JP2005093688A - Semiconductor device and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a semiconductor device capable of attaining the further simplification of a manufacturing process. <P>SOLUTION: In the manufacturing method for the semiconductor device; an inorganic insulating layer 20 is formed to the upper section of a substrate 10; at least one kind of a treatment selected from an ultraviolet irradiation treatment, an electron-beam irradiation treatment, and a plasma treatment is conducted on the surface 20a of the insulating layer 20; and an organic insulating layer 40 is formed on the insulating layer 20. In the manufacturing method for the semiconductor device, a first opening section 72 is formed to the insulating layer 20, a second opening section 74 connected to the first opening section 72 is formed to the insulating layer 40, and a conductive layer 90 is buried to the first and second opening sections 72 and 74. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a wiring structure of a semiconductor device and a manufacturing method thereof.

  Along with the miniaturization of semiconductor devices, the movement to change the wiring material from conventional aluminum to copper is progressing. Since copper has a lower vapor pressure than other metals normally used as a wiring material such as aluminum and is difficult to be finely processed, a damascene method is often used when copper is used as a wiring material. Among these, the dual damascene method is a preferable method in that the manufacturing process of the semiconductor device can be shortened because the via layer and the trench wiring layer formed on the via layer can be formed simultaneously (for example, Patent Document 1 and Patent). (See publication 2). At present, in a wiring structure using silica as an insulating layer, a copper wiring technique to which this dual damascene method is applied is generally spreading.

  In addition, in order to achieve further miniaturization of semiconductor devices, not only the wiring material but also the study of switching the insulating layer material from the current silica (relative dielectric constant 4) to a material having a lower relative dielectric constant has been activated. . Examples of such a low dielectric constant insulating material include a carbon-containing silica insulating layer formed by a CVD method, an organic insulating layer formed by a coating method, and a polysiloxane insulating layer formed by a coating method. Etc.

Now, in this dual damascene method, there is a demand for further simplification of the manufacturing process and further reduction of parasitic capacitance between wirings.
JP 2002-299441 JP2003-110018

  An object of the present invention is to provide a method of manufacturing a semiconductor device that can achieve further simplification of the manufacturing process.

  Another object of the present invention is to provide a semiconductor device in which the parasitic capacitance between wirings is further reduced.

(1) A manufacturing method of a semiconductor device of the present invention includes:
An inorganic insulating layer is formed above the substrate,
The surface of the inorganic insulating layer is subjected to at least one treatment selected from ultraviolet irradiation treatment, electron beam irradiation treatment, and plasma treatment, and then an organic insulating layer is formed on the inorganic insulating layer. Forming,
Forming a first opening in the inorganic insulating layer;
Forming a second opening continuous with the first opening in the organic insulating layer;
Embedding a conductive layer in the first and second openings.

  Here, “form an inorganic insulating layer above the substrate” not only means that the inorganic insulating layer is directly formed on the substrate, but also other layers ( For example, the case where the inorganic insulating layer is formed through a diffusion prevention layer, a wiring layer, and an insulating layer is included.

  Here, the plasma treatment may be at least one treatment selected from oxygen plasma treatment, nitrogen plasma treatment, helium plasma treatment, argon plasma treatment, hydrogen plasma treatment, and ammonia plasma treatment.

  Here, the inorganic insulating layer may be a polysiloxane insulating layer having a relative dielectric constant of 1.5 to 3.2. In this case, the polysiloxane insulating layer may have a hydrocarbon group.

  Here, the inorganic insulating layer can be formed by applying a coating solution for an inorganic insulating layer on the substrate to form a coating film and heating the coating film.

  The organic insulating layer may be made of an organic polymer having a glass transition point of 400 ° C. or higher and a thermal decomposition temperature of 500 ° C. or higher. In this case, the organic polymer is composed of at least one polymer selected from polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, and polyquinoxaline. Can do.

  Here, the ultraviolet irradiation treatment can be performed in an oxygen atmosphere.

(2) The semiconductor device of the present invention
An inorganic insulating layer provided above the substrate;
An organic insulating layer provided on the inorganic insulating layer;
A first opening provided in the inorganic insulating layer;
A second opening provided in the organic insulating layer and continuous with the first opening;
A conductive layer embedded in the first and second openings;
including.

  Here, the inorganic insulating layer may be a polysiloxane insulating layer having a relative dielectric constant of 1.5 to 3.2. In this case, the polysiloxane insulating layer may have a hydrocarbon group.

  The organic insulating layer may be made of an organic polymer having a glass transition point of 400 ° C. or higher and a thermal decomposition temperature of 500 ° C. or higher. In this case, the organic polymer is composed of at least one polymer selected from polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, and polyquinoxaline. Can do.

  According to the method for manufacturing a semiconductor device of the present invention, the surface of the inorganic insulating layer is modified by performing at least one of the above-described processes on the surface of the inorganic insulating layer. Thereafter, by forming the organic insulating layer on the inorganic insulating layer, adhesion between the inorganic insulating layer and the organic insulating layer can be enhanced. Thereby, it is possible to prevent the inorganic insulating layer from being peeled off or cracked when performing planarization by CMP in the step of forming the conductive layer and during a temperature cycle test (heat cycle).

  In addition, since the organic insulating layer can be formed on the inorganic insulating layer without any other layer such as a stopper layer, a semiconductor device in which parasitic capacitance between wirings is further reduced can be obtained. Can do.

  Furthermore, since the properties of the inorganic insulating layer and the organic insulating layer are largely different from each other, a high etching rate selection ratio can usually be obtained between the inorganic insulating layer and the organic insulating layer. . For this reason, even if a stopper layer is not provided between the inorganic insulating layer and the organic insulating layer, the organic insulating layer can be selectively etched, whereby the organic insulating layer can be etched. In addition, the second opening can be formed with high accuracy. As a result, further simplification of the manufacturing process can be achieved.

  In addition, the semiconductor device of the present invention is reduced in cost by simplifying the manufacturing process, reducing the parasitic capacitance between wirings, and preventing the inorganic insulating layer from peeling or cracking for the reasons described above. Yield is good.

  Hereinafter, a semiconductor device and a manufacturing method thereof according to an embodiment of the present invention will be specifically described.

[Structure of semiconductor device]
FIG. 1 is a cross-sectional view schematically showing a semiconductor device 100 according to an embodiment of the present invention.

  As shown in FIG. 1, the semiconductor device 100 of the present embodiment has a conductive layer 90 formed by a dual damascene method. More specifically, the conductive layer 90 includes a via layer 92 and a wiring layer 94 provided continuously on the via layer 92. The via layer 92 is embedded in the first opening 72 provided in the inorganic insulating layer 20, and the wiring layer 94 is embedded in the second opening 74 provided in the organic insulating layer 40. Yes. Note that the wiring layer 94 is not limited to the first wiring layer, and may be a second or higher wiring layer.

  The inorganic insulating layer 20 is provided above the semiconductor substrate 10, and the organic insulating layer 40 is provided on the inorganic insulating layer 20. More specifically, a diffusion prevention layer 82 is provided on the semiconductor substrate 10, and the inorganic insulating layer 20 is provided on the diffusion prevention layer 82. Further, the diffusion prevention layer 82 and the conductive layer 90 are in contact with each other at the bottom surface of the first opening 72. The side surfaces of the first opening 72 and the second opening 74 may be covered with the barrier layer 80. That is, in this case, the inorganic insulating layer 20, the organic insulating layer 40, and the conductive layer 90 are adjacent to each other with the barrier layer 80 interposed therebetween. A cap layer 42 can be provided on the organic insulating layer 40.

  Hereinafter, each component of the semiconductor device 100 illustrated in FIG. 1 will be described.

(Inorganic insulating layer)
In the present invention, the inorganic insulating layer can be composed of a polysiloxane insulating layer having silica or a hydrocarbon group. The inorganic insulating layer made of a polysiloxane insulating layer having silica or a hydrocarbon group can be formed by a CVD method, but is preferably formed using a coating solution.

The coating liquid (inorganic insulating layer coating liquid) used for forming the inorganic insulating layer contains (A) polysiloxane and (B) an organic solvent. Here, as (A) polysiloxane, a compound represented by the following general formula (1) (hereinafter referred to as “compound (1)”), a compound represented by the following general formula (2) (hereinafter referred to as “compound”). Hydrolysis obtained by hydrolyzing and condensing at least one silane compound selected from the group of (2) ”) and a compound represented by the following general formula (3) (hereinafter referred to as“ compound (3) ”) Mention may be made of condensates.
R _a Si (OR ¹ ) _4-a (1)
[Wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ represents a monovalent organic group, and a represents an integer of 1 to 2. ]
Si (OR ² ) ₄ (2)
[Wherein R ² represents a monovalent organic group. ]
^{_{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 ··· (3)
[Wherein R ^{3 to} R ⁶ represent the same or different monovalent organic groups, b and c represent the same or different numbers of 0 to 2, and R ⁷ represents an oxygen atom, a phenylene group or — (CH ₂ ) _n represents a group represented by — (wherein n is an integer of 1 to 6), and d represents 0 or 1. ]
In the present invention, the “hydrolyzate” does not need to have all the alkoxy groups contained in at least one silane compound selected from the compounds (1) to (3) hydrolyzed. Only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. Here, the “condensate” is a product in which the silanol group of the hydrolyzate of the above compounds (1) to (3) is condensed to form a Si—O—Si bond. It is not necessary that all the silanol groups are condensed, and it is a concept that includes a mixture of a small part of the silanol groups, a mixture of those having different degrees of condensation, and the like.

Compound (1): In the above general formula (1), examples of the monovalent organic group represented by R and R ¹ include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Especially, in General formula (1), it is preferable that R is a monovalent organic group, especially an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and preferably 1 to 5 carbon atoms. These alkyl groups may be linear or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Preferred compounds as the compound (1) are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltri Examples thereof include ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. These may be used alone or in combination of two or more.

Compound (2): In the general formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as those shown in the general formula (1). Specific examples of the compound (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxy. Silane, tetraphenoxysilane, etc. are mentioned.

Compound (3): In the general formula (3), examples of the monovalent organic group represented by R ^{3 to} R ⁶ include the same organic groups as those shown in the general formula (1). it can. Among the compounds (3), compounds in which R ⁷ in the general formula (3) is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane. 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3 , 3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3- Preferred examples include diethoxy-1,1,3,3-tetraphenyldisiloxane. In the general formula (3), d = 0 compounds include hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy. -1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy- 1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, etc. It can be mentioned as a preferred example.

Furthermore, in the general formula (3), R ⁷ is a group represented by — (CH ₂ ) _n —, and bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (Trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxy Silyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (di Ethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, Preferred examples include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, and the like.

  In the present invention, as the compounds (1) to (3), one or more of the above compounds (1), (2) and (3) can be used. A catalyst may be used when hydrolyzing and condensing the compounds (1) to (3). Examples of the catalyst used at this time include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-iso-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-iso-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Naruto) titanium, di-t rt-Butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, mono-iso-propoxy tris (acetylacetonato) titanium , Mono-n-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-tert-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium , Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-iso-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetate) Toacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (Ethyl acetoacetate) titanium, di-iso-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di -Tert-butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-iso-propoxy tris (ethyl acetoacetate) G) Titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) Titanium chelate compounds such as acetate) titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium ;
Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-iso-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Natto) zirconium, di-iso-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetate) Nato) zirconium, di-tert-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-iso-propoxy tris (Acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) zirconium, tetrakis (Acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i o-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-tert-butoxy mono (ethyl aceto) Acetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-iso-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis ( Ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (Ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-iso-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono -Sec-butoxy-tris (ethylacetoacetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis Zirconium such as (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium Hexafluorophosphate chelate compounds;
And aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.

  Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples thereof include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide, urea, creatinine and the like can be mentioned. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and organic acids can be more preferable. As the organic acid, acetic acid, oxalic acid, maleic acid, and malonic acid are particularly preferable. When using an organic acid as a catalyst, there is little possibility of polymer precipitation or gelation during hydrolysis and condensation reactions. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.00001 to 0.05 mol, preferably 0.00001 to 0.01 mol, relative to 1 mol of the total amount of R ¹ O groups in the compounds (1) to (3). It is. When the component (A) is a condensate of the compounds (1) to (3), the molecular weight is a polystyrene-equivalent weight average molecular weight, usually 500 to 300,000, preferably 700 to 200,000. More preferably, it is about 1,000 to 100,000.

When each component is converted into a completely hydrolyzed condensate, the compound (3) is 5 to 60% by weight, preferably 5 to 50% by weight based on the total amount of the compound (1), the compound (2) and the compound (3). %, More preferably 5 to 40% by weight, and [weight of compound (1)] <[weight of compound (2)]. When the compound (3) is less than 5% by weight of the total amount of the compound (1) to the compound (3) in the proportion of each component converted into a complete hydrolysis condensate, the mechanical strength of the resulting coating film is reduced. If it exceeds 60% by weight, the water absorption is increased and the electrical characteristics may be deteriorated. Moreover, the intensity | strength of the coating film obtained as the weight of a compound (1) is more than the weight of a compound (2) may be inferior. In the present invention, the completely hydrolyzed condensate means a compound in which the SiOR ¹ group of the compounds (1) to (3) is 100% hydrolyzed to become a SiOH group, and further completely condensed to a siloxane structure. Say.

  In the present invention, the inorganic insulating layer is formed by applying a coating solution obtained by dissolving the hydrolysis and condensate of the silane compound in (B) an organic solvent. It is preferable to form by heating. (B) As an organic solvent, at least 1 sort (s) chosen from the group of alcohol solvent, ketone solvent, amide solvent, ester solvent, and aprotic solvent is mentioned. Here, as alcohol solvents, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec- Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether and the like are preferable.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl. In addition to ketones, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl 3,5-heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and iso acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used alone or in combination of two or more.

  As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methyl-to-3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl- Examples include 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. The above organic solvents can be used alone or in combination of two or more.

(B) As the organic solvent, alcohol solvents are preferable among the above organic solvents. Examples of the coating method for the inorganic insulating layer coating liquid include spin coating, dipping, roller blades, and spraying. In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 1 nm to 1.5 μm by one coating and a thickness of about 2 nm to 3 μm by two coatings. The thickness of the coating film formed with the inorganic insulating layer coating solution is usually 10 nm to 20 μm. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do. Moreover, in order to control the hardening rate of said coating liquid for inorganic type insulating layers, it can heat in steps or can select atmospheres, such as nitrogen, air, oxygen, and pressure reduction, as needed. The silica or polysiloxane insulating layer thus obtained has a relative dielectric constant of 1.5 to 3.2 and a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ^3, more preferably from 0.5 to 1.0 g / cm ^3. When the film density is less than 0.35 g / cm ³ , the mechanical strength of the coating film may be lowered. On the other hand, when the film density exceeds 1.2 g / cm ³ , a low dielectric constant may not be obtained. . In the present invention, the inorganic insulating layer can also be formed by depositing the above silane compound by a CVD method.

(Organic insulating layer)
In the present invention, the organic insulating layer is formed between the inorganic insulating layer and the conductive layer and when the barrier layer is provided between the conductive layer and the inorganic insulating layer. It plays a role of improving the resistance of the inorganic insulating layer to the load on the manufacturing process such as the CMP process and the temperature cycle test by buffering the mismatch of the mechanical characteristics between them. Therefore, the organic insulating layer needs to have sufficient adhesiveness with the inorganic insulating layer, sufficient heat resistance, and a high mechanical toughness value.

  The organic insulating layer is preferably made of an organic polymer having a glass transition point of 400 ° C. or higher and a thermal decomposition temperature of 500 ° C. or higher. In the present invention, since the organic insulating layer remains in the laminated structure without being removed in the manufacturing process of the semiconductor device of the present invention, if the glass transition point is less than 400 ° C., the multilayer wiring is deformed, Wiring connection failure or delamination may occur.

  The film thickness of the organic insulating layer is usually in the range of 1 nm to 1 μm, and preferably in the range of 5 nm to 500 nm.

The organic insulating layer desirably has high toughness in order to exhibit a mechanical buffer effect. As a specific index, 2.5 J / ^{m 2} or more as the critical energy release rate, preferably have a 3.5 J / ^{m 2} or more. The organic insulating layer preferably has a relative dielectric constant of 4.0 or less, and more preferably has a relative dielectric constant of 3.5 or less.

  Examples of the organic insulating layer include organic polymers selected from polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, polyquinoxaline, and particularly polyarylene. Polyarylene ether is preferred. Here, as the organic insulating layer, one or a combination of two or more of the above organic polymers can be used.

  These organic insulating layers can be formed by applying a coating solution for an organic insulating layer obtained by dissolving an organic polymer in an organic solvent to form a coating film and heating the coating film. . This organic insulating layer coating solution may contain a coupling agent in order to further improve the adhesion to the inorganic insulating layer. In this case, an inorganic insulating layer can be formed by applying a silica film coating solution having an organic group to form a coating film, and heating the coating film. Here, the coupling agent preferably has a functional group that forms a chemical bond with the alkoxyl group or silanol group. This alkoxyl group or silanol group forms a chemical bond with the silica film having an organic group in the curing process of the organic insulating layer. Moreover, the heating conditions of the coating liquid for organic type insulation layers can be baked at the temperature of 50-600 degreeC, Preferably it is 200-500 degreeC.

(Diffusion prevention layer)
The inorganic insulating layer can be provided on the diffusion preventing layer. This diffusion prevention layer has a function of preventing the metal in the conductive layer from diffusing into the insulating layer. In particular, when the conductive layer contains copper and the inorganic insulating layer contains silicon, copper in the conductive layer is likely to diffuse into the inorganic insulating layer. Therefore, by providing the diffusion preventing layer, it is possible to effectively prevent copper diffusion into the inorganic insulating layer.

  As the diffusion preventing layer, for example, a silicon nitride insulating layer or a silicon carbide insulating layer formed by a plasma CVD method can be used. The silicon carbide insulating layer may include not only silicon and carbon as constituent elements but also one or more of nitrogen, oxygen, and hydrogen as main constituent elements. Further, in the silicon nitride insulating layer, hydrogen is generally contained as a constituent element in addition to silicon and nitrogen.

(Conductive layer)
In the present invention, as described above, the conductive layer is formed by the dual damascene method. The conductive layer includes a via layer and a wiring layer provided continuously on the via layer. The material of the conductive layer is not particularly limited, and examples thereof include copper, silver, aluminum, and alloys thereof. Particularly when forming fine wiring, it has a low resistance and an excellent electromigration resistance. And copper is preferred. Examples of the method for forming the conductive layer include a sputtering method (for example, a reactive sputtering method), a CVD method, and a plating method.

(Barrier layer and cap layer)
The barrier layer has a function of improving adhesion between the conductive layer and the insulating layer (an inorganic insulating layer or an organic insulating layer). In addition, the barrier layer has a function of preventing diffusion of atoms that occurs between the conductive layer and the insulating layer (an inorganic insulating layer or an organic insulating layer). For example, between an inorganic insulating layer containing silicon and a conductive layer containing copper, silicon diffuses into the conductive layer and copper diffuses into the inorganic insulating layer. The barrier layer can prevent such diffusion of atoms.

  As the barrier layer, for example, a refractory metal or a compound thereof can be used. Specific examples of the barrier layer include titanium, tantalum, and nitrides thereof. The film thickness of the barrier layer is preferably formed in a range where the above functions can be achieved.

  The cap layer has a function as an etching stopper when forming the first opening and the second opening, and a function as an antireflection film.

  Specific examples of the cap layer include a silicon nitride insulating layer and a silicon carbide insulating layer.

[Method for Manufacturing Semiconductor Device]
Next, a method for manufacturing the semiconductor device shown in FIG. 1 will be described with reference to FIGS. 3 to 8 are sectional views schematically showing one manufacturing process of the semiconductor device 100 shown in FIG. 1, and correspond to the section shown in FIG.

  (1) First, the inorganic insulating layer 20 is formed above the substrate 10 (see FIG. 2). More specifically, after forming the diffusion prevention layer 82 above the substrate 10, the inorganic insulating layer 20 is formed on the diffusion prevention layer 82. Although not shown, a semiconductor element (for example, a MOSFET), a wiring layer, or an element isolation region (all not shown) may be formed between the substrate 10 and the diffusion prevention layer 82. The inorganic insulating layer 20 can be formed from the materials described above and can be formed using the method described above.

(2) Next, the surface 20a of the inorganic insulating layer 20 is subjected to at least one process selected from an ultraviolet irradiation process, an electron beam irradiation process, and a plasma process (see FIG. 3). FIG. 3 shows an example in which ultraviolet rays 13 are irradiated. For example, ultraviolet rays having a wavelength of 172 nm are irradiated in an oxygen atmosphere. In this case, although it varies depending the dose and the area and type of inorganic insulating layer 20 of the irradiation time surface 20a of the ultraviolet, it is preferable irradiation amount is 1~100mV / cm ^2, at 5~50mV / cm ² More preferably. Moreover, it is preferable that the irradiation time of an ultraviolet-ray is 0.1-100 s, and it is more preferable that it is 0.5-50 s. By irradiating the surface 20a of the inorganic insulating layer 20 with ultraviolet rays, oxygen in the atmosphere changes to ozone, and this ozone modifies the surface 20a of the inorganic insulating layer 20 from hydrophobic to hydrophilic. By forming the organic insulating layer 40 on the modified surface 20a (see the process described later), the affinity between the inorganic insulating layer 20 and the organic insulating layer 40 is increased.

  As an electron beam used for an electron beam irradiation process, electron beams, such as an X-ray and a gamma ray, can be illustrated, for example. Specific examples of plasma treatment include oxygen plasma treatment, nitrogen plasma treatment, helium plasma treatment, argon plasma treatment, hydrogen plasma treatment, and ammonia plasma treatment, and one or a combination of two or more of these may be used. In particular, oxygen plasma treatment is preferable. In the oxygen plasma treatment, generally, a plasma treatment is performed using a gas containing oxygen (for example, a mixed gas of oxygen and argon). Note that the gas used is not limited to those shown here.

  (3) Next, the organic insulating layer 40 is formed on the inorganic insulating layer 20 (see FIG. 4). The organic insulating layer 40 can be formed from the materials described above and can be formed using the methods described above.

  (4) Next, the cap layer 42 is formed on the organic insulating layer 40 (see FIG. 5).

  (5) Next, an opening (through hole) 70 penetrating the cap layer 42, the organic insulating layer 40, and the inorganic insulating layer 20 is formed (see FIG. 6).

  Specifically, first, after forming a resist layer (not shown) on the cap layer 42, a resist layer R1 having a predetermined pattern is formed by a general photolithography process. The resist layer R1 has a pattern for forming an opening 70 (see FIG. 6) described later. Next, the opening 70 is formed by patterning the cap layer 42, the organic insulating layer 40 and the inorganic insulating layer 20 using the resist layer R 1 as a mask. Thereafter, the resist layer R1 is removed by ashing or the like.

  (6) Next, the first opening 72 is formed in the inorganic insulating layer 20, and the second opening 74 is formed in the organic insulating layer 40 (see FIG. 7).

  Specifically, first, after forming a resist layer (not shown) on the cap layer 42, a resist layer R2 having a predetermined pattern is formed by a general photolithography process. The resist layer R2 has a pattern for forming a second opening 74 (see FIG. 7) described later. Next, the first opening 72 and the second opening 74 are formed by patterning the cap layer 42 and the organic insulating layer 40 using the resist layer R2 as a mask. Thereafter, the resist layer R2 is removed by ashing or the like. In the present embodiment, the step of forming the first opening 72 and the second opening 74 after the opening 70 penetrating the organic insulating layer 40 and the inorganic insulating layer 20 is formed. Alternatively, the first opening 72 may be formed by first patterning the organic insulating layer 40 to form the second opening 74 and then patterning the inorganic insulating layer 20.

  Here, as an etching method of the cap layer 42 and the inorganic insulating layer 20, anisotropic dry etching, reactive ion etching, inductively coupled plasma etching, ECR plasma etching, or the like can be used. Also, as an etching method for the organic insulating layer 40 and an ashing method for the resist layers R1 and R2, oxygen plasma treatment, ammonia plasma treatment, hydrogen / nitrogen mixed gas plasma treatment, and dry containing nitrogen / oxygen mixed gas as main components are possible. An etching process can be exemplified.

  (7) Next, a barrier layer 80 is formed on the surfaces of the first opening 72 and the second opening 74 as necessary. A method for forming the barrier layer 80 can be appropriately selected depending on the material, and for example, a CVD method or a sputtering method can be applied. Here, the barrier layer 80 on the bottom surface of the first opening 72 is removed by etching (see FIG. 7).

  (8) Next, the conductive layer 90 is embedded in the first opening 72 and the second opening 74 (see FIG. 8).

  Specifically, after forming a copper seed layer (not shown) by, for example, the PVD method, the conductive material 90a is embedded in the first opening 72 and the second opening 74 by plating. Next, the conductive material 90a is planarized by CMP. As a result, a portion of the conductive material 90a formed on the cap layer 42 is removed, and the conductive layer 90 is obtained. More specifically, a via layer 92 is formed in the first opening 72, and a wiring layer 94 is formed in the second opening 74 (see FIG. 1). Next, the stopper layer 32 is formed on the conductive layer 90 and the cap layer 42 as necessary. Through the above steps, the semiconductor device 100 is obtained.

[Characteristic]
Next, features of the semiconductor device 100 and the manufacturing method thereof according to the present embodiment will be described. First, a structure of a semiconductor device having a known damascene structure will be described as a comparative example.

(1) Known Semiconductor Device FIGS. 9 and 10 show an example of a known semiconductor device including a conductive layer formed by a damascene method. The semiconductor device 900 has a conductive layer 90 formed by a dual damascene method. In this semiconductor device 900, the same components as those included in the semiconductor device 100 of the present embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

  The conductive layer 90 includes a via layer 92 and a wiring layer 94 provided continuously on the via layer 92. The via layer 92 is embedded in the first opening 72 provided in the inorganic insulating layer 20, and the wiring layer 92 is embedded in the second opening 74 provided in the inorganic insulating layer 60. Yes. The inorganic insulating layer 20 is provided above the semiconductor substrate 10 (on the diffusion prevention layer 82), and the inorganic insulating layer 60 is provided on the inorganic insulating layer 20 via the stopper layer 30. .

  In the semiconductor device 900, as in the semiconductor device 100 of the present embodiment, after an insulating layer (inorganic insulating layers 20 and 60) is stacked, the first and second openings 72 and 74 are formed in the insulating layer. Then, the conductive layer 90 can be embedded in the first and second openings 72 and 74 (see FIG. 10). However, in this semiconductor device 900, the stopper layer 30 is provided between the inorganic insulating layer 20 and the inorganic insulating layer 60. As shown in FIG. 10, the stopper layer 30 uses the difference in etching rate between the stopper layer 30 and the inorganic insulating layer 60 to form the second opening 74 in the inorganic insulating layer 60. It functions as an etching stopper layer.

The inorganic insulating layer 20 is made of a low relative dielectric constant material. For this reason, the inorganic insulating layer 20 has a lower mechanical strength than silica conventionally used as an insulating layer. For example, the elastic modulus of silica is 72 GPa, whereas the elastic modulus of a low dielectric constant material is generally 10 GPa or less. In particular, when the inorganic insulating layer 20 is made of an ultra-low relative dielectric constant material (Ultra low-k) having a relative dielectric constant of 2.5 or less among low dielectric constant materials, the density is 1 g / cm ³ or more. The mechanical strength is much smaller than that of conventional silica.

  On the other hand, the most severe process for forming a damascene structure is a chemical mechanical polishing (CMP) process. This CMP process is used, for example, for etching the conductive layer 90 described above. In the semiconductor device 900 having a damascene structure, there are many interfaces between different materials. Specifically, in the semiconductor device 900 shown in FIGS. 9 and 10, the interface between the inorganic insulating layer 20 and the stopper layer 30, the interface between the inorganic insulating layer 20 and the barrier layer 80, and the inorganic insulating layer 20. And the diffusion preventing layer 82 is an interface between different materials. Here, many of the materials in contact with the low dielectric constant material constituting the inorganic insulating layer 20 have mechanical and thermal properties that are completely different from those of the low dielectric constant material. In particular, the mismatch of the mechanical characteristics may cause stress concentration at the interface in the CMP process, resulting in peeling or cracking in the inorganic insulating layer 20.

  Further, when the stopper layer 30 is made of a material having a higher relative dielectric constant than the inorganic insulating layers 20 and 60 (for example, a silicon nitride insulating layer), the stopper layer 30 may increase the parasitic capacitance between the wirings. .

(2) Semiconductor device 100 of the present embodiment
On the other hand, according to the semiconductor device 100 of the present embodiment, the organic insulating layer 40 is formed after performing the above-described treatment on the surface 20a of the inorganic insulating layer 20. Thereby, the adhesiveness of the inorganic type insulating layer 20 and the organic type insulating layer 40 can be improved. Thereby, for example, in the CMP process used in the formation of the conductive layer 90 and the temperature cycle test, it is possible to prevent the inorganic insulating layer 20 from being peeled or cracked.

  In addition, according to the semiconductor device 100 of the present embodiment, the inorganic insulating layer 20 and the organic insulating layer 40 have large properties, so that the etching rates are greatly different. For this reason, the etching rate selection ratio between the inorganic insulating layer 20 and the organic insulating layer 40 can be obtained without forming a stopper layer. Therefore, since it is not necessary to form a stopper layer, the manufacturing process can be simplified as compared with the known semiconductor device 900. Further, since the organic insulating layer 40 is formed directly on the inorganic insulating layer 20 without using the stopper layer, the presence of the stopper layer does not increase the parasitic capacitance between the wirings. Thereby, the parasitic capacitance between wirings can be reduced.

  Further, the adhesion between the inorganic insulating layer 20 and the organic insulating layer 40 is improved, so that the organic insulating layer 40 is disposed between the inorganic insulating layer 20 and the conductive layer 90 and between the inorganic insulating layer 20 and It can serve to eliminate the mismatch of mechanical properties with the barrier layer 80.

  Next, the present invention will be described more specifically with reference to examples. However, the following description shows the aspect of this invention generally, and this invention is not limited by this description without a particular reason. Moreover, each evaluation in an Example was measured as follows.

(4-point bending method)
First, a SiO ₂ film having a thickness of 500 nm was formed on a sample wafer to be measured (a silicon wafer obtained in each example by which a laminate of an inorganic insulating layer and an organic insulating layer was formed) using a sputtering apparatus. The sample was cut into × 4 cm and used as sample 1. Next, an unused silicon wafer was cut into 3 × 4 cm, and this was used as sample 2. Next, the surfaces of Sample 1 and Sample 2 were joined using an epoxy resin, and heat-cured at 135 ° C. for 2 hours in an oven to obtain Sample 3. Next, the sample 3 was cut into 3 mm × 4 cm using a dicing saw, and a notch was formed in the central portion of one wafer piece for each sample 4 to obtain a sample 4. The sample 4 was sandwiched between four pins, and force was applied from both sides until a crack occurred from the notch. Adhesion was evaluated by the force required for cracking (fracture toughness).

(Relative permittivity)
Aluminum was vapor-deposited on the substrate on which the cured film was formed to produce a dielectric constant evaluation substrate. The relative dielectric constant was calculated from the capacitance value at 10 kHz using an HP16451B electrode and an HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

(1) Preparation of coating solution for inorganic insulating layer 15 g of methyltrimethoxysilane (7.4 g in terms of complete hydrolysis condensate) and tetraethoxysilane in a mixed solution of 5 g of 25% aqueous ammonia, 320 g of ultrapure water and 600 g of ethanol After adding 20 g (5.8 g in terms of complete hydrolysis condensate) and reacting at 60 ° C. for 3 hours, maleic acid was added to adjust the pH of this solution to 2.5. Next, 150 g of propylene glycol monopropyl ether was added to this solution, and then concentrated under reduced pressure to obtain an inorganic insulating layer coating solution (polysiloxane insulating layer coating solution) having a solid content of 6%. .

(2) Preparation of coating solution for organic insulating layer 37.8 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 37.8 g of potassium carbonate were placed in a flask together with 350 g of dimethylacetamide, and the nitrogen atmosphere was 150. Heating was performed at 0 ° C. for 2 hours. At this time, the generated water vapor was removed from the system. 21.8 g of bis (4-fluorophenyl) ketone was added to this solution and reacted at 165 ° C. for 10 hours. After cooling the reaction solution, insoluble matters in the solution were removed by filtration, and reprecipitation was performed in methanol. The precipitate was sufficiently washed with ion exchange water, dissolved in cyclohexanone to remove insoluble matters, and then reprecipitated in methanol. The precipitate was dried in a vacuum oven at 60 ° C. for 24 hours to obtain a polymer. 2 g of this polymer was dissolved in 18 g of cyclohexanone, and then filtered through a filter made of polytetrafluoroethylene (Teflon (registered trademark)) having a pore diameter of 0.2 μm to obtain a coating solution for an organic insulating layer.

(3) Fabrication of Laminate After applying an inorganic insulating layer coating solution obtained in (1) on an 8-inch silicon wafer using a spin coating method to form a coating film, a hot plate in an air atmosphere An inorganic insulating layer (polysiloxane) having a relative dielectric constant of 2.5 is obtained by drying the wafer at 80 ° C. for 1 minute, then drying the wafer at 200 ° C. for 1 minute, and baking the wafer at 400 ° C. for 30 minutes in the air atmosphere. System insulation layer) was obtained. Next, the surface of the obtained inorganic insulating layer was subjected to an ultraviolet irradiation treatment for 3 seconds, and then the organic insulating layer coating solution obtained in (2) was applied onto the inorganic insulating layer. After forming the film, the organic insulating layer was formed by baking at 400 ° C. for 30 minutes in an air atmosphere. Thereby, the laminated body of the inorganic type insulating layer and the organic type insulating layer was obtained. Next, when the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 12 J / m ² .

In Example 1, an inorganic insulating layer and an organic layer were formed in the same manner as in Example 1 except that an inorganic insulating layer having a relative dielectric constant of 2.9 was formed instead of the inorganic insulating layer having a relative dielectric constant of 2.5. A laminate with a system insulating layer was obtained. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 15 J / m ² .

In Example 1, an inorganic insulating layer and an organic layer were formed in the same manner as in Example 1 except that an inorganic insulating layer having a relative dielectric constant of 2.2 was formed instead of the inorganic insulating layer having a relative dielectric constant of 2.5. A laminate with a system insulating layer was obtained. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 10 J / m ² .

In Example 1, a laminate of an inorganic insulating layer and an organic insulating layer was obtained in the same manner as in Example 1 except that the ultraviolet irradiation treatment was performed for 1 second instead of performing the ultraviolet irradiation treatment for 3 seconds. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 10 J / m ² .

Inorganic insulating layer in the same manner as in Example 1, except that the coating liquid for polysiloxane insulating layer was applied in Example 1 and the substrate was dried and then the substrate was not baked at 400 ° C. for 30 minutes in the air atmosphere. And a laminate of the organic insulating layer. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a four-point bending method, it was 12 J / m ² .

[Comparative Example 1]
In Example 1, a laminate of an inorganic insulating layer and an organic insulating layer was obtained in the same manner as in Example 1 except that the ultraviolet irradiation treatment was not performed. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 3 J / m ² .

[Comparative Example 2]
In Example 5, a laminate of an inorganic insulating layer and an organic insulating layer was obtained in the same manner as in Example 1 except that the ultraviolet irradiation treatment was not performed. When the fracture toughness between the inorganic insulating layer and the organic insulating layer in the obtained laminate was measured using a 4-point bending method, it was 3 J / m ² .

  According to Examples 1 to 5 and Comparative Examples 1 and 2 shown above, as a result of forming the organic insulating layer after irradiating the surface of the inorganic insulating layer with ultraviolet rays, the inorganic material in the obtained laminate was obtained. The fracture toughness between the organic insulating layer and the organic insulating layer was improved. Thereby, it was confirmed by the ultraviolet irradiation process with respect to the surface of an inorganic type insulating layer that the adhesiveness of an inorganic type insulating layer and an organic type insulating layer improves.

It is sectional drawing which shows typically the semiconductor device of one embodiment of this invention. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. It is sectional drawing which shows a well-known semiconductor device typically. FIG. 10 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 9.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Semiconductor substrate 13 Ultraviolet ray 20 Inorganic insulating layer 20a Surface of inorganic insulating layer 32 Stopper layer 40 Organic insulating layer 42 Cap layer 70 Opening portion 72 First opening portion 74 Second opening portion 80 Barrier layer 82 Diffusion prevention layer 90 conductive layer 90a conductive material 92 via layer 94 wiring layer 100 semiconductor device R1, R2 resist layer

Claims (13)

An inorganic insulating layer is formed above the substrate,
The surface of the inorganic insulating layer is subjected to at least one treatment selected from ultraviolet irradiation treatment, electron beam irradiation treatment, and plasma treatment, and then an organic insulating layer is formed on the inorganic insulating layer. Forming,
Forming a first opening in the inorganic insulating layer;
Forming a second opening continuous with the first opening in the organic insulating layer;
A method of manufacturing a semiconductor device, comprising embedding a conductive layer in the first and second openings. In claim 1,
The method for manufacturing a semiconductor device, wherein the plasma treatment is at least one treatment selected from oxygen plasma treatment, nitrogen plasma treatment, helium plasma treatment, argon plasma treatment, hydrogen plasma treatment, and ammonia plasma treatment. In claim 1 or 2,
The method for manufacturing a semiconductor device, wherein the inorganic insulating layer is a polysiloxane insulating layer having a relative dielectric constant of 1.5 to 3.2. In claim 3,
The method for manufacturing a semiconductor device, wherein the polysiloxane insulating layer has a hydrocarbon group. In any of claims 1 to 4,
The said inorganic insulation layer is a manufacturing method of a semiconductor device formed by apply | coating the coating liquid for inorganic insulation layers on the said board | substrate, forming a coating film, and heating this coating film. In any of claims 1 to 5,
The method for manufacturing a semiconductor device, wherein the organic insulating layer is made of an organic polymer having a glass transition point of 400 ° C. or higher and a thermal decomposition temperature of 500 ° C. or higher. In claim 6,
The organic polymer is made of at least one polymer selected from polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, and polyquinoxaline. Production method. In claim 1,
A method of manufacturing a semiconductor device, wherein the ultraviolet irradiation treatment is performed in an oxygen atmosphere. An inorganic insulating layer provided above the substrate;
An organic insulating layer provided on the inorganic insulating layer;
A first opening provided in the inorganic insulating layer;
A second opening provided in the organic insulating layer and continuous with the first opening;
A conductive layer embedded in the first and second openings;
Including a semiconductor device. In claim 9,
The inorganic insulating layer is a semiconductor device, which is a polysiloxane insulating layer having a relative dielectric constant of 1.5 to 3.2. In claim 10,
The polysiloxane insulating layer is a semiconductor device having a hydrocarbon group. In any of claims 9 to 11,
The organic insulating layer is a semiconductor device made of an organic polymer having a glass transition point of 400 ° C. or higher and a thermal decomposition temperature of 500 ° C. or higher. In claim 12,
The semiconductor device, wherein the organic polymer is made of at least one polymer selected from polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, and polyquinoxaline.

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