Method for producing semiconductor device comprising low dielectric constant film

Abstract

A method of manufacturing a semiconductor device includes a polymer film including a polymer obtained by polymerizing a compound having the general formula I: X1 mR13-mSi-R3-(R52Si-O) n-Si-R4-SiX2pR2-pI wherein each of X1 and X2 is independently selected from the group consisting of hydrogen and an organic or inorganic hydrolysable group; each R1 and R2 is independently selected from the group of hydrocarbyl residues; each R3 and R4 is independently selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms; each R5 is selected from alkyl having 1 to 4 carbon atoms and phenyl; n is an integer from 1 to 5; m is an integer from 1 to 3; and p is an integer from 1 to 3. The polymer films are useful as low dielectric constant films in semiconductor devices, in particular as barrier layers filling gaps between metal interconnects.

Description

Field of the Invention

[0001] The present invention relates to a method for manufacturing a semiconductor device comprising a low dielectric constant film, the low dielectric constant film comprising polysiloxane. The present invention also relates to the use of a polymer film in a semiconductor device.

[0002] background

[0003] Integrated circuits are built on semiconductor substrates and contain millions of transistors and other devices that communicate electrically with each other and with external packaging materials through multiple layers of vertical and horizontal wiring embedded in dielectric materials. In the metallization structure, "vias" constitute the vertical wiring, while "interconnects" constitute the horizontal wiring. Manufacturing metallization may involve the continuous deposition and patterning of multiple layers of dielectric layers and metals to achieve electrical connections between transistors and with external packaging materials. Patterning of a given layer is usually performed by a multi-step process, including layer deposition on the substrate, photoresist spinning, photoresist exposure, photoresist development, layer etching, and photoresist removal. Alternatively, metal patterning can sometimes be achieved by first etching a pattern into a layer of dielectric material, filling the pattern with metal, and then chemically / mechanically polishing the metal so that the metal is embedded only in the openings of the dielectric material.

[0004] Aluminum has been used for many years 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 the years to improve melting point, diffusion, electromigration and other qualities compared to pure aluminum. Tungsten has traditionally been used as a conductive via plug material across a continuous aluminum layer. The pursuit of faster microprocessors and more powerful electronic devices has led to increasingly higher circuit densities and faster operating speeds, which in turn requires the use of more conductive metals and improved dielectrics with lower dielectric constants (preferably less than 3.0) compared to silicon dioxide. After aluminum metallization, the industry turned to copper damascene processes, in which copper (or copper alloys) are used to increase the conductivity of the wires, and spin coating or CVD processes are used to produce low-k dielectrics that can be used as insulating materials around the wires. In order to avoid etching problems, copper is deposited together with barrier metals on a recessed dielectric structure consisting of interconnects and via openings, followed by polishing in a processing method called "dual damascene". The bottom of the via opening is usually the top of the interconnect from the previous metal layer, or in some cases the contact layer, to the substrate.

[0005] The copper "dual damascene" process has been used successfully by the industry for two decades. The critical dimensions of copper interconnects in future devices will reach 10-20nm or even lower. Therefore, the dielectric materials between the interconnects exhibit similar critical dimensions. This is somewhat problematic for the copper "dual damascene" process because the mobility of copper ions is very strong, which means that these ions will migrate to the dielectric layer. Eventually, the increase in copper ion concentration will lead to dielectric breakdown, making the device or transistor inoperable. In order to prevent the migration of copper ions, various barrier layers have been deposited, which are usually nitrides of titanium or tantalum. In pitch designs below 30nm, the barrier layer will fill most of the space between the metal interconnects, resulting in an insufficient dielectric layer due to the poor dielectric properties of the nitride. Due to the above challenges, people are constantly looking for new metals with interconnect critical dimensions of 10-20nm or less. Potential metals for processes below 20nm include cobalt (Co), ruthenium (Ru), tungsten (W) and molybdenum (Mo). Depending on the metal used, metal lines can be formed using a subtractive process similar to aluminum and tungsten, or they can be formed through a single damascene process, where the replacement metal is deposited first and then the copper is deposited. Therefore, new dielectrics with suitable electrical and mechanical properties are needed, which are also able to fill critical dimensions of 10-20nm or lower to enable future devices and device architectures. In addition, the new dielectrics must withstand the conditions used in subsequent process steps, such as high temperatures (400°C or higher), various chemicals, and mechanical forces (chemical mechanical polishing). Summary of the invention

[0006] The object of the present invention is to provide a semiconductor device comprising a polymer film having a dielectric constant of 2.7 or less. Specifically, the present invention provides a method for manufacturing a semiconductor device comprising a substrate on which a metal selected from cobalt (Co), ruthenium (Ru), tungsten (W) and molybdenum (Mo) is deposited.

[0007] In the present invention, a semiconductor device comprising a low dielectric constant polymer film is provided. The film comprises a polymer obtained by polymerizing a compound having the general formula I

[0008] X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0009] in,

[0010] Each Xl and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group;

[0011] Each R 1 and R 2 independently selected from the group of hydrocarbyl residues, which are optionally substituted;

[0012] Each R 3 and R 4 independently selected from optionally substituted bridged straight or branched divalent hydrocarbon groups, such as alkylene groups having 1 to 6 carbon atoms and arylene groups having 6 to 10 carbon atoms;

[0013] Each R 5 is chosen from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms, such as phenyl or benzyl, said groups being optionally substituted;

[0014] n is an integer from 1 to 5;

[0015] m is an integer from 1 to 3; and

[0016] p is an integer from 1 to 3.

[0017] In one embodiment, a polymer film having a dielectric constant of 2.7 or less at 1 MHz is formed by the following steps:

[0018] - hydrolyzing a first silicon compound having formula I

[0019] X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0020] Where X l ,X 2 ,X 3 ,X 4 ,R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,i and n,m,p have the same meanings as above,

[0021] Optionally hydrolyzing at least one second compound of formula III and / or formula IV

[0022] (R 11 )2R 12 Si-R 13 -SiR 11 3 III

[0023] in,

[0024] R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy,

[0025] R 12 is hydrogen, an organic crosslinking group, a reactive cleavage group or a group that reduces polarizability,

[0026] R 13 A bridged straight or branched divalent hydrocarbon group

[0027] (X 3 ) 4-n S i 14 n IV

[0028] Among them, X 3 ,R 14 and n have the same meaning as above

[0029] and polymerizing or copolymerizing the hydrolyzed compound to produce a siloxane material.

[0030] The siloxane material is typically deposited as a thin layer on a substrate, and the thin layer is cured into a film having a low dielectric constant.

[0031] More specifically, the invention is characterized by what is stated in the independent claims.

[0032] The present invention achieves significant advantages.

[0033] Thus, in the method of manufacturing semiconductor devices according to the present invention, the disclosed siloxane materials provide high modulus and hardness and will help to bind metal interconnects and via labyrinths together, especially in the final chip packaging step. Due to good adhesion properties, these films will help to form a stable interface between dielectric and contact materials.

[0034] The siloxane material used in the semiconductor device manufacturing method of the present invention can be formed into a thin film with a thickness in the range of 50nm to 2500nm, for example, in the range of 50nm to 1000nm; generally, any cracking will not occur even in a thick film structure.

[0035] The substrate used to deposit the siloxane material can contain a variety of morphologies. These include narrow grooves that may have a high aspect ratio, which means that the depth to width ratio (or aspect ratio) of the groove exceeds 2: 1, such as 3: 1 or higher. Therefore, these materials have an excellent ability to fill groove widths even below 20nm or more preferably below 10nm. At the same time, siloxane materials exhibit excellent planarization performance. Planarization performance refers to the ability of the siloxane material to evenly distribute the height differences on the substrate caused by the various morphologies present on the substrate before coating. The ability to planarize the substrate has significant advantages because the subsequent process of planarizing the substrate surface can be eliminated or reduced. In this way, considerable advantages can be obtained in terms of manufacturing cost and time. In addition, in the case where the film thickness needs to be reduced or a flatter surface is required in subsequent manufacturing process steps, the film can be easily processed by chemical mechanical polishing or etching processes.

[0036] In addition, the siloxane material used in the method of manufacturing a semiconductor device according to the present invention exhibits a low coefficient of thermal expansion (CTE). A low coefficient of thermal expansion is very beneficial in preventing the substrate from bending during subsequent process steps. Such bending typically occurs on substrates containing materials with significantly variable CTE. Preferably, the CTE of the cured siloxane material is 50 ppm / °C or less, more preferably, 30 ppm / °C or less, and most preferably, 20 ppm / °C or less.

[0037] According to the present invention, the siloxane material used in the method for manufacturing a semiconductor device also has thermal stability. In order for the coating to withstand the multiple thermal cycles in the semiconductor manufacturing process, good thermal stability is required.

[0038] Importantly, the materials of the present invention exhibit low current leakage, high breakdown voltage and low loss tangent.

[0039] BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 schematically illustrating various stages of fabricating a semiconductor device including a low-k dielectric in accordance with at least some embodiments of the present invention; and

[0041] Figure 2 Various stages in an alternative fabrication of a semiconductor device comprising a low-k dielectric composed of a film of the polysiloxane material disclosed herein are schematically illustrated. Example

[0042] Hereinafter, embodiments of the present technology will be described in more detail.

[0043] Unless otherwise stated herein or clear from the context, any percentages mentioned herein are expressed as weight percentages based on the total weight of the corresponding composition.

[0044] Unless otherwise stated, the properties experimentally measured or determined herein were measured or determined at room temperature. Room temperature is 25°C unless otherwise stated.

[0045] Unless otherwise stated, all properties experimentally measured or determined herein were measured or determined at atmospheric pressure.

[0046] 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 indicated.

[0047] As used herein, the term "about" refers to a value of ± 5% of the stated value.

[0048] As used herein, the term "average molecular weight" refers to the weight average molecular weight (also abbreviated as "M W ” or “M w ”).

[0049] As used herein, molecular weight is measured by gel permeation chromatography using polystyrene standards.

[0050] As used herein, "coefficient of thermal expansion" is measured by a stylus-based profilometer that detects changes in wafer curvature that result from heating a coated substrate.

[0051] The dielectric constant, κ or εr, was measured on a highly doped, low resistivity N+ doped silicon wafer using a metal-insulator-semiconductor (MIS) structure using a mercury probe (Materials Development Corporation, Model 802) and a precision impedance analyzer (Agilent 4294A).

[0052] to determine the capacitance across the dielectric film, which along with the mercury point contact area and film thickness can be used to calculate the dielectric constant using the formula x

[0053]

[0054] Where κ is the dielectric constant, C is the capacitance, d is the film thickness, ε0 is the vacuum dielectric constant, and A is the capacitor area.

[0055] The "breakdown voltage" was measured using a similar MIS structure with a mercury probe (Materials Development Corporation, Model 802) and a semiconductor parameter analyzer (Agilent 4155B).

[0056] The "leakage current" is measured as a function of voltage during a voltage sweep from -20 V to 100 V, and the breakdown voltage is found when the current suddenly surges as the film breaks down. The breakdown voltage is measured in MV / cm and is calculated by dividing the measured breakdown voltage by the film thickness.

[0057] The "refractive index" (RI) is measured using a refractometer at a wavelength of 633 nm. The RI can be calculated from a polymer film sample having a thickness of 400 nm by interferometry, deviation method, or Brewster angle method.

[0058] The "hardness" and "elastic modulus" of the film can be calculated from the indentation curve using the Oliver-Pharr method.

[0059] The embodiments disclose the production of a low dielectric constant polymer film comprising a siloxane polymer having -(Si-O-Si)- segments, wherein the silicon atoms typically carry a hydrocarbyl substituent, such as a lower alkyl group, and the use of the polymer film in a method for manufacturing a semiconductor device. The polymer film is obtained by homopolymerization or copolymerization of a silane monomer.

[0060] Typically, in the present technology, a silane monomer containing a hydrolyzable group is first hydrolyzed and then polymerized, typically in a liquid phase, at a temperature between room temperature and the boiling point of the liquid. In addition to the silicon monomer and water added for the hydrolysis of the monomer, the liquid may also consist of one or more solvents. In particular, suitable solvents include acetone, ethyl methyl ketone, methanol, ethanol, isopropanol, butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and tetrahydrofuran. Particularly suitable solvents are alcohols, ketones, and ethers.

[0061] The hydrolysis of the monomer is controlled by adding an acid or alkaline solution having a molar concentration ranging from 0.0001M to 1M. Organic or inorganic acids can be used in the 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 they have a low boiling point, which makes the purification of the product simple. In other options, various organic acids are used instead of inorganic acids. Organic acids include carboxylic acids, sulfonic acids, alcohols, sulfhydryls, enol groups and phenolic hydroxyl groups. For example, methanesulfonic acid, acetic acid, ethanesulfonic acid, toluenesulfonic acid, formic acid and oxalic acid.

[0062] The base used in the 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 substances are sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, sodium carbonate and sodium bicarbonate. On the other hand, organic bases include a large class including metal salts of organic acids (e.g., sodium acetate, potassium acetate, sodium acrylate, sodium methacrylate, sodium benzoate), linear, branched or cyclic alkylamines (e.g., diaminoethane, putrescine, cadaverine, triethylamine, butylamine, dibutylamine, tributylamine, piperidine), amidines and guanidines (e.g., 8-diazabicyclo(5.4.0)undec-7-ene, 1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo[4.4.0]-dec-5-ene), phosphazenes (e.g., P1-t-Bu, P2-t-Bu, P4-t-Bu) and quaternary ammonium compounds (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide).

[0063] The temperature of the reaction mixture during the hydrolysis and condensation process can vary from -30 to 170°C. Lower reaction temperatures provide improved control of the reaction at the expense of longer reaction times, while too high a temperature may make the process too rapid to be adequately controlled. Preferably, the reaction time is 1 to 48 hours at a temperature of 0 to 100°C. More preferably, the reaction time is 2 to 24 hours.

[0064] Using appropriate conditions, a partially crosslinked organosiloxane polymer is obtained in an organic solvent system having a molecular weight of about 500 to 100,000 g / mol, preferably 800 to 50,000 g / mol, and most preferably 1000 to 10,000 (based on polystyrene standards).

[0065] In some embodiments, the solvent for hydrolysis and polymerization is replaced by a solvent that provides better coating performance and product storage performance for the material through some form of stabilization after polymerization. This stable organic solvent system is composed of an organic ether mixed with one or more other co-solvents. Organic ethers are linear, branched or cyclic ethers, generally containing 4 to 26 carbon atoms and other functional groups, such as hydroxyl groups. Particularly suitable examples are five-membered and six-membered cyclic ethers, which optionally have substituents on their rings, and ethers, such as (C1-20) alkanediol (C1-6) alkyl ethers. Examples of the alkanediol alkyl ethers are 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. Particularly preferred examples of these ethers are methyl tetrahydrofuran methyl ether, tetrahydrofurfuryl alcohol, propylene glycol n-propyl ether, dipropylene glycol dimethyl ether, propylene glycol n-methyl ether, propylene glycol n-ethyl ether and mixtures thereof. The stable solvent system consists of a solvent containing only such ethers or a mixture of such ethers with typical reaction media or other solvents for hydrolysis (e.g. propylene glycol monomethyl ether acetate). In this case, the proportion of ether is about 10 to 90 wt %, in particular about 20 to 80 wt %, of the total amount of solvent.

[0066] The solids content of the formulation consisting of the selected solvent and the hydrolysis and polymerization products is in the range of 0.1 to 60%, preferably 0.5 to 30%, most preferably 1 to 10%.

[0067] In a specific embodiment, the polymer film in the method of manufacturing a semiconductor device is obtained by polymerizing or copolymerizing a compound having the general formula I: 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0068] in,

[0069] Each X l and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group;

[0070] Each R 1 and R 2 independently selected from the group of hydrocarbyl residues, which are optionally substituted;

[0071] Each R 3 and R 4independently selected from the group of optionally substituted bridged straight or branched divalent hydrocarbon groups, such as alkylene groups having 1 to 6 carbon atoms and arylene groups having 6 to 10 carbon atoms;

[0072] Each R 5 is chosen from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms, such as phenyl or benzyl, said groups being optionally substituted;

[0073] n is an integer from 1 to 5;

[0074] m is an integer from 1 to 3; and

[0075] p is an integer from 1 to 3.

[0076] According to one embodiment, in Formula I,

[0077] Each X l and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group;

[0078] Each R 1 and R 2 independently selected from the group of hydrocarbyl residues;

[0079] Each R 3 and R 4 independently selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms;

[0080] Each R 5 is selected from alkyl groups having 1 to 4 carbon atoms and phenyl groups; and

[0081] n, m and p have the same meanings as above.

[0082] In one embodiment, in Formula I, each X l and X 2 Independently selected from the group of hydrogen and a hydrolyzable group, the hydrolyzable group is selected from a halogen, an acyloxy group, an alkoxy group and an OH group. Typically, the halogen is selected from fluorine, chlorine or bromine, and the hydrocarbyl residue of the acyl (alkanoyl) functional group of the acyloxy group is selected from an alkyl group having 1 to 6 carbon atoms.

[0083] In one embodiment, in Formula I, each X l and X 2 are independently selected from hydrogen and 7 O-alkoxy group, where R 7 represents an alkyl group having 1 to 6 carbon atoms.

[0084] In one embodiment, in Formula I, each R 1 and R 2Independently selected from the group consisting of straight chain, branched and cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups containing 1 to 5 aromatic rings, optionally containing 1 to 3 heteroatoms.

[0085] In one embodiment, each R 3 and R 4 represents a divalent hydrocarbon residue, and in particular each R 3 and R 4 R is independently selected from saturated alkylene groups having 1 to 4 carbon atoms, especially 2 carbon atoms. 3 and R 4 It may also be chosen from divalent aromatic hydrocarbon residues, for example arylene radicals, such as phenylene or naphthylene.

[0086] In Formula I, a hydrocarbon group, such as an alkyl group, an alkylene group, an aryl group or an arylene group, such as R 1 , R 2 , R 3 , R 4 and R 5 , may optionally be replaced by 1 to 3 groups selected from halogen, hydroxy, alkoxy, in particular C 1-4 Functional group substitutions include alkoxy, vinyl and acetyl and combinations thereof.

[0087] In one embodiment, a hydrocarbon group, such as R 1 , R 2 , R 3 , R 4 and R 5 , which can decompose during the film curing process and leave behind a crosslinking group or a group that reduces the polarizability, or a combination thereof. If the group is a leaving group, very small pore sizes will still be produced, i.e., typically 1.5 nm or less. However, the polymers formed according to the present technology are also compatible with conventional types of porogens (e.g., cyclodextrins), which can be used to form micropores in the polymer, thereby reducing the dielectric constant of the polymer.

[0088] Examples of organic crosslinking groups, reactive cleavage groups or organic groups that reduce polarizability are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, polycyclic groups or organic silicon-containing groups. The groups may also be fully or partially halogenated.

[0089] In one embodiment, in Formula I, the symbol n represents an integer from 1 to 5, in particular from 1 to 4, for example 1, 2 or 4.

[0090] One embodiment includes using a monomer according to Formula I having Formula Ia

[0091]

[0092] One embodiment includes using a monomer of formula I having formula Ib

[0093]

[0094] One embodiment includes using a monomer of formula I having formula Ic

[0095]

[0096] The compounds of general formula I and formulae Ia to Ic can be obtained by reacting a bifunctional siloxane compound with a silane monomer comprising a hydrolyzable group and at least one reactive group (eg, vinyl group) in the presence of a catalyst (eg, a noble metal catalyst).

[0097] For example, the difunctional siloxane compound may have Formula II

[0098] R 8 p R 9 3-p Si-O-SiR 8 p R 9 3-p II

[0099] in,

[0100] R 8 represents hydrogen or a hydrocarbon having a vinyl group,

[0101] R 9 represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms),

[0102] p represents 0 or an integer from 1 to 3.

[0103] Specifically, R 9 represents methyl, and p represents 1.

[0104] In one embodiment, the polymer film is provided by homopolymerization of a compound of Formula I (eg, Compound Ia, Ib, or Ic) or by copolymerization of two or three compounds of Formula Ia, Ib, or Ic.

[0105] In one embodiment, the polymer film is provided by copolymerization of at least one compound of Formula I (eg, a compound according to Formula Ia, Ib, or Ic) and a compound of Formula III.

[0106] (R 11 )2R 12 Si-R 13 -SiR 11 3 III

[0107] in,

[0108] R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy,

[0109] R 12 is hydrogen, an organic crosslinking group, a reactive cleavage group, or an organic group that reduces polarizability, and

[0110] R 13 It is a bridged linear or branched divalent hydrocarbon group.

[0111] R 11 is preferably selected from halides, alkoxy, acyloxy and hydrogen, R 12 Preferably, R is selected from alkyl, alkenyl, alkynyl and aryl, polycyclic groups or silicon-containing organic groups. 13 It is preferably selected from the group consisting of straight-chain and branched alkylene, alkenylene and alkynylene groups, divalent alicyclic groups (polycyclic groups) and divalent aromatic groups, all of which are included in the definition of divalent hydrocarbon groups.

[0112] As used herein, "alkenyl" includes straight and branched alkenyl groups, such as ethenyl and propenyl. As used herein, the term "alkynyl" includes straight and branched alkynyl groups, preferably ethynyl. "Aryl" refers to a substituted or unsubstituted monocyclic, bicyclic or polycyclic aromatic carbocyclic group; examples of aryl groups are phenyl, naphthyl or pentafluorophenylpropyl. As used herein, "polycyclic" groups include, for example, adamantyl, dimethyladamantylpropyl, norbornyl or norbornene. More specifically, an alkyl, alkenyl or alkynyl group may be straight or branched.

[0113] The divalent alicyclic group may be a polycyclic aliphatic group, including residues derived from a ring structure having 5 to 20 carbon atoms, such as norbornene (norbornenyl) and adamantyl (adamantylene). "Arylene" represents a divalent aromatic group containing 1 to 6 rings, preferably 1 to 6, especially 1 to 5 fused rings, such as phenylene, naphthylene and anthracenyl.

[0114] In one embodiment, the polymer film used in the method of manufacturing a semiconductor device as defined herein is provided by copolymerizing at least one compound of formula I (e.g. a compound according to formula Ia, Ib or Ic) with a compound of formula IV

[0115] (X 3 ) 4-n S i 14 n IV

[0116] In Formula IV,

[0117] X 3 is hydrogen or a hydrolyzable group selected from halogen, acyloxy, alkoxy and OH groups;

[0118] R 14is selected from halogen, acyloxy, alkoxy and OH groups, and alkyl groups having 1 to 6 carbon atoms, vinyl groups having 2 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms; and

[0119] n is an integer having the same meaning as above.

[0120] The acyloxy, alkoxy, alkyl, vinyl and aryl groups have the same meanings as above.

[0121] Specific examples of Formula IV include, but are not limited to, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropropoxysilane, methyltributoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane. silane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-(methacryloyloxy)propylmethyldimethoxysilane, γ-(methacryloyloxy)propylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane , γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxy propyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, 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)ethyltriethoxysilane4-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-glycidoxypropylmethyl , α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, phenylsulfonylaminopropyltriethoxysilane.

[0122] As used herein, "alkoxy" and "acyloxy" groups typically have 1 to 6 carbon atoms.

[0123] As used herein, "halogen" has the conventional meaning and especially represents chlorine, fluorine or bromine.

[0124] As used herein, "halide" has the conventional meaning and refers to a halogen compound.

[0125] In one embodiment, the polymer film is provided by copolymerizing the compound of formula I with compounds of formula III and IV (ie, a mixture of compounds of formula III and IV).

[0126] In one embodiment, where a copolymer is produced, the molar ratio between the compound of formula I and the compound of formula III is in the range of 10:90 to 90:10. For example, the molar ratio between the compound of formula I and the compound of formula III is 20:80 to 80:20, especially 40:60 to 60:40.

[0127] In one embodiment of producing the copolymer, the molar ratio of the compound of formula I to the compound of formula IV is in the range of 10:90 to 90:10. For example, the molar ratio of the compound of formula I to the compound of formula IV is 20:80 to 80:20, in particular 40:60 to 60:40.

[0128] In one embodiment of producing the copolymer, the molar ratio of the compound of formula I to the compounds of formula III and IV is in the range of 10:90 to 90:10. For example, the molar ratio of the compound of formula I to the compounds of formula III and IV is 20:80 to 80:20, specifically 40:60 to 60:40.

[0129] Typically the organic content of the polymer is in the range of 20 to 60 wt%. Typically an organic content of less than 40 wt% is preferred.

[0130] In one embodiment, a polymer film having a dielectric constant of 2.7 or less (e.g., 2.5 or less) at 1 MHz for use in the method of manufacturing a semiconductor device according to the present invention is produced by a method comprising the following steps:

[0131] - hydrolyzing a first silicon compound having formula I

[0132] X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0133] Among them, X l , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , R 4 , R 5 , I and n, m, p have the same meanings as above;

[0134] - optionally hydrolyzing at least one second silicon compound of formula III and / or of formula IV

[0135] (R 11 )2R 12 Si-R 13 -SiR 11 3 III

[0136] in,

[0137] R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy,

[0138] R 12is hydrogen, an organic crosslinking group, a reactive cleavage group, or an organic group that reduces polarizability, and

[0139] R 13 is a bridging linear or branched divalent hydrocarbon group;

[0140] (X 3 ) 4-n S i 14 n IV

[0141] Among them, X 3 , R 14 and n have the same meanings as above,

[0142] - polymerizing the hydrolyzed compound to produce a polymerized siloxane material; and

[0143] - The polymeric material is formed into a layer which solidifies into a film.

[0144] In one embodiment, the siloxane material obtained by homopolymerization or optional copolymerization of the compound according to formula I and optionally formula III and / or formula IV is deposited on the substrate in the form of a layer, and then the deposited material is cured into a film.

[0145] The thickness of this layer is generally less than 2 μm, in particular less than 1 μm, in particular less than about 500 nm.

[0146] These layers solidify into a polymer film having a thickness of typically less than 1 μm, particularly less than about 500 nm, typically about 50 to 350 nm.

[0147] The film of the present invention has good optical properties. Therefore, the refractive index (RI) of the polymer film can be greater than 1.4 when measured at a wavelength of 633 nm.

[0148] Surprisingly, it has been found that by using monomers of formula I in polymer films consisting of or comprising such monomers, excellent electrical properties can be obtained in semiconductor devices comprising a substrate deposited with a metal selected from cobalt (Co), ruthenium (Ru), tungsten (W) and molybdenum (Mo).

[0149] Furthermore, it has been found that by incorporating short linear segments (n having a value of 1 to 5), materials can be obtained which exhibit a combination of low thermal expansion and moderate elasticity / softness or significant hardness.

[0150] In one embodiment, the dielectric constant of the film at 1 MHz is 2.7 or lower, such as 2.5 or lower. In a further embodiment, the dielectric constant of the polymer after curing is 2.45 or lower, preferably 2.30 or lower.

[0151] In one embodiment, the cured polymer film has an electrical breakdown voltage of 3.5 MV / cm or higher, such as 3.55 MV / cm or higher, such as 3.6 MV / cm or higher.

[0152] In one embodiment, the cured polymer film exhibits a coefficient of thermal expansion of less than 10 ppm / °C, such as less than 9.5 ppm / °C or less than 9 ppm / °C.

[0153] In one embodiment, the cured polymer film exhibits an elastic modulus of 6.3 GPa or higher, such as 6.5 GPa or higher, such as 6.7 GPa or higher.

[0154] In one embodiment, the cured polymer film exhibits a hardness of 1.5 GPa or more, such as 1.6 GPa or more, such as 1.7 GPa or more.

[0155] The effect on the mechanical properties is mainly determined by the length of the bridging group in formula I, since an increase in n in formula I reduces the elastic modulus and hardness. Surprisingly, it has been found that the hardness of films prepared by homopolymerization or copolymerization using monomers of formula I with n≤2 is comparable to films prepared from monomers of formula III and / or IV.

[0156] In one embodiment, the electrical properties (eg, electrical breakdown voltage) of polysiloxane films made from silane monomers of Formula II can be significantly improved by using at least 10 mol % of the total amount of silane monomers of Formula I.

[0157] In one embodiment, by using at least 10 mol% of the total amount of silane monomers of formula I, a significant reduction in dielectric constant can be observed compared to films made from only monomers of formula III and / or IV. Surprisingly, a significant reduction in dielectric constant was detected for both homopolymers and copolymers including monomers of formula I.

[0158] In one embodiment, by using at least 10 mol% of the monomer of formula I based on the total amount of silane monomers, a significant reduction in film shrinkage can be observed compared to films made from only monomers of formula III and / or IV. Surprisingly, a significant reduction in shrinkage was detected for both homopolymers and copolymers including monomers of formula I. Small shrinkage is very beneficial for preventing substrate bending in subsequent process steps.

[0159] Various types of surfactants (e.g., silicone or fluorosurfactants) can be used to optimize the formulation because they reduce the surface tension of the silanol-containing polysiloxane formulation coating. If necessary, the use of such surfactants can improve the coating quality. 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%, and most preferably 0.01 to 5% or 0.05 to 2.5%.

[0160] The formulation can be optimized by adding various types of photo- or heat-labile catalysts or compounds to the formulation mixture to enhance the crosslinking of the organosiloxane film. The amount of heat- or photo-labile compounds in the formulation is in the range of 0.05 to 20% by mass relative to the amount of silanol-containing organosiloxane, preferably 0.1 to 10%, most preferably 0.5 to 5% or 0.5 to 3%, corresponding to the solid content of the polymer.

[0161] Figure 1 Various stages in the production of a semiconductor device including a low-k dielectric composed of the polysiloxane films disclosed herein in accordance with the present technology are shown.

[0162] As shown, a substrate 1 is first provided. Such a substrate may, for example, comprise a silicon wafer. In a second stage, the substrate is subjected to metal deposition 2. The metal layer consists of a conductive metal 3. Traditionally, copper has been used for such purposes, but for patterned devices having a diameter of 1 to 50 nm, such as 1 to 20 nm or even 5 to 15 nm, the metal is selected from cobalt, molybdenum, tungsten, ruthenium or some other suitable metal, preferably selected from cobalt (Co), molybdenum (Mo) and ruthenium (Ru).

[0163] The substrate 1 with the metal layer 3 is patterned by known steps in photolithography, including a photoresist coating 4 (and a required photoresist underlayer) using a suitable photoresist coating material 5, for example a material suitable for patterning using electromagnetic radiation in the UV range or even in the extreme UV range (EUV).

[0164] After the exposure and development steps 6, the metal layer 3 is pattern-transferred by etching 7. Thereafter, the remaining photoresist and the photoresist bottom layer 8 are stripped off, leaving the substrate with the patterned metal layer 3.

[0165] In the following two steps, a dielectric coating 10 is applied 9 onto the patterned metal layer 3 and onto the substrate 1 to fill the gaps between the metal patterns. Finally, the metal 10 separated by the dielectric is opened 11 by etching back, for example using gas or chemical mechanical polishing (CMP).

[0166] As a result, a semiconductor device including a dielectric formed of a polymer film according to the present technology is provided.

[0167] In summary, the method for manufacturing a semiconductor device according to the present technology includes or consists of the following steps:

[0168] - providing a substrate;

[0169] - depositing a metal layer on the substrate, the metal layer comprising a metal selected from the group consisting of cobalt (Co), molybdenum (Mo), tungsten (W) and ruthenium (Ru);

[0170] -Deposition of photoresist and auxiliary underlayer on top of the metal;

[0171] - exposing the photoresist stack to light or an electron beam through a mask to form a desired pattern;

[0172] - developing the soluble part of the photoresist by a selective etching process and transferring the formed pattern to the metal layer;

[0173] - removing the remaining parts of the photoresist stack;

[0174] - depositing and curing a low-k dielectric film according to any of the embodiments; and

[0175] -Removing the excess portion of the deposited low-k dielectric film by etching or chemical mechanical polishing process.

[0176] Preferably, the metal is selected from cobalt (Co), molybdenum (Mo) and ruthenium (Ru).

[0177] Figure 2 Various stages of an alternative production of a semiconductor device including a low-k dielectric composed of a film of the polysiloxane material disclosed herein are shown in accordance with the present technique.

[0178] As shown, a substrate 11 is first provided. Such a substrate may, for example, comprise a silicon wafer. In a second stage 12, the substrate is dielectrically coated to provide a layer of low-k dielectric 13 on top of (at least one surface of) the substrate 11. Then, in a second step, the thus coated substrate is etched to remove a predetermined dielectric portion, thereby patterning the surface. In a third stage, overlapping layers of barrier material 16 and metal 17 are deposited on the surface. The metal layer may, for example, comprise a conductive layer, such as copper.

[0179] As can be seen, barrier material 16 and metal 17 generally cover both etched and unetched portions of the surface. In a final fourth stage 18, the multilayer structure is then subjected to metal via openings, for example by chemical mechanical polishing.

[0180] As a result, a semiconductor device is obtained, which includes a low-k dielectric with embedded metal vias.

[0181] The following non-limiting examples illustrate further embodiments.

[0182] Example

[0183] monomer

[0184] Monomer A: (1,2-bis(trimethoxysilylethyl)tetramethyldisiloxane)

[0185]

[0186] Monomer B: (1,3-bis(trimethoxysilylethyl)hexamethyltrisiloxane)

[0187]

[0188] Monomer C: (1,5-bis(trimethoxysilylethyl)decamethylpentasiloxane)

[0189]

[0190] Synthesis of Monomer A:

[0191] Preparation of Monomer A: Vinyl trimethoxysilane (VinTMOS, 971.9 g, 6.56 mol), platinum catalyst (1 g) and acetic acid (0.2 g) were added to a 3 L flask. The solution was thoroughly mixed at 40 ° C, and then tetramethyl disiloxane (TMDS, 400 g, 2.98 mol) was added to the solution. After adding TMDS, the reaction mixture was left at room temperature overnight. After the reaction was completed, it was distilled under reduced pressure. The amount of product obtained was 920 g (yield 71%, GC-MS purity 99%).

[0192] Synthesis of Monomer B:

[0193] Preparation of Monomer B: VinTMOS (39 g, 0.26 mol), platinum catalyst (100 mg) and 2 drops of acetic acid were added to a flask. Hexamethyltrisiloxane (HMTS, 0.12 mol) was slowly added to the solution and stirred overnight. The monomer was purified by vacuum distillation. The amount of the obtained product was 44 g (yield 76%, GC-MS purity 99%).

[0194] Synthesis of Monomer C:

[0195] Preparation of Monomer C: Hexamethylcyclotrisiloxane (D3, 7g, 0.34mol), TMDS (113g, 0.84mol) and toluene (20g) were added to a flask. The flask was kept under ice-cold conditions and purged with nitrogen for five minutes. Trifluoromethanesulfonic acid (300mg) was added to the solution. After five minutes, hexamethyldisilazane (6ml) was added to the solution as a quencher. Stirring was continued for ten minutes under ice-cold conditions. The intermediate product was purified under reduced pressure. The amount of the intermediate product obtained was 81g (yield 67%, GC-MS purity 99%).

[0196] In a 500 ml flask, VinTMOS (46 g, 0.31 mol), a few drops of acetic acid and a platinum catalyst (100 mg) were added. The flask was placed in an oil bath (50 degrees Celsius) and the obtained intermediate product (50 g) was added to the solution. The solution was stirred overnight. The monomer thus obtained was purified by vacuum distillation. The amount of product obtained was 56 g (yield 61%, GC-MS purity 97.5%).

[0197] Polymer preparation

[0198] Example 1: A homopolymer of the resulting monomer A was prepared in a 250 ml round-bottom flask. Monomer A (5.6 g, 0.03 mol), acetone (37 g) and 0.01 M HCl (2.2 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (56 g) was added to the reaction mixture. Acetone and hydrolyzate were removed under reduced pressure to obtain a preparation with a solid content of 23%. The resulting polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 1716 / 968, respectively. 8% polymer preparation PGMEA was prepared and spin-coated on a silicon wafer for refractive index and electrical property measurements.

[0199] Example 2: A copolymer of the obtained monomer A and 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 100 ml round bottom flask. Monomer A (8.6 g, 0.02 mol), 1-trimethoxysilyl-2-dimethoxymethyl-ethylene (5.1 g, 0.02 mol), acetone (41 g) and 0.01 M HCl (4.0 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGMEA (55 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a preparation with a solid content of 15%. The obtained polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The measured weight average molecular weight and number average molecular weight were 1823 / 821, respectively. An 8% polymer formulation was prepared with PGMEA and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0200] Example 3: A copolymer of the obtained monomer A and 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 100 ml round bottom flask. Monomer A (4.3 g, 0.01 mol), 1-trimethoxysilyl-2-dimethoxymethyl-ethylene (22.9 g, 0.09 mol), acetone (82 g) and 0.01 M HCl (9.2 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. MIBK (190 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solid content of 19%. The obtained polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 1833 / 922, respectively. An 8% polymer formulation was prepared with PGMEA and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0201] Example 4: A terpolymer of the obtained monomer A, methyltriethoxysilane (MTEOS) and tetraethylorthosilicate (TEOS) was prepared in a 100 ml round bottom flask. Precursor A (8.6 g, 0.02 mol), MTEOS (1.78 g, 0.01 mol), TEOS (2.08 g, 0.01 mol), acetone (26 g) and 0.01 M HCl (3.4 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGMEA (33 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a preparation with a solid content of 12%. The resulting polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The measured weight average molecular weight and number average molecular weight were 1860 / 893, respectively. An 8% polymer formulation was prepared with PGMEA and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0202] Example 5: A terpolymer of the obtained monomer A, methyltriethoxysilane (MTEOS) and tetraethylorthosilicate (TEOS) was prepared in a 100 ml round bottom flask. Precursor A (8.6 g, 0.02 mol), MTEOS (4.3 g, 0.02 mol), TEOS (4.87 g, 0.02 mol), acetone (26 g) and 0.01 M HCl (5.1 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGMEA (63 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a preparation with a solid content of 19%. The obtained polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The measured weight average molecular weight and number average molecular weight were 2532 / 1200, respectively. An 8% polymer formulation was prepared with PGMEA and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0203] Example 6: A homopolymer of the resulting precursor monomer B was prepared in a 100 ml round-bottom flask. Monomer B (10.1 g, 0.02 mol), acetone (30 g) and 0.01 M HCl (2.2 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGMEA (100 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solid content of 36%. The resulting polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The measured weight average molecular weight and number average molecular weight were 1744 / 652, respectively. An 8% polymer formulation was prepared with PGMEA, MIBK and a surfactant and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0204] Example 7: A copolymer of the obtained monomer B and 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 100 ml round bottom flask. Monomer B (10.1 g, 0.02 mol), 1-trimethoxysilyl-2-dimethoxymethyl-ethylene (5.1 g, 0.02 mol), acetone (46 g) and 0.01 M HCl (4.0 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGMEA (100 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solid content of 40%. The obtained polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 1644 / 602, respectively. A 7% polymer formulation was prepared with PGMEA and MIBK and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0205] Example 8: A copolymer of the obtained precursor monomer C and 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 100 ml round bottom flask. Monomer C (6.5 g, 0.01 mol), 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane (1.1 g, 0.004 mol), acetone (23 g) and 0.01 M HCl (1.6 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. Acetone and hydrolyzate were removed under reduced pressure to obtain a preparation with a solid content of 30%. The resulting polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 3287 / 1547, respectively. An 8% polymer preparation was prepared with MIBK and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0206] Example 9: A copolymer of the obtained precursor monomer C and 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 100 ml round bottom flask. Monomer C (6.5 g, 0.01 mol), 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane (2.5 g, 0.01 mol), acetone (27 g) and 0.01 M HCl (2.2 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a preparation with a solid content of 21%. The obtained polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average and number average molecular weights were determined to be 2758 / 1324, respectively. An 8% polymer preparation was prepared with MIBK and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0207] Example 10: A terpolymer of the resulting precursor monomer C, TEOS and MTEOS was prepared in a 100 ml round bottom flask. Monomer C (6.5 g, 0.01 mol), MTEOS (0.89 g, 0.01 mol), TEOS (1.0 g, 0.005 mol), acetone (25 g) and 0.01 M HCl (1.9 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. Acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solid content of 12%. The resulting polymer solution was filtered using a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 2980 / 1513, respectively. An 8% polymer formulation was prepared using MIBK and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0208] Comparison examples

[0209] Comparative Example 1: A copolymer of tetraethyl silicate (TEOS) and methyltriethoxysilane (MTEOS) was prepared in a 100 ml round-bottom flask. TEOS (83 g, 0.4 mol), MTEOS (71 g, 0.4 mol), acetone (155 g) and 0.01 M HCl (61 g) were added to the flask. The reaction mixture was refluxed for 18 h and then cooled to room temperature. PGEE (500 g) was added to the reaction mixture. Acetone and hydrolyzate were removed under reduced pressure to obtain a formulation with a solid content of 21%. PGMEA was added to the formulation, the resulting polymer solution was filtered with a 0.2 μm PTFE filter, and characterized by gel permeation chromatography (GPC). The measured weight average molecular weight and number average molecular weight were 2061 / 1293, respectively. A 6% polymer formulation was prepared with PGMEA and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0210] Comparative Example 2: A polymer composed of TEOS, MTEOS and triethoxysilane (HTEOS) was prepared in a 4 L flask. TEOS (57 g, 0.27 mol), MTEOS (98 g, 0.55 mol), HTEOS (45 g,

[0211] 0.27mol), isopropanol (301g) and 0.01MHCl (97g) were added to a flask. The reaction mixture was refluxed for 30min and then cooled to room temperature. PGMEA (900g) was added to the reaction mixture. Acetone and hydrolyzate were removed under reduced pressure to obtain a formulation with a solid content of 40%. The resulting polymer solution was filtered with a 0.2μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 1624 / 900, respectively. A 5% polymer formulation was prepared with PGMEA and PGEE and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0212] Comparative Example 3: A homopolymer of 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 4L flask. 1-Trimethoxysilyl-2-methyldimethoxysilyl-ethane (200 g, 0.78 mol), methanol (402 g) and 0.01 M HCl (71 g) were added to the flask. The reaction mixture was refluxed for 30 min and then cooled to room temperature. PGME (870 g) was added to the reaction mixture. Acetone and hydrolyzate were removed under reduced pressure to obtain a formulation with a solid content of 25%. The resulting polymer solution was filtered with a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight average molecular weight and number average molecular weight were determined to be 1313 / 629, respectively. A 5% polymer formulation was prepared with PGMEA and PGEE and spin-coated on a silicon wafer to measure the refractive index and electrical properties.

[0213] The properties of the polymers described in Examples 1 to 10 and Comparative Examples 1 to 3 were analyzed.

[0214] The dielectric constant was measured at 100 kHz on films with a target thickness of 340 nm ± 20 nm. Prior to the measurement, the wafer was pre-baked at 150 °C / 5 min to remove any accumulated moisture, and the measurement was performed at room temperature.

[0215] The leakage current was measured on a film with a target thickness of 100nm ± 20nm. Before the measurement, the wafer was pre-baked at 150℃ / 5min to remove any accumulated moisture, and then the measurement was performed at room temperature.

[0216] Molecular weight measurements were collected by gel permeation chromatography using a Waters HPLC instrument with reference to polystyrene standards of known molecular weight, including a Waters 1515 isocratic HPLC pump, a Waters 2414 refractive index detector, a Waters column block heater 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. It was equipped with a Styragel HR column (guard column, HR1, HR3, HR4) in series. The flow rate of the THF eluent was 1.0 ml / min.

[0217] The film thickness was measured using a JA Woollam M2000D-ESM-200AXY spectroscopic ellipsometer.

[0218] The coefficient of thermal expansion (CTE) was determined using a KLA-Tencor FLX-2320 film stress measurement system, which uses a dual-wavelength laser to determine the change in the radius of curvature of the wafer before and after film deposition. The CTE of the film can be calculated by depositing the same film on two different substrates with known thermal expansion properties and performing stress vs. temperature measurements. Stress vs. temperature was measured at temperatures between 21 and 200°C, and both silicon and GaAs substrates were used. The temperature was increased at a rate of 2.5°C / min during the ramp phase and decreased at a rate of 1.5°C / min during the cooling phase.

[0219] Mechanical properties were measured by nanoindentation using a Nanovea mechanical tester PB1000, with a target load of 0.05 mN, a loading and unloading rate of 0.02 V / min, an approach speed of 0.5 μm / min, a contact load of 0.006 mN, and materials of Berkovich indenter and diamond. Hardness and elastic modulus were calculated directly from the indentation curves using the Oliver-Pharr method.

[0220] Table 1 lists the average molecular weight (Mw), refractive index (RI), electrical breakdown voltage (EBD) and shrinkage of the above 10 polymers according to the present technology, and Table 2 lists the average molecular weight (Mw), refractive index (RI), electrical breakdown voltage (EBD) and shrinkage of three reference samples.

[0221] Table 1

[0222] polymer# Mw(g / mol) n at 633nm EBD(MV / cm) Shrinkage rate (%) 1 1716 1.434 4.5 0.6 2 1823 1.423 4.7 0.8 3 1833 1.426 3.9 0.1 4 1860 1.418 4.5 -0.9 5 2532 1.408 4.5 -0.2 6 1744 1.445 3.6 4.8 7 1649 1.442 4.0 -0.7 8 3287 1.440 4.1 10.2 9 2758 1.432 4.0 6.1 10 2980 1.432 3.7 7.6

[0223] Table 2. Comparison examples

[0224] polymer# Mw(g / mol) n at 633nm EBD(MV / cm) Shrinkage rate (%) C1 2061 1.373 3.2 3.6 C2 1877 1.376 3.6 2.0 C3 1313 1.420 3.6 1.8

[0225] As can be seen from the above, a combination of high electrical breakdown voltage and excellent refractive index can be obtained using the present material.

[0226] Table 3 provides a summary of dielectric constants and refractive indices.

[0227] Table 3. Dielectric constants

[0228] polymer n at 633nm k Comparative Example 2 1.373 2.9 Example 1 1.434 2.5 Example 2 1.423 2.4 Example 10 1.432 2.7

[0229] As described above, a combination of low dielectric constant and excellent refractive index can be obtained using the present material. It is worth noting that the dielectric constant cannot be reduced by increasing the porosity of the film because the refractive index is well above 1.4.

[0230] Table 4 provides a summary of the mechanical properties.

[0231] Table 4. Mechanical properties

[0232]

[0233] Table 5 provides a summary of the coefficient of thermal expansion (CTE).

[0234] Table 5. Thermal expansion coefficient

[0235] polymer CTE Example 1 6.4 Example 6 6.0

[0236] As can be seen from the foregoing description of the present invention and the exemplary experimental examples, the present invention can also be described with reference to the following embodiments:

[0237] 1. A low dielectric constant polymer film comprising a polymer obtained by polymerizing a compound having the general formula I

[0238] X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0239] in,

[0240] Each X l and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group;

[0241] Each R 1 and R 2 independently selected from the group of hydrocarbyl residues, which are optionally substituted;

[0242] Each R 3 and R 4 independently selected from the group of optionally substituted bridged straight or branched divalent hydrocarbon groups, such as alkylene groups having 1 to 6 carbon atoms and arylene groups having 6 to 10 carbon atoms;

[0243] Each R 5 is chosen from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms, such as phenyl or benzyl, said groups being optionally substituted;

[0244] n is an integer from 1 to 5;

[0245] m is an integer from 1 to 3; and

[0246] p is an integer from 1 to 3.

[0247] 2. The polymer film according to embodiment 1, wherein each X l and X 2 Independently selected from the group consisting of hydrogen and a hydrolyzable group selected from the group consisting of halogen, acyloxy, alkoxy and OH groups.

[0248] 3. The polymer film according to embodiment 1 or 2, wherein each X l and X 2 are independently selected from hydrogen and R 7 O-group, where R 7 represents an alkyl group having 1 to 6 carbon atoms.

[0249] 4. The polymer film according to any of the preceding embodiments, wherein each R 1 and R 2 Independently selected from the following groups: straight chain, branched and cyclic alkyl groups having 1 to 10 carbon atoms, and aryl groups containing 1 to 5 aromatic rings, which optionally contain 1 to 3 heteroatoms; each group is optionally substituted by 1 to 3 functional groups selected from halogen, hydroxyl, alkoxy, vinyl and acetyl.

[0250] 5. The polymer film according to any of the preceding embodiments, wherein each R 3 and R 4 Independently selected from alkylene groups having 1 to 4 carbon atoms, particularly 2 carbon atoms.

[0251] 6. The polymer film according to any of the preceding embodiments, wherein n represents an integer from 1 to 5, in particular from 1 to 4, such as 1, 2 or 4.

[0252] 7. The polymer film according to any of the preceding embodiments, wherein, in Formula I,

[0253] Each X land X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group;

[0254] Each R 1 and R 2 independently selected from the group of hydrocarbyl residues;

[0255] Each R 3 and R 4 independently selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms;

[0256] Each R 5 is selected from alkyl groups having 1 to 4 carbon atoms and phenyl groups; and

[0257] n, m and p have the same meanings as above.

[0258] 8. The polymer film according to any of the preceding embodiments, wherein the monomer according to formula I is selected from monomers having formula Ia, Ib or Ic

[0259]

[0260] and combinations thereof.

[0261] 9. The polymer film according to any of the preceding embodiments, obtained by homopolymerization of a compound of formula I, such as compound Ia, Ib or Ic.

[0262] 10. The polymer film according to any one of the preceding embodiments, obtained by copolymerizing a compound of formula I with a silane monomer, wherein the compound of formula I accounts for at least 10 mol % of the total amount of the silane monomer.

[0263] 11. The polymer film according to any of the preceding embodiments, obtained by copolymerizing a compound of formula I with a compound of formula III

[0264] (R 11 )2R 12 Si-R 13 -SiR 11 3 III

[0265] in,

[0266] R 11 is a hydrolyzable group such as hydrogen, halogen, alkoxy or acyloxy;

[0267] R 12 is hydrogen, an organic cross-linking group, a reactive cleavage group, or an organic group that reduces polarizability; and

[0268] R 13 It is a bridged straight chain or branched divalent hydrocarbon group.

[0269] 12. The polymer film according to any one of embodiments 1 to 10, obtained by copolymerizing a compound of formula I with a compound of formula IV

[0270] (X 3 ) 4-n S i 14 n IV

[0271] in,

[0272] X 3 is hydrogen or a hydrolyzable group selected from halogen, acyloxy, alkoxy and OH groups;

[0273] R 14 is selected from halogen, acyloxy, alkoxy and OH groups, and alkyl groups having 1 to 6 carbon atoms, vinyl groups having 2 to 6 carbon atoms and aryl groups having 6 carbon atoms; and

[0274] n is an integer having the same meaning as above.

[0275] 13. The polymer film according to embodiments 10 to 12, wherein the molar ratio between the compound according to formula I and the compound of formula III or formula IV or both is in the range of 10:90 to 90:10, such as 20:80 to 80:20, in particular 40:60 to 60:40.

[0276] 14. The polymer film according to any of the preceding embodiments, wherein the organic content of the polymer is in the range of 30 to 60 wt%, preferably less than 40 wt%.

[0277] 15. The polymer film according to any preceding embodiment, having a dielectric constant of 2.7 or less at 1 MHz.

[0278] 16. The polymer film according to any one of the preceding embodiments, wherein the dielectric constant of the cured polymer is 2.45 or less, preferably 2.30 or less.

[0279] 17. The polymer film according to any one of the preceding embodiments, which has an electrical breakdown voltage of 3.5 MV / cm or higher.

[0280] 18. The polymer film according to any one of the preceding embodiments, having a thickness less than 1 μm, in particular less than 500 nm, typically 50 to 350 nm.

[0281] 19. The polymer film according to any one of the preceding embodiments, wherein the RI thereof measured at a wavelength of 633 nm is greater than 1.4.

[0282] 20. A method for forming a polymer film, comprising:

[0283] - hydrolyzing the first silicon compound having formula I

[0284] X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I

[0285] in,

[0286] X l , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , R 4 , R 5 , I and n, m, p have the same meanings as above, and

[0287] - polymerizing a first silicon compound, optionally with at least one second silicon compound obtained by hydrolysis of a compound of formula III and / or a compound of formula IV

[0288] (R 11 )2R 12 Si-R 13 -SiR 11 3 III

[0289] in,

[0290] R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy,

[0291] R 12 is hydrogen, an organic crosslinking group, a reactive cleavage group or an organic group that reduces polarizability, and R 13 is a bridging linear or branched divalent hydrocarbon group;

[0292] (X 3 ) 4-n S i 14 n IV

[0293] Among them, X 3 , R 14 and n have the same meanings as above,

[0294] to produce a polymerized siloxane material; and

[0295] - The polymerized silicone material is formed into a layer which cures to form a film.

[0296] 21. The method of embodiment 20, comprising depositing the siloxane material as a thin layer on a substrate; and curing the thin layer to form a film.

[0297] 22. The method according to embodiment 21, wherein the substrate is a semiconductor substrate.

[0298] 23. The method according to any one of embodiments 20 to 22, wherein the polymer film has a thickness of less than 1 μm, in particular less than 500 nm, typically 50 to 350 nm.

[0299] 24. The method of any one of embodiments 20 to 23, wherein the polymer film is cured at a temperature of 350°C or higher.

[0300] 25. The method of any one of embodiments 20 to 24, comprising forming a polymer film having a dielectric constant of 2.7 or less at 1 MHz.

[0301] 26. A method for manufacturing a semiconductor device according to any one of embodiments 20 to 25, the method comprising or consisting of the following steps:

[0302] - depositing a metal layer;

[0303] -Deposition of photoresist and auxiliary underlayer on top of the metal;

[0304] - exposing the photoresist stack to light or an electron beam through a mask to form a desired pattern;

[0305] - developing the soluble part of the photoresist by a selective etching process and transferring the formed pattern to the metal layer;

[0306] - removing the remaining parts of the photoresist stack;

[0307] - depositing and curing low-k dielectric films; and

[0308] -Remove excess deposited low-k dielectric film by etch-back or chemical mechanical polishing process.

[0309] 27. Use of the polymer film according to any one of embodiments 1 to 19 as a low dielectric constant film in a semiconductor device.

[0310] 28. A semiconductor device comprising the polymer film according to any one of embodiments 1 to 19 as a low dielectric constant film, in particular as a film having a dielectric constant of 2.7 or less at 1 MHz.

[0311] Industrial Applicability

[0312] The present invention provides a method for manufacturing a semiconductor device comprising a low dielectric constant film, wherein the film comprises a polymer suitable as a barrier layer for filling a gap between metal interconnects, the maximum size of the gap being less than 30 nm, for example, 10 to 20 nm. Specifically, the metal is selected from cobalt (Co), molybdenum (Mo), tungsten (W) and ruthenium (Ru).

[0313] Reference Mark

[0314] 1 = substrate

[0315] 2 = Metal deposition

[0316] 3 = Metal layer, such as Co or Ru

[0317] 4 = Photoresist coating

[0318] 5=Photoresist-EUV materials

[0319] 6 = Exposure and Development

[0320] 7 = Etching

[0321] 8 = Photoresist stripping

[0322] 9 = Dielectric coating

[0323] 10 = Low-k dielectric

[0324] 11 = substrate

[0325] 12 = Dielectric coating

[0326] 13 = Low-k dielectric

[0327] 14 = Etching

[0328] 15 = Barrier materials and metal coatings

[0329] 16 = Barrier material

[0330] 17 = Metal, such as Cu

Claims

1. A method for manufacturing a semiconductor device, the semiconductor device comprising a low dielectric constant polymer film, wherein: The low dielectric constant polymer film includes a polymer obtained by polymerizing a compound having the general formula I X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I in, Each X l and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group; Each R 1 and R 2 independently selected from the group of hydrocarbyl residues, which are optionally substituted; Each R 3 and R 4 independently selected from the group of optionally substituted bridged straight or branched divalent hydrocarbon groups, such as alkylene groups having 1 to 6 carbon atoms and arylene groups having 6 to 10 carbon atoms; Each R 5 is chosen from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 18 carbon atoms, such as phenyl or benzyl, said groups being optionally substituted; n is an integer from 1 to 5; m is an integer from 1 to 3; and p is an integer from 1 to 3; The method comprises or consists of the following steps: - providing a substrate; - depositing a metal layer on the substrate, the metal layer comprising a metal selected from the group consisting of cobalt (Co), molybdenum (Mo), tungsten (W) and ruthenium (Ru); - depositing a photoresist and an auxiliary underlayer on top of the metal; - exposing the photoresist stack to light or an electron beam through a mask to form a desired pattern; - developing the soluble part of the photoresist and transferring the formed pattern to the metal layer by a selective etching process; - removing the remaining parts of the photoresist stack; - depositing and curing a low-k dielectric film; and -Remove excess deposited low-k dielectric film by etch-back or chemical mechanical polishing process.

2. The method according to claim 1, wherein: In the polymer obtained by polymerizing the compound of formula I, each X l and X 2 Independently selected from the group consisting of hydrogen and a hydrolyzable group selected from the group consisting of halogen, acyloxy, alkoxy and OH groups.

3. The method according to claim 1 or 2, wherein: In the polymer obtained by polymerizing the compound of formula I, each X l and X 2 are independently selected from hydrogen and R 7 O-group, where R 7 represents an alkyl group having 1 to 6 carbon atoms.

4. A method according to any one of the preceding claims, wherein: In the polymer obtained by polymerizing the compound of formula I, each R 1 and R 2 Independently selected from the following groups: straight chain, branched and cyclic alkyl groups having 1 to 10 carbon atoms, and aryl groups containing 1 to 5 aromatic rings, which optionally contain 1 to 3 heteroatoms; each group is optionally substituted by 1 to 3 functional groups selected from halogen, hydroxyl, alkoxy, vinyl and acetyl.

5. A method according to any one of the preceding claims, wherein: In the polymer obtained by polymerizing the compound of formula I, each R 3 and R 4 Independently selected from alkylene groups having 1 to 4, especially 2, carbon atoms.

6. A method according to any one of the preceding claims, wherein: In the polymers obtained by polymerization of compounds of formula I, n represents an integer from 1 to 5, in particular from 1 to 4, for example 1, 2 or 4.

7. A method according to any one of the preceding claims, wherein: In the polymer obtained by polymerizing the compound of formula I, Each X l and X 2 independently selected from the group consisting of hydrogen and an organic or inorganic hydrolyzable group; Each R 1 and R 2 independently selected from the group of hydrocarbyl residues; Each R 3 and R 4 independently selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms; Each R 5 is selected from alkyl groups having 1 to 4 carbon atoms and phenyl groups; and n, m and p have the same meanings as above.

8. A method according to any one of the preceding claims, wherein: The compound according to formula I is selected from monomers having formula Ia, Ib or Ic and combinations thereof.

9. The method according to any one of the preceding claims, wherein the low dielectric constant polymer film is obtained by homopolymerization of a compound of formula I, such as compound Ia, Ib or Ic.

10. The method according to any one of the preceding claims, wherein the low dielectric constant polymer film is obtained by copolymerizing a compound of formula I with a silane monomer, wherein: The compound of formula I accounts for at least 10 mol% of the total amount of silane monomers.

11. The method according to any one of the preceding claims, wherein the low dielectric constant polymer film is obtained by copolymerizing a compound of formula I with a compound of formula III (R 11 )2R 12 Si-R 13 -SiR 11 3 III in, R 11 is a hydrolyzable group such as hydrogen, halogen, alkoxy or acyloxy; R 12 is hydrogen, an organic cross-linking group, a reactive cleavage group, or an organic group that reduces polarizability; and R 13 It is a bridged straight chain or branched divalent hydrocarbon group.

12. The method according to any one of claims 1 to 10, wherein the low dielectric constant polymer film is obtained by copolymerizing a compound of formula I with a compound of formula IV (X 3 ) 4-n SiR 14 n IV in, X 3 is hydrogen or a hydrolyzable group selected from halogen, acyloxy, alkoxy and OH groups; R 14 is selected from halogen, acyloxy, alkoxy and OH groups, and alkyl groups having 1 to 6 carbon atoms, vinyl groups having 2 to 6 carbon atoms and aryl groups having 6 carbon atoms; and n is an integer having the same meaning as above.

13. The method according to any one of claims 10 to 12, wherein: In the polymer obtained by polymerizing the compound of formula I and the compound of formula III or formula IV or both, the molar ratio between the compound of formula I and the compound of formula III or formula IV or both is in the range of 10:90 to 90:10, for example 20:80 to 80:20, in particular 40:60 to 60:

40.

14. A method according to any one of the preceding claims, wherein: The organic content of the polymer is in the range of 30 to 60 wt%, preferably less than 40 wt%.

15. The method of any preceding claim, wherein the low dielectric constant polymer film has a dielectric constant of 2.7 or less at 1 MHz.

16. A method according to any one of the preceding claims, wherein: After curing, the dielectric constant of the polymer is 2.45 or less, preferably 2.30 or less.

17. The method of any one of the preceding claims, the low dielectric constant polymer film having an electrical breakdown voltage of 3.5 MV / cm or higher.

18. The method according to any of the preceding claims, the low dielectric constant polymer film having a thickness of less than 1 μm, in particular less than 500 nm, typically 50 to 350 nm.

19. The method of any preceding claim, the low dielectric constant polymer film having a RI greater than 1.4 measured at a wavelength of 633 nm.

20. A method according to any one of the preceding claims, comprising the step of forming a low dielectric constant polymer film, said step comprising - hydrolyzing the first silicon compound having formula I X 1 m R 1 3-m Si-R 3 -(R 5 2Si-O) n -Si-R 4 -SiX 2 p R 2 3-p I in, X l , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , R 4 , R 5 , i and n, m, p have the same meanings as above, and - polymerizing a first silicon compound, optionally with at least one second silicon compound obtained by hydrolysis of a compound of formula III and / or a compound of formula IV (R 11 )2R 12 Si-R 13 -SiR 11 3 III in, R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy, R 12 is hydrogen, an organic crosslinking group, a reactive cleavage group or an organic group that reduces polarizability, and R 13 is a bridging linear or branched divalent hydrocarbon group; (X 3 ) 4-n SiR 14 n IV Among them, X 3 , R 14 and n have the same meanings as above, to produce a polymerized siloxane material; and - The polymerized silicone material is formed into a layer which cures to form a film.

21. The method of claim 20, comprising depositing the silicone material as a thin layer on the substrate; and curing the thin layer to form a film.

22. A method according to any one of the preceding claims, wherein: The polymer film is cured at a temperature of 350° C. or higher.

23. A method according to any one of the preceding claims, wherein: The metal interconnection size of the semiconductor device is less than 50 nm, preferably less than 30 nm, for example, 10-20 nm or less.

24. A semiconductor device according to any one of the preceding claims, wherein the metal interconnect size is less than 50 nm, preferably less than 30 nm, such as 10-20 nm or less.

25. Use of the polymer film obtained by the step of claim 20 as a low dielectric constant film in a semiconductor device comprising a conductive material selected from the group consisting of cobalt, molybdenum, tungsten and ruthenium.

26. A semiconductor device comprising a polymer film obtained by the step of claim 20 as a low dielectric constant film, wherein: The semiconductor device includes a conductive material selected from the group consisting of cobalt, molybdenum, tungsten and ruthenium.

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