Composition, pattern forming method, semiconductor device, and method for manufacturing device

Abstract

Provided are a composition, a pattern forming method, a semiconductor device, and a manufacturing method of a semiconductor device. A composition containing a compound according to an embodiment includes a carbon atom-containing linking group having a carbon atom number of 2 or more and 18 or less, a polymerizable functional group linked to the linking group, a first reactive group linked to the linking group, and a second reactive group linked to the linking group. The polymerizable functional group includes at least one of a (meth)acryl group and a vinyl group. The first reactive group includes at least one selected from a thiol group, a disulfide group, and a thiocyanate group. The second reactive group includes at least one selected from an alkoxysilane group, a chlorosilane group, and a hydroxyl group.

Description

[0001] Related applications

[0002] This application is based on and claims the priority of prior art patent application No. 2021-153336, filed on September 21, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present invention relate to a composition, a pattern forming method, a semiconductor device, and a method for manufacturing a semiconductor device. Background Technology

[0004] In recent years, when embedding wiring with interlayer insulating film, the double embedding method, which can simultaneously form the wiring part and the plug part with a single conductive film by also embedding conductive film in the connection hole that makes the upper layer wiring and the lower layer wiring conductive, has attracted much attention. Summary of the Invention

[0005] One embodiment provides a composition capable of being tightly bonded to a surface containing both a conductive material and an insulating material, a semiconductor device having a first layer obtained from the composition, and a patterning method using the composition.

[0006] The semiconductor device of the embodiment is generally a composition containing a compound. The compound includes: a carbon-containing linking group having 2 to 18 carbon atoms, a polymerizable functional group attached to the linking group, a first reactive group attached to the linking group, and a second reactive group attached to the linking group. The polymerizable functional group includes at least one of (meth)acryloyl and vinyl groups. The first reactive group includes at least one selected from thiol, dithio, and thiocyanate groups. The second reactive group includes at least one selected from alkoxysilyl, chlorosilyl, and hydroxyl groups.

[0007] Based on the above configuration, it is possible to provide a composition capable of being tightly bonded to a surface containing both a conductive material and an insulating material, a semiconductor device having a first layer obtained from the composition, and a patterning method using the composition. Attached Figure Description

[0008] Figure 1 A cross-sectional structure of an example of a semiconductor device according to an embodiment is schematically shown.

[0009] Figure 2 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0010] Figure 3 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0011] Figure 4 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0012] Figure 5 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0013] Figure 6 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0014] Figure 7 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0015] Figure 8 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0016] Figure 9 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0017] Figure 10 The illustration schematically shows one step of a method for manufacturing a semiconductor device according to an embodiment.

[0018] Figure 11 Other examples of semiconductor devices in the embodiments are illustrated schematically. Detailed Implementation

[0019] The embodiments will now be described with reference to the accompanying drawings. In the following description, components having substantially the same function and structure are sometimes denoted by the same reference numerals, and repeated descriptions are omitted. The drawings are schematic, and the relationships between thicknesses and planar dimensions, the proportions of thicknesses of each layer, etc., may differ from reality. Furthermore, the drawings may also include portions with different dimensional relationships or proportions. All descriptions of one embodiment can also be interpreted as descriptions of other embodiments, unless explicitly or obviously excluded. The various embodiments illustrate apparatus and methods for embodying the technical concept of the embodiments; the technical concept of the embodiments does not limit the materials, shapes, structures, arrangements, etc., of the constituent components to the following.

[0020] (First Implementation)

[0021] According to a first embodiment, a composition containing a compound is provided.

[0022] The compounds used in the embodiments are described herein.

[0023] The linking group can be, for example, a group of an organic compound containing 2 to 18 carbon atoms. By having 2 to 18 carbon atoms, the compound can be in a solid state at room temperature rather than a liquid. Examples of groups that can be used in organic compounds include groups of hydrocarbon compounds such as alkyl groups, and groups of aromatic compounds.

[0024] Polymerizable functional groups can form covalent bonds through photoradical reactions. An example of a polymerizable functional group is one that can form covalent bonds with a photocurable resin through a free radical reaction. Details of photocurable resins will be described later. Free radical reactions can occur, for example, through free radicals generated by light irradiation from components contained in the composition. An example of such a component is a photopolymerization initiator. Examples of polymerizable functional groups include those containing at least one of (meth)acryloyl and vinyl groups.

[0025] The first reactive group is capable of forming a covalent bond with a metal atom. The metal may, for example, be contained on the surface of a substrate to which the composition containing the compound of the embodiment is to be tightly bonded. Examples of metals include copper (Cu), aluminum (Al), tungsten (W), etc. One or more types of metal may be used. Examples of the first reactive group include groups containing at least one selected from thiol, dithio, and thiocyanate groups.

[0026] The second reactive group can form covalent bonds with compounds containing Si and O through hydrolysis or dehydration reactions. The Si and O-containing compounds can, for example, be contained on the surface of a substrate to which the composition containing the compounds is to be tightly bonded. Examples of Si and O-containing compounds include organic compounds, inorganic compounds, and organic-inorganic hybrid compounds. Examples of reactions that form covalent bonds with Si and O-containing compounds through hydrolysis or dehydration reactions include, for example, silane coupling reactions. Examples of the second reactive group include groups containing at least one selected from alkoxysilyl, chlorosilyl, and hydroxyl groups.

[0027] The substrate for which the compound-containing composition is to be tightly bonded is not particularly limited, for example, any substrate having a surface including portions containing Si and O compounds and portions containing metal. The substrate may consist entirely of this surface, or at least a portion thereof. This surface may also be located on top of the substrate. As a specific example, a wiring layer of a semiconductor device can be cited. Hereinafter, the substrate for which the composition containing the compound of the embodiment is to be tightly bonded is sometimes referred to as the workpiece.

[0028] An example of a compound is shown in Formulas 1 and 2 below. A compound may include a first compound having the structure represented by Formula 1, a second compound having the structure represented by Formula 2, or both the first and second compounds.

[0029] [Formula 1]

[0030]

[0031] Among them, R 1 and R 6 They are hydrogen atoms or methyl groups, respectively, R 1 and R 6 They can be the same or different. R 2 ~R 4 The atoms are selected from hydrogen, fluorine, chlorine, bromine, and iodine, respectively. R 2 ~R 4 They can be the same or different. Me is a methyl group.

[0032] The first compound contains a (meth)acryloyl group as a polymerizable functional group, a thiol group as a first reactive group, and an alkoxysilyl group as a second reactive group. Furthermore, the number of carbon atoms in the linking group is in the range of 2 to 18.

[0033] [Equation 2]

[0034]

[0035] Among them, R 1 and R 6 They are hydrogen atoms or methyl groups, respectively, R 1 and R 6 They can be the same or different. R 2 ~R 4 The atoms are selected from hydrogen, fluorine, chlorine, bromine, and iodine, respectively. R 2 ~R 4 They can be the same or different. Me is a methyl group.

[0036] The second compound contains a (meth)acryloyl group as a polymerizable functional group, a thiol group as a first reactive group, and an alkoxysilyl group as a second reactive group. Furthermore, the number of carbon atoms in the linking group is in the range of 2 to 18.

[0037] The compounds described in the embodiments can be synthesized, for example, by the Suzuki-Miyaura coupling method. As an example of the Suzuki-Miyaura coupling method, a method that utilizes the action of a nucleophile to cross-couple an organoboron compound with an aryl halogen can be cited.

[0038] The content of the compound in the embodiment of the composition is preferably 40% by mass or more. Wherein, if the composition contains a solvent, the total amount of the component from which the solvent is removed is set to 100% by mass.

[0039] The compounds of the embodiments can exist in the composition in the form of monomers, oligomers, or polymers. For example, various forms such as monomers and oligomers of the compound can exist in the composition.

[0040] The compounds in the composition can be identified using methods such as electrospray ionization-time of flight mass spectrometry (ESI-TOFMS) and nuclear magnetic resonance (NMR). Specifically, mass spectra (MS spectra) are obtained using ESI-TOFMS, and the presence of compounds can be determined by analyzing the molecular weights calculated from the MS spectra, the molecular weights of the fragments, and the chemical shifts in the NMR spectra.

[0041] The composition may contain a photocurable resin. A photocurable resin is a resin that can be cured by light irradiation. An example of a photocurable resin contains at least a polymerizable compound and a photopolymerization initiator.

[0042] The polymerizable compound is not particularly limited and can be an organic compound or an inorganic-organic hybrid compound. Furthermore, the polymerizable compound preferably imparts a film-like viscosity to the composition, for example, a resin having a viscosity of 500 mPa·s or less. Examples of polymerizable compounds include Si-containing monomers and Si-containing polymers. Specific examples of polymerizable compounds include polymers containing silsesquioxanes or polymers containing their derivatives. One or more types of polymerizable compounds can be used. Additionally, the compounds contained in the compositions of the embodiments can also function as polymerizable compounds.

[0043] Photopolymerization initiators are any substances that generate free radicals by irradiation with light, and are not particularly limited, but substances that generate free radicals at the wavelength of the light used during curing are preferred. Examples of the wavelength of the light used during curing include those in the range of 355 nm to 500 nm. In practical applications, a range of 365 nm to 430 nm is preferred. Examples of photopolymerization initiators include acylphosphine oxide compounds, alkylbenzene compounds, and other photoradical polymerization initiators. For example, Irgacure (registered trademark) 819 is an example of an acylphosphine oxide compound. Irgacure (registered trademark) 184 is an example of an alkylbenzene compound. On the other hand, Irgacure (registered trademark) TPO is an example of an acylphosphine oxide compound. One or more types of photopolymerization initiators can be used.

[0044] The content of the photopolymerization initiator in the composition can be in the range of 0.01% by mass to 15% by mass. Where the composition contains a solvent, the total weight of the components excluding the solvent is set as 100% by mass. If the content of the photopolymerization initiator is 0.01% by mass or more, there is a tendency to further improve sensitivity (rapid curing) and coating strength. The preferred range of content is 0.1% by mass to 10% by mass, a more preferred range is 0.5% by mass to 7% by mass, and the most preferred range is 1% by mass to 5% by mass. When using two or more photopolymerization initiators, their total amount is taken as the amount of photopolymerization initiator. As needed, the composition may also contain a non-polymerizable compound, a solvent, or both a non-polymerizable compound and a solvent. The non-polymerizable compound may include at least one selected from sensitizers, hydrogen donors, internal release agents, surfactants, antioxidants, polymer components, and polymerization inhibitors.

[0045] The solvent has at least one functional group selected from ester, carbonyl, hydroxyl, and ether groups. Examples of solvents include 1-methoxy-2-propyl acetate (propylene glycol monomethyl ether acetate (PGMEA)), 1-methoxy-2-propyl acetate, ethyl ethoxypropionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene glycol monomethyl ether, ethyl lactate, and 4-methyl-2-pentanol. PGMEA, γ-butyrolactone, cyclohexanone, and 4-methyl-2-pentanol are preferred. A more preferred solvent is one containing at least PGMEA. One or more types of solvents may be used. The solvent content in the composition may be 90% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass or more. Furthermore, the solvent content in the composition may be 99.999% by mass or less. When the composition contains two or more solvents, the total amount of solvent preferably satisfies the above range.

[0046] The composition may also contain modifiers such as blend compounds and other polymers. Modifiers have the effect of improving the spin-coating film-forming properties of the composition and its embedding properties in stepped substrates (including stepped workpieces).Examples of such modifiers include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-triphenylmethylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2- Methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2, 2'-Dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-diallyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethoxy-4,4 '-(9H-fluorene-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirodiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirodiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3' -Tetrahydro-(1,1')-spirodiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirodiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirodiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl The modifiers used include 1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, and dihydroxynaphthols such as 1,5-dihydroxynaphthol, 1,7-dihydroxynaphthol, and 2,6-dihydroxynaphthol; methyl 3-hydroxynaphthyl-2-carboxylate; indene; hydroxyindene; benzofuran; hydroxyanthracene; acenaphthene; biphenyl; bisphenol; triphenol; dicyclopentadiene; tetrahydroindene; 4-vinylcyclohexene; norbornene; 5-vinyl-2-norbornene; α-pinene; β-pinene; limonene and other phenolic varnish resins; polyhydroxystyrene; polystyrene; polyvinylnaphthalene; polyvinyl anthracene; polyvinyl carbazole; polyindene; polyacenaphthene; polynorbornene; polycyclodecene; polytetracyclododecene; polynortricycloene; poly(meth)acrylates and their copolymers. One or more types of modifiers may be used.

[0047] The composition of the embodiments described above comprises a compound. This compound includes a carbon-containing linking group having 2 to 18 carbon atoms, a polymerizable functional group attached to the linking group, a first reactive group attached to the linking group, and a second reactive group attached to the linking group. The polymerizable functional group includes at least one selected from (meth)acryloyl and vinyl groups. The first reactive group includes at least one selected from thiol, dithio, and thiocyanate groups. The second reactive group includes at least one selected from alkoxysilyl, chlorosilyl, and hydroxyl groups. The first and second reactive groups of the compound can bond to surfaces containing compounds and metals containing Si and O, and are cured by light irradiation. As a result, a photocurable composition with excellent adhesion to the aforementioned surfaces can be achieved.

[0048] (Second Implementation)

[0049] According to a second embodiment, a pattern forming method is provided. The pattern forming method includes the following steps: forming a composition on the surface of a workpiece having a surface comprising portions containing compounds containing Si and O and portions containing metal (hereinafter referred to as step A); forming a second composition containing Si and O on the composition (hereinafter referred to as step B); clamping the second composition with a template and the workpiece (hereinafter referred to as step C); and curing the second composition by light while it is clamped with the template and the workpiece (hereinafter referred to as step D). The composition may be, for example, the composition of the first embodiment. Each step will be described below.

[0050] (Process A)

[0051] The portion containing Si and O compounds can be formed, for example, by imprinting. Imprinting allows the transfer of a template onto an object. Therefore, the portion containing Si and O compounds can have a desired pattern shape. An imprinting method, for example, can be a method of transferring the pattern onto an imprinting material layer formed by coating and curing the imprinting material. The portion containing metal can be formed on the imprinting material with the transferred pattern, for example, by sputtering or vapor deposition. Examples of metals can be given by examples described in the first embodiment. The pattern formed on the template can be a nanometer-scale or micrometer-scale pattern. The linewidth can be set, for example, to be 10 nm or more and 50 nm or less.

[0052] Methods for applying embossing materials to a substrate include spin coating and inkjet coating. Spin coating can increase throughput per unit time, but the embossing material is a viscous liquid before light exposure.

[0053] As the imprinting material, it can be a material containing Si and O and having a low relative permittivity k, preferably in the range of 4.0 or less. Examples of compounds satisfying the above-mentioned relative permittivity include polymers containing silsesquioxanes or polymers containing their derivatives, Si oxides, etc. The imprinting material is cured, for example, by applying curing energy. As the curing energy, electromagnetic waves, heat, etc. can be used. The electromagnetic waves can be light selected, for example, from the range of wavelengths from 10 nm to 1 mm, such as infrared light, visible light, ultraviolet light, etc. The photocurable composition cured by light irradiation contains at least a polymerizable compound and a photopolymerization initiator, and may also contain a non-polymerizable compound or solvent as needed. Examples of non-polymerizable compounds include at least one selected from sensitizers, hydrogen donors, internal release agents, surfactants, antioxidants, and polymer components. Details of the components that the photocurable composition may contain, namely polymerizable compounds, photopolymerization initiators, non-polymerizable compounds, and solvents, are as described in the first embodiment.

[0054] As a method for forming a composition on a surface containing portions of compounds containing Si and O and portions containing metals formed by the above-described imprinting method, firstly, for example, the composition is coated onto the surface. Examples of coating methods may include vapor deposition, spin coating, dip coating, etc.

[0055] Then, a step of holding the composition while it is coated on the surface of the workpiece is preferably performed. This holding step can be carried out, for example, by storing the composition coated on the surface of the workpiece in a constant temperature bath. An example of a holding atmosphere is atmospheric air. The temperature of the atmosphere can be, for example, in the range of 20°C to 200°C. The holding time is, for example, 1 minute to 60 minutes. By holding the composition coated on the surface of the workpiece for 1 minute to 60 minutes in an atmospheric environment at 20°C to 200°C, the second reactive group of the compound in the composition can be bonded to a compound containing Si and O through, for example, a silane coupling reaction. Through the silane coupling reaction, the second reactive group can undergo a dehydration reaction with the compound containing Si and O, thereby forming a covalent bond. Furthermore, through this holding step, a covalent bond can be formed between the first reactive group of the compound in the composition and the metal-containing portion. Therefore, the adhesion between the composition and the surface of the workpiece can be improved through the holding step.

[0056] After the holding process, it is preferable to cool the workpiece coated with the composition until the temperature of the atmosphere reaches 20-30°C.

[0057] Then, the composition is cured, for example, by light irradiation, thereby forming a layer of the composition. Alternatively, the curing of the composition can be performed before the holding process.

[0058] (Process B)

[0059] A second composition containing Si is coated onto the formed composition.

[0060] Examples of the second composition include the embossing material described in step A. Examples of methods for applying the second composition to the composition are as described in step A.

[0061] (Process C)

[0062] Following step B, a process is performed where the second composition is held between a template and the workpiece. The template is not particularly limited as long as it is a light-transmitting component; for example, it can be made of transparent materials such as glass or quartz. Examples of patterns formed on the template are described in step A.

[0063] (Process D)

[0064] Next, while the second composition is held between a template and the workpiece, it is cured by light irradiation.

[0065] After step D, the template is demolded from the cured second composition.

[0066] Then, metal is formed in a second composition that forms a pattern as a template. Then, by repeating steps A through D, a multilayer wiring structure can be achieved using an imprinting method.

[0067] According to the second embodiment described above, a covalent bond can be formed between the first reactive group of the composition of the first embodiment and the metal-containing portion of the workpiece surface, and a covalent bond can be formed between the second reactive group of the composition of the first embodiment and the portion of the workpiece surface containing Si and O compounds through hydrolysis or dehydration reaction. As a result, the composition of the first embodiment can be tightly bonded to the workpiece surface.

[0068] (Third Implementation)

[0069] According to a third embodiment, a semiconductor device is provided, comprising a substrate, an insulating layer disposed above the substrate, a conductive layer disposed on the insulating layer, and a first layer in contact with the insulating layer and the conductive layer and containing a composition. For example, the composition of the first embodiment is used in the composition. The first layer may be a layer formed by curing the composition. In the first layer, the compounds of the embodiments in the composition may exist as units constituting a polymer (including oligomers) or may exist alone. The first layer is a tight-fitting layer that improves adhesion to the insulating layer and the conductive layer.

[0070] The compounds in the first layer can be identified, for example, in the same manner as described in the first embodiment.

[0071] The composition contained in the first layer may be a polymer containing the compounds of the embodiments. The polymer may be an oligomer. Examples of polymers include polymers of the first compound with the structure represented by Formula 1 and polymers of the second compound with the structure represented by Formula 2.

[0072] Examples of polymers of the first compound with the structure represented by Formula 1 are shown in the following chemical formula I.

[0073]

[0074] For each chemical formula in formulas I and II, R 1 and R 6 They are either hydrogen atoms or methyl groups, R 1 and R 6 They can be the same or different. R 2 ~R 4 The atoms are selected from hydrogen, fluorine, chlorine, bromine, and iodine, respectively. R 2 ~R 4 They can be the same or different. Me is a methyl group. n can be a natural number greater than 2, or a number between 2 and 10,000.

[0075] Next, the substrate, insulating layer, and conductive layer will be described.

[0076] As a substrate, a Si substrate can be cited as an example. As an example of a Si substrate, a semiconductor wafer can be cited.

[0077] The insulating layer contains compounds containing Si and O. The details of the Si and O-containing compounds are the same as those described in the second embodiment.

[0078] The conductive layer contains a metal. The details of the metal are the same as those described in the first embodiment.

[0079] Semiconductor devices may also include components other than a substrate, insulating layer, and conductive layer. For example, a barrier metal layer may be disposed between the insulating layer and the conductive layer. The barrier metal layer may be formed of materials such as SiCN, SiOC, Ta, TaN, and TiN.

[0080] The structure of a semiconductor device is not particularly limited; for example, it can also have... Figure 1 The structure shown.

[0081] Figure 1 A cross-sectional structure of the semiconductor device according to an embodiment is schematically shown. (e.g.) Figure 1As shown, the semiconductor device includes a substrate 1, a plurality of wiring layers L disposed above the upper surface of the substrate 1 along the xy-plane, and a first layer 2. Wiring layers Ln-1 (where n is a natural number) are located above the upper surface of the substrate 1 along the xy-plane. Wiring layer Ln-1 includes an insulating layer 3, conductive plugs 4a, wiring 4b, and a barrier metal layer 5. The insulating layer 3 extends along the xy-plane on the upper surface of the substrate 1. Conductive plugs 4a are disposed on the insulating layer 3. Plugs 4a extend along the z-axis. Wiring 4b is disposed on the insulating layer 3 and extends along the xy-plane. A wiring 4b is connected at its bottom surface to the upper surface of a plug 4a. The plugs 4a and wiring 4b constitute a conductive layer. The barrier metal layer 5 is disposed between the insulating layer 3 and the plugs 4a, and between the insulating layer 3 and the wiring 4b.

[0082] Wiring layer Ln is located at a higher position than wiring layer Ln-1 (away from substrate 1), and includes an insulating layer 6, a conductive plug 7a, wiring 7b, and a barrier metal layer 8. The insulating layer 6 is disposed on the upper surface of the insulating layer 3 and extends along the xy plane. The plug 7a is disposed on the insulating layer 6 and extends along the z-axis. The wiring 7b is disposed on the insulating layer 6 and extends along the xy plane. The wiring 7b is connected at its bottom surface to the upper surface of a plug 7a. The plug 7a and the wiring 7b constitute a conductive layer. The barrier metal layer 8 is disposed between the insulating layer 6 and the plug 7a, and between the insulating layer 6 and the wiring 7b.

[0083] The first layer 2 is disposed between the upper surface of the wiring layer Ln-1 along the xy-plane and the lower surface of the wiring layer Ln along the xy-plane. The upper surface of a plug 4a or a wire 4b of the wiring layer Ln-1 is tightly bonded to the lower surface of the first layer 2 along the xy-plane, and the upper surface of the insulating layer 3 of the wiring layer Ln-1 is tightly bonded to the lower surface of the first layer 2 along the xy-plane. On the other hand, the bottom surface of the insulating layer 6 of the wiring layer Ln is tightly bonded to the upper surface of the first layer 2 along the xy-plane. Furthermore, the first layer 2 has at least one through-hole extending along the z-axis. A plug 7a of the wiring layer Ln extends along the z-axis within the insulating layer 6 to reach the through-hole of the first layer 2, and its bottom surface is connected to the upper surface of a wire 4b of the wiring layer Ln-1. This structure is called a dual damascene structure. Additionally, a barrier metal layer 8 is disposed between the inner circumferential surface of the through-hole and the plug 7a.

[0084] The first layer 2 is unlikely to react with metals such as Cu and Al. Furthermore, since it is essentially formed from organic polymers, it is unlikely to be porous and therefore lacks high-speed diffusion pathways. Thus, the first layer 2 can also function as a diffusion-blocking layer.

[0085] Other wiring L between substrate 1 and wiring layer L, and wiring L located above wiring layer Ln (all omitted from the diagram), may also have the same structure as wiring layer Ln or wiring layer Ln-1.

[0086] Reference Figures 2 to 10 illustrate Figure 1 An example of a method for manufacturing a semiconductor device is shown.

[0087] like Figure 2 As shown, an insulating layer 3 with a desired pattern 3a is formed by coating a layer of imprinting material on the substrate 1 and using an imprinting method with a template 10 having a desired pattern 10a to transfer the pattern 10a onto the layer of imprinting material.

[0088] like Figure 3 As shown, the bottom of the recess in the pattern 3a of the insulating layer 3, which should be the plug, is removed by, for example, reactive ion etching (RIE) using O2 to form a through hole.

[0089] Next, as Figure 4 As shown, a barrier metal layer 5 is formed on the inner surface of the recess and through hole of the pattern 3a of the insulating layer 3, which will become the plug or wiring.

[0090] like Figure 5 As shown, conductive material 11 is embedded in the recesses and through holes of the pattern 3a in the insulating layer 3, for example, by sputtering or vapor deposition. Thus, plugs 4a and wiring 4b are formed within the insulating layer 3.

[0091] Next, the surface is subjected to chemical mechanical polishing (CMP) treatment, such as... Figure 6 As shown, the wiring layer Ln-1 is obtained.

[0092] Then, as Figure 7 As shown, a first layer 2 is formed on the surface of the wiring layer Ln-1 along the xy plane by process A of the method of the second embodiment.

[0093] Next, after applying an imprinting material to the first layer 2, the imprinting material is clamped between a template 10 having the desired pattern 10a and a substrate 1. While the imprinting material is clamped between the template 10 and the substrate 1, it is cured by light. Thus, as... Figure 8 As shown, pattern 10a is transferred onto an imprinting material layer to form an insulating layer 6 having the desired pattern 6a. Furthermore, the application and curing of the imprinting material can be performed, for example, through steps B to D of the method of the second embodiment.

[0094] like Figure 9As shown, by reactive ion etching using, for example, O2, the bottom of the recess in the pattern 6a of the insulating layer 6, which is to be a plug, and the first layer 2 at the portion connected to the bottom, are removed to form a through hole. Then, a barrier metal layer 8 is formed on the inner surface of the recess in the pattern 6a of the insulating layer 6, which is to be a plug or wiring, and the through hole.

[0095] like Figure 10 As shown, conductive material 12 is embedded, for example by sputtering or vapor deposition, within the recesses and through-holes of the pattern 6a in the insulating layer 6. This forms plugs and wiring within the insulating layer 6.

[0096] Then, by performing chemical mechanical polishing (CMP) on the surface, the second wiring layer Ln is obtained. As described above, a semiconductor device can be manufactured using a dual damascene method with imprinting technology. Furthermore, the manufacturing method described with reference to the accompanying drawings can also be applied to wiring layers Ln-1 and L other than wiring layer Ln.

[0097] Furthermore, according to the third embodiment, a method for manufacturing a semiconductor device having a substrate having multiple semiconductor elements can be provided. This method includes the following steps:

[0098] The composition of the embodiment is formed on the surface of a substrate, wherein the surface is the surface of a film formed on the substrate, and the surface includes portions containing compounds containing Si and O and portions containing metal;

[0099] A second composition containing Si and O is formed on the aforementioned composition;

[0100] The second composition is held between a patterned template and the substrate;

[0101] With the second composition held between the template and the substrate, the second composition is cured by light irradiation;

[0102] The template is demolded from the cured second composition to form the pattern on the cured second composition.

[0103] The substrate can be a semiconductor substrate, such as a Si substrate. Multiple semiconductor elements are formed on the substrate. These multiple semiconductor elements can also be disposed on the aforementioned film. Furthermore, the multiple semiconductor elements can be connected to portions containing Si and O compounds or portions containing metal, or both. Wiring for electrically connecting the multiple semiconductor elements is formed on the pattern of the cured second composition.

[0104] The steps included in the above method can be performed in the same manner as those described in the first to third embodiments. According to the above method, the adhesion between the upper and lower layers can be improved. Therefore, upper and lower layer wirings for electrically connecting multiple semiconductor elements can be formed by imprinting. Figure 11 An example of a semiconductor device manufactured by the above method is shown.

[0105] Figure 11 The semiconductor device 21 shown includes a substrate 23 on which multiple semiconductor elements are formed. The substrate 23 may be a semiconductor substrate such as a Si substrate. One semiconductor element 22a is a transistor including a gate electrode 24a, a sidewall spacer 25a, a source electrode, and a drain electrode 26a. Another semiconductor element 22b is a transistor including a gate electrode 24b, a sidewall spacer 25b, a source electrode, and a drain electrode 26b. Gate electrodes 24a and 24b are formed on the substrate 23. Sidewall spacers 25a and 25b are formed on the substrate 23. Sidewall spacers 25a cover the gate electrode 24a. Sidewall spacers 25b cover the gate electrode 24b. The source electrode and drain electrode 26a are formed on the substrate 23 on both sides of the gate electrode 24a. The source electrode and drain electrode 26b are formed on the substrate 23 on both sides of the gate electrode 24b.

[0106] Lower insulating layers 27a and 27b extend along the upper surface of the substrate 23 along the xy plane. Lower insulating layer 27a covers semiconductor element 22a. Lower insulating layer 27b covers semiconductor element 22b. Furthermore, a conductive first plug 28a and a first wiring 29a are provided in the lower insulating layer 27a. A conductive second plug 28b and a second wiring 29b are provided in the lower insulating layer 27b. The first plug 28a and the first wiring 29a constitute a first conductive layer. The second plug 28b and the second wiring 29b constitute a second conductive layer. The first plug 28a and the second plug 28b extend along the z-axis direction. On the other hand, the first wiring 29a and the second wiring 29b extend along the xy plane. The upper surface of a certain first plug 28a is connected to the bottom surface of the first wiring 29a, and the source and drain 26a are connected to the lower surface of the first plug 28a. Thus, the source and drain 26a of semiconductor element 22a are electrically connected to the first wiring 29a. Additionally, the upper surface of a second plug 28b is connected to the bottom surface of the second wiring 29b, and the source and drain 26b are connected to the lower surface of the second plug 28b. Thus, the source and drain 26b of semiconductor element 22b are electrically connected to the second wiring 29b.

[0107] A first layer 30 is formed on the upper surface of the lower insulating layers 27a, 27b, the first wiring 29a, and the second wiring 29b along the xy plane. The first layer 30 has multiple through holes 31 for inserting plugs. Upper insulating layers 32a and 32b extend along the xy plane of the first layer 30. A conductive third plug 33a is provided in the upper insulating layer 32a. A conductive fourth plug 33b is provided in the upper insulating layer 32b. The third plug 33a and the fourth plug 33b extend along the z-axis. A third wiring 34 extends along the x-axis and is formed on both the upper insulating layers 32a and 32b. The third plug 33a, the fourth plug 33b, and the third wiring 34 constitute a third conductive layer. The third wiring 34 connects at its bottom surface to the upper surface of a third plug 33a and the upper surface of a fourth plug 33b. The lower end of the third plug 33a is inserted into the through hole 31 of the first layer 30 and connected to the upper surface of the first wiring 29a. Additionally, the lower end of the fourth plug 33b is inserted into the through hole 31 of the first layer 30 and connected to the upper surface of the second wiring 29b. Thus, the source and drain 26a of the semiconductor element 22a are electrically connected to the source and drain 26b of the semiconductor element 22b through the first conductive layer, the second conductive layer, and the third conductive layer.

[0108] Figure 11 The components shown can be the same as those described in the first to third embodiments. Alternatively, they can be formed according to the method of the embodiments. Figure 11 The upper layer shown is the layer above.

[0109] The semiconductor device according to the third embodiment described above includes a first layer that is in contact with an insulating layer and a conductive layer and contains the composition of the first embodiment. Since the first layer has excellent adhesion to both the insulating and conductive layers, the adhesion between the upper and lower layers can be improved. Furthermore, the first layer is substantially formed of an organic material and has a non-porous structure, making it difficult for metals such as Cu or Al to diffuse, thus functioning as a diffusion-blocking layer. In addition, according to the third embodiment, a dual damascene method using imprinting technology can be implemented.

[0110] [Example]

[0111] The following describes the embodiments in detail.

[0112] (Example 1)

[0113] Compound Synthesis

[0114] In a 50 mL pear-shaped flask equipped with a magnetic stirrer, under an Ar atmosphere, 100 mg of compound A was added. Then, 189 mg of compound B was added, followed by 20 mL of tetrahydrofuran (THF). While stirring with a stir bar, 31.3 mg of NaOMe and 8.5 mg of dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium were added. The mixture was then heated and stirred under reflux for 8 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the ethyl acetate was evaporated to give the crude product. Purification was performed by silica gel column chromatography (using ethyl acetate as the mobile phase) to obtain the target compound C. The target compound C is an example of a compound represented by Formula 1.

[0115] The chemical structural formulas of compounds A, B and target compound C are shown in Formulas 3 to 5 below.

[0116] [Formula 3]

[0117]

[0118] [Formula 4]

[0119]

[0120] [Formula 5]

[0121]

[0122] Preparation of the composition

[0123] A composition was obtained by mixing 5% by mass of target compound C, 0.1% by mass of Irgacure 819 (manufactured by BASF) as a photopolymerization initiator, 2% by mass of polymethyl methacrylate as a modifier, 0.5% by mass of Polyflow No. 36 (trade name of Kyoeisha Chemicals) as a leveling agent, and 92.4% by mass of PGMEA as a solvent. The composition, after removing the solvent, contained 66% by mass of target compound C and 1.3% by mass of photopolymerization initiator. Target compound C also functions as a polymerizable compound.

[0124] (Example 2)

[0125] Compound Synthesis

[0126] In a 50 mL pear-shaped flask equipped with a magnetic stirrer, under an Ar atmosphere, 100 mg of compound D was added. Then, 1.7 equivalents of compound B were added, along with 20 mL of THF. While stirring with a stir bar, 1.5 equivalents of K₃PO₄ and 2.5 equivalents of water were added. 0.03 equivalents of Pd(Ir)(cinnamyl)(Cl) were added. The mixture was then heated to 90 °C and stirred for 2 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the ethyl acetate was evaporated to obtain the crude product. Purification was performed by silica gel column chromatography (using ethyl acetate as the mobile phase) to obtain the target compound E. Target compound E is an example of the compound represented by formula 2. The reaction formula for the synthesis is shown in formula 6. Target compound E is also a polymerizable compound.

[0127] [Formula 6]

[0128]

[0129] Preparation of the composition

[0130] The composition was obtained in the same manner as in Example 1, except that target compound E was used instead of target compound C. The composition, after solvent removal, contained 66% by mass of target compound E and 1.3% by mass of photopolymerization initiator.

[0131] (Example 3)

[0132] exist Figure 1 After coating the upper surface of the xy plane of the wiring layer Ln-1 of the semiconductor device shown with the composition of Example 1, the semiconductor device was placed in a thermostat bath with the temperature adjusted to 80°C and heated for 15 minutes under atmospheric conditions. Then, after cooling at room temperature for 15 minutes, it was cured by light irradiation or the like.

[0133] Next, after coating the composition of Example 1 with a photocurable resin containing Si, the composition of Example 1 and the imprinting material are clamped together using a template 10 having the desired pattern 10a and a substrate 1. With the composition of Example 1 and the imprinting material clamped together using the template 10 and the substrate 1, the mixture is subjected to a nitrogen atmosphere at 100 mW / cm². 2 Expose the material to 365nm light for 120 seconds to cure the imprint material, thereby forming the first layer and the insulating layer of the wiring layer Ln on the upper surface of the wiring layer Ln-1.

[0134] The insulating layer of wiring layer Ln was not stripped from the first layer. Next, according to reference... Figures 8-10 The described process forms the wiring layer Ln, manufacturing... Figure 1 The semiconductor device is shown. The insulating layer is formed of an organic compound containing Si, O, and C, and the conductive layer is formed of Cu. Additionally, the first layer contains a compound represented by chemical formula I and R...1 ~R 6 Polymers consisting of hydrogen atoms.

[0135] (Example 4)

[0136] exist Figure 1 After coating the upper surface of the xy plane of the wiring layer Ln-1 of the semiconductor device shown with the composition of Example 2, the semiconductor device was placed in a thermostat bath with the temperature adjusted to 80°C and heated for 15 minutes under atmospheric conditions. Then, after cooling at room temperature for 15 minutes, it was cured by light irradiation or the like.

[0137] Next, after coating the composition of Example 2 with a photocurable resin containing Si, the composition of Example 2 and the imprinting material are clamped together with a template 10 having the desired pattern 10a and a substrate 1. With the composition of Example 2 and the imprinting material clamped together with the template 10 and the substrate 1, the mixture is subjected to a nitrogen atmosphere at 100 mW / cm². 2 Expose the material to 365nm light for 120 seconds to cure the imprint material, thereby forming the first layer and the insulating layer of the wiring layer Ln on the upper surface of the wiring layer Ln-1.

[0138] The insulating layer of wiring layer Ln was not stripped from the first layer. Next, according to reference... Figures 8-10 The described process forms the wiring layer Ln, manufacturing... Figure 1 The semiconductor device is shown. The insulating layer is formed of an organic compound containing Si, O, and C, and the conductive layer is formed of Cu. Additionally, the first layer contains a compound represented by chemical formula II and R... 1 ~R 6 Polymers consisting of hydrogen atoms.

[0139] (Comparative Example)

[0140] exist Figure 1 In the semiconductor device shown, a diffusion barrier layer made of SiCN is formed on the upper surface of the xy plane of the wiring layer Ln-1 to replace the first layer. Next, when an insulating layer for the wiring layer Ln is formed on the diffusion barrier layer using an imprinting method, the insulating layer does not adhere tightly to the diffusion barrier layer and instead peels off. Therefore, it is impossible to stack upper layers.

[0141] Furthermore, for the compounds shown in Formula 1, those other than the compounds of Example 1 are compounds whose structure and electronic state are substantially equivalent to those of Example 1, and can therefore be synthesized using a method similar to that of Example 1, with the effect shown in Example 3 expected. Similarly, for the compounds shown in Formula 2, those other than the compounds of Example 2 are compounds whose structure and electronic state are substantially equivalent to those of Example 2, and can therefore be synthesized using a method similar to that of Example 2, with the effect shown in Example 4 expected.

[0142] According to the above embodiments and examples, a composition containing a compound is provided. The compound comprises a carbon-containing linking group having 2 to 18 carbon atoms, a polymerizable functional group connected to the linking group, a first reactive group connected to the linking group, and a second reactive group connected to the linking group. The polymerizable functional group includes at least one selected from (meth)acryloyl and vinyl groups. The first reactive group includes at least one selected from thiol, dithio, and thiocyanate groups. The second reactive group includes at least one selected from alkoxysilyl, chlorosilyl, and hydroxyl groups. As a result, a composition with excellent adhesion to composite surfaces containing compounds and metals containing Si and O can be provided.

[0143] The invention with embodiments described below.

[0144] According to one embodiment, a composition containing a compound is provided. The compound includes: a carbon-containing linking group having 2 to 18 carbon atoms; a polymerizable functional group connected to the linking group and capable of forming a covalent bond with a photocurable resin via a free radical reaction; a first reactive group connected to the linking group and capable of forming a covalent bond with a metal atom; and a second reactive group connected to the linking group and capable of forming a covalent bond with a compound containing Si and O via a hydrolysis or dehydration reaction.

[0145] According to one embodiment, a semiconductor device is provided, comprising:

[0146] substrate;

[0147] An insulating layer, disposed above the substrate, contains compounds containing Si and O;

[0148] A conductive layer, which is disposed inside the insulating layer; and

[0149] The first layer, which is in contact with the surface of the insulating layer and the surface of the conductive layer, contains the composition of the embodiment.

[0150] Furthermore, according to one embodiment, a pattern forming method is provided, comprising the following steps:

[0151] The composition of the embodiment is formed on the surface of a substrate, wherein the surface is the surface of a film formed on the substrate, and the surface includes portions containing compounds containing Si and O and portions containing metal;

[0152] A second composition containing Si is formed on the aforementioned composition;

[0153] The second composition is held between a template and a substrate; and

[0154] While the second composition is held between a template and a substrate, it is cured by light.

[0155] The foregoing has described some embodiments of the present invention, which are given by way of example and are not intended to limit the scope of the invention. These new embodiments can be implemented in various other ways, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, and are included within the scope of the invention equivalents described in the claims.

Claims

1. A composition, characterized in that, Contains compounds and photopolymerization initiators. The compound contains: Linking groups containing carbon atoms with a carbon number of 2 to 18; Polymerizable functional groups connected to the linking group; The first reactive group connected to the linking group; and The second reactive group connected to the linking group, The polymerizable functional group includes at least one of (meth)acryloyl and vinyl groups. The first reactive group includes at least one selected from thiol, dithio, and thiocyanate groups. The second reactive group includes at least one selected from alkoxysilyl and chlorosilyl groups.

2. The composition according to claim 1, characterized in that, The polymerizable functional group is a group that can form covalent bonds through photoradical reactions.

3. The composition according to claim 1, characterized in that, The first reactive group is a group that can form a covalent bond with a metal atom.

4. The composition according to claim 1, characterized in that, The second reactive group is a group that can form covalent bonds with compounds containing Si and O through hydrolysis or dehydration reactions.

5. The composition according to claim 1, characterized in that, It also contains solvents.

6. The composition according to claim 1, characterized in that, The compound includes at least one of the compounds represented by Formula 1 and Formula 2 below. [Formula 1] [Equation 2] In Equations 1 and 2 respectively, R 1 R is a hydrogen atom or a methyl group. 6 For hydrogen atoms, R 2 ~R 4 R is selected from hydrogen, fluorine, chlorine, bromine, and iodine atoms, respectively. 2 ~R 4 They can be the same or different.

7. A semiconductor device, characterized in that, have: substrate; An insulating layer, disposed above the substrate, contains a compound containing Si and O; A conductive layer disposed in the insulating layer; and The first layer, which is in contact with the insulating layer and the conductive layer, contains the composition of claim 1.

8. The semiconductor device according to claim 7, characterized in that, The polymerizable functional groups of the composition in the first layer are groups capable of forming covalent bonds through photoradical reactions.

9. The semiconductor device according to claim 7, characterized in that, The first reactive group of the composition in the first layer is a group capable of forming a covalent bond with a metal atom.

10. The semiconductor device according to claim 7, characterized in that, The second reactive group of the composition in the first layer is a group capable of forming covalent bonds with compounds containing Si and O through hydrolysis or dehydration reactions.

11. The semiconductor device according to claim 7, characterized in that, The compounds in the composition of the first layer include at least one of the compounds represented by Formula 1 and Formula 2. [Formula 1] [Equation 2] In Equations 1 and 2 respectively, R 1 R is a hydrogen atom or a methyl group. 6 For hydrogen atoms, R 2 ~R 4 R is selected from hydrogen, fluorine, chlorine, bromine, and iodine atoms, respectively. 2 ~R 4 They can be the same or different.

12. The semiconductor device according to claim 7, characterized in that, The composition of the first layer is a polymer containing the compound.

13. A method for forming a pattern, characterized in that, The following steps are required: The composition of claim 1 is formed on the surface of a workpiece, wherein the surface comprises a portion containing a compound containing Si and O and a portion containing a metal; A second composition containing Si and O is formed on the aforementioned composition; The second composition is held in place by a template and the workpiece; While the second composition is held between the template and the workpiece, it is cured by light irradiation; and Demold the template from the cured second composition.

14. The pattern forming method according to claim 13, characterized in that, The polymerizable functional group of the composition is a group capable of forming covalent bonds through photoradical reactions.

15. The pattern forming method according to claim 13, characterized in that, The first reactive group of the composition is a group capable of forming a covalent bond with a metal atom.

16. The pattern forming method according to claim 13, characterized in that, The second reactive group of the composition is a group capable of forming covalent bonds with compounds containing Si and O through hydrolysis or dehydration reactions.

17. The pattern forming method according to claim 13, characterized in that, The composition also contains a solvent.

18. The pattern forming method according to claim 13, characterized in that, The compound includes at least one of the compounds represented by Formula 1 and Formula 2 below. [Formula 1] [Equation 2] In Equations 1 and 2 respectively, R 1 R is a hydrogen atom or a methyl group. 6 For hydrogen atoms, R 2 ~R 4 R is selected from hydrogen, fluorine, chlorine, bromine, and iodine atoms, respectively. 2 ~R 4 They can be the same or different.

19. The pattern forming method according to claim 13, characterized in that, The second composition contains a photocurable resin.

20. A method for manufacturing a semiconductor device, characterized in that, The following steps are required: The composition of claim 1 is formed on the surface of a substrate, wherein the surface is the surface of a film formed on the substrate, and the surface includes portions containing compounds containing Si and O and portions containing metal; A second composition containing Si and O is formed on the aforementioned composition; The second composition is held between a patterned template and the substrate; While the second composition is held between the template and the substrate, it is cured by light irradiation; and The template is separated from the cured second composition to form the pattern on the cured second composition. The substrate is a semiconductor substrate on which multiple semiconductor elements are formed. Wiring that electrically connects the plurality of semiconductor elements is formed on the pattern of the cured second composition.

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