index, absorption coefficient at lithography wavelengths, etch resistance, and to facilitate the curing process, and to increase the surface energy of the coating.

[0032] A primer polymer composition comprising a novel aromatic substituent of the present invention, such as at least one sulfur and nitrogen containing butterfly shaped aromatic derivative having a dihedral angle between the two benzene rings of less than 165° and a C-S-C bond angle of less than 110°, the resulting coating has a high refractive index in the visible wavelength range and can be used to tune the optical constants at the lithography wavelength in coating compositions. Furthermore, the novel precursors of the present invention, in particular the sulfur and nitrogen containing butterfly shaped aromatic derivatives, have a surprising beneficial effect on the resulting coating at the interface of a subsequent layer when used as a polymer precursor.

[0033] Due to the simplicity of the process, the good optical properties, the room temperature applicability and the time saving, the organic-inorganic hybrid material is extremely attractive for antireflective coating (ARC) applications, such as displays and other technologies where a reduction of reflection is desired. Furthermore, the high silicon content in the organic-inorganic hybrid material makes it resistant to oxygen plasma etching, enabling efficient pattern transfer to the underlying organic layer.

[0034] Further features and advantages of the present technology will appear from the detailed description of the embodiments below.

[0035] BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The main steps to form a three layer lithography stack are schematically shown in side view;

[0037] Figure 2 A four layer lithography stack is schematically shown in side view; and

[0038] Figure 3 A gas chromatography-mass spectrometry (GC-MS) of a butterfly shaped aromatic compound containing sulfur and nitrogen atoms, having a dihedral angle between the two benzene rings of less than 165° and a C-S-C bond angle of less than 110° is shown.

[0039] Figure 4 The suitability of the present invention as functional layer 120 in a lithography stack is shown, wherein the functional layer 120 is composed of a typical photoresist 110, a silicon hard mask Si-BARC or silicon oxynitride or metal oxide 130, a SOC or CVD carbon or high temperature SOC 140 and a substrate 150, respectively. EMBODIMENTS

[0040] Unless otherwise stated herein or apparent from context, all percentages mentioned herein are expressed as weight percentages based on the total weight of the respective composition.

[0041] Unless otherwise stated herein, all properties measured or determined herein are measured or determined at room temperature. Unless otherwise stated, room temperature is 25 °C.

[0042] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified.

[0043] The word "about" as used herein when used in connection with a quantity is used to mean the quantity ± 5%. The word "about" as used herein when used in connection with a given value means both the actual given value and an approximate value of the given value that is reasonably inferable by one of ordinary skill in the art, including an approximate value that is based on experimental and / or measurement conditions of the given value.

[0044] Unless otherwise indicated, "molecular weight" or "average molecular weight" means weight average molecular weight (also abbreviated "M W ").

[0045] Molecular weights used herein are determined by gel permeation chromatography using polystyrene as a standard.

[0046] Unless otherwise indicated, the term "viscosity" as used herein means dynamic viscosity, measured at 25°C by a rheometer at a shear rate of 2.5 s -1 .

[0047] Viscosity can be measured with a viscometer, such as a Brookfield or Cole-Parmer viscometer. The viscometer rotates a disc or cylinder in the fluid sample and measures the torque required to overcome the viscous resistance thus created. The rotational speed can be set arbitrarily, for example, from 1 to 30 rpm, preferably 5 rpm, and the temperature of the material being measured is preferably 25°C.

[0048] Thin film contact angles can be measured using a KSV Instruments CAM100. The tool has an error of + / - 0.1 degrees and is used to measure the angle that a water droplet makes at the intersection boundary of a liquid (deionized water), a gas (air), and a solid (thin film). Deionized water droplets are dispensed onto a thin film (typically coated on a silicon wafer) using a syringe with microscrews to determine the static contact angle. In addition, the built-in software automatically calculates the contact angle using a curve fit of the Young-Laplace equation from the static images taken by the camera. The resulting static contact angle is the average of the left and right angle measurements. Three measurements are taken for each sample and the average is reported.

[0049] In the present context, the term "precursor" is used synonymously with "monomer" and refers to a molecule that can be incorporated into a polymer, either alone or as a comonomer with other monomers, particularly as part of the backbone of a linear or branched polymer.

[0050] The material can be referred to as a "polysiloxane resin", or collectively as a "poly(organosiloxane) resin", and in specific embodiments as a "polyaromatic poly(silesquioxane) resin". Such materials contain residues derived from both organic and inorganic compounds, as described below. In addition, the material contains silanol groups, i.e., groups having Si-O-H connectivity. The material also contains other functional groups attached to Si, typically along the main chain of Si, and in particular along its main siloxane chain.

[0051] In this document, the term "butterfly precursor" refers to a compound having two pendant ring structures, in particular aromatic ring structures, flanking a central moiety, similar to the body of a butterfly, the pendant ring structures typically extending in two mutually intersecting geometric planes and forming a dihedral angle of less than 180°, typically 165° or less.

[0052] Typically, the dihedral angle between the two benzene rings is in the range of 110° to less than 165°, and the C-S-C bond angle is in the range of 90° to less than 110°.

[0053] Typically, the poly(organosiloxane) or poly(silesquioxane) resin main chain contains about 70-99 mole percent of the novel butterfly precursor per repeat unit. In one embodiment, the poly(organosiloxane) or poly(silesquioxane) resin main chain contains on average about 90-98 mole percent of the polyaromatic precursor per unit. These materials are made by incorporating a novel precursor containing nitrogen and sulfur between two benzene rings, where the C-S-C bond angle of the benzene rings is less than 110°, to produce a coating having a high refractive index, greater than 1.5, preferably greater than 1.52, and more preferably greater than 1.55, when measured at a wavelength of 663 nm.

[0054] In another embodiment, the poly(organosiloxane) or poly(silesquioxane) resin main chain contains about 1-20 mole percent of the novel precursor per repeat unit. In yet another embodiment, the poly(organosiloxane) or poly(silesquioxane) resin main chain contains less than 1 mole percent of the polyaromatic precursor per repeat unit.

[0055] Embodiments of the present technology relate to a method of making a poly(organosiloxane) or poly(silesquioxane) resin solution containing a novel silicon precursor having a substituent containing an aromatic structure containing sulfur and nitrogen atoms, in particular a dihedral angle between two benzene rings of less than 165° and a C-S-C bond angle of less than 110°, where the hydrolyzable silicon precursor is hydrolyzed / condensed alone or with suitable other silicon-containing precursors.

[0056] The present invention also relates to the use of functional poly(organosiloxane) or polysilsesquioxane solutions in photolithography processes for casting a coating on a semiconductor substrate and forming a pattern by subsequent baking, irradiation and development steps. In particular, the present invention relates to a method of controlling the microstructure of a resin, which is industrially feasible and solves the drawbacks of the prior art.

[0057] Embodiments of the present technology relate to the use of novel silicon-containing functional coatings in photolithography stacks Figure 4 ) In this approach, the stack consists of a 40-50 nm photoresist layer 110, a 5-10 nm thick functional layer 120, a 20-50 nm Si-BARC or silicon oxynitride or metal oxide layer 130, a 200-400 nm spin-on carbon (SOC) layer or high temperature SOC layer or amorphous carbon layer obtained by chemical vapor deposition 140 and a substrate 150. In this stack, we surprisingly found that the functional layer can reduce the dose required for patterning by 15-30%. This improvement is very advantageous because the dose on the substrate is controlled by the exposure time. Thus, a dose reduction means a shorter exposure step time, which leads to higher efficiency and throughput. Moreover, a dose reduction can have a positive impact on the necessary maintenance procedures, thus increasing the economic benefits obtained by using such a functional layer.

[0058] According to an embodiment, the present technology relates to a composition suitable for forming a siloxane layer on a substrate, said composition comprising a siloxane polymer comprising SiO moieties, a plurality of sites distributed along said polymer comprising a first polyaromatic moiety, said first polyaromatic moiety comprising nitrogen and sulfur atoms, a dihedral angle between two benzene rings of less than 165°, a C-S-C bond angle of less than 110°, and intervening aromatic and non-aromatic moieties, wherein the molecular weight of said polymer is comprised between 500 and 50,000 g / mol, and said composition preferably further comprises an acid and / or a base and a solvent.

[0059] According to an embodiment, a polymer composition is provided, which is suitable for producing a coating formulation that can be cast on a substrate, wherein the polymer in the formulation produces a coating layer represented by the general formula (I)

[0060]

[0061] In formula I,

[0062] R a 1 and R b 2 represent halogen or hydrocarbyl groups, which can be independently selected from the group consisting of optionally functionalized linear, branched or cyclic alkyl groups, optionally functionalized aromatic or polyaromatic groups;

[0063] R 3represent hydrogen, hydroxyl, halogen, alkoxy, acyloxy, or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched, or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0064] R 4 represent hydrogen, hydroxyl, halogen, alkoxy, acyloxy, or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched, or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0065] R 5 and R 6 represent hydrogen, hydroxyl, halogen, alkoxy, acyloxy, or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched, or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0066] a and b are independently selected from an integer in the range of 0 to 4;

[0067] m and n are independently selected from an integer in the range of 1 to 1000.

[0068] The above composition is obtained by hydrolyzing a first monomeric silicon compound (hereinafter "Precursor A") having a substituent comprising an aromatic structure containing sulfur and nitrogen atoms, and at least one hydrolysable group attached to silicon, the substituent comprising at least one hydrolysable group, the substituent comprising one or more monomeric silicon compounds, i.e. "Precursor B".

[0069] The ratio of the precursors used in the present invention can vary.

[0070] In one embodiment, Precursor A is used in an amount of 1-100 mole %, e.g. 20-90 mole %, e.g. 30-80 mole % or 40-70 mole %. Precursor B can be used in an amount of 0-99 mole %, e.g. 10-80 mole %, e.g. 20-70 mole % or 30-60 mole %. The siloxane composition can be obtained by hydrolysis and condensation reactions in the same reaction vessel or separately using each precursor in the specified ratio.

[0071] The present invention is particularly suitable for producing a composition comprising a poly(organosiloxane) obtained by hydrolyzing a first silicon compound having the general formula II or Precursor A

[0072] (R 7 -R 3 ) p -SiR 8 q -R 4o (II)

[0073] In this composition,

[0074] R 7 represents an optionally substituted polyaromatic hydrocarbon group containing nitrogen and sulfur atoms;

[0075] R 8 represents an alkoxy, acyloxy or halogen group;

[0076] R 3 and R 4 have the same meaning as in formula I above;

[0077] p and q are independently integers from 1 to 3,

[0078] o is an integer from 1 or 2, and

[0079] the sum of p+q+o is not more than 4.

[0080] When substituted, R 7 typically bears a substituent R 1 a and R 2 b where R 1 , R 2 , a and b have the same meaning as in formula I.

[0081] In one embodiment, the compound of formula II typically has a butterfly shape.

[0082] Substituted or unsubstituted phenothiazine. In phenothiazine, the central C4SN ring has a folded shape.

[0083] The substituents can be selected from the group consisting of halogen, alkyl, alkoxy, cyano, oxo, thioxo, alkylsulfonyl, sulfonyl, acyl and perfluoroalkyl.

[0084] R 7 residue in formula (II) can be derived from the following structures, which are given as non-limiting examples:

[0085] In one embodiment, the residue R 3 of formula (II) is derived from an aliphatic or aromatic or cyclic or heterocyclic vinyl or alkynyl precursor compound, such as the following compounds:

[0086]

[0087] The present application also relates to a composition comprising a copoly(organosiloxane) obtained by hydrolysis of a first silicon compound having general formula II in combination with a precursor B having general formula III

[0088] R 10 t -SiR 9 r -R 11 s (III)

[0089] wherein

[0090] R 9 represents an alkoxy, acyloxy, or halogen group,

[0091] R 10 and R 11 are independently selected from the group consisting of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, organic groups having one or more epoxy groups, mercapto, alkoxyaryl, acyloxyaryl, isocyanurate, hydroxyl, cyclic amino, cyano, and combinations thereof; or R 10 and R 11 are independently selected from the group consisting of alkoxy, acyloxy, and halogen groups,

[0092] t is an integer from 0 to 3,

[0093] r is an integer from 1 to 4,

[0094] s is an integer from 0 to 3,

[0095] wherein the total value of t + r + s must not exceed 4.

[0096] Specific examples of precursors B of formula (III) include, but are not limited to: tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n- propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, methyltribenzoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, glycidoxy-methyltrimethoxysilane, glycidoxy-methyltriethoxysilane, α-glycidoxy-ethyltrimethoxysilane, α-glycidoxy-ethyltriethoxysilane, β-glycidoxy-ethyltrimethoxysilane, β-glycidoxy-ethyltriethoxysilane, α-glycidoxy-propyltrimethoxysilane, α-glycidoxy-propyltriethoxysilane, β-glycidoxy-propyltrimethoxysilane, β-glycidoxy-propyltriethoxysilane, γ-glycidoxy-propyltrimethoxysilane, γ-glycidoxy-propyltriethoxysilane, γ-glycidoxy-propyltripropoxysilane, γ-glycidoxy-propyltributoxysilane, γ-glycidoxy-propyltriphenoxysilane, α-glycidoxy-butyltrimethoxysilane, α-glycidoxy-butyltriethoxysilane, β-glycidoxy-butyltriethoxysilane, γ-glycidoxy-butyltrimethoxysilane, γ-glycidoxy-butyltriethoxysilane, δ-glycidoxy-butyltrimethoxysilane, δ-glycidoxy-butyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltripropoxysilane, δ-(3,4-epoxycyclohexyl)butyltributoxysilane, δ-(3,4-epoxycyclohexyl)butyltriphenoxysilane, and the like.4-epoxycyclohexyl)butyltriethoxysilane, glycidyloxy-methyldimethoxysilane, glycidyloxy-methyldiethoxysilane, a-glycidyloxy-ethyldimethoxysilane, a-glycidyloxy-ethyldiethoxysilane, β-glycidyloxy-ethyldimethoxysilane, β-glycidyloxy-ethyldiethoxysilane, a-glycidyloxy-propyl-dimethoxysilane, a-glycidyloxy-propyl-diethoxysilane, β-glycidyloxy-propyl-dimethoxysilane, β-glycidyloxy-propyl-diethoxysilane, γ-glycidyloxy-propyl-dimethoxysilane, γ-glycidyloxy-propyl-diethoxysilane, γ-glycidyloxy-propyl-dipropoxysilane, γ-glycidyloxy-propyl-dibutoxysilane, γ-glycidyloxy-propyl-diphenoxysilane, γ-glycidyloxy-propyl-ethyldimethoxysilane, γ-glycidyloxy-propyl-ethyldiethoxysilane, γ-glycidyloxy-propyl-vinyldimethoxysilane, γ-glycidyloxy-propyl-vinyldiethoxysilane, phenylsulfonamidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methylvinyl-dimethoxysilane, methylvinyl-diethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl-methyldimethoxysilane, γ-methacryloyloxypropyl-methyldiethoxysilane, (methacryloyloxymethyl)methyldiethoxysilane, (methacryloyloxymethyl)methyldimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltrichlorosilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltriisopropoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyl-methyldimethoxysilane, γ-chloropropyl-methyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 4-acetyloxyphenethyltrimethoxysilane, 4-acetyloxyphenethyltriethoxysilane, 4-(acetyloxyphenethyl)methyldichlorosilane, 4-(acetyloxyphenethyl)methyldimethoxysilane, 4-(acetyloxyphenethyl)methyldiethoxysilane, triethoxysilanylpropylcarbamic acid ester, triethoxysilanylpropylmaleamic acid, N-(3-triethoxysilylpropyl)-4-hydroxybutyramide, N-(3-triethoxysilylpropyl)glucamid, (3-triethoxysilylpropyl)succinic anhydride, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, 3-hydroxy-3,3-bis(trifluoromethyl)propyltriethoxysilane, 4-(methoxymethoxy)trimethoxysilylbenzene, 6-(methoxymethoxy)-2-(trimethoxysilyl)naphthalene.

[0097] According to one embodiment, the novel butterfly-shaped aromatic compound of formula (II) containing sulfur and nitrogen atoms and having a dihedral angle between the two benzene rings of less than 165° and a C-S-C bond angle of less than 110° is hydrolyzed and polymerized alone or in various mole percentages with other silicon-containing monomers, completely without the need for a solvent.

[0098] In another embodiment, the novel aromatic compound of formula (II) containing sulfur and nitrogen atoms and having a dihedral angle between the two benzene rings of less than 165° and a C-S-C bond angle of less than 110° is hydrolyzed and polymerized alone or in various mole percentages with other silicon-containing monomers. The compound is hydrolyzed and polymerized in an organic solvent such as an alcohol, ester, ketone, ether or mixtures thereof. Specifically, suitable solvents are acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and tetrahydrofuran (THF). Particularly suitable solvents are alcohols, ketones, ethers and mixtures thereof.

[0099] The hydrolysis of the monomer can be carried out in an acid or base solution having a molar concentration of acid or base of 0.0001 M to 1 M.

[0100] In one embodiment, the acid solution used in the hydrolysis process comprises an inorganic acid or an organic acid or mixtures thereof. Examples of inorganic acids include nitric acid, sulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid, boric acid, perchloric acid, carbonic acid and phosphoric acid and mixtures thereof. Nitric acid or hydrochloric acid is preferred because of their low boiling points, which facilitates purification of the product. Alternatively, an organic acid can be used. Examples of organic acids or acidic compounds include carboxylic acids, sulfonic acids, alcohols, thiols, enols and phenolic groups. Specific examples include methanesulfonic acid, acetic acid, ethanesulfonic acid, toluenesulfonic acid, formic acid and oxalic acid and mixtures thereof.

[0101] In one embodiment, the basic solution used in the hydrolysis process comprises an inorganic or organic base. Typical inorganic bases as well as metal hydroxides, carbonates, bicarbonates and other salts which produce aqueous basic solutions. Examples of such materials include sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, sodium carbonate and sodium bicarbonate. On the other hand, organic bases include a large class of materials including organic acid metal salts (such as sodium acetate, potassium acetate, sodium acrylate, sodium methacrylate, sodium benzoate), straight chain, branched chain or cyclic alkyl amines (such as ethylenediamine, putrescine, cadaverine, triethylamine, butylamine, dibutylamine, tributylamine, piperidine), amidine and guanidine compounds (such as 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene), phosphazenes (such as P1-t-butyl, P2-t-butyl, P4-t-butyl) and quaternary ammonium compounds (such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide).

[0102] The temperature of the reaction mixture during hydrolysis and condensation can vary from -30 to 170 °C. Lower reaction temperatures generally allow better control of the reaction, while higher temperatures increase the rate of reaction. In one embodiment, the reaction time is from 1 to 48 hours, and the temperature ranges from 0 to 100 °C. Preferably, the reaction time is from 2 to 24 hours.

[0103] Using appropriate conditions, the process of the present application produces a partially crosslinked organosiloxane polymer containing sulfur and nitrogen, having a molecular weight (Mw) of about 5,000 to 100,000 g / mol, particularly about 1,000 to 10000 g / mol, measured against a polystyrene standard, in an organic solvent system.

[0104] In another embodiment, the solvent in which hydrolysis and polymerization are carried out ("first solvent") is replaced after polymerization by another solvent or mixture of solvents ("second solvent"). Typically, the second solvent is chosen to impart better coating properties and product storage properties to the material.

[0105] In one embodiment, this is achieved by stabilization.

[0106] One embodiment provides a composition comprising a liquid phase poly(organosiloxane) resin, the composition comprising a poly(organosiloxane) as described herein in a liquid phase formed from at least one organic solvent for the poly(organosiloxane) resin, optionally mixed with water. The composition can be formulated for use in a method of coating a substrate by casting.

[0107] In one embodiment, the organic liquid has a flash point of preferably at least 10 °C, and a vapor pressure at 20 °C of less than about 10 kPa.

[0108] Examples of stabilizing organic solvent systems include one or more organic ethers, optionally mixed with other one or more co-solvents.

[0109] In one embodiment, the organic ether is a linear, branched or cyclic ether, typically comprising 4 to 26 carbon atoms, and optionally comprising other functional groups, such as hydroxyl groups. Particularly suitable examples are five- and six-membered cyclic ethers, optionally bearing substituents on the ring, and ethers such as (Ci-20)alkanediol (Ci-6)alkyl ethers. Examples of the alkanediol alkyl ethers include propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol monomethyl ether, and mixtures thereof.

[0110] Particularly preferred examples of ethers according to the present application are methyltetrahydrofurfuryl ether, tetrahydrofurfuryl alcohol, propylene glycol n-propyl ether, dipropylene glycol dimethyl ether, propylene glycol n-methyl ether, propylene glycol n-ethyl ether (PGEE), and mixtures thereof. The stable solvent system consists of solvents containing such ethers alone, or mixtures of such ethers with hydrolyzed typical reaction media or other solvents, such as propylene glycol monomethyl ether acetate (PGMEA). In this case, the proportion of ethers is about 10 to 90 wt.%, in particular about 20 to 80 wt.%, for example 25 to 75 wt.%, of the total amount of solvent.

[0111] In one embodiment, the liquid phase of the composition of the present application comprises a solvent selected from the group consisting of PGMEA, PGEE, THF, and mixtures thereof.

[0112] The solid content of the formulation comprising, consisting of, or consisting essentially of, the solvent and the resin material is in the range of 0.1% to no more than 50%. Most preferably, the solid content is in the range of 0.5% to 10%, for example 1% to 4%. The viscosity of the polymer solution is typically about 0.5 centipoise (cP) to about 150 cP, for example 1 to 100 cP, for example 5 to 75 cP.

[0113] The solid content (or polymer content) is used to adjust the final film thickness in the coating process.

[0114] In one embodiment, the silicon content of the composition of the present application is higher than 20%, more preferably higher than 25%, most preferably higher than 30%, calculated on the dry weight of the composition.

[0115] To improve coating uniformity, different surfactants, such as one or more organosilicon surfactants, fluorosurfactants, or combinations thereof, can be used to reduce the surface tension of the poly(organosiloxane) or polysilsesquioxane formulation coating. The use of such surfactants can improve the coating quality. The amount of surfactant used should be in the range of 0.001% to no more than 10% of the mass of the silanol-containing polysilsesquioxane.

[0116] In a particular embodiment, a compound selected from the group consisting of a photo- or thermal-labile catalyst or compound is added to the formulation mixture to enhance the crosslinking of the polysiloxane film. The content of the thermal or photo-labile compound in the formulation is in the range of 0.1% to 20%, most preferably 0.2% to 10%, for example 0.5% to 7.5% of the solid content of the polysiloxane.

[0117] The polysilsesquioxane or composition thereof of the present application can be used to spin coat a substrate, such as a silicon substrate, for example a silicon wafer. Through such a coating, the molar absorptivity can be improved.

[0118] The bow-tie shaped nitrogen and sulfur-containing material of the present application can be used as an additive to adjust (i.e., "tune") the polymer film thickness, refractive index (n), molar absorptivity (k), and contact angle (CA) of the corresponding siloxane-based photoresist polymer.

[0119] In one embodiment, by coating such layers on a substrate such as a silicon wafer, the absorption coefficient (k) at 248 nm increases from 1 mole percent to 100 mole percent when the inventive sulfur and nitrogen containing precursor is introduced, whereas the absorption coefficient (k) of the corresponding unmodified polysilsesquioxane or composition thereof is 0.02, thus the absorption coefficient (k) at 248 nm can be increased to 0.55.

[0120] The polymer composition of formula (I) comprises at least one sulfur and nitrogen containing butterfly shaped aromatic group having a dihedral angle of less than 165° between two benzene rings, a C-S-C bond angle of less than 110°, and the aromatic group has a strong absorption in the wavelength range of 200 to 600 nm. The refractive index of the composition is between 1.3 and 1.7 depending on the content of the sulfur and nitrogen containing aromatic monomer, such as the monomer of formula (IV), in the polymer composition. The refractive index of the polymer composition of formula (I) spin coated on a silicon wafer at a wavelength of 248 nm increases with increasing content of the monomer of formula (IV) in the siloxane based polymer composition.

[0121] The present invention also relates to a process for preparing the silicon based precursor of formula (II).

[0122] In one embodiment, the compound of formula (II) is prepared by a two-step process as shown in Scheme 1.

[0123] Figure 1 General synthesis method of sulfur, nitrogen containing precursors or additives

[0124]

[0125] In the above method, the aromatic compound, in particular the compound in the shape of a butterfly, containing sulfur and nitrogen heteroatoms, is dissolved in a suitable solvent and then subjected to a normal alkylation reaction using a reactant containing a halogen atom and an unsaturated carbon-carbon bond, such as allyl bromide, in the presence of a suitable inorganic / organic base, as shown in Scheme 1.

[0126] The reaction can be carried out at different temperatures, preferably at a temperature of 25 to 150 °C, more preferably at a temperature of 30 to 120 °C, most preferably at a temperature of 40 to 100 °C or 50 to 100 °C. The reaction time can be adjusted until the completion of the reaction is determined by thin layer chromatography, gas chromatography or liquid chromatography. The intermediate product can then be purified by column chromatography, crystallization, sublimation or distillation, etc.

[0127] The crude intermediate or its purified form is introduced into a silicon precursor containing Si-H bonds (e.g. triethoxysilane, optionally with a solvent) and a catalytic hydrosilylation reaction is carried out in which the Si-H bonds add to the unsaturated carbon-carbon bond. One example of such a catalyst is a platinum complex of 1,3-divinyltetramethyldisiloxane. Again, the reaction can be carried out at different temperatures, preferably between 25 and 150 °C, more preferably between 30 and 120 °C, most preferably between 40 and 100 °C or between 50 and 100 °C. The reaction time can be adjusted until the reaction is complete as determined by thin layer chromatography, gas chromatography or liquid chromatography.

[0128] Finally, the optional solvent and excess reagents are removed before the final purification of the desired compound.

[0129] The above method can also be used to obtain any polycyclic aromatic compound with a substituted group attached to a halogenated hydrocarbon (containing a vinyl or alkyne double bond) via a normal alkylation reaction. The corresponding compound is further reacted with a Si-H containing precursor or compound to obtain the desired aromatic compound via hydrosilylation.

[0130] Examples of particularly preferred compounds corresponding to formula (IV) are as follows:

[0131]

[0132]

[0133]

[0134] In the above formulae,

[0135] R a 1 , R b 2 and R 3 have the same meaning as in formula I above.

[0136] The introduction of this novel aromatic compound containing sulfur and nitrogen atoms into a polymeric composition results in a high refractive index (n) coating. Surprisingly, in one example (Example 1), the homopolymer prepared from the sulfur and nitrogen containing precursor had a refractive index of up to 1.66 at 633 nm, while the material in the comparative example had an n of only 1.65 at 633 nm. Thus, the present invention can be used to further increase the refractive index.

[0137] Figure 1A typical lithography process is schematically shown, which consists of or comprises the successive deposition of a carbon based underlayer material 12, a silicon based intermediate layer 14 and a radiation sensitive photoresist layer 16. In this process, the underlayer coatings 12 and 14 are applied and baked in sequence before the next coating is deposited. Thereafter, the radiation sensitive photoresist layer is selectively irradiated, for example by means of a mask comprising the desired pattern. The pattern is then developed and the resulting pattern is transferred to the underlying layer 14 by means of an etching process using a gaseous or liquid phase fluorine chemistry. The pattern is then transferred to the carbon based underlayer 12 by means of a gaseous plasma enhanced etching process. In this step, the etch selectivity between the layers 12 and 14 is often of crucial importance. Generally, a better etch selectivity can be obtained by means of a silicon based intermediate layer having a high silicon content and a low carbon content. Finally, the resulting pattern is transferred to the substrate. Typically, after the process is completed, the photoresist and the underlayer are removed.

[0138] Figure 1 A typical three layer lithography process is shown, in which different layers are applied.

[0139] Furthermore, in a four layer lithography process, an organic bottom antireflective (OBARC) layer 18 is used to adjust the refractive index (n) and extinction coefficient (k) and increases the Figure 2 The device construction steps are shown.

[0140] Figure 3 The mass spectrum of the newly prepared monomer is shown, as well as its corresponding fragmentation pattern.

[0141] Figure 4 A lithography process is shown, in which a functional layer is used in the lithography process. On a substrate 150, a layer 140 based on spin-on carbon (SOC) or alpha-carbon is deposited by means of chemical vapor deposition, having a thickness of 200-400 nm. Thereafter, a high silicon based intermediate layer Si-BARC or silicon oxynitride or metal oxide layer 130 is deposited on the layer 140, having a thickness of 20-50 nm. Thereafter, a functional coating 120 based on the present application is deposited, having a layer thickness of, for example, 5-10 nm. Finally, a radiation / photo (for example 13.5 nm, 193 nm, 248 nm, 365 nm, but not limited to these) or electron beam radiation sensitive photoresist layer 110 is deposited on the layer 120, having a thickness of 40-50 nm.

[0142] In the device manufacturing step, the photoresist layer 110 is irradiated with a selected wavelength or electron beam through a mask of the predetermined pattern. The pattern is then developed and the resulting pattern is transferred to the subsequent functional layer 120 and high silicon content Si-BARC layer shown here by means of an etching process. By means of a silicon based intermediate layer having a high silicon content and a low carbon content, a higher etch selectivity can be obtained. Finally, the resulting pattern is transferred to the substrate. Typically, after the process is completed, the photoresist and the underlayer are removed.

[0143] It has been found that the use of the functional layer of the present application can reduce the required dose by 15% to 30% in line and space patterning process with half pitch of 32 nm, as shown in Example 14.

[0144] It is worth noting that with the polysiloxane composition containing the sulfur and nitrogen containing monomer of the present application, by adjusting the n and k parameters, the advantage over the four layer architecture can be provided without utilizing the OBARC layer, thus simplifying the photolithography process.

[0145] Thus, the present application can be used as an antireflection coating composition not only because of its high refractive index, but also as a polysiloxane composition for deep ultraviolet ArF / KrF lithography technology to adjust the n and k parameters. Furthermore, by introducing a newly designed monomer (typically having a butterfly shape), the n and k parameters of the polymer composition and the contact angle can be significantly adjusted, as described above.

[0146] In an embodiment, the coating material is sensitive to a selected radiation, such as extreme ultraviolet light, ultraviolet light, and / or electron beam.

[0147] Furthermore, in an embodiment, the precursor solution is formulated to be stable with a predetermined shelf life for commercial distribution.

[0148] Formation of integrated electronic devices and the like often involves patterning of materials to form individual elements or components within a structure. Such patterning can involve covering selected portions of a stack of layers of different compositions that are interconnected in a vertical and / or horizontal direction to produce a desired functionality.

[0149] The various materials can include semiconductors, which can have selected dopants, dielectrics, electrical conductors, and / or other types of materials. To form high resolution patterns, radiation sensitive organic compositions can be used to introduce the pattern, and these compositions can be referred to as photoresists because portions of the composition are treated to have resistivity to development / etching, and thus can be used to introduce a selected pattern by selective material removal.

[0150] The present technology also provides for underlayer coatings for, for example, semiconductors and components thereof.

[0151] In an embodiment, a photoresist underlayer coating for photolithography comprises

[0152] a silane selected from at least one of hydrolysable organosilanes, hydrolysis products thereof, and hydrolytic condensation products thereof, wherein

[0153] the silane includes only silane compounds represented by Formula (I), or as a copolymer with one or more silane compounds represented by Formula (II).

[0154] In an embodiment, the photoresist primer film is obtained by coating a poly(organosiloxane) composition onto a semiconductor substrate and baking.

[0155] In an embodiment, the functional layer coating of the present invention is used to form a photoresist stack that includes at least the following layers:

[0156] 40-50 nm thick photoresist (organic, inorganic, hybrid, metal oxide) layer;

[0157] 5-10 nm thick functional layer of the new polymer composition presented in the present technology;

[0158] 20-50 nm thick Si-BARC or silicon oxynitride or metal oxide layer; and

[0159] 00-360 °C thick low and high temperature spin-on carbon or 200-400 nm thick chemical vapor deposition (CVD) a-carbon layer (containing SOC) and the final substrate.

[0160] The metal oxide can include metal oxides commonly used for photoresists, such as Group 4 metal oxides.

[0161] Another embodiment provides a method of producing a semiconductor device. The method generally includes the steps of:

[0162] coating a poly(organosiloxane) composition described herein for forming a photoresist primer film onto a semiconductor substrate;

[0163] baking the composition to form a photoresist primer film;

[0164] coating a composition for photoresist onto the photoresist primer film to form a photoresist film;

[0165] exposing the photoresist film;

[0166] developing the photoresist film after exposure to obtain a patterned photoresist film;

[0167] etching the photoresist primer film according to the pattern of the patterned photoresist film; and

[0168] processing the semiconductor substrate according to the pattern of the photoresist film and the photoresist primer film.

[0169] An embodiment for producing a semiconductor device includes:

[0170] forming an organic primer film on a semiconductor substrate;

[0171] coating a poly(organosiloxane) composition described herein for forming a photoresist primer film onto the organic primer film;

[0172] baking the composition to form a photoresist underlayer film;

[0173] Optionally, an organic bottom antireflective film is formed on the poly(organosiloxane) photoresist underlayer;

[0174] A composition for forming a photoresist is coated onto the photoresist underlayer film to form a photoresist film;

[0175] The photoresist film is exposed;

[0176] The photoresist film is developed after exposure to obtain a patterned photoresist film;

[0177] The photoresist underlayer film is etched according to the pattern of the patterned photoresist film;

[0178] The organic bottom antireflective film is etched according to the pattern of the patterned photoresist underlayer film; and

[0179] The semiconductor substrate is processed according to the pattern of the patterned organic bottom antireflective film.

[0180] The present technology provides a method of forming a photoresist underlayer film by coating the above-mentioned composition for forming a photoresist underlayer film on a semiconductor substrate and baking the composition.

[0181] In one embodiment, a method of producing a semiconductor device is provided, comprising:

[0182] One or more photoresist underlayer films are formed on a semiconductor substrate by coating a composition for forming a photoresist underlayer film on the semiconductor substrate and baking the composition to form one or more photoresist underlayer films;

[0183] A composition according to claim 1 is coated as a photoresist underlayer film onto one or more photoresist underlayer films to form a photoresist film;

[0184] The photoresist film is exposed;

[0185] The photoresist film is developed after exposure to form a photoresist pattern;

[0186] The photoresist underlayer film is etched using the photoresist pattern; and

[0187] A semiconductor substrate is manufactured using the thus patterned photoresist film and the thus patterned photoresist underlayer film.

[0188] In one embodiment, a method of producing a semiconductor device is provided, comprising:

[0189] An organic bottom antireflective film is formed on a semiconductor substrate;

[0190] A composition for forming a photoresist film is coated onto the organic bottom antireflective film and baked to form a photoresist film;

[0191] The photoresist film is exposed;

[0192] after exposure, developing the photoresist film to form a photoresist pattern;

[0193] etching the photoresist underlayer film using the photoresist pattern;

[0194] etching the organic underlayer film using the photoresist underlayer film thus patterned; and

[0195] manufacturing a semiconductor substrate using the organic underlayer film thus patterned.

[0196] The present technology also provides a method of producing a semiconductor device, the method comprising:

[0197] applying one or more photoresist underlayer films on a semiconductor substrate and baking the composition to form the one or more photoresist underlayer films;

[0198] applying the composition according to claim 1 as an ARC to the one or more photoresist underlayer films to form a photoresist film;

[0199] exposing the photoresist film;

[0200] after exposure, developing the photoresist film to form a photoresist pattern;

[0201] etching the photoresist underlayer film using the photoresist pattern; and

[0202] manufacturing a semiconductor substrate using the photoresist film thus patterned and the photoresist underlayer film thus patterned.

[0203] Further, the present invention also provides a method of manufacturing a semiconductor device, comprising the steps of:

[0204] forming an organic underlayer film on a semiconductor substrate;

[0205] coating a composition for forming a photoresist film on the organic underlayer film and baking the composition to form a photoresist film;

[0206] exposing the photoresist film;

[0207] after exposure, developing the photoresist film to form a photoresist pattern;

[0208] etching the photoresist underlayer film using the photoresist pattern;

[0209] etching the organic underlayer film using the photoresist underlayer film thus patterned; and

[0210] manufacturing a semiconductor substrate using the organic underlayer film thus patterned.

[0211] The present solution can be used for casting coating on semiconductor substrates as a bottom anti-reflective coating (BARC) before photoresist layer coating. Specifically, the newly synthesized nitrogen and sulfur containing butterfly shaped compounds (with a dihedral angle between the benzene rings less than 165° and a C-S-C bond angle less than 110°) and their compositions, when used as BARC, effectively address the limitations of the photolithography process such as substrate reflectivity, swing effects, and reflective etching.

[0212] Notably, the nanoparticle-free high refractive index composition presented in this study makes it extremely attractive and effectively addresses the issues of storage stability, high optical loss, and poor processability. Furthermore, the addition of the newly prepared sulfur and nitrogen containing compounds in the underlayer formulation significantly improves the long-term stability of the polymer composition by enhancing / modulating the water contact angle of the base material, making it hydrophobic. More importantly, due to its organic-inorganic hybrid nature, in one embodiment, the polysiloxane composition can be used to provide resistance to oxygen plasma, thereby achieving high etch selectivity.

[0213] The present solution achieves a refractive index of up to 1.66 at a wavelength of 633 nm without the use of external nanoparticles or additives. Furthermore, the present solution also employs a coating containing sulfur and nitrogen containing butterfly shaped compounds (with a dihedral angle between the two benzene rings less than 165° and a C-S-C bond angle less than 110°), photoacid generators, photosensitizers added according to specific photolithography wavelength requirements, high boiling point organic solvents, additives, and surfactants.

[0214] Surprisingly, in some embodiments, the refractive index of the material can be significantly increased after introducing the present monomer into the polysiloxane composition, up to 1.66 at a wavelength of 633 nm. By varying the proportion of the present monomer in the polysiloxane composition, a predetermined refractive index can be achieved. The amount of the present monomer can vary in the range of 1 to 100 mole percent compared to other silane monomers, thereby achieving a refractive index in the range of 1.42 to 1.66 at a wavelength of 633 nm.

[0215] Notably, the refractive index of the present solution is significantly increased at deep ultraviolet lithography wavelengths, from 1.34 to 1.72 at 193 nm (ArF) and from 1.49 to 1.99 at 248 nm (KrF).

[0216] In one embodiment, the water contact angle of the base polymer composition is increased from 58 degrees to 62 degrees after adding the precursor of the present solution as an additive to the polysiloxane composition. Furthermore, as an additive, the present solution can stabilize the properties (contact angle, thickness, refractive index, and molecular weight) of the base polymer for up to 42 days, which indicates the potential of this material to improve the hydrophobicity of the polymer composition, thereby enhancing the stability of the underlayer polymer composition.

[0217] Thus, generally, thin films having a thickness of 30 to 60 nm, in particular 35 nm, can be obtained by using the poly(organosiloxane) described herein as an additive in a siloxane polymer composition, and exhibit a substantially constant molecular weight and contact angle over 42 days at room temperature.

[0218] The polymer composition of formula (I) contains at least one sulfur-nitrogen containing group, such as a butterfly-shaped aromatic group located between two benzene rings with a C-S-C bond angle less than 110° and a dihedral angle less than 165°, which has a strong absorption in the wavelength range of 200 to 400 nm. In some embodiments, the refractive index of the polymer is between 1.3 and 1.7, depending on the content of the sulfur-nitrogen containing aromatic monomer of formula (IV) in the polymer composition.

[0219] The polymer composition of formula (I) is spin-coated on a silicon wafer, and the refractive index at a wavelength of 248 nm increases as the amount of monomer of formula (IV) in the siloxane-based polymer composition increases.

[0220] In addition, the polymer composition of formula (I) is spin-coated on a silicon wafer, and the molar absorptivity (k) increases as the mole percentage of the novel monomer (IV) in the polymer composition increases.

[0221] The polymer composition of formula (I) can be used to prepare high refractive index materials and can be used in the application of ARC (antireflection coating) in the photolithography process, whether before or after the photoresist, to prevent standing wave and thin film interference.

[0222] The following non-limiting examples illustrate embodiments of the present technology.

[0223] Synthesis of precursor 10-(3-(triethoxysilyl)propyl)-10H-phenothiazine (“PTTEOS”)

[0224] A silicon precursor containing an aromatic substituent with nitrogen and sulfur atoms (“PTTEOS”) was synthesized in a 500 mL round bottom flask. Phenothiazine (50.0 g, 0.250 mol), potassium carbonate (52.0 g, 0.370 mol), and acetone (200 mL) were added to a round bottom flask equipped with a magnetic stirrer and a reflux condenser. After the phenothiazine was completely dissolved, the reaction was refluxed and allowed to react for 30 minutes. Then, allyl bromide (48.6 g, 0.400 mol) was added and allowed to react for 24 hours. Thin layer chromatography (TLC) confirmed that the reaction was complete.

[0225] The reaction mixture was then cooled and filtered. The acetone and excess allyl bromide were then removed under reduced pressure. The resulting solution was diluted with THF (200 mL) and Karstedt's catalyst was added to the reaction mixture. The reaction mixture was refluxed and triethoxysilane (62.0 g) was added and reacted for 24 hours. The solvent and excess triethoxysilane were evaporated under reduced pressure. The resulting residue was distilled (155 °C, 0.01 mbar) and 65.0 g of product was collected and confirmed by gas chromatography mass spectrometry. Figure 4

[0226] Example 1

[0227] A homopolymer of the resulting precursor ("PTTEOS") was prepared in a 100 mL round bottom flask. The precursor (10.0 g, 0.024 mol), 0.01 M HC1 (2.0 g), and acetone (10.0 g) were added. The reaction mixture was refluxed and allowed to react for 4 hours. The reaction was then cooled to room temperature and PGMEA (50.0 g) was added. The acetone and hydrolysis products were removed under reduced pressure to give a formulation with a solids content of 35%. Finally, the resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) to give a Mw / Mn of 1556 / 1163. A 1% solution of the polymer in PGMEA was prepared and spin coated on a silicon wafer to measure the refractive index and molar extinction of the polymer at different lithography wavelengths (193 and 248 nm) as known to those skilled in the art.

[0228] Example 2

[0229] Following the procedure of Example 1, PTTEOS (10.0 g, 0.024 mol), glycidyl ether propyltrimethoxysilane (GPTMOS, 1.0 g, 0.004 mol), 0.01 M HC1 (2.0 g), and acetone (11.0 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) to give a Mw / Mn of 2518 / 2234.

[0230] Comparative Example 1

[0231] Following the procedure described in Example 1, GPTMOS (108.0 g, 0.450 mol), 9-phenanthryltriethoxysilane (EtoPhen, 612.0 g, 1.790 mol), 0.01 M HNO3 (244.0 g), acetone (540.0 g, 9.290 mol), and PGMEA (1200.0 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) to give a Mw / Mn of 1294 / 1703.

[0232] Example 3​

[0233] Following the procedure described in Example 1, PTTEOS (5.0 g, 0.024 mol), tetraethoxysilane (TEOS, 6.0 g, 0.029 mol), methyltriethoxysilane (MTEOS, 5.6 g, 0.031 mol), 0.01 M HC1 (6.7 g), and acetone (23.4 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1517 / 1074.

[0234] Example 4

[0235] Following the procedure of Example 1, PTTEOS (3.0 g, 0.007 mol), TEOS (62.03 g, 0.290 mol), MTEOS (57.0 g, 0.320 mol), EtoPhen (40.5 g, 0.110 mol), 0.01 M HC1 (68.7 g), and acetone (231.3 g) were added sequentially. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1591 / 930.

[0236] Comparative Example 2

[0237] Following the procedure of Example 1, EtoPhen (95.2 g, 0.279 mol), MTEOS (149.5 g, 0.838 mol), TEOS (155.2 g, 0.745 mol), 0.01 M HC1 (114.1 g), acetone (440.0 g), PGMEA (1100.0 g), PGEE (1000.0 g), and MTBE (500.0 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1323 / 960.

[0238] Example 5

[0239] Following the procedure of Example 1, MTEOS (12.6 g, 0.070 mol), TEOS (59.6 g, 0.280 mol), PTTEOS (10.0 g, 0.024 mol), 0.01 M HC1 (38.8 g), and acetone (120.5 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 2425 / 1284.

[0240] Example 6

[0241] Following the procedure of Example 1, MTEOS (17.7 g, 0.099 mol), TEOS (77.5 g, 0.370 mol), PTTEOS (10.0 g, 0.024 mol), 0.01 M HC1 (50.5 g), and acetone (155.7 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 2591 / 1377.

[0242] Example 7

[0243] Following the procedure of Example 1, MTEOS (32.4 g, 0.180 mol), TEOS (129.2 g, 0.620 mol), PTTEOS (10.0 g, 0.024 mol), 0.01 M HC1 (84.2 g), and acetone (255.8 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 5683 / 2414.

[0244] Example 8

[0245] Following the procedure of Example 1, PTTEOS (2.0 g, 0.005 mol), TEOS (77.5 g, 0.370 mol), MTEOS (16.4 g, 0.091 mol), phenyltrimethoxysilane (PhTMOS, 5.4 g, 0.027 mol), 0.01 M HC1 (50.5 g), and acetone (101.3 g) were added sequentially. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1109 / 1846.

[0246] Example 9

[0247] Following the procedure described in Example 1, MTEOS (82.7 g, 0.460 mol), PhTMOS (5.4 g, 0.027 mol), PTTEOS (10.0 g, 0.005 mol), 0.01 M HC1 (40.4 g), and acetone (130.6 g) were used. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1587 / 931.

[0248] Example 10 (PTTEOS as an additive)

[0249] An additive solution was prepared with PTTEOS and used to formulate a siloxane-based polymer composition for use as a 193 nm underlayer material.

[0250] Example 1 2.8 g PTTEOS (0.007 mol) and 1.62 g maleic acid (0.014 mol) were dissolved in 17.6 g propylene glycol methyl ether acetate (PGMEA) with stirring in a 50 °C water bath to give an additive solution having a solids content of 20%. The additive solution was filtered through a 0.45 μm PTFE filter. 0.3 g of the filtered additive solution was added to 100.0 g of a siloxane-based polymer formulation having a solids content of 1.94% to give a formulation having an additive content of 0.25% (relative to the solid polymer).

[0251] Comparative Example 3

[0252] Polymerization was carried out according to the procedure described in Example 1 using PhTMOS (27.7 g, 0.139 mol), MTEOS (81.7 g, 0.458 mol), TEOS (290.6 g, 1.395 mol), 0.01 M HC1 (132.8 g), acetone (400.0 g), PGMEA (1100.0 g), and PGEE (1000.0 g), respectively. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1306 / 1912.

[0253] Example 11

[0254] Polymerization was carried out according to the procedure of Example 1 using PTTEOS (5.0 g, 0.013 mol), TEOS (35.3 g, 0.169 mol), MTEOS (7.5 g, 0.041 mol), 0.01 M HC1 (23.0 g), and acetone (70.5 g). The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 2475 / 1436.

[0255] Example 12

[0256] Polymerization was carried out according to the procedure of Example 1 using PTTEOS (3.0 g, 0.008 mol), TEOS (62.0 g, 0.290 mol), MTEOS (57.0 g, 0.320 mol), PhTMOS (23.6 g, 0.110 mol), 0.01 M HC1 (68.7 g), and acetone (214.5 g), in that order. The resulting polymer solution was filtered through a 0.2 micron filter and characterized by gel permeation chromatography (GPC) with a Mw / Mn of 1639 / 1039.

[0257] Example 13

[0258] Following the method in Example 1, PTTEOS (2.0 g, 0.005 mol), TEOS (77.6 g, 0.370 mol), MTEOS (16.4 g, 0.091 mol), EtoPhen (9.3 g, 0.027 mol), 0.01 M HCl (50.5 g), and acetone (155.7 g) were added sequentially. The resulting polymer solution was filtered through a 0.2-micron filter and characterized by gel permeation chromatography (GPC), with a Mw / Mn ratio of 1415 / 693.

[0259] As described above, this novel aromatic butterfly-shaped compound containing sulfur and nitrogen atoms exhibits a high refractive index. Furthermore, this compound and its derivatives exhibit high absorbance in the ultraviolet region near wavelengths below 400 nm. The combination of high refractive index and high molar absorptivity makes compositions containing this novel aromatic butterfly-shaped compound highly useful in photolithography applications; even small amounts of this compound can be used to adjust the refractive index and absorbance at wavelengths commonly used in photolithography, such as 248 nm and 193 nm.

[0260] Example 14

[0261] The solution obtained in Example 7 was spin-coated onto a wafer to a thickness of 9 nm to form a functional coating. A chemically amplified photoresist was then coated onto it. The photoresist was exposed to light at 13.5 nm. After exposure and baking according to the photoresist manufacturer's instructions, the coating was developed. A dose-size image of the line and space patterns was obtained with a half-pitch of 32 nm. The dose required to obtain this dose-size image was 23% lower than that without the functional coating.

[0262] experiment

[0263] Gel permeation chromatography was used to measure the molecular weight of polystyrene using a polystyrene standard with a known molecular weight. The instrument used was a Waters HPLC system, including a Waters 1515 isocratic HPLC pump, a Waters 2414 differential refractive index detector, a Waters column heating module, a Waters 717plus autosampler, a Waters valve selector, a Waters switching valve, a Waters online degasser AF, and a Waters temperature control module II. The instrument was equipped with a tandem Styragel HR column (guard column, HR). 1 HR 3 HR 4 The flow rate of the THF eluent was 1.0 ml / min.

[0264] Thin film thickness was measured using a JAWoollam M2000D-ESM-200AXY spectroelastic ellipsometry.

[0265] "Refractive index" (RI) was measured using a refractometer at a wavelength of 633 nm. The RI can be calculated from a polymer film sample with a thickness of 400 nm by methods such as interferometry, deviation, or the Brewster angle method.

[0266] Thin film contact angles can be measured using a KSV Instruments CAM100. The tool has an error of + / - 0.1 degrees and is used to measure the angle that a water droplet makes at the intersection boundary of a liquid (deionized water), gas (air), and solid (thin film). A deionized water droplet is dispensed onto a thin film (typically coated on a silicon wafer) using a syringe with a microscrew to determine the static contact angle. In addition, the built-in software automatically calculates the contact angle using a curve fit of the Young-Laplace equation from the static images taken by the camera. The resulting static contact angle is the average of the left and right angle measurements. Three measurements are taken for each sample and the average is reported.

[0267] Results

[0268] Polysiloxane compositions containing different proportions of the newly designed monomers can effectively adjust the refractive index (n) and extinction coefficient (k) at different wavelengths, as shown in Tables 1 and 2. The refractive index of the composition at visible wavelengths increases with increasing PTTEOS content.

[0269] Table 1

[0270]

[0271]

[0272] Table 2

[0273]

[0274] It can be seen that the composition described in Example 3 has a refractive index (n) of 1.54 at a wavelength of 248 nm, which is higher than the composition in Comparative Example 2 with n of 1.52, indicating its potential application in 248 nm or KrF photolithography technology.

[0275] In addition, after adding less than 1% of the newly designed monomers in the polymer composition shown in Table 2, Example 8 can adjust the refractive index and extinction coefficient (k) at a wavelength of 193 nm deep ultraviolet photolithography to 1.54 and 0.19, while the n and k in Comparative Example 3 are 1.67 and 0.17, respectively (as shown in Table 2). These adjustable properties indicate its potential application in deep ultraviolet photolithography, especially in 193 nm photolithography applications.

[0276] When the newly designed sulfur and nitrogen containing compounds were added as external additives to the polymer composition of Comparative Example 3, the water contact angle (CA) increased to values greater than 60°, resulting in more hydrophobic silicone compositions as shown in Table 3.

[0277] Table 3.

[0278]

[0279] More importantly, by hydrolyzing as little as 1% of the newly designed monomer into Comparative Example 3, the water contact angle of Example 8 was significantly increased to greater than 60° compared to the parent polymer in Table 3 or Comparative Example 3. Thus, the designed monomer can act as an effective surface modifier to achieve the desired surface properties.

[0280] From the foregoing description and the exemplary experimental examples of the present application, the present application can be described with reference to the following examples:

[0281] 1. A poly(organosiloxane) obtained by polymerization of a first silicon compound of general formula II

[0282] (R 7 -R 3 ) p -SiR 8 q -R 4 o (II)

[0283] wherein

[0284] R 3 represents a bridging hydrocarbyl group, which can be independently selected from an optionally functionalized linear, branched, or cyclic, divalent, saturated or unsaturated hydrocarbyl group, such as an optionally functionalized linear, branched, or cyclic alkylene, alkenylene, or alkynylene group; and an optionally functionalized divalent aromatic or polyaromatic group.

[0285] R 4 represents hydrogen, hydroxyl, halogen, alkoxy, acyloxy, or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched, or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0286] p and q are integers independently selected from the range of 1 to 3,

[0287] o is an integer of 1 or 2, and

[0288] the total value of p + q + o is not more than 4,

[0289] R 7 represents an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0290] R 8 represents an alkoxy, acyloxy, or halogen group.

[0291] 2. The poly(organosiloxane) according to embodiment 1, obtained by hydrolysis of a first silicon compound according to general formula II with one or more second silicon compounds according to general formula III.

[0292] R 10 t -SiR 9 r -R 11 s (III)

[0293] wherein,

[0294] R 9 represents an alkoxy, acyloxy, or halogen group,

[0295] t is an integer from 0 to 3,

[0296] r is an integer from 1 to 4,

[0297] s is an integer from 0 to 3,

[0298] wherein the total value of t+r+s must not exceed 4.

[0299] R 10 and R 11 are independently selected from the group consisting of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, organic groups having one or more epoxy groups, mercapto, alkoxyaryl, acyloxyaryl, isocyanurate, hydroxyl, cyclic amino, or cyano groups, and combinations thereof; or

[0300] R 10 and R 11 are independently selected from the group consisting of alkoxy, acyloxy, and halogen groups;

[0301] 3. The poly(organosiloxane) according to embodiment 1 or 2, comprising at least partially crosslinked organosiloxane polymers having a molecular weight (Mw) measured against polystyrene standards of about 500 to 100,000 g / mol, in particular about 1,000 to 50,000 g / mol.

[0302] 4. The poly(organosiloxane) according to any of the preceding embodiments, having general formula I

[0303]

[0304] wherein

[0305] R 1 a and R2 b represents halogen or a hydrocarbyl group, which can be independently selected from optionally functionalized linear, branched or cyclic alkyl groups, optionally functionalized aromatic or polyaromatic groups;

[0306] R 3 represents a bridging hydrocarbyl group, which can be independently selected from optionally functionalized linear, branched or cyclic divalent saturated or unsaturated hydrocarbyl groups, such as optionally functionalized linear, branched or cyclic alkylene, alkenylene or alkynylene groups; and optionally functionalized divalent aromatic or polyaromatic groups;

[0307] R 4 represents hydrogen, hydroxyl, halogen, alkoxy or acyloxy or a hydrocarbyl group, which can be independently selected from optionally functionalized linear, branched or cyclic alkyl groups, optionally functionalized aromatic or polyaromatic groups, or optionally substituted polyaromatic hydrocarbyl groups containing nitrogen and sulfur atoms;

[0308] R 5 and R 6 represents hydrogen, hydroxyl, halogen, alkoxy, acyloxy or a hydrocarbyl group, which can be independently selected from optionally functionalized linear, branched or cyclic alkyl groups, and optionally functionalized aromatic or polyaromatic groups;

[0309] a and b are independently selected from integers in the range of 0 to 4;

[0310] m and n are independently selected from integers in the range of 1 to 1000.

[0311] 5. The poly(organosiloxane) according to any of the preceding embodiments, wherein R 7 represents an optionally substituted polyaromatic hydrocarbyl radical having nitrogen and sulfur atoms, which exhibits a butterfly-shaped aromatic structure with a dihedral angle between the two benzene rings of less than 165° and a C-S-C angle of less than 110°.

[0312] 6. A poly(organosiloxane) polymerized from a first silicon compound represented by general formula II

[0313] (R 7 -R 3 ) p -SiR 8 q -R 4 o (II)

[0314] wherein

[0315] R 3representing a bridged hydrocarbyl group, which can be independently selected from an optionally functionalized straight-chain, branched, or cyclic, divalent, saturated or unsaturated hydrocarbyl group, such as an optionally functionalized straight-chain, branched, or cyclic alkylene, alkenylene, or alkynylene group; and an optionally functionalized divalent aromatic or polyaromatic group;

[0316] R 4 representing hydrogen, hydroxyl, halogen, alkoxy, or acyloxy, or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized straight-chain, branched, or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms;

[0317] p and q are each an integer in the range of 1 to 3;

[0318] o is an integer of 1 or 2, and

[0319] the sum of p + q + o is not more than 4;

[0320] R 7 representing an optionally substituted polyaromatic hydrocarbyl group, which contains both nitrogen and sulfur atoms, and exhibits a butterfly-shaped aromatic structure, with a dihedral angle between the two benzene rings of less than 165°, and a C-S-C angle of less than 110°;

[0321] R 8 representing an alkoxy, acyloxy, or halogen group.

[0322] 7. The poly(organosiloxane) according to any of the preceding embodiments, wherein the first silicon compound is selected from the group of compounds having the general formula

[0323]

[0324]

[0325] wherein R a 1 , R b 2 and R 3 have the same meaning as in formula I above.

[0326] 8. The poly(organosiloxane) according to any of the preceding embodiments, wherein the second silicon compound is selected from the group consisting of tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, methyltribenzoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, glycidyloxy-methyltrimethoxysilane, glycidyloxy-methyltriethoxysilane, α-glycidyloxy-ethyltrimethoxysilane, α-glycidyloxy-ethyltriethoxysilane, β-glycidyloxy-ethyltrimethoxysilane, β-glycidyloxy-ethyltriethoxysilane, α-glycidyloxy-propyltrimethoxysilane, α-glycidyloxy-propyltriethoxysilane, β-glycidyloxy-propyltrimethoxysilane, β-glycidyloxy-propyltriethoxysilane, γ-glycidyloxy-propyltrimethoxysilane, γ-glycidyloxy-propyltriethoxysilane, γ-glycidyloxy-propyltripropoxysilane, γ-glycidyloxy-propyltributoxysilane, γ-glycidyloxy-propyltriphenoxysilane, α-glycidyloxy-butyltrimethoxysilane, α-glycidyloxy-butyltriethoxysilane, β-glycidyloxy-butyltriethoxysilane, γ-glycidyloxy-butyltrimethoxysilane, γ-glycidyloxy-butyltriethoxysilane, δ-glycidyloxy-butyltrimethoxysilane, δ-glycidyloxy-butyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltripropoxysilane, δ-(3,4-epoxycyclohexyl)butyltributoxysilane, δ-(3,4-epoxycyclohexyl)butyltriphenoxysilane, and mixtures thereof.4-epoxycyclohexyl)butyltriethoxysilane, glycidyloxy-methyldimethoxysilane, glycidyloxy-methyldiethoxysilane, a-glycidyloxy-ethyldimethoxysilane, a-glycidyloxy-ethyldiethoxysilane, β-glycidyloxy-ethyldimethoxysilane, β-glycidyloxy-ethyldimethoxysilane, a-glycidyloxy-propyl-dimethoxysilane, a-glycidyloxy-propyl-diethoxysilane, β-glycidyloxy-propyl-dimethoxysilane, β-glycidyloxy-propyl-dimethoxysilane, γ-glycidyloxy-propyl-dimethoxysilane, γ-glycidyloxy-propyl-diethoxysilane, γ-glycidyloxy-propyl-diethoxysilane, γ-glycidyloxy-propyl-dipropoxysilane, γ-glycidyloxy-propyl-dibutoxysilane, γ-glycidyloxy-propyl-diphenoxysilane, γ-glycidyloxy-propyl-ethyldimethoxysilane, γ-glycidyloxy-propyl-ethyldiethoxysilane, γ-glycidyloxy-propyl-vinyldimethoxysilane, γ-glycidyloxy-propyl-vinyldiethoxysilane, phenylsulfonamidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methylvinyl-dimethoxysilane, methylvinyl-diethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl-methyldimethoxysilane, γ-methacryloyloxypropyl-methyldiethoxysilane, (methacryloyloxymethyl)methyldiethoxysilane, (methacryloyloxymethyl)methyldimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltrichlorosilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltriisopropoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyl-methyldimethoxysilane, γ-chloropropyl-methyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 4-acetyloxyphenethyltrimethoxysilane, 4-acetyloxyphenethyltriethoxysilane, 4-(acetyloxyphenethyl)methyldichlorosilane, 4-(acetyloxyphenethyl)methyldimethoxysilane, 4-(acetyloxyphenethyl)methyldiethoxysilane, triethoxysilanylpropylcarbamic acid ester, triethoxysilanylpropylmaleamic acid, N-(3-triethoxysilylpropyl)-4-hydroxybutyramide, N-(3-triethoxysilylpropyl)glucamid, (3-triethoxysilylpropyl)succinic anhydride, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, 3-hydroxy-3,3-bis(trifluoromethyl)propyltriethoxysilane, 4-(methoxymethoxy)trimethoxysilylbenzene, 6-(methoxymethoxy)-2-(trimethoxysilyl)naphthalene, and combinations thereof.

[0327] 9. The poly(organosiloxane) according to any of the preceding embodiments, wherein the residue R of formula (II) 7 derived from the group of compounds:

[0328]

[0329] 10. A composition comprising a liquid phase poly(organosiloxane) resin comprising the poly(organosiloxane) according to any of the preceding embodiments in a liquid phase formed by at least one organic solvent for poly(organosiloxane) resins, optionally mixed with water.

[0330] 11. The composition according to embodiment 10, wherein the liquid phase comprises an organic liquid and about 0.001 M to about 1 M of the poly(organosiloxane), and the polymer solution has a viscosity of about 0.5 centipoise (cP) to about 150 cP, the organic liquid preferably having a flash point of at least 10 °C and a vapor pressure of less than about 10 kPa at 20 °C.

[0331] 12. A coating / film obtained according to embodiments 10 or 11 by casting / coating a composition onto a substrate, the composition being formulated for use in a process of casting a substrate.

[0332] 13. The composition according to any of embodiments 10 to 12, obtained after a thermal curing step at a temperature higher than 100 °C.

[0333] 14. The composition according to any of embodiments 10 to 13, exhibiting a silicon content higher than 20 %, more preferably higher than 25 %, most preferably higher than 30 %, calculated on the dry weight of the composition.

[0334] 15. The composition according to any of embodiments 10 to 14, wherein the liquid phase comprises a solvent selected from the group consisting of PGMEA, PGEE, THF and mixtures thereof.

[0335] 16. The composition according to any of embodiments 10 to 15, wherein the solid content of the polymer in the liquid phase is comprised between 1 and 4 % by weight.

[0336] 17. A polymeric film comprising the poly(organosiloxane) according to any of embodiments 1 to 9.

[0337] 18. The polymeric film according to embodiment 17, comprising a film obtained by depositing the composition according to any of embodiments 10 to 16 on a substrate.

[0338] 19. The polymeric film according to embodiment 18, forming an antireflective coating before or after a photoresist layer in a lithographic process to reduce standing waves and film interference.

[0339] 20. The polymer film according to any one of embodiments 17 to 19, obtained by spin coating a composition according to any one of embodiments 10 to 16 on a substrate, in particular a silicon substrate.

[0340] 21. A photoresist underlayer coating composition for use in photolithography, comprising:

[0341] a silane selected from at least one of hydrolysable organosilanes, hydrolysis products thereof, and hydrolytic condensation products thereof, wherein

[0342] the silane comprises only silane compounds of formula (I), or comprises a copolymer with one or more silane compounds of formula (II) and / or (III) as described in any one of embodiments 1 to 9.

[0343] 22. The photoresist underlayer film forming composition of embodiment 21, obtained by coating a photoresist underlayer film composition according to any one of embodiments 10 to 16 on a semiconductor substrate and baking.

[0344] 23. A method of manufacturing a semiconductor device, the method comprising:

[0345] coating a photoresist underlayer film forming composition according to any one of embodiments 10 to 16 on a semiconductor substrate and baking the composition to form a photoresist underlayer film;

[0346] coating a photoresist forming composition on the photoresist underlayer film to form a photoresist film;

[0347] exposing the photoresist film to light or electron beam radiation, for example at 13.5 nm, 193 nm, 248 nm, 365 nm;

[0348] after exposure, developing the photoresist film to obtain a patterned photoresist film;

[0349] etching the photoresist underlayer film according to the pattern of the patterned photoresist film; and

[0350] processing the semiconductor substrate according to the pattern of the photoresist film and the photoresist underlayer film.

[0351] 24. A method for producing a semiconductor device, the method comprising:

[0352] forming an organic underlayer film on a semiconductor substrate;

[0353] coating a photoresist underlayer film forming composition according to any one of embodiments 10 to 16 on the organic underlayer film and baking the composition to form a photoresist underlayer film;

[0354] applying a composition for photoresist onto the photoresist underlayer film to form a photoresist film;

[0355] exposing the photoresist film to light or electron beam radiation, for example, 13.5 nm, 193 nm, 248 nm, or 365 nm;

[0356] after exposure, developing the photoresist film to obtain a patterned photoresist film;

[0357] etching the photoresist underlayer film according to the pattern of the patterned photoresist film;

[0358] etching the organic underlayer film according to the pattern of the patterned photoresist underlayer film; and

[0359] processing the semiconductor substrate according to the pattern of the patterned organic underlayer film.

[0360] 25. A method for producing an optical or semiconductor device, the method comprising:

[0361] applying a spin-on carbon (SOC) having various thermal stabilities, for example, a high-temperature (350-400 °C) SOC, or an a-carbon layer obtained by chemical vapor deposition (CVD), on a substrate.

[0362] applying a composition of a high-silicon content layer, a silicon oxynitride layer, or a layer of various metal oxides.

[0363] applying a functional coating layer comprising a poly(organosiloxane) according to any one of embodiments 1 to 10.

[0364] applying a photoresist composition onto a photoresist underlayer functional layer to obtain a photoresist film.

[0365] exposing the photoresist film to light or electron beam radiation, for example, 13.5 nm, 193 nm, 248 nm, or 365 nm.

[0366] developing the photoresist film after exposure to obtain a patterned photoresist film, which can have a dose reduction of 15% to 30% compared to when there is no functional layer;

[0367] etching the photoresist underlayer film according to the pattern of the patterned photoresist film; and

[0368] processing the substrate according to the pattern of the photoresist film and the photoresist underlayer film.

[0369] 26. Use of a poly(organosiloxane) according to any one of embodiments 1 to 9 or a composition according to any one of embodiments 10 to 16 as an additive, in particular for adjusting the polymer film thickness, refractive index (n), molar absorptivity (k) and contact angle (CA) of a siloxane-based photoresist polymer.

[0370] 27. Use of a poly(organosiloxane) according to any one of embodiments 1 to 9 or a composition according to any one of embodiments 10 to 16 as an additive in a siloxane polymer composition to obtain a thin film having a thickness of 30 to 60 nm, in particular 35 nm, and preferably exhibiting a substantially constant molecular weight and contact angle over a period of 42 days at room temperature.

[0371] 28. A method for producing an optical element or an optically active device:

[0372] coating a composition for forming a photoresist primer film as disclosed in any one of embodiments 10 to 16 onto a substrate and baking the composition to form a photoresist primer film;

[0373] coating a composition for forming a photoresist onto the photoresist primer film to form a photoresist film;

[0374] exposing the photoresist film to light or electron beam radiation, for example at 13.5 nm, 193 nm, 248 nm, 365 nm;

[0375] developing the photoresist film after exposure to obtain a patterned photoresist film;

[0376] etching the photoresist primer film according to the pattern of the patterned photoresist film; and

[0377] processing the substrate according to the pattern of the photoresist film and the photoresist primer film.

[0378] 29. The method according to embodiment 28, wherein the substrate is TiO2, Si, GaAs or other substrates for diffractive or super-optical elements.

[0379] 30. A method for patterning a semiconductor substrate, the method comprising:

[0380] forming an organic primer film on a semiconductor substrate;

[0381] forming an inorganic oxide-containing intermediate layer on the organic primer film;

[0382] coating a photoresist primer film forming composition according to any one of embodiments 10 to 16 on the inorganic oxide-containing intermediate layer film and baking the composition to form a photoresist primer film;

[0383] a composition for a photoresist is coated on the photoresist underlayer film to form a photoresist film;

[0384] the photoresist film is exposed to light, for example, 13.5 nm, 193 nm, 248 nm, 365 nm, or electron beam radiation;

[0385] after exposure, the photoresist film is developed to obtain a patterned photoresist film;

[0386] the photoresist underlayer film is etched according to the pattern of the patterned photoresist film;

[0387] the inorganic oxide-containing intermediate layer film is etched according to the pattern of the patterned photoresist film;

[0388] the organic underlayer film is etched according to the pattern of the patterned photoresist underlayer film; and

[0389] the semiconductor substrate is processed according to the pattern of the patterned organic underlayer film.

[0390] Abbreviations:

[0391] ARC antireflective coating

[0392] BARC bottom antireflective coating

[0393] CA contact angle

[0394] CMOS complementary metal-oxide semiconductor

[0395] SOC silicon on carbon

[0396] GC-MS gas chromatography mass spectrometry

[0397] GPC gel permeation chromatography

[0398] PGMEA propylene glycol monomethyl ether acetate

[0399] PGEE propylene glycol n-ethyl ether

[0400] THF tetrahydrofuran

[0401] EtoPhen phenyltriethoxysilane

[0402] GPTMOS glycidoxypropyltrimethoxysilane

[0403] MTEOS methoxytriethoxysilane

[0404] PhTMOS phenyltrimethoxysilane

[0405] TMOS tetramethoxysilane

[0406] TEOS tetraethoxysilane

[0407] PTTEOS 10-(3-(triethoxysilyl)propyl)-10H-phenothiazine

[0408] CITATION

[0409] US 2005 / 0042538 Al

[0410] US 2007 / 0148586 Al

[0411] US 2010 / 167203 Al.

Claims

1. A photoresist underlayer coating composition for use in photolithography, comprising: - a silane selected from at least one of hydrolysable organosilanes, hydrolysis products thereof, and hydrolytic condensation products thereof, wherein - the silane comprises only silane compounds represented by Formula (I) wherein R 1 a and R 2 b represents halogen or a hydrocarbyl group, which can be independently selected from optionally functionalized linear, branched or cyclic alkyl groups, optionally functionalized aromatic or polyaromatic groups; R 3 represents a bridging hydrocarbon group, which can be independently selected from optionally functionalized straight-chain, branched or cyclic divalent saturated or unsaturated hydrocarbon groups, such as optionally functionalized straight-chain, branched or cyclic alkylene groups, alkylene or alkynylene; and optionally functionalized divalent aromatic or polyaromatic groups; R 4 represents hydrogen, hydroxyl, halogen, alkoxy or acyloxy or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms; R 5 and R 6 represents hydrogen, hydroxyl, halogen, alkoxy, acyloxy, or a hydrocarbyl group, where the hydrocarbyl group can be independently selected from linear, branched, or cyclic alkyl groups, and aromatic or polyaromatic groups, which can be optionally functionalized; a and b are independently selected from integers in the range of 0 to 4; m and n are independently selected from integers in the range of 1 to 1000; - or, the silane is as a copolymer with one or more silane compounds of formula (II) and / or (III), wherein, the silane compound of Formula II has the following chemical formula; (R 7 -R 3 ) p -SiR 8 q -R 4 o (II) wherein, R 3 represents a bridging hydrocarbyl group, which can be independently selected from optionally functionalized straight-chain, branched, or cyclic, divalent, saturated or unsaturated hydrocarbyl groups, such as optionally functionalized straight-chain, branched, or cyclic alkylene, alkenylene, or alkynylene groups; and optionally functionalized divalent aromatic or polyaromatic groups; R 4 represents hydrogen, hydroxyl, halogen, alkoxy or acyloxy or a hydrocarbyl group, wherein the hydrocarbyl group can be independently selected from an optionally functionalized linear, branched or cyclic alkyl group, an optionally functionalized aromatic or polyaromatic group, or an optionally substituted polyaromatic hydrocarbyl group containing nitrogen and sulfur atoms; p and q are each an integer in the range of 1 to 3, o is an integer of 1 or 2, and the sum of p + q + o is no more than 4, R 7 represents an optionally substituted polyaromatic hydrocarbon group containing nitrogen and sulfur atoms, R 8 represents an alkoxy, acyloxy or halogen group; and the silane compound of Formula III has the following chemical formula: R 10 t -SiR 9 r -R 11 s (III) wherein R 9 represents an alkoxy, acyloxy or halogen group, t is an integer of 0 to 3, r is an integer of 1 to 4, s is an integer of 0 to 3, wherein the total value of t + r + s is no more than 4; R 10 and R 11 are independently selected from alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, organic groups having one or more epoxy groups, mercapto, alkoxyaryl, acyloxyaryl, isocyanurate, hydroxyl, cyclic amino, or cyano groups, and combinations thereof; or R 10 and R 11 are independently selected from alkoxy, acyloxy and halogen groups.

2. The photoresist underlayer coating composition of claim 1, including at least partially crosslinked organosiloxane polymers having a molecular weight (Mw) measured against polystyrene standards of about 500 to 100,000 g / mol, in particular about 1,000 to 50,000 g / mol.

3. The photoresist primer coating composition according to claim 1 or 2, wherein, R 7 represents an optionally substituted polyaromatic group having nitrogen and sulfur atoms, exhibiting a butterfly-shaped aromatic structure with a dihedral angle between the two benzene rings of less than 165° and a C-S-C bond angle of less than 110°.

4. The photoresist primer coating composition according to any one of the preceding claims, wherein, the compounds of Formula II are selected from the group of compounds having the following general formula wherein R a 1 , R b 2 and R 3 have the same meaning as above in formula I.

5. The photoresist primer coating composition according to any one of the preceding claims, wherein, The compound of formula III is selected from the group consisting of tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n- propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, methyltribenzoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, glycidoxy-methyltrimethoxysilane, glycidoxy-methyltriethoxysilane, α-glycidoxy-ethyltrimethoxysilane, α-glycidoxy-ethyltriethoxysilane, β-glycidoxy-ethyltrimethoxysilane, β-glycidoxy-ethyltriethoxysilane, α-glycidoxy-propyltrimethoxysilane, α-glycidoxy-propyltriethoxysilane, β-glycidoxy-propyltrimethoxysilane, β-glycidoxy-propyltriethoxysilane, γ-glycidoxy-propyltrimethoxysilane, γ-glycidoxy-propyltriethoxysilane, γ-glycidoxy-propyltripropoxysilane, γ-glycidoxy-propyltributoxysilane, γ-glycidoxy-propyltriphenoxysilane, α-glycidoxy-butyltrimethoxysilane, α-glycidoxy-butyltriethoxysilane, β-glycidoxy-butyltriethoxysilane, γ-glycidoxy-butyltrimethoxysilane, γ-glycidoxy-butyltriethoxysilane, δ-glycidoxy-butyltrimethoxysilane, δ-glycidoxy-butyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltripropoxysilane, δ-(3,4-epoxycyclohexyl)butyltributoxysilane, δ-(3,4-epoxycyclohexyl)butyltriphenoxysilane, δ-(3,4-epoxycyclohexyl)butyltriacetoxysilane, δ-(3,4-epoxycyclohexyl)butyltrichlorosilane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-propoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-butoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-phenoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-benzyloxyphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-methoxylphenyl)silane, δ-(3,4-epoxycyclohexyl)butyltris(2,6-dimethyl-4-ethoxylphenyl)silane4-epoxycyclohexyl)butyltriethoxysilane, glycidoxy-methyldimethoxysilane, glycidoxy-methyldiethoxysilane, alpha-glycidoxy-ethyldimethoxysilane, alpha-glycidoxy-ethyldiethoxysilane, beta-glycidoxy-ethyldimethoxysilane, beta-glycidoxy-ethyldiethoxysilane, alpha-glycidoxy-propyldimethoxysilane, alpha-glycidoxy-propyldiethoxysilane, beta-glycidoxy-propyldimethoxysilane, beta-glycidoxy-propyldiethoxysilane, gamma-glycidoxy-propyldimethoxysilane, gamma-glycidoxy-propyldiethoxysilane, gamma-glycidoxy-propyldipropoxysilane, gamma-glycidoxy-propyldibutoxysilane, gamma-glycidoxy-propyldiphenoxysilane, gamma-glycidoxy-propylethyldimethoxysilane, gamma-glycidoxy-propylethyldiethoxysilane, gamma-glycidoxy-propylvinyl-dimethoxysilane, gamma-glycidoxy-propylvinyl-diethoxysilane, phenylsulfonamidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methylvinyl-dimethoxysilane, methylvinyl-diethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyl-methyldimethoxysilane, gamma-methacryloxypropyl-methyldiethoxysilane, (methacryloyloxymethyl)methyldiethoxysilane, (methacryloyloxymethyl)methyldimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltrichlorosilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltriisopropoxysilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropyltriethoxysilane, gamma-chloropropyltriacetoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, gamma-chloropropyl-methyldimethoxysilane, gamma-chloropropyl-methyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 4-acetoxyphenethyltrimethoxysilane, 4-acetoxyphenethyltriethoxysilane, 4-(acetoxyphenethyl)methyldichlorosilane, 4-(acetoxyphenethyl)methyldimethoxysilane, 4-(acetoxyphenethyl)methyldiethoxysilane, triethoxysilanylpropylcarbamic acid ester, triethoxysilanylpropylmaleamic acid, N-(3-triethoxysilylpropyl)-4-hydroxybutyramide, N-(3-triethoxysilylpropyl)glucamide, (3-triethoxysilylpropyl)succinic anhydride, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, 3-hydroxy-3,3-bis(trifluoromethyl)propyltriethoxysilane, 4-(methoxymethoxy)trimethoxysilylbenzene, 6-(methoxymethoxy)-2-(trimethoxysilyl)naphthalene, and combinations thereof.

6. The photoresist primer coating composition according to any one of the preceding claims, wherein, the residue R of formula (II) 7 a compound derived from the group consisting of 7. The photoresist underlayer coating composition according to any of the preceding claims, obtained after a thermal curing step at a temperature higher than 100°C.

8. The photoresist underlayer coating composition according to any of the preceding claims, exhibiting a silicon content higher than 20%, more preferably higher than 25%, most preferably higher than 30%, calculated on the dry weight of the composition.

9. The photoresist underlayer coating composition according to any of the preceding claims, obtained by applying to a semiconductor substrate a liquid phase of a photoresist underlayer coating composition comprising at least one organic solvent, optionally mixed with water, and baking the composition.

10. The photoresist primer coating composition of claim 9, wherein, The liquid phase includes an organic liquid and about 0.001 M to about 1 M of a silane polymer, the polymer solution having a viscosity of about 0.5 centipoise (cP) to about 150 cP, the organic liquid having a flash point of preferably at least 10°C, and a vapor pressure at 20°C of less than about 10 kPa.

11. The photoresist primer coating composition according to claim 9 or 10, wherein, The liquid phase includes a solvent selected from PGMEA, PGEE, THF, and mixtures thereof.

12. The photoresist primer coating composition according to any one of claims 9 to 11, wherein, The silane polymer in the liquid phase has a solids content of 1 to 4 wt.%.

13. A method of manufacturing a semiconductor device, the method comprising: applying to a semiconductor substrate a photoresist underlayer film forming composition according to any of claims 1 to 12 and baking the composition to form a photoresist underlayer film; applying to the photoresist underlayer film a composition for forming a photoresist to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example at 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; and processing the semiconductor substrate according to the pattern of the photoresist film and the photoresist underlayer film. ​ 14. A method of manufacturing a semiconductor device, the method comprising: forming an organic underlayer film on a semiconductor substrate; coating an underlayer film forming composition according to any one of claims 1 to 12 onto the organic underlayer film and baking the composition to form a photoresist underlayer film; coating a composition for photoresist onto the photoresist underlayer film to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; etching the organic underlayer film according to the pattern of the patterned photoresist underlayer film; and processing the semiconductor substrate according to the pattern of the patterned organic underlayer film.

15. A method for producing an optical or semiconductor device, the method comprising: coating a spin-on carbon (SOC) with various thermal stabilities, for example, high temperature (350-400 °C) SOC, or an a-carbon layer obtained by chemical vapor deposition (CVD), on a substrate; coating a composition of a high silicon content layer or silicon oxynitride or various metal oxide layers; coating a functional coating layer comprising a composition according to any one of claims 1 to 12; coating a composition for photoresist onto the photoresist underlayer functional layer to obtain a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, 13.5 nm, 193 nm, 248 nm, or 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film, which can be reduced by 15% to 30% in dosage compared to when there is no functional layer; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; and processing the substrate according to the patterns of the photoresist film and the photoresist underlayer film.

16. Use of the composition according to any one of claims 1 to 12 as an additive, in particular for adjusting the polymer film thickness, refractive index (n), molar absorptivity (k), and contact angle (CA) of a siloxane-based photoresist polymer.

17. Use of the composition according to any one of claims 1 to 12 as an additive in a siloxane polymer composition to obtain a thin film with a thickness of 30 to 60 nm, in particular 35 nm, and preferably exhibiting a substantially constant molecular weight and contact angle over a period of 42 days at room temperature.

18. A method for producing an optical element or an optically active device: coating an underlayer film forming composition according to any one of claims 1 to 12 onto a substrate and baking the composition to form a photoresist underlayer film; coating a composition for photoresist onto the photoresist underlayer film to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; and ​ The substrate is processed according to the pattern of the photoresist film and the photoresist underlayer film.

19. The method of claim 18, wherein the substrate is Ti02, Si, GaAs or other substrates used for diffractive or super optical elements.

20. A method for patterning a semiconductor substrate, the method comprising: forming an organic underlayer film on a semiconductor substrate; forming an inorganic oxide-containing intermediate layer on the organic underlayer film; applying a photoresist underlayer film-forming composition according to any one of claims 1 to 12 on the inorganic oxide-containing intermediate layer film, and baking the composition to form a photoresist underlayer film; applying a composition for photoresist on the photoresist underlayer film to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, at 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; etching the inorganic oxide-containing intermediate layer film according to the pattern of the patterned photoresist film; etching the organic underlayer film according to the pattern of the patterned photoresist underlayer film; and processing the semiconductor substrate according to the pattern of the patterned organic underlayer film.

21. A method for patterning a semiconductor substrate, the method comprising: forming an inorganic oxide-containing intermediate layer on a semiconductor substrate; applying a photoresist underlayer film-forming composition according to any one of claims 1 to 12 on the inorganic oxide-containing intermediate layer film, and baking the composition to form a photoresist underlayer film; applying a composition for photoresist on the photoresist underlayer film to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, at 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the inorganic oxide-containing intermediate layer film according to the pattern of the patterned photoresist film; processing the semiconductor substrate according to the pattern of the patterned photoresist film.

22. A method for patterning a semiconductor substrate, the method comprising: forming an inorganic oxide-containing intermediate layer on a semiconductor substrate; applying a photoresist underlayer film-forming composition according to any one of claims 1 to 12 on the inorganic oxide-containing intermediate layer film, and baking the composition to form a photoresist underlayer film; applying a composition for photoresist on the photoresist underlayer film to form a photoresist film; exposing the photoresist film to light or electron beam radiation, for example, at 13.5 nm, 193 nm, 248 nm, 365 nm; after exposure, developing the photoresist film to obtain a patterned photoresist film; etching the photoresist underlayer film according to the pattern of the patterned photoresist film; processing the semiconductor substrate according to the pattern of the patterned photoresist film.

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