High dielectric breakdown voltage dielectric polymer film, method for producing the same, and use thereof

Abstract

According to one aspect of the present invention, a dielectric polymer film comprising a gap-filling material-forming composition is provided, as well as the use of said dielectric polymer film in semiconductor devices, optical elements, and optically active devices. The present invention also relates to a method for producing a gap-filling material-forming composition, and a method for producing a dielectric polymer film comprising said composition.

Description

[Technical Field]

[0001] This invention relates to a polymer composition capable of forming a gap-fill material used in the manufacture of dielectric polymer films. The invention also relates to a dielectric polymer film containing the polymer composition, and to the use of the dielectric polymer film in semiconductor devices, optical elements, and optically active devices. Furthermore, the invention relates to a method for manufacturing a gap-fill material-forming composition and a method for manufacturing a dielectric polymer film containing the composition. [Background technology]

[0002] Integrated circuits built on semiconductor substrates contain millions of transistors and other devices that communicate electrically with each other and with external packaging materials via multiple layers of vertical and horizontal wiring embedded in dielectric materials. In metallization structures, "vias" constitute vertical wiring, and "interconnects" form horizontal wiring. Forming a metallization structure may involve sequentially depositing and patterning multiple layers of dielectric and metal to achieve electrical connections between transistors and with external packaging materials. Patterning a given layer is often carried out by a multi-step process including layer deposition on the substrate, photoresist spinning, photoresist exposure, photoresist development, layer etching, and photoresist removal. Alternatively, the metal may be patterned by first etching a pattern into the dielectric material layer, filling that pattern with metal, and then chemically / mechanically polishing the metal so that it is embedded only in the apertures of the dielectric.

[0003] Aluminum has long been used as an interconnect material due to its high conductivity, good adhesion to SiO2, known processing methods (sputtering and etching), and low cost. Initially, aluminum alloys were also developed over many years to improve melting point, diffusivity, electromigration, and other properties compared to pure aluminum. Traditionally, tungsten has been used as a conductive via plug material spanning continuous layers of aluminum. With the increasing speed of microprocessors and the performance of electronic devices, circuit density and operating speed have become increasingly high, resulting in a demand for the use of more conductive metals and improved dielectrics with lower dielectric constants (preferably less than 3.0) than silicon dioxide. Following aluminum metallization, the industry moved to the copper damascene process, where highly conductive copper (or copper alloys) is used for the conductor wires, and low-k (low dielectric constant) dielectrics that can be used as insulating materials surrounding the conductor wires are formed by spin-on or CVD processes. To avoid etching problems, copper is deposited along with a barrier metal onto a concave dielectric structure consisting of interconnects and via openings using a blanket deposit method, which is then polished using a process known as "dual damascene." The bottom of the via openings is typically above the interconnect from the previous metal layer, or in some cases above the contact layer to the substrate.

[0004] The copper "dual damascene" process has been successfully used in industry for 20 years. The critical dimensions of copper interconnects in future devices are predicted to reach 10-20 nm or less. Consequently, the dielectric materials between interconnects will also exhibit similar critical dimensions. In the copper "dual damascene" process, the high mobility of copper ions, which migrate to the dielectric layer, poses a significant problem. Ultimately, the increase in copper ion concentration causes dielectric breakdown, rendering devices and transistors inoperable. Various barrier layers have been deposited to prevent copper ion migration, but these barrier layers are typically titanium or tantalum nitrides. In pitch designs below 30 nm, these barrier layers occupy a large portion of the space between metal interconnects, and the poor dielectric properties of these nitrides make the dielectric layer unsuitable. Due to the aforementioned challenges, the search for novel metals with interconnect critical dimensions of 10-20 nm or less is underway. Depending on the metal used, the metal wire can be formed by a subtractive process similar to that used for aluminum and tungsten, or by a single damascene process in which copper is deposited after the deposit of an alternative metal. Therefore, to realize future devices and device architectures, novel dielectrics are needed that possess appropriate electrical and mechanical properties and can fill critical dimensions of 10-20 nm or less. Furthermore, these novel dielectrics must withstand the conditions used in subsequent process steps, such as high temperatures (above 400°C), various chemicals, and mechanical forces (chemical and mechanical polishing).

[0005] Furthermore, conventionally used CVD dielectric coatings cannot meet the requirements of next-generation processes and devices due to the reduction in interconnect dimensions, thus necessitating novel and advanced spin-on dielectrics for back-of-line (BEOL) interlayer dielectric films of logic chips. Advantages of spin-on dielectrics include, for example, superior gap-filling properties, cost-effective processing, and lower dielectric constants compared to CVD silicon oxide-based materials.

[0006] U.S. Patent No. 7074690 (US7074690B1) discloses a gap-filling process based on vapor deposition, describing CVD and ALD (atomic layer deposition), as well as their plasma-assisted processes. U.S. Patent Application Publication No. 2019 / 177488 (US2019177488A1) relates to a solvent-free particulate silicone composition and its hydrosilylation in the presence of a metal catalyst (typically a Pt catalyst). Japanese Patent Application Publication No. 2015-206019 (JP2015206019A1) describes the use of surface-treated metal oxide particles to impart improvement to silicone resins. Japanese Patent Application Publication No. 2007-254595 (JP2007254595A) relates to a film-forming composition comprising a polymer obtained by hydrolyzing a silane monomer and a hydrolyzable polycarbosilane.

[0007] Current siloxane-based spin-on dielectric coatings have lower dielectric constants compared to silicon oxides, but their dielectric breakdown voltage (BDV) is not comparable. Therefore, CVD dielectrics remain commonly used due to the low dielectric breakdown voltage of spin-on dielectric siloxane coatings. A higher dielectric breakdown voltage is required to guarantee the reliability of the final device. On the other hand, a lower dielectric constant reduces capacitance and RC delay, thus improving processing speed.

[0008] Other common problems with spin-on dielectrics include poor mechanical properties and a high coefficient of thermal expansion (CTE).

[0009] In addition to microelectronics, coatings required for several optoelectronic applications need to have optimized optical properties, such as refractive index, or properties that affect optical properties. For example, this may involve minimizing reflections at the interface between multilayer coatings or maximizing light output from optoelectronic devices to improve optical transparency and image resolution.

[0010] One object of the present invention is to provide a dielectric polymer film with an increased breakdown voltage value without impairing other properties such as dielectric constant and solving at least a part of the problems related to the prior art. Another object of the present invention is to provide a gap filling material forming composition that provides a dielectric film having advantageous properties such as being deposited in liquid form by a spin coating method, having a high breakdown voltage, a low shrinkage rate, a low dielectric constant, and being capable of filling a gap width of 20 nm or less. SUMMARY OF THE INVENTION

[0011] The present invention is defined by the features of the independent claims. Some specific embodiments are defined in the dependent claims.

[0012] The present invention is based on the concept of providing a semiconductor device, an optical element, and / or an optically active device including a dielectric polymer film containing a gap filling material forming composition disclosed herein. The novel gap filling material forming composition and the dielectric polymer film containing the same provide, in addition to the improvement of properties such as particularly high breakdown voltage, other advantageous properties such as low shrinkage rate and low dielectric constant as compared with the solutions in the prior art. This gap filling material composition contains an alkyltriorganosilyl side group in a siloxane polymer, as will be described in more detail below.

[0013] According to a first aspect of the present invention, a gap filling material forming composition containing a polymer obtained by polymerizing a monomer represented by formula I R 1 R 2 R 3 Si-X 1 -SiX 2 n R 4 3-n I is provided. Here, each X 1 is selected from the group consisting of oxygen and an optionally substituted crosslinked linear or branched divalent hydrocarbon group (e.g., alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms), and each X 2 is selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group, and each R1 , R 2 , and R 3 Each of these is independently selected from C1-C6 alkyl groups and C6-C18 aryl groups (e.g., phenyl or benzyl groups), and the groups are optionally substituted, and each R 4 n is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl or benzyl groups), and the group may be optionally substituted, with n being an integer from 1 to 3.

[0014] The present invention also provides the use of the gap-filling material-forming composition for manufacturing gap-filling dielectric films for semiconductor devices or optical elements. Typically, the gap-filling material-forming composition is deposited on a substrate in the form of a thin layer, and a gap-filling dielectric polymer film is formed by curing this thin layer. In particular, gap-filling material-forming compositions containing siloxane or silsesquioxane polymers in solution are deposited in liquid form by a spin-coating method.

[0015] A further aspect of the present invention provides a dielectric polymer film comprising a cured product of the gap-filling material forming composition defined above.

[0016] A further aspect of the present invention relates to a method for forming a gap-filling dielectric polymer film, the method being: Formula I R 1 R 2 R 3 Si-X 1 -SiX 2 n R 4 3-n I The first silicon compound represented by (where R 1 , R 2 , R 3 , X 1 , R 4 , X 2 The steps include hydrolyzing (where n is synonymous with the above), The first silicon compound can be optionally, Formula II (X 3 ) m(R 5 ) 3-m Si-R 6 -Si(X 4 ) m (R 7 ) 3-m II At least one second silicon compound obtained by hydrolyzing the compound represented by (where each X 3 and X 4 Each of these is independently selected from the group consisting of hydrogen, organic, or inorganic hydrolyzable groups, and each R 5 and R 7 Each of these is independently selected from C1-C6 alkyl groups and C6-C18 aryl groups (e.g., phenyl or benzyl groups), and the groups are optionally substituted, and each R 6 m is selected from the group of optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms), and / or, formula III (X 4 ) 4-n SiR 14 n III The compound represented by (where each X 4 R is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, and each R 14 The step of polymerizing a molecule (selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl or benzyl groups), wherein the group is optionally substituted and n is an integer from 1 to 3) to provide a gap-filling coating composition, The steps include: depositing the gap-filling coating composition onto a substrate and curing the composition to form a gap-filling dielectric polymer film; Includes.

[0017] A further aspect of the present invention provides a method for manufacturing a semiconductor device, the method being: The steps include providing a semiconductor device substrate, The steps include: applying the gap-filling material forming composition of the present invention onto the semiconductor device substrate, curing the composition, and forming a gap-filling dielectric film on the semiconductor device substrate. Includes.

[0018] According to yet another aspect of the present invention, a method for manufacturing an optical element or an optically active device is provided, and the method is The steps include providing an optical element or optically active device substrate, The steps include: applying the gap-filling material forming composition of the present invention onto the optical element or optically active device substrate, and firing the composition to form a gap-filling dielectric film; Includes.

[0019] The present invention also provides a semiconductor device comprising the dielectric polymer film of the present invention. The present invention further provides an optical element or optical device comprising the dielectric polymer film of the present invention.

[0020] The present invention offers significant advantages. Firstly, the material provides a higher dielectric breakdown voltage (BDV) value than existing siloxane-based spin-on dielectric coatings. A high dielectric breakdown voltage is important for ensuring the reliability of the final device. Typically, the dielectric polymer film of the present invention has an electrical dielectric breakdown voltage of at least 3.8 MV / cm.

[0021] Secondly, this material provides a dielectric constant that is lower than that of silicon oxide and comparable to that of existing siloxane-based spin-on dielectric coatings. Typically, the dielectric polymer film of the present invention has a dielectric constant of 2.9 or less at 1 MHz.

[0022] Therefore, this material achieves improved dielectric breakdown voltage without impairing other material properties such as dielectric constant, coefficient of thermal expansion, modulus of elasticity, and hardness. Furthermore, this material exhibits a low shrinkage rate, reducing the amount of stress formation in the polymer film during high-temperature curing. For example, the dielectric polymer film of the present invention has a shrinkage rate of less than 5% between soft baking and curing, more preferably less than 3%, and most preferably less than 1%.

[0023] Further features and advantages of this technology will become apparent from the description of the embodiments shown below. [Modes for carrying out the invention]

[0024] (definition)

[0025] Unless otherwise specified or as is evident from the context, percentages referred to herein are expressed as weight percentages based on the total weight of each composition.

[0026] Unless otherwise specified, the properties experimentally measured or determined in this specification were measured or determined at room temperature. Unless otherwise specified, room temperature is 25°C.

[0027] Unless otherwise specified, the properties experimentally measured or determined in this specification were measured or determined at atmospheric pressure.

[0028] In this specification, the term "approximately" refers to a value within ±5% of the stated value.

[0029] As used herein, the term "average molecular weight" refers to weight-average molecular weight ("Mw" or "M"). w This refers to (also abbreviated as '').

[0030] The term "molecular weight" as used herein is measured by gel permeation chromatography using a polystyrene standard.

[0031] The dielectric constant (κ or εr) is measured using a metal-insulator-semiconductor (MIS) structure on a highly doped, low-resistance N+-doped silicon wafer. Capacitance across the dielectric film is measured using a mercury probe (Materials Development Corporation, Model 802) and a high-precision impedance analyzer (Agilent 4294A). From this capacitance, the mercury dot contact area, and the film thickness, the dielectric constant can be calculated using the following formula:

number

[0032] "Film thickness" can be measured using means and apparatus known to those skilled in the art, for example, a JA Woollam M2000D-ESM-200AXY spectroscopic ellipsometer.

[0033] The "dielectric breakdown voltage" is measured using a similar MIS structure equipped with a mercury probe (Materials Development Corporation, Model 802) and a semiconductor parameter analyzer (Agilent 4155B).

[0034] The refractive index (RI) is determined using a refractometer at a wavelength of 633 nm. The RI can be calculated, for example, from a polymer film sample with a thickness of 400 nm using interferometry, angular declination, or Brewster's angle method.

[0035] The "shrinkage rate" is determined by measuring the decrease in film thickness between low-temperature soft baking and high-temperature curing. Thickness measurement is performed using a spectroscopic ellipsometer.

[0036] The "hardness" and "elastic modulus" of a film can be calculated from the nanoindentation curve using the Oliver-Pharr method.

[0037] In this specification, the term "gap-filling material" refers to a material capable of filling gaps between different topographic layers on a semiconductor device substrate or an optical element or optically active device substrate, and typically refers to a gap-filling material that enables such filling when deposited on the substrate as a thin layer in liquid form and cured. "Gap-filling material forming composition" refers to a material capable of forming a polymer film on the surface of a semiconductor device, optical element, or optically active device upon curing. The gap-filling material forming composition of the present invention is capable of filling gaps with a width of 20 nm or less, especially when applied by spin coating.

[0038] As used herein, "alkenyl" includes linear and branched alkenyl groups such as vinyl and allyl groups. As used herein, "alkynyl" includes linear and branched alkynyl groups, preferably acetylene. "Aryl" means a substituted or unsubstituted monocyclic, bicyclic, or more cyclic aromatic carbocyclic group, examples of which include phenyl, naphthyl, and pentafluorophenylpropyl. More specifically, alkyl, alkenyl, or alkynyl may be linear or branched. As used herein, "alkoxy" and "acyloxy" groups typically have 1 to 6 carbon atoms.

[0039] The embodiments of this technology will be described in more detail below.

[0040] The present invention is based on the finding that polymer compositions can be obtained by polymerizing a monomer of formula I together with a silane monomer of formula II and / or formula III, thereby forming a dielectric polymer film that has a high electrical breakdown voltage, particularly an electrical breakdown voltage of at least 3.8 MV / cm, upon curing.

[0041] This embodiment discloses the production and use of dielectric polymer films containing alkyltriorganosilyl side groups in a siloxane polymer. Such polymer films are obtained by polymerizing at least a silane monomer of formula I by homopolymerization or copolymerization. The polymer is a siloxane or silsesquioxane, and is different from linear siloxanes commonly known as silicones. Preferably, the polymer does not contain polycarbosilane.

[0042] Typically, this technology involves first hydrolyzing a silane monomer containing a hydrolyzable group, and then polymerizing it, typically in a liquid phase, at a temperature ranging from room temperature to the boiling point of the liquid. The liquid may consist of one or more solvents in addition to the silicon monomer and water added for the hydrolysis of the monomer. Specific and preferred solvents include acetone, ethyl methyl ketone, methanol, ethanol, isopropanol, butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and tetrahydrofuran. Particularly preferred solvents are alcohols, ketones, and ethers.

[0043] Controlled hydrolysis of monomers is achieved by adding an acid or base solution having a molar concentration of 0.0001 M to 1 M. Organic or inorganic acids can be used for synthesis. Inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid, boric acid, perchloric acid, carbonic acid, and phosphoric acid can be used. Nitric acid or hydrochloric acid is preferably used because of its low boiling point and ease of product purification. Alternatively, various organic acids can be used instead of inorganic acids. Examples of organic acids include carboxylic acids, sulfonic acids, alcohols, thiols, enols, and phenolic groups. Examples include methanesulfonic acid, acetic acid, ethanesulfonic acid, toluenesulfonic acid, formic acid, and oxalic acid.

[0044] The bases used in synthesis can also be inorganic or organic. Typical inorganic bases include metal hydroxides, carbonates, bicarbonates, and other salts that produce alkaline aqueous 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 comprise a broader group consisting of metal salts of organic acids (such as sodium acetate, potassium acetate, sodium acrylate, sodium methacrylate, and sodium benzoate), linear, branched, or cyclic alkylamines (such as diaminoethane, putrescine, cadaverine, triethylamine, butylamine, dibutylamine, tributylamine, and piperidine), amidines and guanidines (such as 8-diazabicyclo(5.4.0)undeca-7-ene, 1,1,3,3-tetramethylguanidine, and 1,5,7-triazabicyclo[4.4.0]deca-5-ene), phosphazanes (such as P1-t-Bu, P2-t-Bu, and P4-t-Bu), and quaternary ammonium compounds (such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide).

[0045] The temperature of the reaction mixture during the hydrolysis and condensation processes can be varied within the range of -30 to 170°C. Lower reaction temperatures improve reaction control but increase the reaction time. On the other hand, if the reaction temperature is too high, the process may become excessively fast, making proper control impossible. A reaction time of 1 to 48 hours at a temperature of 0 to 100°C is preferred. A reaction time of 2 to 24 hours is even more preferred.

[0046] By using appropriate conditions, in the embodiment of this method, a polymer is obtained in an organic solvent system, and the molecular weight of the polymer measured relative to a polystyrene standard is approximately 500 to 100,000 g / mol, preferably 800 to 50,000 g / mol, and most preferably 1,000 to 10,000 g / mol.

[0047] In a particular embodiment, formula I R 1 R 2 R3 Si-X 1 -SiX 2 n R 4 3-n I A gap-filling material forming composition is obtained, which contains a polymer obtained by polymerizing monomers represented by . Here, each X 1 X is selected from the group consisting of oxygen, optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms), and each X 2 R is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, and each R 1 , R 2 , and R 3 Each of these is independently selected from C1-C6 alkyl groups and C6-C18 aryl groups (e.g., phenyl or benzyl groups), and the groups are optionally substituted, and each R 4 n is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl or benzyl groups), and the group may be optionally substituted, with n being an integer from 1 to 3.

[0048] Typically, the gap-filling material-forming composition contains at least 5 mol%, preferably at least 10 mol%, for example 10 to 20 mol%, and more preferably about 15 mol%, of the polymer of formula I.

[0049] In some embodiments, the gap-filling material-forming composition is obtained by copolymerizing a compound of formula I with a silane monomer. Preferably, the compound of formula I accounts for at least 5 mol% of the total amount of monomers in the polymer composition obtained by copolymerizing the compound of formula I with the silane monomer.

[0050] In some embodiments, the gap-filling material forming composition comprises a compound of formula I and formula II (X 3 ) m (R 5 ) 3-m Si-R 6 -Si(X 4 ) m (R 7 )3-m II It is obtained by copolymerizing with a compound represented by . Here, each X 3 and X 4 Each of these is independently selected from the group consisting of hydrogen, organic, or inorganic hydrolyzable groups, and each R 5 and R 7 Each of these is independently selected from C1-C6 alkyl groups and C6-C18 aryl groups (e.g., phenyl or benzyl groups), and the groups are optionally substituted, and each R 6 m is selected from the group of optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms), and m is an integer from 1 to 3.

[0051] Preferably, in formulas I and II, each X 1 and R 6 Each of these is independently selected from alkylenes having 1 to 4 carbon atoms, particularly 2 carbon atoms.

[0052] More preferably, the monomer of formula I is formula Ia [ka] Selected from monomers represented by [the specified format].

[0053] The synthesis of the monomer of formula Ia, namely 1-trimethylsilyl-2-triethoxysilyl-ethane, was described by Khudobin et al. (1976).

[0054] In some preferred embodiments, the compound of formula I accounts for at least 10 mol% of the total amount of monomers in the gap-filling material forming composition, and the compound of formula II accounts for at least 40 mol% of the total amount of monomers in the gap-filling material forming composition.

[0055] In some embodiments, the monomers of the gap-filling material-forming composition consist of a compound of formula I and a compound of formula II, wherein the compound of formula I accounts for at least 10 mol%, preferably at least 15 mol%, of the total amount of monomers in the gap-filling material-forming composition.

[0056] Specific examples of compounds of formula II include, but are not limited to, 1,2-bis(trimethoxysilyl)ethane, 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane, and 1,2-bis(dimethoxymethylsilyl)ethane.

[0057] In some embodiments, the monomers of the gap-filling material-forming composition consist of compounds of formula I, particularly 1-trimethylsilyl-2-triethoxysilyl-ethane, and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane as a compound of formula II.

[0058] In some embodiments, the monomer of the gap-filling material forming composition consists of 1-trimethylsilyl-2-triethoxysilyl-ethane in an amount of at least 10 mol%, preferably at least 15 mol%, or about 20 mol% of the total amount of monomer of the gap-filling material forming composition, and a compound of formula II, preferably 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane.

[0059] In some embodiments, the gap-filling material forming composition comprises a compound of formula I and formula III (X 4 ) 4-n SiR 14 n III It is obtained by polymerizing the compound represented by . Here, each X 4 R is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, and each R 14 n is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl or benzyl groups), and the group may be optionally substituted, with n being an integer from 1 to 3.

[0060] Preferably, in the above formulas (I, II, and III), each X 2 , X 3 , and X 4 is independently selected from the group consisting of hydrogen and organic or inorganic hydrolyzable groups selected from halogen groups, acyloxy groups, alkoxy groups, and OH groups. Usually, the halogen is selected from fluoro, chloro, and bromo. More preferably, each X 2 , X 3 , and X 4 is independently selected from the group consisting of hydrogen and R 9 O-, where R 9 represents alkyl having 1 to 6 carbon atoms.

[0061] In some embodiments, each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , and R 14 in the above formula is independently selected from alkyl groups having 1 to 4 carbon atoms and phenyl groups.

[0062] Specific examples of compounds of formula III include tetramethoxysilane, tetraacetoxysilane, tetrachlorosilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, β-Cyanoethyltriethoxysilane, Chloromethyltrimethoxysilane, Chloromethyltriethoxysilane, Dimethyldimethoxysilane, Phenylmethyldimethoxysilane, Dimethyldiethoxysilane, Phenylmethyldiethoxysilane, γ-Chloropropylmethyldimethoxysilane, γ-Chloropropylmethyldiethoxysilane, Dimethyldi Acetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyl Triethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyl Rietoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (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, Glycidoxymethylmethyldimethoxysilane, Glycidoxymethylmethyldiethoxysilane, α-Glycidoxyethylmethyldimethoxysilane, α-Glycidoxyethylmethyldiethoxysilane, β-Glycidoxyethylmethyldimethoxysilane, β-Glycidoxyethylethyldimethoxysilane, α- Examples include, but are not limited to, glycidoxypropyl methyldimethoxysilane, α-glycidoxypropyl methyldiethoxysilane, β-glycidoxypropyl methyldimethoxysilane, β-glycidoxypropyl ethyldimethoxysilane, γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyl methyldipropoxysilane, γ-glycidoxypropyl methyldibutoxysilane, γ-glycidoxypropyl methyldiphenoxysilane, γ-glycidoxypropyl ethyldimethoxysilane, γ-glycidoxypropyl ethyldiethoxysilane, γ-glycidoxypropyl vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, and phenylsulfonylaminopropyltriethoxysilane.

[0063] The polymer material of the gap-filling material forming composition may typically include a polymer material having a (weight-average) molecular weight of 500 to 100,000 g / mol, preferably 800 to 50,000 g / mol, and most preferably 1,000 to 10,000 g / mol, measured relative to a polystyrene standard.

[0064] The polymer material of the gap-filling material forming composition is typically formulated in an organic solvent. In some embodiments, the polymer is formulated in an organic solvent containing a curing catalyst. These curing catalysts are intended to promote crosslinking of organosiloxane films by condensing silanols. Typically, such metal-free silanol condensation catalysts are acids or bases, particularly latent acids or bases, which can be activated, for example, by light. As an example, it is also possible to use an acid that decomposes during the heating step of film formation to release a latent organic base.

[0065] In some embodiments, the polymer is blended in an organic solvent having a thermally unstable curing catalyst to promote crosslinking of the organosiloxane film.

[0066] In some embodiments, the polymer is compounded in an organic solvent having a photobase-containing curing catalyst.

[0067] In some embodiments, the polymer is compounded in an organic solvent having a photoacid-containing curing catalyst.

[0068] The amount of curing catalyst in the gap-filling material forming composition may be in the range of 0.05 to 10% by weight, based on the solid content of the polymer, and preferably 0.1 to 5% by weight, for example, 0.5 to 3% by weight.

[0069] Various types of surfactants, such as silicone-based surfactants and fluorine-based surfactants, can be used to optimize the formulation by reducing the surface tension of silanol-containing polysiloxane-based coatings. The use of such surfactants can improve coating quality as needed. The amount of surfactant is in the range of 0.001 to 20% by mass relative to the amount of silanol-containing organosiloxane, preferably 0.005 to 10% by mass, most preferably 0.01 to 5% by mass or 0.05 to 2.5% by mass.

[0070] The gap-filling material forming composition of the present invention is used in the manufacture of semiconductor devices, optical elements, and gap-filling dielectric polymer films for optical devices.

[0071] The dielectric polymer film of the present invention includes a cured product of the gap-filling material forming composition described above. The gap-filling material forming composition of the present invention and the dielectric film containing the cured gap-filling material forming composition can fill gaps with a gap width of 20 nm or less located between different topographics, such as metal interconnects on semiconductor device substrates or optical elements or optically active device substrates. Typically, such dielectric films themselves do not contain metals that cause dielectric breakdown.

[0072] Surprisingly, it has been found that excellent electrical and mechanical properties can be obtained by optionally using the monomer of formula I in the polymer film together with the compound of formula II and / or the compound of formula III. Dielectric polymer films containing cured products of this type of gap-filling composition have an electrical breakdown voltage of at least 3.8 MV / cm, preferably at least 3.9 MV / cm, and more preferably at least 4.0 MV / cm. In some embodiments, the dielectric polymer film may have an electrical breakdown voltage of at least 4.2 MV / cm when measured in MIS structure using a mercury probe (Materials Development Corporation, Model 802) and a semiconductor parameter analyzer (Agilent 4155B).

[0073] A dielectric polymer film containing a cured product of this type of gap-filling composition may have a dielectric constant of 2.9 or less at 1 MHz.

[0074] This dielectric polymer film exhibits good optical properties. In some embodiments, the dielectric polymer film has a refractive index of at least 1.37, as measured at a wavelength of 633 nm.

[0075] Typically, dielectric polymer films exhibit a shrinkage rate of less than 5%, more preferably less than 3%, and most preferably less than 1% between soft baking and curing. Furthermore, dielectric polymer films exhibit a combination of low thermal expansion and moderate elasticity / flexibility, or significant hardness.

[0076] In some embodiments, the dielectric polymer film exhibits an elastic modulus of 8.5 GPa or higher, for example, 9.0 GPa or higher.

[0077] In some embodiments, the dielectric polymer film exhibits a hardness of 2.0 GPa or higher, for example, 2.2 GPa or higher.

[0078] In some embodiments, using monomers of formula I, particularly monomers of formula Ia, in an amount of at least 10 mol% of the total monomers in the polymer composition results in an increase in dielectric breakdown voltage compared to dielectric films consisting solely of monomers of formula II or formula III. Simultaneously, a low dielectric constant is achieved.

[0079] The thickness of dielectric polymer films is typically less than 1 μm, especially less than 500 nm, and more typically between 50 and 350 nm.

[0080] The present invention also relates to a method for forming a gap-filling dielectric polymer film, the method being: Formula I R 1 R 2 R 3 Si-X 1 -SiX 2 n R 4 3-n I The first silicon compound represented by (where R 1 , R 2 , R 3 , X 1 , R 4 , X 2 The steps include hydrolyzing (where n is synonymous with the above), The first silicon compound can be optionally, Formula II (X 3 ) m (R5 ) 3-m Si-R 6 -Si(X 4 ) m (R 7 ) 3-m II Compounds represented by (where R 5 , R 6 , R 7 , X 3 , X 4 At least one second silicon compound obtained by hydrolyzing (where m is the same as above), and / or Formula III (X 4 ) 4-n SiR 14 n III Compounds represented by (where R 14 , X 3 The steps include polymerizing with (where n is the same as above) to provide a gap-filling coating composition, The steps include: depositing the gap-filling coating composition onto a substrate and curing the composition to form a gap-filling dielectric polymer film; Includes.

[0081] In some embodiments, the substrate is a semiconductor substrate. In some embodiments, the substrate is an optical element or an optically active device.

[0082] A semiconductor device may be manufactured by a method comprising the steps of providing a semiconductor device substrate and applying a gap-filling material forming composition disclosed herein onto the semiconductor device substrate, curing the composition, and thereby forming a gap-filling dielectric film on the semiconductor device substrate.

[0083] In some embodiments, the gap-filling material forming composition may be applied to a semiconductor substrate, for example, by spin coating. In some embodiments, the curing step may include a combination of thermal curing and UV curing.

[0084] An optical element or optically active device may be manufactured by a method comprising the steps of providing an optical element or optically active device substrate and applying a gap-filling material forming composition disclosed herein onto the optical element or optically active device substrate, and curing the composition to provide a gap-filling dielectric film.

[0085] It should be understood that the embodiments of the present invention disclosed herein are not limited to any specific structures, process steps, or materials disclosed herein, but extend to their equivalents as recognized by those skilled in the art. It should also be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to limit them.

[0086] Throughout this specification, any reference to “one embodiment” or “a particular embodiment” means that certain features, structures, or characteristics described in relation to that embodiment are included in at least one embodiment of the present invention. Therefore, expressions such as “in one embodiment” or “in a particular embodiment” in this specification do not necessarily refer to the same embodiment. Also, where terms such as “about” or “substantially” are used to refer to numerical values, the exact numerical values ​​themselves are also disclosed.

[0087] In this specification, for convenience, multiple items, structural elements, compositional elements, and / or materials may be presented in common lists. However, these lists should be interpreted as each element in the list being individually identified as a distinct and unique element. Therefore, unless otherwise indicated, no component in a list should be interpreted as a de facto equivalent of any other component simply because it is presented in the same list. Furthermore, various embodiments and examples of the present invention may be referred to along with alternative examples of their various components. It should be understood that such embodiments, examples, and alternatives should not be interpreted as de facto equivalents of each other, but rather as distinct and independent aspects of the present invention.

[0088] Furthermore, the described features, structures, or properties can be combined in any suitable manner in one or more embodiments. The following description provides numerous specific details, including examples of length, width, shape, etc., to allow for a full understanding of embodiments of the invention. However, those skilled in the art will recognize that the invention can be implemented without using some or all of these specific details, or using other methods, components, materials, etc. Also, detailed descriptions of well-known structures, materials, or operations have been omitted to avoid obscuring embodiments of the invention.

[0089] The following non-limiting examples illustrate further embodiments. Experiment

[0090] monomer

[0091] Monomer A: 1-(trimethylsilyl)-2-(triethoxysilyl)-ethane [ka]

[0092] Synthesis of monomer A: Monomer A was prepared by adding vinyltrimethylsilane (VinTMS, 30 g), platinum catalyst (0.06 g), and acetic acid (0.02 g) to a 250 mL flask. The solution was thoroughly mixed at 35°C, and triethoxysilane (HTEOS, 41 g) was added to the solution. After the addition of HTEOS, the reaction mixture was kept at 35°C overnight. After the reaction was complete, distillation was performed under reduced pressure. The obtained product was 58 g (yield 88%, GC-MS purity 100%).

[0093] Polymer preparation

[0094] Polymer 1: A copolymer of monomer A and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane was prepared in a 250 mL round-bottom flask. Monomer A (2.4 g), 1-trimethoxysilyl-2-dimethoxymethyl-ethane (20.4 g), methanol (45 g), and 0.01 M hydrochloric acid (HCl) (8.5 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (60 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 44%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1086 and 773, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0095] Polymer 2: A copolymer of monomer A and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane was prepared in a 250 mL round-bottom flask. Monomer A (3.7 g), 1-trimethoxysilyl-2-dimethoxymethyl-ethane (20.4 g), methanol (48 g), and 0.01 M hydrochloric acid (8.8 g) were added to the flask. The reaction mixture was refluxed for 1 hour and then cooled to room temperature. PGMEA (90 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 31%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 996 and 729, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0096] Polymer 3: A copolymer of monomer A and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane was prepared in a 250 mL round-bottom flask. Monomer A (5.3 g), 1-trimethoxysilyl-2-dimethoxymethyl-ethane (20.4 g), methanol (51 g), and 0.01 M hydrochloric acid (9.1 g) were added to the flask. The reaction mixture was refluxed for 1 hour and then cooled to room temperature. PGMEA (90 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 38%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 979 and 725, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0097] Polymer 4: Polymers of monomer A with TEOS, MTEOS, and HTEOS were prepared in 250 mL round-bottom flasks. Monomer A (5.7 g), TEOS (7.4 g), MTEOS (8.9 g), HTEOS (5.9 g), isopropanol (42 g), and 0.01 M hydrochloric acid (12.5 g) were added to the flask. The reaction mixture was refluxed for 1 hour and then cooled to room temperature. PGMEA (90 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with 50% solids. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1517 and 1057, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0098] Polymer 5: Polymers of monomer A with TEOS, MTEOS, and HTEOS were prepared in 250 mL round-bottom flasks. Monomer A (6.2 g), TEOS (6.1 g), MTEOS (6.2 g), HTEOS (4.8 g), isopropanol (35 g), and 0.01 M hydrochloric acid (10.2 g) were added to the flask. The reaction mixture was refluxed for 1 hour and then cooled to room temperature. PGMEA (90 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 38%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1369 and 996, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0099] Polymer 6: A copolymer of monomer A and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane was prepared in a 250 mL round-bottom flask. Monomer A (3.5 g), 1-trimethoxysilyl-2-dimethoxymethyl-ethane (5.1 g), methanol (13 g), and 0.01 M hydrochloric acid (2.8 g) were added to the flask. The reaction mixture was refluxed overnight and then cooled to room temperature. PGMEA (60 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 39%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 2061 and 1225, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0100] Polymer 7: A copolymer of monomer A and 1-trimethoxysilyl-2-dimethoxymethylsilyl-ethane was prepared in a 250 mL round-bottom flask. Monomer A (11.9 g), 1-trimethoxysilyl-2-dimethoxymethyl-ethane (7.6 g), methanol (30 g), and 0.01 M hydrochloric acid (5.6 g) were added to the flask. The reaction mixture was refluxed overnight and then cooled to room temperature. PGMEA (60 g) was added to the reaction mixture. Methanol and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 30%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1407 and 1001, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated onto a silicon wafer to evaluate film properties.

[0101] Polymer data The properties of polymers 1-7 and comparative examples 1-2 below were analyzed. The dielectric constant was measured at a frequency of 100 kHz for a film with a target thickness of 340 nm ± 20 nm. Before measurement, the wafer was pre-baked at 150°C for 5 minutes to remove accumulated moisture, and then measured at room temperature. Mechanical properties were measured by nanoindentation using a Nanovea PB1000 mechanical testing machine. A Berkovich indenter and diamond were used as materials under a target load of 0.05 mN, loading and unloading rates of 0.02 V / min, approach speed of 0.5 μm / min, and contact load of 0.006 mN. Hardness and modulus were calculated directly from the indentation curve using the Oliver-Pharr method.

[0102] [Table 1]

[0103] [Table 2]

[0104] [Table 3]

[0105] As is clear from the above, this material makes it possible to achieve both a high electrical breakdown voltage and a low dielectric constant while maintaining sufficient mechanical properties. Furthermore, this material also shows a significant improvement in shrinkage performance.

[0106] Comparative Example

[0107] Comparative Example 1 (C1): Polymers consisting of TEOS, MTEOS (methyltriethoxysilane), and triethoxysilane (HTEOS) were prepared in a 4 L flask. TEOS (57 g, 0.27 mol), MTEOS (98 g, 0.55 mol), HTEOS (45 g, 0.27 mol), isopropyl alcohol (301 g), and 0.01 M hydrochloric acid (97 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (900 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a composition with 40% solids. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1624 and 900, respectively. 5% polymer formulations were prepared in PGMEA and PGEE, and the film properties were evaluated by spin coating onto silicon wafers.

[0108] Example 2 (C2): A homopolymer of 1-trimethoxysilyl-2-methyldimethoxysilylethane was prepared in a 4 L flask. 1-trimethoxysilyl-2-methyldimethoxysilylethane (200 g, 0.78 mol), methanol (402 g), and 0.01 M hydrochloric acid (71 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGME (870 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a composition with a solid content of 25%. The obtained polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average molecular weight and number-average molecular weight were 1313 and 629, respectively. 5% polymer formulations were prepared with PGMEA and PGME, and the film properties were evaluated by spin coating onto silicon wafers. Embodiments

[0109] As can be understood from the foregoing description and exemplary embodiments of the present invention, the present invention can be described by reference to the following embodiments: [Embodiment 1] Equation I R 1 R 2 R 3 Si-X 1 -SiX 2 n R 4 3-n I A gap-filling material forming composition comprising a polymer obtained by polymerizing monomers represented by, Here, each X 1 This is selected from the group consisting of oxygen and optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms). each X 2 This is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, Each R 1 , R 2 , and R 3 Each of these is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms (e.g., a phenyl group or a benzyl group), and the said group is optionally substituted. Each R 4 The group is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl group or benzyl group), and the group is optionally substituted. n is an integer between 1 and 3. Gap-filling material forming composition. [Embodiment 2] A gap-filling material-forming composition according to Embodiment 1, comprising at least 5 mol%, preferably at least 10 mol%, for example 10 to 20 mol%, more preferably about 15 mol%, of the polymer of Formula I. [Embodiment 3] A gap-filling material-forming composition according to Embodiment 1 or 2, obtained by copolymerizing a compound of Formula I with a silane monomer. [Embodiment 4] A gap-filling material forming composition obtained by copolymerizing a compound of formula I with a silane monomer, wherein the compound of formula I constitutes at least 5 mol% of the total amount of monomers in the polymer composition, according to any one of Embodiments 1 to 3. [Embodiment 5] Compounds of formula I and formula II (X 3 ) m (R 5 ) 3-m Si-R 6 -Si(X 4 ) m (R 7 ) 3-m II A gap-filling material forming composition obtained by copolymerizing a compound represented by, Here, each X 3 and X 4 Each of these is independently selected from the group consisting of hydrogen, organic, or inorganic hydrolyzable groups. Each R 5 and R 7 Each of these is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms (e.g., a phenyl group or a benzyl group), and the said group is optionally substituted. Each R 6This is selected from the group of optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms), m is an integer between 1 and 3. A gap-filling material forming composition according to any of the prior embodiments. [Embodiment 6] each X 1 and R 6 Each of these is independently selected from alkylenes having 1 to 4 carbon atoms, particularly 2 carbon atoms, to form a gap-filling material-forming composition according to any one of the prior embodiments. [Embodiment 7] The monomer of formula I is formula Ia [ka] A gap-filling material-forming composition according to any one of the prior embodiments, selected from monomers represented by . [Embodiment 8] A gap-filling material-forming composition according to any one of Embodiments 4 to 6, wherein the compound of Formula I accounts for at least 10 mol% of the total amount of monomers, and the compound of Formula II accounts for at least 40 mol% of the total amount of monomers. [Embodiment 9] Compounds of formula I and formula III (X 4 ) 4-n SiR 14 n III A gap-filling material forming composition obtained by copolymerizing a compound represented by, Here, each X 4 This is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, Each R 14 The group is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl group or benzyl group), and the group is optionally substituted. n is an integer between 1 and 3. A gap-filling material forming composition according to any of the prior embodiments. [Embodiment 10] each X 2 , X 3 , and X 4 A gap-filling material-forming composition according to any one of the prior embodiments, wherein each is independently selected from hydrogen and an organic or inorganic hydrolyzable group selected from halogen groups, acyloxy groups, alkoxy groups, and OH groups. [Embodiment 11] each X 2 , X 3 , and X 4 These are, independently, hydrogen and R 9 Selected from the O- group, R 9 A gap-filling material forming composition according to any one of the prior embodiments, wherein is an alkyl group having 1 to 6 carbon atoms. [Embodiment 12] Each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , and R 14 The gap-filling material forming composition according to any one of the prior embodiments, wherein each is independently selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group. [Embodiment 13] A gap-filling material forming composition according to any one of the prior embodiments, comprising a polymer material having a (weight-average) molecular weight of 500 to 100,000 g / mol. [Embodiment 14] A gap-filling material-forming composition according to any one of the prior embodiments, comprising a polymer blended in an organic solvent. [Embodiment 15] A gap-filling material forming composition according to any one of the prior embodiments, comprising a polymer blended in an organic solvent having a curing catalyst. [Embodiment 16] A gap-filling material-forming composition according to any one of the prior embodiments, comprising a polymer blended in an organic solvent having a thermally unstable curing catalyst. [Embodiment 17] A gap-filling material forming composition according to any one of the prior embodiments, comprising a polymer blended in an organic solvent having a photobase-containing curing catalyst. [Embodiment 18] A gap-filling material forming composition according to any one of the prior embodiments, comprising a polymer blended in an organic solvent having a photoacid-containing curing catalyst. [Embodiment 19] Use of a gap-filling material-forming composition according to any one of the prior embodiments for manufacturing a gap-filling dielectric film for semiconductor devices or optical elements. [Embodiment 20] A dielectric polymer film comprising a cured product of a gap-filling material-forming composition described in any one of Embodiments 1 to 18. [Embodiment 21] A dielectric polymer film according to Embodiment 20, having an electrical breakdown voltage of at least 3.8 MV / cm, preferably at least 3.9 MV / cm, and more preferably at least 4.0 MV / cm. [Embodiment 22] A dielectric polymer film according to embodiment 20 or 21, having an electrical dielectric breakdown voltage of 4.2 MV / cm or more. [Embodiment 23] A dielectric polymer film according to any one of embodiments 20 to 22, wherein the dielectric constant at 1 MHz is 2.9 or less. [Embodiment 24] A dielectric polymer film according to any one of embodiments 20 to 23, wherein the refractive index measured at a wavelength of 633 nm is at least 1.37. [Embodiment 25] A dielectric polymer film according to any one of embodiments 20 to 24, having an elastic modulus of 8.5 GPa or greater. [Embodiment 26] A dielectric polymer film according to any one of embodiments 20 to 25, wherein the shrinkage rate between soft baking and curing is less than 5%, more preferably less than 3%, and most preferably less than 1%. [Embodiment 27] A dielectric polymer film according to any one of embodiments 20 to 26, having a thickness of less than 1 μm, particularly less than 500 nm, typically 50 to 350 nm. [Embodiment 28] A method for forming a gap-filling dielectric polymer film, Formula I R 1 R 2 R 3 Si-X 1 -SiX 2 n R 4 3-n I The first silicon compound represented by (where R 1 , R 2 , R 3 , X 1 , R 4 , X 2 The steps include hydrolyzing (where n is synonymous with the above), The first silicon compound can be optionally, Formula II (X 3 ) m (R 5 ) 3-m Si-R 6 -Si(X 4 ) m (R 7 ) 3-m II Compounds represented by (where R 5 , R 6 , R 7 , X 3 , X 4 At least one second silicon compound obtained by hydrolyzing (where m is the same as above), and / or Formula III (X 4 ) 4-n SiR 14 n III Compounds represented by (where R 14 , X 4 The steps include polymerizing with (where n is the same as above) to provide a gap-filling coating composition, The steps include: depositing the gap-filling coating composition onto a substrate and curing the composition to form a gap-filling dielectric polymer film; A method that includes this. [Embodiment 29] The method according to embodiment 28, wherein the substrate is a semiconductor substrate. [Embodiment 30] The method according to embodiment 28, wherein the substrate is an optical element or an optically active device. [Embodiment 31] A method for manufacturing semiconductor devices, The steps include providing a semiconductor device substrate, The steps include: applying a gap-filling material forming composition according to any one of embodiments 1 to 18 onto the semiconductor device substrate, curing the composition, and providing a gap-filling dielectric film on the semiconductor device substrate. A method that includes this. [Embodiment 32] The method according to Embodiment 31, wherein the gap-filling material forming composition is cured by a combination of thermal curing and UV curing to form the gap-filling dielectric film. [Embodiment 33] A method for manufacturing an optical element or optically active device, The steps include providing an optical element or optically active device substrate, The steps include: applying the gap-filling material forming composition described in any one of Embodiments 1 to 18 onto the optical element or optically active device substrate, and firing the composition to form a gap-filling dielectric film; A method that includes this. [Embodiment 34] A semiconductor device comprising a dielectric polymer film as described in any one of embodiments 20 to 27. [Embodiment 35] An optical element or optical device substrate comprising a dielectric polymer film as described in any one of embodiments 20 to 27.

[0110] While the above embodiments illustrate the principles of the present invention in one or more specific applications, it will be apparent to those skilled in the art that numerous modifications can be made to the form, applications, and details of implementation without departing from the principles and concepts of the present invention and without requiring inventive ability. Therefore, the present invention is not limited except as defined by the following claims.

[0111] The verbs “comprise” and “include” are used herein as open limitations, not excluding or requiring the presence of features not described herein. Features described in dependent claims may be freely combined with each other unless otherwise specified. Furthermore, it should be understood that throughout this specification, the use of “a” or “an,” i.e., the singular form, does not exclude the plural form. [Industrial applicability]

[0112] At least some embodiments of the present invention are industrially applicable to semiconductor devices, optical elements, and optically active devices. This dielectric polymer film can be used for coating semiconductor device substrates, optical elements, and optically active devices, providing a high dielectric breakdown voltage and a low dielectric constant. (Abbreviations)

[0113] CVD: Chemical vapor deposition GC-MS: Gas chromatography-mass spectrometry GPC: Gel permeation chromatography HTEOS: Triethoxysilane MIS: Metal-insulator-semiconductor MTEOS: Methyltriethoxysilane PGEE: Propylene glycol ethyl ether PGME: Propylene glycol methyl ether PGMEA: Propylene glycol methyl ether acetate PTFE: Polytetrafluoroethylene TEOS: Tetraethyl orthosilicate VinTMS: Vinyltrimethylsilane [Prior art documents] [Patent Documents]

[0114] US7,074,690B1 US2019 / 177488A1 JP2015-206019A1 JP2007-254595A [Non-patent literature]

[0115] Khudobin, YI, Makarskaya, VM, Makarskii, VV et al. 1-(Triorganylsilyl)-2-(triethoxysilyl)ethanes. Russ Chem Bull 25, 1538-1540(1976). https: / / doi.org / 10.1007 / BF00920837

Claims

1. Equation I R １ R ２ R ３ Si-X １ -SiX ２ ｎ R ４ ３－ｎ I A gap-filling material forming composition comprising a polymer obtained by polymerizing monomers represented by, Here, Each X １ is selected from the group consisting of oxygen and an optionally substituted crosslinked straight-chain or branched divalent hydrocarbon group (e.g., alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms), Each X ２ This is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, Each R １ , R ２ , and R ３ Each of these is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms (e.g., a phenyl group or a benzyl group), and the said group is optionally substituted. Each R ４ This is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl group or benzyl group), and the said group may be optionally substituted. n is an integer between 1 and 3. Gap-filling material forming composition.

2. The gap-filling material-forming composition according to claim 1, comprising at least 5 mol%, preferably at least 10 mol%, for example 10 to 20 mol%, more preferably about 15 mol%, of the polymer of formula I.

3. A gap-filling material-forming composition according to claim 1 or 2, obtained by copolymerizing a compound of formula I with a silane monomer.

4. A gap-filling material forming composition obtained by copolymerizing a compound of formula I with a silane monomer, wherein the compound of formula I constitutes at least 5 mol% of the total amount of monomers in the polymer composition, according to any one of claims 1 to 3.

5. Compounds of formula I and formula II (X ３ ) ｍ (R ５ ) ３－ｍ Si-R ６ -Si(X ４ ) ｍ (R ７ ) ３－ｍ II A gap-filling material forming composition obtained by copolymerizing a compound represented by, Here, Each X ３ and X ４ Each of these is independently selected from the group consisting of hydrogen, organic, or inorganic hydrolyzable groups. Each R ５ and R ７ Each of these is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms (e.g., a phenyl group or a benzyl group), and the said group is optionally substituted. Each R ６ This is selected from the group of optionally substituted crosslinked linear or branched divalent hydrocarbon groups (e.g., alkylenes with 1 to 6 carbon atoms and arylenes with 6 to 10 carbon atoms), m is an integer between 1 and 3. A gap-filling material forming composition according to any of the prior claims.

6. Each X １ and R ６ Each of these is independently selected from alkylenes having 1 to 4 carbon atoms, particularly 2 carbon atoms, to form a gap-filling material forming composition according to any one of the prior claims.

7. The monomer of formula I is formula Ia 【Chemistry 1】 A gap-filling material-forming composition according to any one of the prior claims, selected from monomers represented by .

8. A gap-filling material-forming composition according to any one of the prior claims, wherein the compound of formula I or formula Ia accounts for at least 10 mol% of the total amount of monomers, and the compound of formula II accounts for at least 40 mol% of the total amount of monomers.

9. Compound of formula I and compound of formula III (X ４ ) ４－ｎ SiR １４ ｎ III A gap-filling material forming composition obtained by copolymerizing a compound represented by, Here, Each X ４ This is selected from the group consisting of hydrogen, organic or inorganic hydrolyzable groups, Each R １４ This is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms (e.g., phenyl group or benzyl group), and the said group may be optionally substituted. n is an integer between 1 and 3. A gap-filling material forming composition according to any of the prior claims.

10. Each X ２ , X ３ , and X ４ The gap-filling material-forming composition according to any one of the prior claims, wherein each is independently selected from hydrogen and an organic or inorganic hydrolyzable group selected from halogen groups, acyloxy groups, alkoxy groups, and OH groups.

11. Each X ２ , X ３ , and X ４ These are, independently, hydrogen and R ９ Selected from the O- group, R ９ A gap-filling material forming composition according to any one of the prior claims, wherein is an alkyl group having 1 to 6 carbon atoms.

12. Each R １ , R ２ , R ３ , R ５ , R ６ , R ７ , R ８ , and R １４ The gap-filling material forming composition according to any one of the prior claims, wherein each is independently selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group.

13. A gap-filling material-forming composition according to any one of the prior claims, comprising a polymer material having a (weight-average) molecular weight of 500 to 100,000 g / mol, preferably 800 to 50,000 g / mol, more preferably less than 10,000 g / mol, and typically 1,000 to 10,000 g / mol.

14. A gap-filling material-forming composition according to any one of the prior claims, comprising a polymer blended in an organic solvent.

15. A gap-filling material forming composition according to any one of the prior claims, which is particularly capable of filling gaps with a width of 20 nm or less when deposited by spin coating.

16. A gap-filling material-forming composition according to any one of the prior claims, comprising a polymer blended in an organic solvent having a curing catalyst.

17. A gap-filling material-forming composition according to any one of the prior claims, comprising a polymer blended in an organic solvent having a thermally unstable curing catalyst.

18. A gap-filling material forming composition according to any one of the prior claims, comprising a polymer blended in an organic solvent having a photobase-containing curing catalyst.

19. A gap-filling material forming composition according to any one of the prior claims, comprising a polymer blended in an organic solvent having a photoacid-containing curing catalyst.

20. Use of a gap-filling material-forming composition according to any one of the prior claims for manufacturing a gap-filling dielectric film for semiconductor devices or optical elements.

21. The gap-filling dielectric film is - Having an electrical dielectric breakdown voltage of at least 3.8 MV / cm, preferably at least 3.9 MV / cm, and more preferably at least 4.0 MV / cm, - The dielectric constant at 1 MHz is 2.9 or less. The refractive index measured at a wavelength of 633 nm is at least 1.

37. - Having an elastic modulus of 8.5 GPa or higher, The shrinkage rate between soft baking and hardening is less than 5%, more preferably less than 3%, and most preferably less than 1%. The use described in claim 20.

22. A dielectric polymer film comprising a cured product of a gap-filling material-forming composition according to any one of claims 1 to 19.

23. The dielectric polymer film according to claim 22, having an electrical dielectric breakdown voltage of at least 3.8 MV / cm, preferably at least 3.9 MV / cm, and more preferably at least 4.0 MV / cm.

24. A dielectric polymer film according to claim 22 or 23, having an electrical dielectric breakdown voltage of 4.2 MV / cm or more.

25. A dielectric polymer film according to any one of claims 22 to 24, wherein the dielectric constant at 1 MHz is 2.9 or less.

26. A dielectric polymer film according to any one of claims 22 to 25, wherein the refractive index measured at a wavelength of 633 nm is at least 1.

37.

27. A dielectric polymer film according to any one of claims 22 to 26, having an elastic modulus of 8.5 GPa or higher.

28. A dielectric polymer film according to any one of claims 22 to 27, wherein the shrinkage rate between soft baking and curing is less than 5%, more preferably less than 3%, and most preferably less than 1%.

29. A dielectric polymer film according to any one of claims 22 to 28, having a thickness of less than 1 μm, particularly less than 500 nm, typically 50 to 350 nm.

30. A method for forming a gap-filling dielectric polymer film, Equation I R １ R ２ R ３ Si-X １ -SiX ２ ｎ R ４ ３－ｎ I The first silicon compound represented by (where R １ , R ２ , R ３ , X １ , R ４ , X ２ The steps include hydrolyzing (where n is the same as above), - The first silicon compound may be optionally, Formula II (X ３ ) ｍ (R ５ ) ３－ｍ Si-R ６ -Si(X ４ ) ｍ (R ７ ) ３－ｍ II Compounds represented by (where R ５ , R ６ , R ７ , X ３ , X ４ At least one second silicon compound obtained by hydrolyzing (where m is the same as above), and / or formula III (X ４ ) ４－ｎ SiR １４ ｎ III Compounds represented by (where R １４ , X ４ The steps include polymerizing with (where n is the same as above) to provide a gap-filling coating composition, - The steps of depositing the gap-filling coating composition onto a substrate and curing the composition to form a gap-filling dielectric polymer film. A method that includes this.

31. The method according to claim 30, wherein the substrate is a semiconductor substrate.

32. The method according to claim 30, wherein the substrate is an optical element or an optically active device.

33. The method according to any one of claims 30 to 32, wherein the gap-filling coating composition is deposited on the substrate in liquid form by a spin coating method.

34. A method for manufacturing semiconductor devices, - The step of providing a semiconductor device substrate, - The steps of applying the gap-filling material forming composition according to any one of claims 1 to 18 onto the semiconductor device substrate, curing the composition, and providing a gap-filling dielectric film on the semiconductor device substrate. A method that includes this.

35. The method according to claim 34, wherein the gap-filling material forming composition is cured by a combination of thermosetting and UV curing to provide the gap-filling dielectric film.

36. A method for manufacturing an optical element or optically active device, - The step of providing an optical element or optically active device substrate, - The steps of applying the gap-filling material forming composition according to any one of claims 1 to 18 onto the optical element or optically active device substrate, and firing the composition to form a gap-filling dielectric film. A method that includes this.

37. A semiconductor device comprising a dielectric polymer film according to any one of claims 22 to 29.

38. An optical element or optical device substrate comprising a dielectric polymer film according to any one of claims 22 to 29.

Images