Method for manufacturing a semiconductor device with a low dielectric constant thin film

Abstract

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 A method for producing a semiconductor device having a polymer film containing a polymer obtained by polymerizing a compound having the formula: l and X 2 are each independently selected from the group consisting of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues; R 3 and R 4 are each independently selected from the group consisting of alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group; n is an integer of 1 to 5; m is an integer of 1 to 3; and p is an integer of 1 to 3. The polymer film is used as a low dielectric constant film in semiconductor devices, particularly as a barrier layer to fill the space between metal interconnects.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a semiconductor device having a low dielectric constant thin film comprising polysiloxane. The present invention also relates to the use of polymeric films in semiconductor devices. [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 through multiple levels of vertical and horizontal wiring embedded in dielectric materials. Within metallization structures, "vias" form the vertical wiring and "interconnects" form the horizontal wiring. Metallization fabrication can involve sequentially depositing and patterning multiple layers of dielectric and metal to achieve electrical connections between transistors and with external packaging materials. Patterning of a given layer is often accomplished by a multi-step process that includes layer deposition on the substrate, photoresist spin, photoresist exposure, photoresist development, layer etching, and photoresist removal. Alternatively, the metal may be patterned 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 remains only embedded in the openings in the dielectric.

[0003] Aluminum has long been used as an interconnect material due to its high electrical conductivity, good adhesion to SiO2, known processing methods (sputtering and etching), and low cost. Aluminum alloys have also been developed over the years, initially to improve qualities such as melting point, diffusion, and electromigration compared to pure aluminum. Tungsten has traditionally served as a conductive via plug material, spanning successive layers of aluminum. Increasing microprocessor speeds and the performance of electronic devices have led to higher circuit density and faster operating speeds, which in turn have necessitated the use of highly conductive metals and improved dielectrics with lower dielectric constants (preferably 3.0 or less) compared to silicon dioxide. Following aluminum metallization, the industry transitioned to copper damascene processes, in which copper (or copper alloys) are used for the high conductance of the conductor lines, and spin-on or CVD processes are used to produce low-k dielectrics that can be used for the insulating material surrounding the conductor lines. To avoid etching problems, copper, along with a barrier metal, is blanket deposited onto the recessed dielectric structure consisting of the interconnect and via opening, and then polished back in a process known as "dual damascene." The bottom of the via opening is typically the top of the interconnect from the previous metal layer, and sometimes also the contact layer to the substrate.

[0004] Copper "dual damascene" processes have been successfully used in industry for 20 years. The critical dimensions of copper interconnects in future devices will reach 10–20 nm or even less. As a result, the dielectric materials between the interconnects will also exhibit similar critical dimensions. This is particularly problematic for copper "dual damascene" processes, in part because copper ions are highly mobile, meaning they can migrate into the dielectric layer. Eventually, high copper ion concentrations can cause dielectric breakdown and render the device or transistor inoperable. To prevent copper ion migration, various barrier layers, typically titanium or tantalum nitride, are deposited. For designs with a pitch of 30 nm or less, the barrier layers fill most of the space between the metal interconnects, rendering the dielectric layers insufficient due to the poor dielectric properties of nitrides. Due to these challenges, the search for new metals continues for interconnect critical dimensions of 10–20 nm or less. Candidate metals for sub-20 nm processes include cobalt (Co), ruthenium (Ru), tungsten (W), and molybdenum (Mo). Depending on the metal used, metal lines can be formed using subtractive processes similar to those used for aluminum and tungsten, or by a single damascene process in which Cu is deposited after the alternative metal is deposited. Thus, to enable future devices and device architectures, new dielectrics are needed that have suitable electrical and mechanical properties and can meet critical dimensions of 10-20 nm and below. Furthermore, these new dielectrics must be able to withstand the conditions used in subsequent process steps, such as high temperatures (above 400°C) and various chemical and mechanical forces (chemical-mechanical polishing). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a semiconductor device having a polymer film with a dielectric constant of 2.7 or less. In particular, the present invention provides a method for manufacturing a semiconductor device including a substrate on which a metal selected from cobalt (Co), ruthenium (Ru), tungsten (W), and molybdenum (Mo) is vapor-deposited.

[0006] In accordance with the present invention, a semiconductor device is provided that includes a low dielectric constant polymer film. The film is represented by the general formula I [ka] and a polymer obtained by polymerizing a compound having the formula: During the ceremony, X l and X 2 are each independently selected from the group of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues, optionally substituted; R 3 and R 4 are each independently selected from the group of optionally substituted crosslinkable linear or branched divalent hydrocarbyl groups, such as alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms, such as a phenyl or benzyl group, which groups are optionally substituted; n is an integer from 1 to 5; m is an integer from 1 to 3; p is an integer of 1 to 3.

[0007] In one embodiment, the polymer film having a dielectric constant of 2.7 or less at 1 MHz is hydrolyzing a first silicon compound having formula I, [ka] (In the formula, X l , X2 , X 3 , X 4 , R 1 , R 2 , R 3 , R 4 , R 5 , i, n, m, p have the same meanings as above) Optionally, a compound of formula III [ka] (In the formula, R 11 is a hydrolyzable group such as hydrogen, a halide group, an alkoxy group, or an acyloxy group, R 12 is hydrogen, an organic bridging group, a reactive cleavage group, or a polarizability reducing organic group; R 13 is a crosslinkable linear or branched divalent hydrocarbyl group and / or at least one compound of formula IV [ka] (In the formula, X 3 , R 14 and n has the same meaning as above) hydrolyzing a second compound having They are formed by polymerizing or copolymerizing the hydrolyzed compounds to produce siloxane materials.

[0008] Siloxane materials are typically deposited onto a substrate in the form of a thin film that is cured to provide a thin film with a low dielectric constant.

[0009] More specifically, the invention is characterized in what is stated in the independent claims.

[0010] The present invention provides significant advantages.

[0011] Therefore, in the method for fabricating semiconductor devices according to the present invention, the disclosed siloxane materials provide high modulus and hardness, which contributes to the bonding of labyrinthine metal interconnects and vias, especially in the final chip packaging step. As a result of their good adhesion properties, the films contribute to the formation of stable interfaces between dielectric and contact materials.

[0012] The siloxane material used in the method for manufacturing a semiconductor device according to the present invention can be formed into a film having a thickness in the range of 50 nm to 2500 nm, for example, a thickness in the range of 50 nm to 1000 nm; generally, no cracks occur even in thick film structures.

[0013] Substrates used for the deposition of siloxane materials can contain a variety of topographies. These include narrow trenches that may have high aspect ratios, meaning that the trenches exhibit a depth-to-width ratio (or aspect ratio) greater than 2:1, e.g., 3:1 or greater. Thus, the material has excellent ability to fill trench widths of less than 20 nm, or even more preferably less than 10 nm. In parallel, siloxane materials exhibit excellent planarization properties. Planarization properties refer to the ability of a siloxane material to even out height differences on a substrate resulting from the various topographies present on the substrate prior to coating. The ability to planarize a substrate is a significant advantage, as subsequent processes to planarize the substrate surface are eliminated or reduced. This provides significant advantages in terms of manufacturing cost and time. Furthermore, if a thinner film thickness is required or a flatter topography is required in subsequent manufacturing steps, the material can be easily processed by chemical-mechanical polishing or etch-back processes.

[0014] Additionally, the siloxane materials used in the method for fabricating semiconductor devices according to the present invention exhibit a low coefficient of thermal expansion (CTE). A low coefficient of thermal expansion is highly beneficial in preventing substrate warpage during subsequent process steps. Such warpage typically occurs on substrates containing materials with significantly varying CTEs. 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.

[0015] The siloxane materials used in the method for fabricating semiconductor devices according to the present invention are also thermally stable. Good thermal stability is necessary for the coating to withstand multiple thermal cycles in the semiconductor fabrication process.

[0016] Importantly, the materials of the present invention exhibit low leakage current, high breakdown voltage and low dissipation factor. [Brief explanation of the drawings]

[0017] [Figure 1] 1A-1D illustrate various stages in the fabrication of a semiconductor device including a low-k dielectric, in accordance with at least some embodiments of the present invention. [Figure 2] 1A-1D are schematic diagrams illustrating various stages in the fabrication of an alternative semiconductor device including a low-k dielectric film of a polysiloxane material as disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0018] In the following, embodiments of the present technology will be described in more detail.

[0019] Percentages referred to herein are expressed as weight percent based on the total weight of the respective composition, unless otherwise stated or apparent from the context.

[0020] Unless otherwise specified, experimentally measured or determined properties herein were measured or determined at room temperature, which is 25° C. unless otherwise specified.

[0021] Unless otherwise specified, experimentally measured or determined properties herein are measured or determined at atmospheric pressure.

[0022] Also, please note that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless specifically stated otherwise.

[0023] As used herein, the term "about" refers to a value of ±5% of the stated value.

[0024] As used herein, the term "average molecular weight" refers to the weight average molecular weight ("M W " or "M w " (also abbreviated as ").

[0025] As used herein, molecular weight is determined by gel permeation chromatography using polystyrene standards.

[0026] As used herein, "coefficient of thermal expansion" is measured by a stylus-based profiler that detects changes in wafer curvature caused by heating a substrate having a coating thereon.

[0027] Measurement of the "dielectric constant" κ or εr is achieved using a metal-insulator-semiconductor (MIS) structure on a highly doped, low-resistivity N+ doped silicon wafer. The capacitance across the dielectric film is measured using a mercury probe (Materials Development Corporation, Model 802) and a precision impedance analyzer (Agilent 4294A), and together with the contact area of ​​the mercury dot and the film thickness, the dielectric constant can be calculated using the formula x:

number

[0028] The "breakdown voltage" is measured using a similar MIS structure with a mercury probe (Materials Development Corporation, Model 802) and a semiconductor parameter analyzer (Agilent 4155B).

[0029] The "leakage current" as a function of voltage is measured during a voltage sweep from -20V to 100V, and the breakdown voltage is determined by the sudden increase in current 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.

[0030] The "refractive index" (RI) is measured using a refractometer at a wavelength of 633 nm. RI can be calculated, for example, from a polymer film sample having a thickness of 400 nm by interference, deviation, or Brewster angle methods.

[0031] The "hardness" and "elastic modulus" of the film can be calculated from the indentation curve using the Oliver-Pharr method.

[0032] The present embodiments disclose the preparation of low dielectric constant polymeric films comprising siloxane polymers exhibiting -(Si-O-Si)- segments, where the silicon atoms typically have hydrocarbyl substituents such as lower alkyl groups, and the use of said polymeric films in methods for fabricating semiconductor devices. Such polymeric films can be obtained by either homopolymerization or copolymerization of silane monomers.

[0033] Typically, in this technology, the silane monomer containing hydrolyzable group is first subjected to hydrolysis, and then typically subjected to polymerization in liquid phase at a temperature between room temperature and the boiling point of the liquid.The liquid may be composed of one or more solvents in addition to the silicon monomer and water added for the hydrolysis of the monomer.Specific 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.

[0034] Controlled hydrolysis of the monomer is achieved by adding an acid or base solution with 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 of its low boiling point, which simplifies product purification. Alternatively, various organic acids can be used instead of inorganic acids. Organic acids include carboxylic acids, sulfonic acids, alcohols, thiols, enols, and phenols. Examples include methanesulfonic acid, acetic acid, ethanesulfonic acid, toluenesulfonic acid, formic acid, and oxalic acid.

[0035] The base used in the synthesis may likewise be inorganic or organic. Typical inorganic bases are metal hydroxides, carbonates, bicarbonates, and other salts that form aqueous alkalis. 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 group consisting of metal salts of organic acids (sodium acetate, potassium acetate, sodium acrylate, sodium methacrylate, sodium benzoate, etc.), linear, branched, or cyclic alkylamines (diaminoethane, pultecin, cadaverine, triethylamine, butylamine, dibutylamine, tributylamine, piperidine, etc.), amidines, guanidines (8-diazabicyclo(5.4.0)undec-7-ene, 1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene), phosphazanes (P1-t-Bu, P2-t-Bu, P4-t-Bu, etc.), and quaternary ammonium compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc.).

[0036] The temperature of the reaction mixture during the hydrolysis and condensation process can be varied in the range of -30 to 170°C. Lower reaction temperatures improve reaction control at the expense of longer reaction times, while higher temperatures can cause the process to run too fast and not be well controlled. Temperatures of 0 to 100°C and reaction times of 1 to 48 hours are preferred. Reaction times of 2 to 24 hours are even more preferred.

[0037] Using appropriate conditions, partially crosslinked organosiloxane polymers can be obtained in organic solvent systems, said polymers having molecular weights of about 500 to 100,000 g / mol, preferably 800 to 50,000 g / mol, and most preferably 1000 to 10,000, as measured against polystyrene standards.

[0038] In some embodiments, the solvent in which hydrolysis and polymerization are carried out is converted after polymerization into a solvent that, through some stabilization, provides the material with excellent coating performance and product storage properties. Such a stabilizing organic solvent system is formed by an organic ether, optionally mixed with other cosolvents. The organic ether is generally a linear, branched, or cyclic ether containing 4 to 26 carbon atoms and, optionally, other functional groups, such as hydroxyl groups. Particularly suitable examples are ethers such as 5- and 6-membered cyclic ethers optionally bearing substituents on the ring and (C1-20)alkanediol(C1-6)alkyl ethers. Examples of the alkanediol alkyl ethers include propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol monomethyl ether, and mixtures thereof. Particularly preferred examples of ethers of the present invention are methyl tetrahydrofurfuryl 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 stabilizing solvent system may consist of a solvent containing such an ether alone or in combination with a typical reaction medium for hydrolysis or another solvent, such as propylene glycol monomethyl ether acetate. In such cases, the proportion of ether is about 10 to 90 wt. %, particularly about 20 to 80 wt. %, based on the total amount of solvent.

[0039] The solids content of the blend of the selected solvent and the hydrolysis and polymerization product ranges from 0.1 to 60%, preferably from 0.5 to 30%, and most preferably from 1 to 10%.

[0040] In certain embodiments, the polymeric film in the method for manufacturing a semiconductor device is obtained by polymerization or copolymerization of a compound having general formula I, [ka] During the ceremony, X l and X 2 are each independently selected from the group of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues, optionally substituted; R 3 and R 4 are each independently selected from the group of optionally substituted crosslinkable linear or branched divalent hydrocarbyl groups, such as alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms, such as a phenyl or benzyl group, which groups are optionally substituted; n is an integer from 1 to 5; m is an integer from 1 to 3; p is an integer of 1 to 3.

[0041] According to one embodiment, in formula I: X l and X 2 are each independently selected from the group of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues; R 3 and R 4 are each independently selected from the group consisting of alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group; n, m, and p have the same meanings as above.

[0042] In one embodiment, in Formula I, X l and X 2are each independently selected from the group of hydrolyzable groups selected from hydrogen and halogen, acyloxy, alkoxy, and OH groups. Typically, the halogen is selected from fluoro, chloro, or bromo, and the hydrocarbyl radical of the acyl (alkanoyl) functionality of the acyloxy group is selected from alkyl groups having 1 to 6 carbon atoms.

[0043] In one embodiment, in Formula I, X l and X 2 are each independently hydrogen and a group of formula R 7 O-, where R 7 represents alkyl having 1 to 6 carbon atoms.

[0044] In one embodiment, in Formula I, R 1 and R 2 are each independently selected from the group consisting of linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, and aryl groups containing 1 to 5 aromatic rings, optionally containing 1 to 3 heteroatoms.

[0045] In one embodiment, R 3 and R 4 each represents a divalent hydrocarbyl radical, particularly R 3 and R 4 are each independently selected from the group of saturated alkylene radicals having 1 to 4, especially 2, carbon atoms. 3 and R 4 may also be selected from divalent aromatic hydrocarbyl radicals, such as arylene, for example phenylene or naphthylene.

[0046] In Formula I, R 1 , R 2 , R 3 , R 4 and R 5 Hydrocarbyl groups such as alkyl, alkylene, aryl or arylene groups may also be selected from halo, hydroxy, alkoxy, especially C 1-4It may be optionally substituted with 1 to 3 functional groups selected from alkoxy, vinyl and acetyl groups, and combinations thereof.

[0047] In one embodiment, R 1 , R 2 , R 3 , R 4 and R 5 Hydrocarbyl groups such as may decompose during the film curing procedure, leaving behind crosslinking groups or polarizability-reducing groups, or a combination thereof. When the group is a leaving group, it still results in very small pore sizes, i.e., typically 1.5 nm or less. However, the polymers formed according to the present technology are also compatible with conventional porogens, such as cyclodextrins, which can be used to form micropores in the polymer and reduce the dielectric constant of the polymer.

[0048] Examples of organic bridging groups, reactive cleavage groups, or polarizability-reducing organic groups include organic groups containing alkyl, alkenyl, alkynyl, aryl, polycyclic, or silicon groups, which may also be fully or partially halogenated.

[0049] In one embodiment, in formula I the symbol n represents an integer from 1 to 5, in particular 1 to 4, such as 1, 2 or 4.

[0050] One embodiment is a compound of formula Ia [ka] This involves using a monomer according to general formula I having:

[0051] One embodiment is a compound of formula Ib [ka] This involves using a monomer according to general formula I having:

[0052] One embodiment is a compound of formula Ic [ka] This involves using a monomer according to general formula I having:

[0053] The compounds of general formula I and formulas Ia to Ic can be obtained by reacting a difunctional siloxane compound with a silane monomer containing at least one reactive group, such as a hydrolyzable group and a vinyl group, in the presence of a catalyst, such as a noble metal catalyst.

[0054] For example, the difunctional siloxane compound may be represented by Formula II [ka] and During the ceremony, R 8は , hydrogen or a hydrocarbon having a vinyl group; R 9は represents an alkyl group having 1 to 6, preferably 1 to 4, carbon atoms, p represents 0 or an integer of 1 to 3;

[0055] In particular, R 9 represents methyl, and p represents 1.

[0056] In one embodiment, the polymeric membrane is provided by homopolymerization of a compound of general formula I, such as compound Ia, Ib, or Ic, or copolymerization of two or three compounds of formula Ia, Ib, or Ic.

[0057] In one embodiment, the polymeric membrane comprises at least one compound of formula I, such as a compound of formula Ia, Ib, or Ic, and a compound of formula III. [ka] is provided by copolymerization with a compound of During the ceremony, R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy group, R 12 is hydrogen, an organic bridging group, a reactive cleavage group, or a polarizability reducing organic group; R13 is a crosslinkable linear or branched divalent hydrocarbyl group.

[0058] R 11 is preferably selected from the group consisting of halides, alkoxy groups, acyloxy groups and hydrogen, and R 12 is preferably selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, polycyclic groups, or organic silicon-containing groups; R 13 is preferably selected from linear and branched alkylene, alkenylene and alkynylene groups, divalent alicyclic (polycyclic) groups and divalent aromatic groups, all of which are included in the definition of divalent hydrocarbyl groups.

[0059] As used herein, "alkenyl" includes straight-chain and branched alkenyl groups, such as vinyl and allyl groups. As used herein, the term "alkynyl" includes straight-chain and branched alkynyl groups, and is preferably acetylene. "Aryl" means a substituted or unsubstituted mono-, bi-, or multi-cyclic aromatic carbocyclic group; examples of aryl are phenyl, naphthyl, or pentafluorophenylpropyl. As used herein, "polycyclic" groups include, for example, adamantyl, dimethyladamantylpropyl, norbornyl, or norbornene. More specifically, alkyl, alkenyl, or alkynyl may be straight-chain or branched.

[0060] The divalent alicyclic group may be a polycyclic aliphatic group containing a residue derived from a ring structure having 5 to 20 carbon atoms, such as norbornene (norbornenyl) and adamantyl (adamantylene). "Arylene" refers to a divalent aryl containing 1 to 6 rings, preferably 1 to 6, and especially 1 to 5 fused rings, such as phenylene, naphthylene, and anthracenyl.

[0061] In one embodiment, the polymeric film for use in the method for manufacturing a semiconductor device as defined herein comprises a compound of at least one compound of formula I, such as a compound of formula Ia, Ib, or Ic, and a compound of formula IV [ka] is provided by copolymerization with a compound of In formula IV, X 3 is hydrogen or a hydrolyzable group selected from halogen, acyloxy, alkoxy and OH groups; R 14 is selected from halogen, acyloxy, alkoxy, OH group, alkyl group having 1 to 6 carbon atoms, vinyl group having 2 to 6 carbon atoms and aryl group having 6 to 10 carbon atoms; n is an integer with the same meaning as above.

[0062] The acyloxy group, alkoxy group, alkyl group, vinyl group and aryl group have the same meanings as above.

[0063] Specific examples of IV include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, 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-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltrimethoxysilane Iethoxysilane, 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)ethyl tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl triphenoxysilane, γ-(3,4-epoxycyclohexyl)propyl trimethoxysilane, γ-(3,4-epoxycyclohexyl)propyl triethoxysilane, δ-(3,4-epoxycyclohexyl)butyl trimethoxysilane, δ-(3,4-epoxycyclohexyl)butyl triethoxysilane, glycidoxymethyl methyl dimethoxysilane, glycidoxymethyl methyl diethoxysilane, α-glycidoxyethyl methyl dimethoxysilane, α-glycidoxyethyl methyl diethoxysilane, β-glycidoxyethyl methyl dimethoxysilane, β-glycidoxyethyl dimethoxysilane, α- Examples of suitable silanes include, but are not limited to, glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, and phenylsulfonylaminopropyltriethoxysilane.

[0064] As used herein, "alkoxy" and "acyloxy" groups typically have from 1 to 6 carbon atoms.

[0065] As used herein, "halogen" has its conventional meaning and particularly refers to chloro, fluoro or bromo.

[0066] As used herein, "halide" has its conventional meaning and refers to a halogen compound.

[0067] In one embodiment, the polymeric membrane is provided by copolymerization of a compound of formula I with compounds of formulas III and IV, ie, a mixture of compounds of formulas III and IV.

[0068] In one embodiment in which a copolymer is produced, the molar ratio between the compound of formula I and the compound of formula III ranges from 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, particularly 40:60 to 60:40.

[0069] In one embodiment in which a copolymer is produced, the molar ratio between the compound of formula I and the compound of formula IV ranges from 10:90 to 90:10, for example, the molar ratio between the compound of formula I and the compound of formula IV is 20:80 to 80:20, particularly 40:60 to 60:40.

[0070] In one embodiment in which a copolymer is produced, the molar ratio between the compound of formula I on the one hand and the compounds of formulae III and IV on the other hand ranges from 10:90 to 90:10, for example, the molar ratio between the compound of formula I and the compounds of formulae III and IV on the other hand is 20:80 to 80:20, particularly 40:60 to 60:40.

[0071] Typically, the organic content of the polymer is in the range of 20-60 wt %. Generally, an organic content of less than 40 wt % is preferred.

[0072] In one embodiment, the polymer film having a dielectric constant of 2.7 or less (e.g., 2.5 or less) at 1 MHz used in the method for manufacturing a semiconductor device according to the present invention is Formula I [ka] (In the formula, 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 hydrolyzing the first silicon compound having the formula: optionally at least one compound of formula III [ka] (In the formula, R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy group, R 12 is hydrogen, an organic bridging group, a reactive cleavage group, or a polarizability reducing organic group; R 13 is a crosslinkable linear or branched divalent hydrocarbyl group and / or Formula IV [ka] (In the formula, X 3 , R 14 and n has the same meaning as above) Hydrolyzing a second silicon compound having the formula: - polymerizing the hydrolyzed compound to produce a polymerized siloxane material; - casting the polymerized material into a layer and curing it into a film.

[0073] In one embodiment, a siloxane material obtained by homopolymerization or optionally copolymerization of compounds of Formula I and optionally Formula III and / or IV is deposited in the form of a layer onto a substrate, and the deposited material is then cured into a film.

[0074] The thickness of this layer is usually less than 2 μm, in particular less than 1 μm, especially less than about 500 nm.

[0075] The layer is cured to a polymeric film generally having a thickness of less than 1 μm, particularly less than about 500 nm, typically about 50 to 350 nm.

[0076] The films of the present invention have good optical properties. Thus, the polymer film can have a refractive index (RI) greater than 1.4 determined at a wavelength of 633 nm.

[0077] It has surprisingly been found that the use of monomers of formula I in polymeric films consisting of or comprising such monomers results in excellent electrical properties in semiconductor devices comprising substrates deposited with a metal selected from cobalt (Co), ruthenium (Ru), tungsten (W) and molybdenum (Mo).

[0078] Furthermore, it has been found that the incorporation of short linear segments (n having values ​​between 1 and 5) results in materials that exhibit a combination of low thermal expansion and moderate elasticity / softness or considerable hardness.

[0079] In one embodiment, the film has a dielectric constant at 1 MHz of 2.7 or less, such as 2.5 or less. In a further embodiment, the dielectric constant of the polymer after curing is 2.45 or less, preferably 2.30 or less.

[0080] In one embodiment, the cured polymeric film has an electric breakthrough voltage of 3.5 MV / cm or greater, such as 3.55 MV / cm or greater, such as 3.6 MV / cm or greater.

[0081] 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.

[0082] In one embodiment, the cured polymeric film exhibits a modulus of elasticity of 6.3 GPa or greater, such as 6.5 GPa or greater, such as 6.7 GPa or greater.

[0083] In one embodiment, the cured polymeric film exhibits a hardness of 1.5 GPa or greater, such as 1.6 GPa or greater, such as 1.7 GPa or greater.

[0084] The effect on mechanical properties is governed by the length of the crosslinking group in Formula I, with both modulus and hardness decreasing as n in Formula I increases. Surprisingly, it has been found that when monomers of Formula I with n≦2 are used, films prepared by either homopolymerization or copolymerization have hardness comparable to films prepared from monomers of Formula III and / or IV.

[0085] In one embodiment, the use of the monomer of Formula I in an amount of at least 10 mol % of the total amount of silane monomers can significantly improve the electrical properties, such as electrical breakthrough voltage, of polysiloxane films prepared from the silane monomer of Formula II.

[0086] In one embodiment, by using the monomer of formula I in an amount of at least 10 mol% of the total amount of silane monomers, a significant decrease in the dielectric constant can be observed compared to films made with only the monomers of formula III and / or IV. Surprisingly, a significant decrease in the dielectric constant is detected for both homopolymers and copolymers containing the monomer of formula I.

[0087] In one embodiment, by using the monomer of formula I in an amount of at least 10 mol% of the total amount of silane monomers, a significant reduction in the shrinkage of the film can be observed compared to a film made only with the monomers of formula III and / or IV. Surprisingly, a significant reduction in shrinkage is detected in both homopolymers and copolymers containing the monomer of formula I. The low shrinkage is very beneficial in preventing substrate warpage in subsequent process steps.

[0088] To reduce the surface tension of silanol-containing polysiloxane-based coatings, various types of surfactants, such as silicone-based or fluorine-based surfactants, can be used to optimize the formulation. The use of such surfactants may improve coating quality, if desired. The amount of surfactant is 0.001% to 20% by weight, preferably 0.005% to 10%, and most preferably 0.01% to 5% or 0.05% to 2.5% of the silanol-containing organosiloxane.

[0089] The formulation can be optimized by adding various types of photo- or heat-labile catalysts or compounds to the formulation mixture to promote crosslinking of the organosiloxane film. The amount of the heat- or photo-labile compound in the formulation corresponds to the solid content of the polymer and ranges from 0.05 to 20% by weight, preferably 0.1 to 10%, and most preferably 0.5 to 5% or 0.5 to 3% based on the amount of silanol-containing organosiloxane.

[0090] FIG. 1 illustrates various stages in the fabrication of a semiconductor device according to the present technology, including a low-k dielectric comprising a film of the polysiloxane disclosed herein.

[0091] As can be seen, first a substrate 1 is provided. Such a substrate may comprise, for example, a silicon wafer. In a second step, the substrate is subjected to metal deposition 2. The metal layer consists of a conductive metal 3. Conventionally, copper has been used for such purposes, but for patterning devices with spaces having a diameter of 1-50 nm, for example 1-20 nm or even 5-15 nm, the metal is selected from cobalt, tungsten, ruthenium or other suitable metals, preferably cobalt (Co), molybdenum (Mo) or ruthenium (Ru).

[0092] The substrate 1 with the metal layer 3 is patterned by known steps in lithography, including photoresist coating 4 (and any necessary photoresist underlayer) with a suitable photoresist coating material 5, for example a material suitable for patterning by electromagnetic radiation in the UV range or even the extreme UV range (EUV).

[0093] After an exposure and development step 6, the pattern transfer is performed by etching 7 into the metal layer 3. The remaining photoresist and photoresist underlayer are then stripped 8, leaving the patterned metal layer 3 on the substrate.

[0094] In the next two steps, a dielectric coating 10 is applied 9 onto the patterned metal layer 3 and onto the substrate 1, filling the spaces between the metal patterns. Finally, the metal 10 separated by the dielectric is opened 11 by etch-back, for example using gases or chemical mechanical polishing (CMP).

[0095] As a result, the present technology provides a semiconductor device having a dielectric formed from a polymer film.

[0096] In summary, the method for manufacturing a semiconductor device according to the present technology includes the following steps: - providing a substrate; - depositing on said substrate a metal layer comprising a metal selected from cobalt (Co), molybdenum (Mo), tungsten (W) and ruthenium (Ru); - depositing a photoresist and an auxiliary underlayer on said metal; - irradiating the photoresist stack with light or an electron beam through a mask to form a desired pattern; - developing the soluble portions of the photoresist and transferring the resulting pattern into a metal layer by a selective etching process; - removing the remaining portions of said photoresist stack; - depositing and curing a low-k dielectric film according to any of the present embodiments; - removing excess of the deposited low-k dielectric film by an etch-back or chemical-mechanical polishing process.

[0097] Preferably, the metal is selected from cobalt (Co), molybdenum (Mo) and ruthenium (Ru).

[0098] FIG. 2 illustrates various stages in the fabrication of an alternative semiconductor device including a low-k dielectric film of a polysiloxane material as disclosed herein in accordance with the present technique.

[0099] As can be seen, first a substrate 11 is provided. Such a substrate may comprise, for example, a silicon wafer. This substrate is dielectrically coated in a second step 12 to provide a layer of low-k dielectric 13 on (at least one surface of) the substrate 11. The thus coated substrate is then subjected to etching in a second step to remove predetermined portions of the dielectric, resulting in a patterned surface. In a third step, overlapping layers of a barrier material 16 and a metal 17 are deposited on the surface. The metal layer may comprise, for example, a conductive layer such as copper.

[0100] As can be seen, barrier material 16 and metal 17 typically cover both the etched and unetched portions of the surface. In a final fourth step 18, the multilayer structure is subjected to metal via opening, for example by chemical mechanical polishing. The result is a semiconductor device comprised of a low-k dielectric with embedded metal vias.

[0101] The following non-limiting examples illustrate further embodiments. [Example] monomer

[0102] Monomer A: (1,2-bis(trimethoxysilylethyl)tetramethyldisiloxane [ka]

[0103] Monomer B: (1,3-bis(trimethoxysilylethyl)hexamethyltrisiloxane) [ka]

[0104] Monomer C: (1,5-bis(trimethoxysilylethyl)decamethylpentasiloxane) [ka]

[0105] Synthesis of Monomer A: Monomer A was prepared by adding vinyltrimethoxysilane (VinTMOS, 971.9 g, 6.56 mol), platinum catalyst (1 g), and acetic acid (0.2 g) to a 3 L flask. The solution was thoroughly mixed at 40 °C, and tetramethyldisiloxane (TMDS, 400 g, 2.98 mol) was added to the solution. After the addition of TMDS, the reaction mixture was allowed to stand overnight at room temperature. After the reaction was complete, the product was distilled under reduced pressure. The amount of the obtained product was 920 g (71% yield, 99% purity by GC-MS).

[0106] Synthesis of Monomer B: Monomer B was prepared by adding VinTMOS (39 g, 0.26 mol), platinum catalyst (100 mg), and two drops of acetic acid to a flask. Hexamethyltrisiloxane (HMTS, 0.12 mol) was slowly added to the solution and stirred overnight. The monomer was purified by distillation under reduced pressure. The amount of product obtained was 44 g (76% yield, 99% purity by GC-MS).

[0107] Synthesis of Monomer C: Monomer C was prepared by adding hexamethylcyclotrisiloxane (D3, 7 g, 0.34 mol), TMDS (113 g, 0.84 mol), and toluene (20 g). The flask was kept under ice cooling and purged with nitrogen gas for 5 minutes. Triflic acid (300 mg) was added to the solution. After 5 minutes, hexamethyldisilazane (6 mL) was added to the solution as a quencher. Stirring was continued for 10 minutes under ice cooling. The intermediate product was purified under reduced pressure. The amount of the obtained intermediate product was 81 g (yield 67%, GC-MS purity 99%).

[0108] A 500 mL flask was charged with VinTMOS (46 g, 0.31 mol), a few drops of acetic acid, and platinum catalyst (100 mg). The flask was placed in an oil bath (50 °C), and the resulting intermediate product (50 g) was added to the solution. The solution was stirred overnight. The resulting monomer was purified by distillation under reduced pressure. The amount of the product obtained was 56 g (yield 61%, GC-MS purity 97.5%).

[0109] Polymer preparation

[0110] 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 hydrochloric acid (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. The acetone and hydrolysis products were removed under reduced pressure to obtain a blend with a solids content of 23%. The resulting 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 1716 and 968, respectively. An 8% blend of the polymer with PGMEA was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0111] Example 2. The resulting copolymer of 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 hydrochloric acid (4.0 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (55 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a 15% solids blend. The resulting polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average and number-average molecular weights were 1823 and 821, respectively. An 8% blend of the polymer with PGMEA was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0112] Example 3. The resulting copolymer of 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 hydrochloric acid (9.2 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. MIBK (190 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a 19% solids blend. The resulting 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 1833 and 922, respectively. An 8% blend of the polymer with PGMEA was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0113] Example 4. A terpolymer of the resulting monomer A, methyltriethoxysilane (MTEOS), and tetraethyl orthosilicate (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 hydrochloric acid (3.4 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (33 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solids content of 12%. The resulting 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 1860 and 893, respectively. An 8% formulation of the polymer was prepared with PGMEA and spin-coated onto silicon wafers for refractive index and electrical property measurements.

[0114] Example 5. A terpolymer of the resulting monomer A, methyltriethoxysilane (MTEOS), and tetraethyl orthosilicate (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 hydrochloric acid (5.1 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (63 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a solids content of 19%. The resulting 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 2532 / 1200, respectively. An 8% formulation of the polymer was prepared with PGMEA and spin-coated onto silicon wafers for refractive index and electrical property measurements.

[0115] 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 hydrochloric acid (2.2 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (100 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a blend with a solids content of 36%. The resulting 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 determined to be 1744 / 652, respectively. An 8% blend of the polymer was prepared using PGMEA, MIBK, and a surfactant and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0116] Example 7. The resulting copolymer of 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 hydrochloric acid (4.0 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. PGMEA (100 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a 40% solids content. The resulting 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 1644 / 602, respectively. A 7% formulation of the polymer was prepared using PGMEA and MIBK and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0117] Example 8. A copolymer of the resulting 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 hydrochloric acid (1.6 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a formulation with a 30% solids content. The resulting 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 3287 and 1547, respectively. An 8% formulation of the polymer was prepared using MIBK and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0118] Example 9. A copolymer of the resulting 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 hydrochloric acid (2.2 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a blend with a solids content of 21%. The resulting 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 2758 and 1324, respectively. An 8% blend of the polymer with MIBK was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0119] 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 hydrochloric acid (1.9 g) were added to the flask. The reaction mixture was refluxed for 30 minutes and then cooled to room temperature. MIBK (100 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a 12% solids blend. The resulting 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 2980 and 1513, respectively. An 8% blend of the polymer with MIBK was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0120] Comparative Example

[0121] Comparative Example 1. A copolymer of tetraethyl orthosilicate (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 hydrochloric acid (61 g) were added to the flask. The reaction mixture was refluxed for 18 hours and then cooled to room temperature. PGEE (500 g) was added to the reaction mixture. The acetone and hydrolysis products were removed under reduced pressure to obtain a blend with a 21% solids content. PGMEA was added to the blend, and the resulting 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 / 1293, respectively. A 6% blend of the polymer with PGMEA was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0122] Comparative Example 2. A polymer consisting 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, 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 40% solids blend. The resulting polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average and number-average molecular weights were 1624 and 900, respectively. A 5% blend of this polymer with PGMEA and PGEE was prepared and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0123] Comparative Example 3. A homopolymer of 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane was prepared in a 4 L flask. The flask was charged with 1-trimethoxysilyl-2-methyldimethoxysilyl-ethane (200 g, 0.78 mol), methanol (402 g), and 0.01 M hydrochloric acid (71 g). 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 yield a 25% solids blend. The resulting polymer solution was filtered through a 0.2 μm PTFE filter and characterized by gel permeation chromatography (GPC). The weight-average and number-average molecular weights were 1313 and 629, respectively. A 5% blend of the polymer was prepared with PGMEA and PGEE and spin-coated onto a silicon wafer for refractive index and electrical property measurements.

[0124] The properties of the polymers described in Examples 1 to 10 and Comparative Examples 1 to 3 were analyzed.

[0125] The dielectric constant was measured at a frequency of 100 kHz for a film with a target thickness of 340 nm ± 20 nm. Before the measurement, the wafer was pre-baked at 150 °C for 5 minutes to remove accumulated moisture, and then the measurement was performed at room temperature.

[0126] The leakage current was measured using a film with a target thickness of 100 nm ± 20 nm. Before the measurement, the wafer was pre-baked at 150°C for 5 minutes to remove accumulated moisture, and then the measurement was performed at room temperature.

[0127] Molecular weight measurements were collected by gel permeation chromatography against polystyrene standards of known molecular weight using a Waters HPLC system containing 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 inline degasser AF, and a Waters temperature control module II. It was equipped with a series of Styragel HR columns (guard columns, HR1, HR3, and HR4). The THF eluent flow rate was 1.0 mL / min.

[0128] Film thickness measurements were performed using a JA Woollam M2000D-ESM-200AXY spectroscopic ellipsometer.

[0129] The coefficient of thermal expansion (CTE) was measured using a KLA-Tencor FLX-2320 thin film stress measurement system. This system uses a dual-wavelength laser to measure the change in wafer radius of curvature before and after film deposition. By depositing the same film on two dissimilar substrates with known thermal expansion properties and performing stress versus temperature measurements, the CTE of the film can be calculated. Stress versus temperature measurements were performed at temperatures from 21 to 200°C, using silicon and GaAs substrates. The temperature was increased at 2.5°C / min during the heating phase and decreased at 1.5°C / min during the cooling phase.

[0130] 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, and a contact load of 0.006 mN, using a Berkovich indenter and diamond as the material. Hardness and elastic modulus were calculated directly from the indentation curves using the Oliver-Pharr method.

[0131] Table 1 summarizes the average molecular weight (Mw), refractive index (RI), electrical breakthrough voltage (EBD), and shrinkage of the 10 polymers described above, and Table 2 summarizes the average molecular weight (Mw), refractive index (RI), electrical breakthrough voltage (EBD), and shrinkage of the three reference sample polymers.

[0132] [Table 1]

[0133] [Table 2]

[0134] As can be seen from the above, the material of the present invention can be used to obtain a combination of high electrical breakthrough voltage and excellent refractive index.

[0135] Table 3 summarizes the dielectric constants and refractive indices.

[0136] [Table 3]

[0137] As can be seen, the materials of the present invention provide a combination of low dielectric constant and excellent refractive index. It is noteworthy that the reduction in dielectric constant is not achieved by increasing the porosity of the film, as refractive indices well above 1.4 are obtained.

[0138] Table 4 summarizes the mechanical properties.

[0139] [Table 4]

[0140] Table 5 summarizes the coefficient of thermal expansion (CTE).

[0141] [Table 5]

[0142] As will be understood from the foregoing description and illustrative examples of the invention, the present invention can also be described with reference to the following embodiments:

[0143] 1. General formula I [ka] (In the formula, X l and X 2 are each independently selected from the group of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues, optionally substituted; R 3 and R 4 are each independently selected from the group of optionally substituted crosslinkable linear or branched divalent hydrocarbyl groups, such as alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms, such as a phenyl or benzyl group, which groups are 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. A low dielectric constant polymer film comprising a polymer obtained by polymerizing a compound having the formula: 2.X l and X 2 are each independently selected from the group of hydrolyzable groups selected from hydrogen and halogen, acyloxy, alkoxy, and OH groups. 3.X l and X 2 are each independently hydrogen and R 7O-, where R 7 3. The polymeric membrane of embodiment 1 or 2, wherein represents alkyl having 1 to 6 carbon atoms. 4.R 1 and R 2 are each independently selected from the group consisting of linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, and aryl groups containing 1 to 5 aromatic rings, optionally containing 1 to 3 heteroatoms, each of which is optionally substituted with 1 to 3 functional groups selected from halo, hydroxy, alkoxy, vinyl, and acetyl groups. 5.R 3 and R 4 are each independently selected from alkylene having 1 to 4, in particular 2, carbon atoms. 6. A polymeric membrane according to any of the previous embodiments, wherein n represents an integer from 1 to 5, in particular from 1 to 4, such as 1, 2 or 4. 7. The polymeric membrane of any of the previous embodiments, wherein in Formula I: X l and X 2 are each independently selected from the group of hydrogen and organic or inorganic hydrolyzable groups; R 1 and R 2 are each independently selected from the group of hydrocarbyl residues; R 3 and R 4 are each independently selected from the group consisting of alkylene having 1 to 6 carbon atoms and arylene having 6 to 10 carbon atoms; R 5 are each selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group; A polymer membrane wherein n, m and p have the same meanings as above. 8. The monomer according to general formula I is of formula Ia, Ib or Ic [ka] and combinations thereof. 9. A polymeric membrane according to any of the previous embodiments, obtained by homopolymerization of a compound of general formula I, such as compound Ia, Ib or Ic. 10. A polymeric membrane according to any of the previous embodiments, obtained by copolymerization of a compound of general formula I with a silane monomer, wherein the amount of the compound of formula I is at least 10 mol % of the total amount of silane monomer. 11. Compounds of Formula I and Formula III [ka] (In the formula, R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy group; R 12 is hydrogen, an organic bridging group, a reactive cleavage group, or a polarizability reducing organic group; R 13 is a crosslinkable linear or branched divalent hydrocarbyl group 3. The polymeric membrane according to any of the previous embodiments, obtained by copolymerization with a compound of formula (I). 12. Compounds of Formula I and Formula IV [ka] (In the formula, 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, alkyl groups having 1 to 6 carbon atoms, vinyl groups having 2 to 6 carbon atoms and aryl groups having 6 carbon atoms; n is an integer with the same meaning as above) 11. The polymeric membrane according to any of the preceding embodiments, obtained by copolymerization with a compound of formula (I). 13. The polymeric membrane according to embodiments 10 to 12, wherein 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. The polymeric membrane according to any of the previous embodiments, wherein the organic content of the polymer is in the range of 30-60 wt%, preferably less than 40 wt%. 10. The polymer film of any of the previous embodiments, wherein the polymer film has a dielectric constant of 2.7 or less at 15.1 MHz. 16. The polymeric film according to any of the previous embodiments, wherein the dielectric constant of the polymer after curing is 2.45 or less, preferably 2.30 or less. 17. The polymer membrane of any of the previous embodiments, having an electrical breakthrough voltage of 3.5 MV / cm or greater. The polymeric membrane according to any of the previous embodiments, having a thickness of less than 18.1 μm, in particular less than 500 nm, typically between 50 and 350 nm. 19. A polymeric film according to any of the previous embodiments, having an RI measured at a wavelength of 633 nm of greater than 1.4. 20. A method for forming a polymeric film, comprising: Formula I [ka] (In the formula, X l , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , R 4 , R 5 , I, and n, m, and p have the same meanings as above), and hydrolyzing a first silicon compound having the above structure; the first silicon compound is optionally a compound of formula III [ka] (In the formula, R 11 is a hydrolyzable group such as hydrogen, halide, alkoxy or acyloxy group, R 12 is hydrogen, an organic bridging group, a reactive cleavage group, or a polarizability reducing organic group; R 13 is a crosslinkable linear or branched divalent hydrocarbyl group and / or Formula IV [ka] (In the formula, X 3 , R 14 and n has the same meaning as above) to produce a polymerized siloxane material; and - casting the polymerized siloxane material into a layer and curing it into a film. 21. The method of embodiment 20, comprising depositing a siloxane material in the form of a thin film on a substrate; and curing the thin film to form a film. 22. The method of embodiment 21, wherein the substrate is a semiconductor substrate. 23. The method according to any of embodiments 20 to 22, wherein the polymeric film has a thickness of less than 1 μm, in particular less than 500 nm, typically 50 to 350 nm. 24. The method of any one of embodiments 20-23, wherein the polymeric film is cured at a temperature of 350°C or higher. 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 25.1 MHz. 26. A method for manufacturing a semiconductor device according to any one of embodiments 20 to 25, the method comprising the steps of: - depositing a metal layer; - depositing a photoresist and an auxiliary underlayer on the metal; - irradiating the photoresist stack with light or an electron beam through a mask to form a desired pattern; - developing the soluble portion of the photoresist and transferring the formed pattern into the metal layer by a selective etching process; - removing the remaining parts of the photoresist stack; - depositing and curing a low-k dielectric film; - removing excess of the deposited low-k dielectric film by an etch-back or chemical-mechanical polishing process. 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. 28. A semiconductor device comprising the polymer film according to any one of embodiments 1 to 19 as a low dielectric constant film, particularly as a film having a dielectric constant of 2.7 or less at 1 MHz. [Industrial Applicability]

[0144] The present invention provides a method for manufacturing a semiconductor device with a low dielectric constant film, the film comprising a polymer suitable as a barrier layer for filling spaces between metal interconnects having a maximum dimension of less than 30 nm, e.g., 10-20 nm, wherein the metal is selected from cobalt (Co), molybdenum (Mo), tungsten (W), and ruthenium (Ru).

[0145] Reference number 1=board 2=Metal deposition 3 = metal layer, e.g. Co or Ru 4 = Photoresist coating 5 = Photoresist - EUV material 6=Exposure and development 7=Etching 8 = Photoresist stripping 9=Dielectric coating 10=Low k dielectric 11=Platform 12=Dielectric coating 13=Low-k dielectric 14=Etching 15 = Barrier materials and metal coatings 16 = Barrier material 17 = Metal, e.g. Cu

Claims

1. A method for manufacturing a semiconductor device comprising a low dielectric constant polymer film, wherein the low dielectric constant polymer film is general formula I 【Chemistry 1】 (In the formula, X ｌ and X ２ Each is independently selected from the group consisting of hydrogen and organic or inorganic hydrolyzable groups; R １ and R ２ Each of these is independently selected from the group of hydrocarbyl residues and is arbitrarily substituted; R ３ and R ４ Each is independently selected from the group of optionally substituted, crosslinkable linear or branched divalent hydrocarbyl groups, such as alkylenes having 1 to 6 carbon atoms and arylenes having 6 to 10 carbon atoms; R ５ Each of these is selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 18 carbon atoms, such as a phenyl or benzyl group, and the group is optionally substituted; n is an integer between 1 and 5; m is an integer between 1 and 3; (p is an integer between 1 and 3) The polymer includes a polymer obtained by polymerizing a compound having the following characteristics: The above method is as follows: - The step of providing a substrate; - A step of depositing a metal layer containing a metal selected from cobalt (Co), molybdenum (Mo), tungsten (W), and ruthenium (Ru) onto the substrate; - The step of depositing a photoresist and an auxiliary underlayer onto the metal; - The step of irradiating the photoresist stack with light or an electron beam through a mask to form a desired pattern; - The steps of developing the soluble portion of the photoresist and transferring the formed pattern to the metal layer by a selective etching process; - The step of removing the residual portion of the photoresist stack; - The steps of depositing and curing the low-k dielectric film; A method comprising or consisting of the steps of: - removing excess of the deposited low-k dielectric film by an etch-back or chemical mechanical polishing process.

2. In the polymer obtained by polymerization of the compound of formula I, X ｌ and X ２ each independently selected from the group of hydrolyzable groups selected from hydrogen and halogen, acyloxy, alkoxy and OH groups, the method according to claim 1.

3. In the polymer obtained by polymerization of the compound of formula I, X ｌ and X ２ Each of them independently, hydrogen and R ７ Selected from the O- group, R ７ The method according to claim 1, wherein is an alkyl having 1 to 6 carbon atoms.

4. In the polymer obtained by polymerization of the compound of formula I, R １ and R ２ The method according to claim 1, wherein each of the members is independently selected from the group consisting of linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, and aryl groups containing 1 to 5 aromatic rings, optionally containing 1 to 3 heteroatoms, and each is optionally substituted with 1 to 3 functional groups selected from halo, hydroxy, alkoxy, vinyl, and acetyl groups.

5. In the polymer obtained by polymerization of the compound of formula I, R ３ and R ４ The method according to claim 1, wherein each is independently selected from alkylenes having 1 to 4, particularly 2, carbon atoms.

6. The method according to claim 1, wherein in the polymer obtained by polymerization of the compound of formula I, n represents an integer of 1 to 5, particularly 1 to 4, for example, 1, 2, or 4.

7. A method according to claim 1, wherein the polymer obtained by polymerization of a compound of formula I, X ｌ and X ２ Each of these is independently selected from the group consisting of hydrogen and organic or inorganic hydrolyzable groups; R １ and R ２ Each of these is independently selected from the group of hydrocarbyl residues; R ３ and R ４ Each is independently selected from the group of alkylenes having 1 to 6 carbon atoms and arylenes having 6 to 10 carbon atoms; R ５ Each of these is selected from alkyl groups and phenyl groups having 1 to 4 carbon atoms; A method in which n, m, and p have the same meaning as above.

8. A compound of general formula I, formula Ia, Ib, or Ic 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 The method according to claim 1, selected from monomers having and combinations thereof.

9. The method according to claim 1, wherein the low dielectric constant polymer film is obtained by the homopolymerization of a compound of general formula I, such as compound Ia, Ib, or Ic.

10. The method according to claim 1, wherein the low dielectric constant polymer film is obtained by copolymerization of a compound of general formula I and a silane monomer, and the amount of the compound of formula I is at least 10 mol% of the total amount of silane monomers.

11. The low dielectric constant polymer film comprises the compound of formula I and formula III. 【Transformation 5】 (In the formula, R １１ These are hydrolyzable groups such as hydrogen, halides, alkoxys, or acyloxy groups; R １２ These are hydrogen, an organic crosslinking group, a reactive cleaving group, or an organic group that reduces polarizability. R １３ (This is a crosslinkable linear or branched divalent hydrocarbyl group.) The method according to claim 1, obtained by copolymerization with a compound.

12. The low dielectric constant polymer film comprises the compound of formula I and formula IV 【Transformation 6】 (In the formula, X ３ is a hydrolyzable group selected from hydrogen, halogen, acyloxy, alkoxy, and OH groups; R １４ These are selected from halogens, acyloxy, alkoxy and OH groups, alkyl groups having 1 to 6 carbon atoms, vinyl groups having 2 to 6 carbon atoms, and aryl groups having 6 carbon atoms; (n is an integer with the same meaning as above.) The method according to claim 1, obtained by copolymerization with a compound.

13. The method according to claims 10 to 12, wherein the polymer obtained by polymerization of a compound of formula I with a compound of formula III or formula IV, or both, has a molar ratio between the compound of formula I and the compound of formula III or formula IV, or both, in the range of 10:90 to 90:10, for example, 20:80 to 80:20, and particularly 40:60 to 60:

40.

14. The method according to claim 1, wherein the organic content of the polymer is in the range of 30 to 60 wt%, preferably less than 40 wt%.

15. The method according to claim 1, wherein the dielectric constant of the low dielectric constant polymer film at 1 MHz is 2.7 or less.

16. The method according to claim 1, wherein the dielectric constant of the cured polymer is 2.45 or less, preferably 2.30 or less.

17. The method according to claim 1, wherein the electrical breakthrough voltage of the low dielectric constant polymer film is 3.5 MV / cm or more.

18. The method according to claim 1, wherein the thickness of the low dielectric constant polymer film is less than 1 μm, particularly less than 500 nm, and typically 50 to 350 nm.

19. The method according to claim 1, wherein the RI of the low dielectric constant polymer film, measured at a wavelength of 633 nm, is greater than 1.

4.

20. A method according to claim 1, comprising the step of forming the low dielectric constant polymer film, the step of - Equation I 【Transformation 7】 (In the formula, X ｌ , X ２ , X ３ , X ４ , R １ , R ２ , R ３ , R ４ , R ５ Hydrolysis of a first silicon compound having i and n, m, and p (where i and n have the same meaning as above), - The first silicon compound can be any of the following formulas: 【Transformation 8】 (In the formula, R １１ These are hydrolyzable groups such as hydrogen, halides, alkoxys, or acyloxy groups. R １２ These are hydrogen, an organic crosslinking group, a reactive cleaving group, or an organic group that reduces polarizability. R １３ (This is a crosslinkable linear or branched divalent hydrocarbyl group.) and / or formula IV 【Chemistry 9】 (In the formula, X ３ , R １４ (and n has the same meaning as above) A polymerized siloxane material is produced by polymerizing it with at least one second silicon compound obtained by hydrolyzing a compound having the above, - A method comprising forming the polymerized siloxane material into layers and curing them to form a film.

21. The method according to claim 20, comprising: depositing the siloxane material on the substrate in the form of a thin film; and curing the thin film to form a film.

22. The method according to claim 1, wherein the polymer film is cured at a temperature of 350°C or higher.

23. The method according to any one of claims 1 to 12 and 14 to 22, wherein the semiconductor device has a metal interconnect dimension of less than 50 nm, preferably less than 30 nm, for example, 10 to 20 nm or less.

24. A semiconductor device obtained according to claim 1, having a metal interconnect dimension of less than 50 nm, preferably less than 30 nm, for example, 10 to 20 nm or less.

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

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

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