JP5141885B2 - Silicon-containing insulating film and method for forming the same - Google Patents

Description

  The present invention relates to a silicon-containing insulating film and a method for forming the same.

  In recent years, large-scale semiconductor integrated circuits (ULSI) have been strongly demanded for higher-speed processing in order to cope with an increasing amount of information processing and complexity of functions. The speeding up of ULSI has been realized by miniaturization and high integration of elements in a chip and multilayering of films. However, with the miniaturization of elements, wiring resistance and inter-wiring parasitic capacitance increase, and wiring delay is becoming a dominant factor in signal delay of the entire device. In order to avoid this problem, introduction of a low resistivity wiring material or a low dielectric constant (Low-k) interlayer insulating film material is an essential technique.

Examples of the low dielectric constant interlayer insulating film include inorganic interlayer insulating films such as a porous silica film having a reduced silica (SiO ₂ ) film density, FSG which is a silica film doped with F, and a SiOC film doped with C. Examples thereof include an organic interlayer insulating film such as a film, polyimide, polyarylene, and polyarylene ether. Since many of the widely used interlayer insulating films are formed by chemical vapor deposition (CVD), many proposals have been made by chemical vapor deposition. In particular, many silane compounds used for the reaction have been proposed. For example, those using dialkoxysilane (Japanese Patent Laid-Open Nos. 11-288931 and 2002-329718) have been proposed. By using such a material, a film having a low dielectric constant and sufficient adhesion with a barrier metal or the like is obtained.

However, since conventional silane compounds are chemically stable, they require extreme conditions during film formation by chemical vapor deposition, and on the contrary, they are chemically unstable and are supplied into the chamber. There are those that cause a reaction in the piping and those that have poor storage stability of the silane compound itself. In addition, depending on the selected compound, the insulating film after film formation has a high hygroscopic property, which causes a problem of increasing the leakage current. Further, in the actual manufacturing process of a semiconductor device, a process of processing an interlayer insulating film using RIE (Reactive Ion Etching) is often used, and the problem that the dielectric constant of the film increases during the RIE, There is a problem that the interlayer insulating film is damaged by the fluoric acid chemical used in the subsequent cleaning process, and an interlayer insulating film having high processing resistance is required.
JP-A-11-288931 JP 2002-329718 A

  The object of the present invention can be suitably used in a semiconductor device or the like for which high integration and multilayering are desired, and is optimal for chemical vapor deposition while being chemically stable and has high mechanical strength. An object of the present invention is to provide a silicon-containing insulating film having excellent low dielectric constant, low hygroscopicity and high processing resistance, and a method for forming the same.

A method for forming a silicon-containing insulating film according to one embodiment of the present invention includes:
Supplying a first composition containing an organosilane compound represented by the following general formula (1) onto a substrate;
Supplying a second composition containing another silane compound onto the substrate;
including.

(1)
(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a phenyl group, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, an acetyl group, Represents a phenyl group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2)
In the method for forming a silicon-containing insulating film, the other silane compound may be at least one silane compound selected from the following general formulas (2) to (4).
R ⁶ _a Si (OR ⁷ ) _4-a (2)
(Wherein R ⁶ is the same or different and represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ⁷ is the same or different and represents a monovalent organic group, and a represents an integer of 0 to 4)
_{^{R 8 b (R 9 O)}} 3-b Si- (R 12) d -O e -Si (OR 10) 3-c R 11 c
... (3)
(Wherein R ^{8 to} R ¹¹ are the same or different and each represents a hydrogen atom, a fluorine atom or a monovalent organic group; b and c are the same or different and each represents a number of 0 to 3; R ¹² represents phenylene; A group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), and d and e represent 0 or 1.)

(4)
(Wherein R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, a fluorine atom or a group selected from a monovalent organic group, and R ¹⁵ represents an oxygen atom, a phenylene group or — (CH ₂ ) _n —. (Wherein n is an integer of 1-6), f is an integer of 0-2, g is 0 or 1, and h is a number of 2-30.)
The method for forming a silicon-containing insulating film may further include a step of supplying a third composition containing an organic molecule as a pore forming agent onto the substrate.

  The silicon-containing insulating film can be formed using a chemical vapor deposition method.

In the method for forming the silicon-containing insulating film, at least the first composition and the second composition are supplied onto the substrate to form a deposited film.
The method may further include a step of curing the deposited film by at least one selected from heating, electron beam irradiation, ultraviolet irradiation, and oxygen plasma.

  The silicon-containing insulating film according to one embodiment of the present invention is obtained by the method for forming a silicon-containing insulating film.

  The method for forming a silicon-containing insulating film includes a step of supplying a first composition containing an organosilane compound represented by the general formula (1) onto a substrate, and a second composition containing another silane compound. Can be suitably used in semiconductor elements and the like that are desired to be highly integrated and multi-layered, and are optimal for chemical vapor deposition while being chemically stable. Thus, an insulating film having excellent mechanical strength, a low relative dielectric constant, low hygroscopicity, and high processing resistance can be formed.

  The present invention will be specifically described below.

1. Method for Forming Silicon-Containing Insulating Film A method for forming a silicon-containing insulating film according to an embodiment of the present invention is an organosilane compound represented by the following general formula (1) (hereinafter also referred to as “component (I)”). And a step of supplying a second composition containing another silane compound (hereinafter also referred to as “component (II)”) onto the substrate. . The above two steps are performed in different steps. In other words, the first composition and the second composition are supplied onto the substrate after being separately gasified, for example, in a CVD method. The timing of supplying the first composition and the second composition onto the substrate may be the same or different, but the composition of the formed silicon-containing insulating film is made uniform. Therefore, it is preferable to be simultaneous.

(1)
(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a phenyl group, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, an acetyl group, Represents a phenyl group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2)
The component (II) can be at least one silane compound selected from the following general formulas (2) to (4).
R ⁶ _a Si (OR ⁷ ) _4-a (2)
(In the formula, R ⁶ is the same or different and represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ⁷ is the same or different and represents a monovalent organic group, and a represents an integer of 0 to 3.)
_{^{R 8 b (R 9 O)}} 3-b Si- (R 12) d -O e -Si (OR 10) 3-c R 11 c
... (3)
(Wherein R ^{8 to} R ¹¹ are the same or different and each represents a hydrogen atom, a fluorine atom or a monovalent organic group; b and c are the same or different and each represents a number of 0 to 3; R ¹² represents phenylene; A group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), and d and e represent 0 or 1.)

(4)
(Wherein R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, a fluorine atom or a group selected from a monovalent organic group, and R ¹⁵ represents an oxygen atom, a phenylene group or — (CH ₂ ) _n —. (Wherein n is an integer of 1-6), f is an integer of 0-2, g is 0 or 1, and h is a number of 2-30.)
The method for forming a silicon-containing insulating film may further include a step of supplying a third composition containing an organic molecule (hereinafter also referred to as “component (III)”) as a pore forming agent onto the substrate. Good. This step can be performed simultaneously with the above two steps.

  In the method for forming a silicon-containing insulating film according to the present embodiment, the molar ratio of the component (I) to the component (II) is (I) when the sum of the components (I) and (II) is 100 mol%. ) Component is 10 mol% to 90 mol%, more preferably 15 mol% to 85 mol%.

  Since the first composition according to this embodiment contains the organosilane compound represented by the general formula (1), it is used to form an insulating film containing silicon, carbon, oxygen, and hydrogen. it can. Such an insulating film is characterized by high resistance to processing because it has high resistance to a hydrofluoric acid chemical solution widely used in a cleaning process during a semiconductor manufacturing process. Moreover, the 2nd composition which concerns on this embodiment is represented with the said general formula (2)-(4) with many crosslinkable substituents compared with the organosilane compound represented with the said general formula (1). Therefore, by using such a composition, an insulating film having excellent mechanical strength and a low relative dielectric constant can be formed.

  Further, in all the compositions for forming the silicon-containing insulating film according to this embodiment, the content of elements other than silicon, carbon, oxygen, and hydrogen (hereinafter also referred to as “impurities”) is less than 10 ppb. It is preferable that the water content is less than 100 ppm. By forming an insulating film using such a composition, an insulating film having a low relative dielectric constant and excellent processing resistance can be obtained with high yield.

  Hereafter, each component used for the formation method of the silicon-containing insulating film which concerns on this Embodiment is demonstrated in detail.

1.1. (I) Component 1.1.1. (I) Structure of Component The organosilane compound as the component (I) according to this embodiment is represented by the general formula (1).

In the general formula (1), R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a phenyl group. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As R ^{1 to} R ⁴ , a methyl group, a vinyl group, and a hydrogen atom are particularly preferable.

In the general formula (1), ^{R 5} represents an alkyl group having 1 to 4 carbon atoms, an acetyl group, a phenyl group. The alkyl group having 1 to 4 carbon atoms, for example, include the same alkyl groups as those exemplified as the R ¹ to R ^4. R ⁵ is particularly preferably a methyl group or an ethyl group.

  Furthermore, in the said General formula (1), n shows the integer of 1-3 and m shows the integer of 1-2.

  In the above general formula (1), examples of the organosilane compound with n = 1 and m = 1 include the following.

  In the above general formula (1), examples of the organosilane compound in which n = 1 and m = 2 include those shown below.

  In the above general formula (1), examples of the organosilane compound in which n = 2 and m = 1 include the following.

  In the above general formula (1), examples of the organosilane compound in which n = 2 and m = 2 include the following.

  In the above general formula (1), examples of the organosilane compound in which n = 3 and m = 1 include the following.

  In the above general formula (1), examples of the organosilane compound in which n = 3 and m = 2 include the following.

In the organosilane compound represented by the general formula (1), the total number of hydrogen atoms in R ^{1 to} R ⁴ is preferably 0 to 2 from the viewpoints of ease of synthesis and purification and ease of handling. More preferably, it is 0-1.

  In the organosilane compound represented by the general formula (1), m = 1 and 2 are preferable, and m = 1 is more preferable from the viewpoint of mechanical strength of the silicon-containing insulating film.

1.1.2. (I) Method for Producing Component The method for producing the organosilane compound represented by the general formula (1) is not particularly limited. For example, the organosilane compound represented by the following general formula (5) The method of coupling-reacting with the organosilane compound shown by following General formula (6) in presence of a metal can be mentioned. As the metal, magnesium is usually used.

(5)
(Wherein R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group, X represents a halogen atom, and a represents an integer of 0 to 2) Show.)

(6)
(Wherein R ⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, an acetyl group or a phenyl group. Y represents a halogen atom, a hydrogen atom, or an alkoxy group, and m represents an integer of 1 to 2.)
In the general formula (5) and ^(6), the alkyl group having 1 to 4 carbon atoms represented by R 1 to R ^5, the number of carbon atoms represented by ^R 1 to R ⁵ in the general formula (1) 1 And the halogen atom represented by X and Y include, for example, a bromine atom and a chlorine atom, and the alkoxy group represented by Y represents the above general formula (1). those exemplified as the alkoxy group represented by -OR ⁵ and the like.

1.2. (II) Component The silane compound as the component (II) according to the present embodiment includes the compound 1 represented by the general formula (2), the compound 2 represented by the general formula (3), and the general formula (4). And at least one selected from the compound 3 shown below. About compound 1-3, you may use 1 type (s) or 2 or more types simultaneously.

  Below, the detail of the compounds 1-3 is demonstrated.

1.2.1. Compound 1
In the general formula (2), examples of the monovalent organic group represented by R ⁶ and R ⁷ include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. Especially, it is preferable that the monovalent organic group represented by R ⁶ and R ⁷ is 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 the like. Preferably, the alkyl group has 1 to 5 carbon atoms, and these alkyl groups may be linear or branched. Further, a hydrogen atom may be substituted with a fluorine atom or the like. 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. Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  In the general formula (2), specific examples of the compound 1 with a = 0 include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra -Sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane and the like can be mentioned, and particularly preferred compounds include tetramethoxysilane and tetraethoxysilane.

  In the general formula (2), specific examples of the compound 1 with a = 1 include, for example, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, triphenoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrif Enoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec -Butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n- Butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltri Phenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec- Butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butylto-n-propoxysilane tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, etc. Particularly preferred compounds include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyl Examples include tri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

  In the general formula (2), as specific examples of the compound 1 in which a = 2, for example, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldiisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, Diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldipheno Sisilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane , Di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyl Diisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di- -Butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di -N-butyldi-tert-butoxysilane, di-n-butyldi-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec -Butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldi-phenoxysilane, di -Tert-butyldimethoxysilane, di-tert-butyldiethoxy Silane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi -Tert-butoxysilane, di-tert-butyldi-phenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec -Butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, and particularly preferable compounds include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane Dimethyl diethoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diphenyl dimethoxy silane, and diphenyl diethoxy silane and the like.

  In the general formula (2), specific examples of the compound 1 in which a = 3 include, for example, dimethylmethoxysilane, dimethylethoxysilane, dimethyl-n-propoxysilane, dimethyl-iso-propoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. , Trimethyl-n-propoxysilane, trimethyl-iso-propoxysilane, trimethyl-n-butoxysilane, trimethyl-sec-butoxysilane, trimethyl-tert-butoxysilane, trimethylphenoxysilane, triethylmethoxysilane, triethylethoxysilane, triethyl- n-propoxysilane, triethyl-iso-propoxysilane, triethyl-n-butoxysilane, triethyl-sec-butoxysilane, triethyl-tert-butoxysilane Triethylphenoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-propyl-n-propoxysilane, tri-n-propyl-iso-propoxysilane, tri-n-propyl-n- Butoxysilane, tri-n-propyl-sec-butoxysilane, tri-n-propyl-tert-butoxysilane, tri-n-propyl-phenoxysilane, tri-iso-propylmethoxysilane, tri-iso-propylethoxysilane, Tri-iso-propyl-n-propoxysilane, tri-iso-propyl-iso-propoxysilane, tri-iso-propyl-n-butoxysilane, tri-iso-propyl-sec-butoxysilane, tri-iso-propyl- tert-Butoxysilane Tri-iso-propyl-phenoxysilane, tri-n-butylmethoxysilane, tri-n-butylethoxysilane, tri-n-butyl-n-propoxysilane, tri-n-butyl-iso-propoxysilane, tri-n -Butyl-n-butoxysilane, tri-n-butyl-sec-butoxysilane, tri-n-butyl-tert-butoxysilane, tri-n-butyl-phenoxysilane, tri-sec-butylmethoxysilane, tri-sec -Butylethoxysilane, tri-sec-butyl-n-propoxysilane, tri-sec-butyl-iso-propoxysilane, tri-sec-butyl-n-butoxysilane, tri-sec-butyl-sec-butoxysilane, tri -Sec-butyl-tert-butoxysilane, tri-sec-butyl Til-phenoxysilane, tri-tert-butylmethoxysilane, tri-tert-butylethoxysilane, tri-tert-butyl-n-propoxysilane, tri-tert-butyl-iso-propoxysilane, tri-tert-butyl-n -Butoxysilane, tri-tert-butyl-sec-butoxysilane, tri-tert-butyl-tert-butoxysilane, tri-tert-butyl-phenoxysilane, triphenylmethoxysilane, triphenyl-ethoxysilane, triphenyl-n -Propoxysilane, triphenyl-iso-propoxysilane, triphenyl-n-butoxysilane, triphenyl-sec-butoxysilane, triphenyl-tert-butoxysilane, triphenylphenoxysilane, etc. Particularly preferred compounds are dimethylmethoxysilane, dimethylethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane, triethylethoxysilane, triethyl-n-propoxysilane, triphenylmethoxy. Silane, triphenyl-ethoxysilane, triphenyl-n-propoxysilane and the like can be mentioned.

  In the general formula (2), specific examples of the compound 1 in which a = 4 are, for example, monosilane, methylsilane, ethylsilane, dimethylsilane, diethylsilane, trimethylsilane, tetramethylsilane, triethylsilane, tetraethylsilane, tri-n- Propylsilane, tetra-n-propylsilane, tri-iso-propylsilane, tetra-iso-propylsilane, tri-n-butylsilane, tetra-n-butylsilane, tri-sec-butylsilane, tetra-sec-butylsilane, tri- Examples thereof include tert-butylsilane, tetra-tert-butylsilane, triphenylsilane, and tetraphenylsilane, and particularly preferable compounds include trimethylsilane and tetramethylsilane.

  These may be used alone or in combination of two or more.

1.2.2. Compound 2
In the general formula (3), examples of the monovalent organic group represented by R ^{8 to} R ¹¹ include the same groups as those exemplified as R ⁶ and R ^{7 in} the general formula (2).

  In the above general formula (3), as the compound 2 in which d = e = 0, disilane, 1,2-dimethyldisilane, 1,1,2,2-tetramethyldisilane, hexamethyldisilane, hexaethyldisilane, hexa- n-propyldisilane, hexa-isopropyldisilane, hexaphenyldisilane, 1,1,2,2-tetramethoxydisilane, 1,2-dimethoxy-1,2-dimethyldisilane, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy- 2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1,2,2-penta Toxi-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2 , 2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1 , 2,2-Tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1, 2-diphenyl Silane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2, 2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1, 2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy- 1,1,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, , 2-Dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetra Methyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2 -Tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1, Examples include 2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, and the like.

  Of these, 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-tetramethyl Preferred examples include disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, and the like.

  In the above general formula (3), examples of the compound 2 having d = 1 and e = 0 include bis (methylsilyl) methane, bis (dimethylsilyl) methane, bis (dimethylmethoxysilyl) methane, and bis (dimethoxymethylsilyl) methane. Bis (methoxymethylsilyl) methane, bis (dimethoxysilyl) methane, bis (tetramethoxysilyl) methane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane Bis (tri-iso-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (Trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2 -Bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethyl) Silyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (Tri-iso-propoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec- Toximethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2 -(Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2- (tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (Di-sec-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethyl) Silyl) methane, bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) Ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2 -Bis (di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) Tan, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri- n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxysilyl) benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) Benzene, 1,2-bis (tri-tert-butoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n -Propoxysilyl) benzene, 1,3-bis (tri-iso-propoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-tert-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxy) Silyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1 , 4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-tert-butoxysilyl) benzene, and the like.

  Of these, bis (dimethylmethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethyl) Silyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2 -Bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) Tan, 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 general formula (3), examples of the compound 2 having d = 0 and e = 1 include 1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3 -Tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,3-dimethyl-1,3-dimethoxydisiloxane, 1,1,3,3- Tetramethoxydisiloxane, hexamethyldisiloxane, hexaethyldisiloxane, hexa-n-propyldisiloxane, hexaisopropyldisiloxane, hexa-n-butyldisiloxane, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane 1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3,3-pe Taethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-ethyldisiloxane, 1,1, 1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyl Disiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-phenyldisiloxane, 1,1,3,3-tetra Methoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1, 1, , 3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldi Siloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy -1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3 -Triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triethyldisiloxane, 1,1,3-triethoxy-1,3,3-trie Tildisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy- 1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3 3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimeth Si-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraphenyl A disiloxane etc. can be mentioned. Of these, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, hexamethyldisiloxane, 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-diethoxy-1,1,3,3-tetraphenyldisiloxane, etc. It can be cited as a preferable example.

  In the above general formula (3), examples of the compound 2 with d = 1 and e = 1 include 1- (trimethylsilyl) -1- (trimethoxysiloxy) methane, 1- (trimethylsilyl) -1- (methyldimethoxysiloxy). ) Methane, 1- (trimethylsilyl) -1- (dimethylmethoxysiloxy) methane, 1- (trimethylsilyl) -1- (trimethylsiloxy) methane, 1- (trimethylsilyl) -2- (trimethoxysiloxy) ethane, 1- ( Trimethylsilyl) -2- (methyldimethoxysiloxy) ethane, 1- (trimethylsilyl) -2- (dimethylmethoxysiloxy) ethane, 1- (trimethylsilyl) -2- (trimethylsiloxy) ethane, 1- (trimethoxysilyl) -1 -(Trimethoxysiloxy) methane, 1- (trimethoxysilyl) 2- (trimethoxysiloxy) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysiloxy) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysiloxy) ethane, 1- (methoxydimethylsilyl) -1- (trimethoxysiloxy) methane, 1- (methoxydimethylsilyl) -2- (trimethoxysiloxy) ethane, 1- (trimethoxysilyl) -1- (dimethoxymethylsiloxy) methane, 1- (trimethoxysilyl) ) -2- (dimethoxymethylsiloxy) ethane, 1- (dimethoxymethylsilyl) -1- (dimethoxymethylsiloxy) methane, 1- (dimethoxymethylsilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (methoxydimethyl) Silyl) -1- (dimethoxymethylsiloxy) methane, 1- Methoxydimethylsilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (trimethoxysilyl) -1- (methoxydimethylsiloxy) methane, 1- (trimethoxysilyl) -2- (methoxydimethylsiloxy) ethane, 1- (Dimethoxymethylsilyl) -1- (methoxydimethylsiloxy) methane, 1- (dimethoxymethylsilyl) -2- (methoxydimethylsiloxy) ethane, 1- (methoxydimethylsilyl) -1- (methoxydimethylsiloxy) methane, -(Methoxydimethylsilyl) -2- (methoxydimethylsiloxy) ethane, 1- (triethoxysilyl) -1- (trimethoxysiloxy) methane, 1- (triethoxysilyl) -2- (trimethoxysiloxy) ethane, 1- (diethoxymethylsilyl) -1- (trimethoxy) (Siloxy) methane, 1- (diethoxymethylsilyl) -2- (trimethoxysiloxy) ethane, 1- (ethoxydimethylsilyl) -1- (trimethoxysiloxy) methane, 1- (ethoxydimethylsilyl) -2- ( Trimethoxysiloxy) ethane, 1- (triethoxysilyl) -1- (dimethoxymethylsiloxy) methane, 1- (triethoxysilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (diethoxymethylsilyl) -1 -(Dimethoxymethylsiloxy) methane, 1- (diethoxymethylsilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (ethoxydimethylsilyl) -1- (dimethoxymethylsiloxy) methane, 1- (ethoxydimethylsilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (triethoxy Ryl) -1- (methoxydimethylsiloxy) methane, 1- (triethoxysilyl) -2- (methoxydimethylsiloxy) ethane, 1- (diethoxymethylsilyl) -1- (methoxydimethylsiloxy) methane, 1- ( Diethoxymethylsilyl) -2- (methoxydimethylsiloxy) ethane, 1- (ethoxydimethylsilyl) -1- (methoxydimethylsiloxy) methane, 1- (ethoxydimethylsilyl) -2- (methoxydimethylsiloxy) ethane, 1 -(Triphenoxysilyl) -1- (trimethoxysiloxy) methane, 1- (triphenoxysilyl) -2- (trimethoxysiloxy) ethane, 1- (diphenoxymethylsilyl) -1- (trimethoxysiloxy) methane , 1- (diphenoxymethylsilyl) -2- (trimethoxysiloxane) ) Ethane, 1- (phenoxydimethylsilyl) -1- (trimethoxysiloxy) methane, 1- (phenoxydimethylsilyl) -2- (trimethoxysiloxy) ethane, 1- (triphenoxysilyl) -1- (dimethoxymethyl) Siloxy) methane, 1- (triphenoxysilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (diphenoxymethylsilyl) -1- (dimethoxymethylsiloxy) methane, 1- (diphenoxymethylsilyl) -2- (Dimethoxymethylsiloxy) ethane, 1- (phenoxydimethylsilyl) -1- (dimethoxymethylsiloxy) methane, 1- (phenoxydimethylsilyl) -2- (dimethoxymethylsiloxy) ethane, 1- (triphenoxysilyl) -1 -(Methoxydimethylsiloxy) methane, 1- (tri Phenoxysilyl) -2- (methoxydimethylsiloxy) ethane, 1- (diphenoxymethylsilyl) -1- (methoxydimethylsiloxy) methane, 1- (diphenoxymethylsilyl) -2- (methoxydimethylsiloxy) ethane, 1 Examples include-(phenoxydimethylsilyl) -1- (methoxydimethylsiloxy) methane, 1- (phenoxydimethylsilyl) -2- (methoxydimethylsiloxy) ethane, and the like. Of these, 1- (trimethylsilyl) -1- (trimethoxysiloxy) methane, 1- (trimethylsilyl) -1- (methyldimethoxysiloxy) methane, 1- (trimethylsilyl) -1- (dimethylmethoxysiloxy) methane, -(Trimethylsilyl) -1- (trimethylsiloxy) methane, 1- (trimethoxysilyl) -1- (trimethoxysiloxy) methane, 1- (trimethoxysilyl) -2- (trimethoxysiloxy) ethane, 1- ( Preferred examples include triethoxysilyl) -1- (trimethoxysiloxy) methane and 1- (triethoxysilyl) -2- (trimethoxysiloxy) ethane.

  The compound 2 mentioned above may use 1 type (s) or 2 or more types simultaneously.

1.2.3. Compound 3
Compound 3 according to the present embodiment is an oligomer having a repeating structure represented by the general formula (4) and may have a cyclic structure.

In the general formula (4), examples of the monovalent organic group represented by R ¹³ and R ¹⁴ include the same groups as those exemplified as R ⁶ and R ^{7 in} the general formula (2).

  In the general formula (4), examples of the compound 3 include octamethyltrisilane, octaethyltrisilane, octaphenyltrisilane, 2,2,4,4,6,6-hexamethyl-2,4,6- Trisilaheptane, 2,2,4,4,6,6-hexaethyl-2,4,6-trisilaheptane, 2,2,4,4,6,6-hexaphenyl-2,4,6-tri Silaheptane, 1,1,1,3,3,5,5,5-octamethyltrisiloxane, 1,1,1,3,3,5,5,5-octaethyltrisiloxane, 1,1,1 , 3,3,5,5,5-octaphenyltrisiloxane, 1,2,3-trimethoxy-1,1,2,3,3-pentamethyltrisilane, 1,2,3-trimethoxy-1,1 , 2,3,3-pentaethyltrisilane, 1,2,3- Riphenoxy-1,1,2,3,3-pentamethyltrisilane, 2,4,6-trimethoxy-2,4,6-trimethyltrisilaheptane, 2,4,6-trimethoxy-2,4,6 -Triethyltrisilaheptane, 2,2,4,4,6,6-hexaphenyl-2,4,6-trisilaheptane, 1,3,5-trimethoxy-1,1,3,5,5-penta Methyltrisiloxane, 1,3,5-trimethoxy-1,1,3,5,5-pentaethyltrisiloxane, 1,3,5-trimethoxy-1,1,3,5,5-pentaphenyltrisiloxane, Octamethoxytrisilane, octaethoxytrisilane, octaphenoxytrisilane, 2,2,4,4,6,6-hexamethoxy-2,4,6-trisilaheptane, 2,2,4,4,6 6-hexa Toxi-2,4,6-trisilaheptane, 2,2,4,4,6,6-hexaphenoxy-2,4,6-trisilaheptane, 1,1,1,3,3,5,5 , 5-octamethoxytrisiloxane, 1,1,1,3,3,5,5,5-octaethoxytrisiloxane, 1,1,1,3,3,5,5,5-octaphenoxytrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane, 1,1,3,3-tetraethoxy-1,3 -Disilacyclobutane, 1,1,3,3,5,5-hexamethoxy-1,3,5-trisilacyclohexane, 1,3,5-trimethoxy-1,3,5-trimethyl-1,3 5-Trisilacyclohexane and the like can be mentioned. In particular, octamethyltrisilane, octaethyltrisilane, 1,2,3-trimethoxy-1,1,2,3,3-pentamethyltrisilane, 1,2,3-trimethoxy-1,1,2,3 3-pentaethyltrisilane, octamethoxytrisilane, octaethoxytrisilane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octamethylcyclo A preferred example is tetrasiloxane.

  The above-mentioned compound 3 may be used alone or in combination of two or more.

1.3. (III) Component The 3rd composition can further contain an organic molecule as a pore formation agent.

  Examples of the pore-forming agent include a compound having a ring structure, preferably a compound having two or more rings in the molecule (polycyclic compound), more preferably a compound having a condensed ring. , For example, a polycyclic hydrocarbon or a monocyclic hydrocarbon, and a compound containing a hetero atom (an oxygen atom, a nitrogen atom, or a fluorine atom, preferably an oxygen atom).

  In order to obtain an insulating film having a low relative dielectric constant and sufficient mechanical strength, the size and number of porous holes present in the insulating film are important, and factors determining the size of the porous holes One is the type of pore-forming agent used.

  In order to obtain an insulating film having a low relative dielectric constant and sufficient mechanical strength, the pore-forming agent is preferably a polycyclic compound, and the polycyclic compound is, for example, a 3-membered ring compound or a 4-membered ring A compound and / or a compound having a 7-membered ring structure or more, for example, an oxabicyclo compound such as cyclopentene oxide or bicycloheptadiene (BCHD).

  In the method for forming a silicon-containing insulating film according to this embodiment, the amount of the (III) component introduced is 0.05 to 10,000 with respect to the total molar amount 100 of the component (I) and the component (II). Preferably, it is 0.1-5000. Here, when the content of the pore forming agent is less than 0.05 with respect to the total molar amount 100 of the component (I) and the component (II), it may be difficult to reduce the dielectric constant. On the other hand, if it exceeds 10,000, a uniform film may not be obtained.

1.3.1. Oxabicyclo Compound As the oxabicyclo compound, for example, 6-oxabicyclo [3.1.0] hexane (cyclopentene oxide), 7-oxabicyclo [4.1.0] heptane (cyclohexene oxide), 9-oxabicyclo [ 6.1.0] nonane (cyclooctene oxide), 7-oxabicyclo [2.2.1] heptane (1,4-epoxycyclohexane).

  In addition, examples of the oxabicyclo compound include compounds such as 9-oxabicyclo [6.1.0] non-4-ene. Further, the oxabicyclo compound is not limited, for example, 7-oxabicyclo [4.1.0] heptan-2-one or 3-oxabicyclo [3.1.0] hexane-2,4-dione. May be a compound having an additional functional group such as ketone, aldehyde, amine, amide, imide, ether, ester, anhydride, carbonate, thiol, or thioether.

1.3.2. Polycyclic hydrocarbon The polycyclic hydrocarbon preferably has 6 to 12 carbon atoms. For example, 2,5-norbomadiene (bicyclo [2.2.1] hepta-2,5-diene), norbomylene 2,5-norbornadiene (bicyclo [2.2.1] hepta-2,5-diene), norbornane (bicyclo [2.2.1] heptane), tricyclo [3.2.1.0] octane, tricyclo [ 3.2.2.0] Nonane, spiro [3.4] octane, spiro [4.5] nonane, spiro [5.6] decane and other bonded ring hydrocarbons.

1.3.3. Monocyclic hydrocarbon Examples of the monocyclic hydrocarbon include alicyclic hydrocarbons having 5 to 12 carbon atoms such as cyclopentane and cyclohexane, benzene, toluene, xylene (o-xylene, m-xylene, n -Xylene) and the like, and aromatic hydrocarbons having 6 to 12 carbon atoms.

2. Formation method of silicon-containing insulating film (chemical vapor deposition)
A method for forming a silicon-containing insulating film according to an embodiment of the present invention is performed, for example, by chemical vapor deposition (CVD). In particular, it is preferably performed by a plasma excitation CVD method (PECVD method). In the PECVD apparatus, each of the above-described components is vaporized by a vaporizer and introduced into a film forming chamber, applied to an electrode in the film forming chamber by a high frequency power source, and plasma is generated, thereby generating a film forming chamber. A plasma CVD film can be formed on the inner substrate.

Examples of the substrate on which the silicon-containing insulating film according to the present embodiment is formed include Si-containing layers such as Si, SiO ₂ , SiN, SiC, and SiCN. At this time, a gas such as argon or helium, or an oxidant such as oxygen or nitrous oxide can be introduced into the film formation chamber for the purpose of generating plasma. A thin film (deposited film) suitable as a low dielectric constant material for a semiconductor device can be formed by forming a film using the above-described composition with a PECVD apparatus.

  The plasma generation method of the PECVD apparatus is not particularly limited, and for example, inductively coupled plasma, capacitively coupled plasma, ECR plasma, or the like can be used.

  The film thickness of the silicon-containing deposited film thus obtained is preferably 0.05 to 5.0 μm. Thereafter, a silicon-containing film (insulating film) can be formed by subjecting the obtained deposited film to a curing treatment.

  The curing treatment may be at least one selected from heating, electron beam irradiation, ultraviolet irradiation, and oxygen plasma, and a plurality of treatments may be selected from these and performed simultaneously.

  When curing is performed by heating, for example, a deposited film formed by chemical vapor deposition is heated to 80 ° C. to 450 ° C. under an inert atmosphere or under reduced pressure. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere can be performed under an inert atmosphere or under reduced pressure.

  Further, in order to control the curing rate of the deposited film, it is possible to heat it stepwise or to select an atmosphere such as nitrogen, air, oxygen, or reduced pressure as necessary. Through the above steps, a silicon-containing insulating film can be formed.

  Moreover, when hardening, you may irradiate an ultraviolet-ray, for example, heating. Such curing treatment can further reduce the relative dielectric constant of the silicon-containing insulating film and improve the mechanical strength.

3. Silicon-containing insulating film A silicon-containing insulating film according to an embodiment of the present invention can be obtained by the above-described forming method.

  Since the silicon-containing insulating film according to this embodiment has a low dielectric constant and excellent surface flatness and chemical resistance, it is particularly suitable as an interlayer insulating film for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM. Protective film such as etching stopper film, surface coating film of semiconductor element, intermediate layer of semiconductor manufacturing process using multilayer resist, interlayer insulating film of multilayer wiring board, protective film and insulation for liquid crystal display element It can be suitably used for a film or the like. Moreover, the silicon-containing insulating film according to the present embodiment is suitable for a semiconductor device formed by, for example, a copper damascene process.

  The silicon-containing insulating film according to the present embodiment is excellent in mechanical strength, has a low relative dielectric constant, and is excellent in moisture absorption resistance and chemical resistance. Therefore, it is suitably used as an interlayer insulating film for semiconductor elements and the like. be able to.

4). Examples and Comparative Examples Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the examples and comparative examples, “%” indicates% by weight unless otherwise specified.

4.1. Evaluation method Various evaluations were performed as follows.

4.1.1. Measurement of relative dielectric constant A silicon-containing insulating film was formed on an 8-inch silicon wafer by PECVD under the conditions described later. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. With respect to the sample, the relative dielectric constant of the insulating film was measured at a frequency of 100 kHz by the CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. Δk is the difference between the relative dielectric constant (k @ RT) measured in an atmosphere of 24 ° C. and 40% RH and the relative dielectric constant (k @ 200 ° C.) measured in an atmosphere of 200 ° C. and dry nitrogen (Δk = k @ RT-k @ 200 ° C.). With this Δk, it is possible to mainly evaluate the increase in relative dielectric constant due to moisture absorption of the film. Usually, when Δk is 0.15 or more, it can be said that the silicon-containing insulating film has high water absorption.

4.1.2. Hardness and Elastic Modulus (Young's Modulus) Evaluation of Silicon-Containing Insulating Film A Berkovic indenter was attached to an ultra-small hardness meter (Nanoindenter XP) manufactured by MTS, and the universal hardness of the obtained insulating film was determined. The elastic modulus was measured by a continuous stiffness measurement method.

4.1.3. Chemical Solution Resistance An 8-inch wafer on which a silicon-containing insulating film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 3 minutes, and the change in film thickness of the silicon-containing film before and after immersion was observed. If the remaining film rate defined below is 99% or more, it is judged that the chemical resistance is good.

Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100
A: The remaining film rate is 99% or more.

    B: The remaining film rate is less than 99%.

4.2. Production of first composition 4.2.1. Synthesis example 1 of component (I)
A three-necked flask equipped with a cooling condenser and a dropping funnel was dried at 50 ° C. under reduced pressure, and then charged with nitrogen. Next, 20 g of magnesium and 500 ml of THF were added to the flask, and 25 g of (chloromethyl) trimethylsilane was added with stirring at room temperature. After stirring for a while and confirming heat generation, 55 g of (chloromethyl) trimethylsilane was added from a dropping funnel over 30 minutes. After the completion of the dropwise addition, after confirming that the liquid temperature had returned to room temperature, a mixture of 250 ml of THF and 237 g of methyltrimethoxysilane was added to the flask, followed by heating to reflux at 70 ° C. for 6 hours to complete the reaction. It was. After cooling the reaction solution to room temperature, the produced magnesium salt and unreacted magnesium were separated by filtration, and the filtrate was fractionated to obtain 75 g (yield 70%) of [(trimethylsilyl) methyl] methyldimethoxysilane. (Confirmed by GC method). The obtained component (I) is referred to as Compound A.

4.2.2. Synthesis example 2 of component (I)
A three-necked flask equipped with a cooling condenser and a dropping funnel was dried at 50 ° C. under reduced pressure, and then charged with nitrogen. Next, 20 g of magnesium and 500 ml of THF were added to the flask, and 25 g of (chloromethyl) trimethylsilane was added with stirring at room temperature. After stirring for a while and confirming heat generation, 55 g of (chloromethyl) trimethylsilane was added from a dropping funnel over 30 minutes. After the completion of the dropwise addition, after confirming that the liquid temperature had returned to room temperature, a mixture of 250 ml of THF and 258 g of vinyltrimethoxysilane was added to the flask, followed by heating to reflux at 70 ° C. for 6 hours to complete the reaction. It was. After cooling the reaction solution to room temperature, the produced magnesium salt and unreacted magnesium were separated by filtration, and the filtrate was fractionated to obtain 80 g (yield 65%) of [(trimethylsilyl) methyl] vinyldimethoxysilane. (Confirmed by GC method). The obtained component (I) is referred to as Compound B.

4.3. Formation of silicon-containing insulating film (Examples 1 to 9, Comparative Examples 1 to 3)
In Examples 1 to 4 and 7 to 9, a silicon-containing insulating film is formed using the compound A or B ((I) component) obtained in 1 or 2 and another silane compound ((II) component). did. In Examples 5 and 6, a silicon-containing insulating film was formed using the component (III) in addition to the components (I) and (II). In Comparative Examples 1 and 2, a silicon-containing insulating film was formed using only the component (I). In Comparative Example 3, a silicon-containing insulating film was formed using only the component (II).

  Specifically, a plasma CVD apparatus PD-220N manufactured by Samco Co., Ltd. was used, and the flow rates of the raw material gases of the respective components were controlled to the conditions shown in Table 1, Ar gas flow rate 3 sccm, RF power 250 W, substrate temperature 380 ° C., reaction A silicon-containing insulating film of 0.5 μm was formed on the silicon substrate by plasma CVD under a pressure of 10 Torr.

4.4. Evaluation Results Each of the insulating films was evaluated as described in “4.1. Evaluation Method”. The evaluation results are shown in Table 2.

  The silicon-containing insulating films obtained in Examples 1-4 and 7-9 were excellent in mechanical strength, had a low Δk, which is an index indicating the relative dielectric constant and hygroscopicity, and were excellent in chemical resistance.

  Specifically, the silicon-containing insulating films obtained in Examples 1-4 and 7-9 have a mechanical strength as compared with the insulating films (Comparative Examples 1 and 2) formed only from the component (I). In addition to being high, the dielectric constant was low. This is considered to be due to the fact that the compositions in Comparative Examples 1 and 2 are composed only of silicon compounds with few crosslinkable substituents.

  In addition, the silicon-containing insulating film obtained in Example 1-9 was very excellent in chemical resistance as compared with the insulating film obtained from only the component (II) (Comparative Example 3).

  In addition, the insulating films (Examples 5 and 6) formed by adding BCHD as the component (III) have Δk, which is an index indicating the relative dielectric constant and hygroscopicity, as compared with the insulating film not added with the component (III). It was low and excellent in chemical resistance.

  As described above, the silicon-containing insulating film according to the present invention is excellent in mechanical strength, has a low relative dielectric constant, and is excellent in moisture absorption resistance and chemical resistance. It was confirmed that it can be used.

4.5. Ultraviolet irradiation treatment after formation of silicon-containing insulating film For Example 1-4 and Comparative Example 1, after plasma CVD film formation shown in 4.3, in a chamber with an oxygen partial pressure of 0.01 kPa on a hot plate While the coating film was heated at 400 ° C., it was irradiated with ultraviolet rays. As the ultraviolet light source, white ultraviolet light having a wavelength of 250 nm or less was used. Since this ultraviolet light is white ultraviolet light, the illuminance cannot be measured by an effective method.

  Table 3 shows the evaluation results of the insulating film obtained by this treatment.

  As is apparent from the results in Table 3, it is found that ultraviolet irradiation is effective in improving the mechanical strength while maintaining or reducing the relative dielectric constant and Δk of the silicon-containing insulating film according to the present embodiment. It was.

  This is the end of the description of the embodiment according to the present invention. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same purposes and results). In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. Further, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (5)

Supplying a first composition containing an organosilane compound represented by the following general formula (1) onto a substrate;
Supplying a second composition containing at least one silane compound selected from the following general formulas (2) to (4) onto the substrate;
A method for forming a silicon-containing insulating film, comprising:

(1)
(Wherein R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a phenyl group, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms, an acetyl group, Represents a phenyl group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2)
R ⁶ _a Si (OR ⁷ ) _4-a (2)
(Wherein R ⁶ is the same or different and represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ⁷ is the same or different and represents a monovalent organic group, and a represents an integer of 0 to 4)
_{^{R 8 b (R 9 O)}} 3-b Si- (R 12) d -O e -Si (OR 10) 3-c R 11 c
... (3)
(Wherein R ^{8 to} R ¹¹ are the same or different and each represents a hydrogen atom, a fluorine atom or a monovalent organic group; b and c are the same or different and each represents a number of 0 to 3; R ¹² represents phenylene; A group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), and d and e represent 0 or 1.)

(4)
(Wherein R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, a fluorine atom or a group selected from a monovalent organic group, and R ¹⁵ represents an oxygen atom, a phenylene group or — (CH ₂ ) _n —. (Wherein n is an integer of 1-6), f is an integer of 0-2, g is 0 or 1, and h is a number of 2-30.)   The method for forming a silicon-containing insulating film according to claim 1, further comprising a step of supplying a third composition containing an organic molecule as a pore-forming agent onto the substrate. Forming a silicon-containing insulating film using the chemical vapor deposition method for forming a silicon-containing insulating film according to claim 1 or 2. After supplying at least the first composition and the second composition onto the substrate to form a deposited film,
The method for forming a silicon-containing insulating film according to claim 3 , further comprising a step of curing the deposited film by at least one selected from heating, electron beam irradiation, ultraviolet irradiation, and oxygen plasma. It claims 1 obtained by the forming method according to any one of 4, the silicon-containing insulating film.