JP2018182077A - Method of forming low-permittivity film and method of manufacturing semiconductor element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a low-permittivity film with low permittivity and high mechanical strength.SOLUTION: The present invention relates to a method of forming a low-permittivity film and a method of manufacturing a semiconductor element using the same, and more specifically to a method that comprises using a silicon precursor of the present invention to form a preliminary dielectric film on a substrate, and performing energy processing on the preliminary dielectric film to form a dielectric film. The dielectric film has a ratio of Si-CHbonding units/Si-O bonding units from 0.5 to 5.SELECTED DRAWING: Figure 1B

Description

  The present invention relates to a method of forming a low dielectric film and a method of manufacturing a semiconductor device using the same, and more particularly to a method of forming a low dielectric film using a novel silicon precursor.

  Semiconductor devices are often used in the electronics industry due to their properties such as miniaturization, multifunctionality, and / or low manufacturing cost. The semiconductor device may include a memory device for storing data, a logic device for processing data, and a hybrid device capable of performing various functions simultaneously.

  With the high development of the electronics industry, the demand for high integration of semiconductor devices is increasing. In accordance with this, various problems such as a reduction in process margin of the exposure process which defines a fine pattern occur, and the implementation of the semiconductor device becomes increasingly difficult. In addition, with the development of the electronics industry, the demand for speeding up of semiconductor devices also becomes higher. Various studies have been conducted to satisfy the demand for high integration and / or high speed of such semiconductor devices.

U.S. Patent No. 8,293,001 U.S. Patent No. 8,137,764 U.S. Patent No. 9,018,107 US Patent Publication No. 2005/0227502 US Patent Publication No. 2013/0175680

  The problem to be solved by the present invention is to provide a method for forming a low dielectric film having a low dielectric constant and high mechanical strength.

  Another problem to be solved by the present invention is to provide a method of manufacturing a semiconductor device capable of reducing the capacitance between wires.

According to the concept of the present invention, a method for forming a low dielectric film comprises forming a preliminary dielectric film on a substrate using a silicon precursor containing a compound of the following chemical formula 1, and treating an energy on the preliminary dielectric film And forming a dielectric film. The dielectric film has a ratio of Si-CH ₃ bonding units / Si-O bonding units of 0.5 to 5.

化学式１で、ｎは１又は２の整数であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも２つは−Ｏ−Ｒ_７であり、残りは各々独立して水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル又は（Ｃ１−Ｃ１０）アルコキシであり、Ｒ_７は水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル又は（Ｃ３−Ｃ１０）アルキニルであり、Ｒ_４はポロゲン基（ｐｏｒｏｇｅｎ ｇｒｏｕｐ）であり、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、（Ｃ３−Ｃ１０）アリール、（Ｃ３−Ｃ１０）ヘテロアリール、（Ｃ３−Ｃ１０）シクロアルキル、（Ｃ３−Ｃ１０）シクロアルケニル、（Ｃ３−Ｃ１０）シクロアルキニル、（Ｃ３−Ｃ１０）ヘテロシクロアルキル、（Ｃ３−Ｃ１０）アリール（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）シクロアルキル（Ｃ１−Ｃ１０）アルキル、又は（Ｃ３−Ｃ１０）ヘテロシクロアルキル（Ｃ１−Ｃ１０）アルキルである。

In Chemical Formula 1, n is an integer of 1 or 2, and at least two of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are —O—R ₇ , and the rest are each independently Hydrogen, (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl or (C1-C10) alkoxy, R ₇ is hydrogen, (C1-C10) alkyl, (C3-C10) alkenyl Or (C3-C10) alkynyl, R ₄ is a porogen group, (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl , (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3-C10) heterocycloalkyl (C1-C10) alkyl.

  Aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkynyl and heterocycloalkyl are unsubstituted or each independently (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl, (C1) -C10) may be substituted with one or more selected from the group consisting of alkoxy, halogen, cyano, nitro and hydroxyl.

_-NR 8 independently each heteroaryl and heterocycloalkyl -, - contains one or more heteroatoms selected from the group consisting of O- and -S-, _{R 8} is hydrogen or (C1-C10) alkyl It is.

Among R ₁ , R ₂ , R ₃ , R ₅ and R ₆ , at least two are (C 1 -C 5) alkoxy and the remainder is (C 1 -C 5) alkyl.

Of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ , at least three are methoxy and the remainder is (C 1 -C 5) alkyl.

R ₄ is 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -Hexenyl group, 5-hexenyl group, phenyl group, xylene group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group, cycloheptaden group Group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, penten oxide A terpinene group, a limonene group, butadiene oxide, styrene or fulvene.

  The vapor pressure of the compound is 0.1 Torr to 100 Torr at 100.degree.

Forming the pre-dielectric film includes performing chemical vapor deposition (CVD), and the reactive gas of the chemical vapor deposition is O ₂ , O ₃ , N ₂ O, CO ₂ or a combination thereof.

  The energy treatment is a heat treatment performed at 200 ° C. to 800 ° C.

  The energy treatment is UV curing treatment, and when the UV curing treatment is performed, the temperature of the substrate is 0 ° C. to 700 ° C.

  The UV curing process may be performed at a power of 10 W to 200 W for 0.1 to 120 minutes.

  The carbon content of the dielectric film is 1 at% to 40 at%.

  The average diameter of the pores of the dielectric film is 0.5 nm to 5 nm.

  The total volume of pores in the dielectric film is 8% to 35% of the total volume of the dielectric film.

  The diameter distribution of the pores of the dielectric layer may have a full width at half maximum of 0.1 nm to 2.5 nm.

  The dielectric film can have a dielectric constant of 2.2 to 3.

  The dielectric layer may have a Young's modulus of 6 GPa to 15 GPa.

  The dielectric film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.

  According to another aspect of the present invention, a method of forming a low dielectric film can include forming a dielectric film on a substrate using a silicon precursor containing a compound of Formula 1 below.

化学式１で、ｎは１又は２の整数であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも２つは−Ｏ−Ｒ_７であり、残りは各々独立して水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル又は（Ｃ１−Ｃ１０）アルコキシであり、Ｒ_７は水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル又は（Ｃ３−Ｃ１０）アルキニルであり、Ｒ_４はポロゲン基であり、（Ｃ３−Ｃ１０）アリール、（Ｃ３−Ｃ１０）ヘテロアリール、（Ｃ３−Ｃ１０）シクロアルケニル、（Ｃ３−Ｃ１０）シクロアルキニル、（Ｃ３−Ｃ１０）ヘテロシクロアルキル、（Ｃ３−Ｃ１０）アリール（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）シクロアルキル（Ｃ１−Ｃ１０）アルキル、又は（Ｃ３−Ｃ１０）ヘテロシクロアルキル（Ｃ１−Ｃ１０）アルキルである。

In Chemical Formula 1, n is an integer of 1 or 2, and at least two of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are —O—R ₇ , and the rest are each independently Hydrogen, (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl or (C1-C10) alkoxy, R ₇ is hydrogen, (C1-C10) alkyl, (C3-C10) alkenyl Or (C3-C10) alkynyl, R ₄ is a porogen group, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, ((C3-C10)) C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3 C10) heterocycloalkyl (C1-C10) alkyl.

  Aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkynyl and heterocycloalkyl are unsubstituted or each independently (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl, (C1) -C10) may be substituted with one or more selected from the group consisting of alkoxy, halogen, cyano, nitro and hydroxyl.

Wherein said heteroaryl and said heterocycloalkyl are each independently _NR 8 -, - include O- and one or more heteroatoms selected from the group consisting of -S-, _{R 8} is hydrogen or (C1-C10) It is an alkyl.

  Forming the dielectric film can include forming a preliminary dielectric film on the substrate using a silicon precursor and performing energy processing on the preliminary dielectric film.

  The total volume of pores in the dielectric film is 8% to 35% of the total volume of the dielectric film.

  According to another aspect of the present invention, a method of forming a low dielectric film includes forming a preliminary dielectric film on a substrate using a silicon precursor containing a compound of Formula 1 below, and forming a preliminary dielectric film on the preliminary dielectric film. Performing energy processing to form a dielectric film. The dielectric film may have a Young's modulus of 6 GPa to 15 GPa.

前記化学式１で、ｎは１又は２の整数であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも３つはメトキシであり、残りは各々独立して水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、又は（Ｃ１−Ｃ１０）アルコキシであり、Ｒ_４はポロゲン基であり、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、（Ｃ３−Ｃ１０）アリール、（Ｃ３−Ｃ１０）ヘテロアリール、（Ｃ３−Ｃ１０）シクロアルキル、（Ｃ３−Ｃ１０）シクロアルケニル、（Ｃ３−Ｃ１０）シクロアルキニル、（Ｃ３−Ｃ１０）ヘテロシクロアルキル、（Ｃ３−Ｃ１０）アリール（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）シクロアルキル（Ｃ１−Ｃ１０）アルキル、又は（Ｃ３−Ｃ１０）ヘテロシクロアルキル（Ｃ１−Ｃ１０）アルキルである。

In the above Chemical Formula 1, n is an integer of 1 or 2, at least three of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are methoxy, and the rest are each independently hydrogen ( C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl, or (C1-C10) alkoxy, _{R 4} is porogen group, (C3-C10) alkenyl, (C3-C10) Alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3-C10) Telocycloalkyl (C1-C10) alkyl.

  Aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkynyl and heterocycloalkyl are unsubstituted or each independently (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl, (C1) -C10) may be substituted with one or more selected from the group consisting of alkoxy, halogen, cyano, nitro and hydroxyl.

Heteroaryl and heterocycloalkyl are each independently _NR 8 -, - contains one or more heteroatoms selected from the group consisting of O- and -S-, _{R 8} is hydrogen or (C1-C10) alkyl is there.

  The dielectric film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.

  Energy processing may be performed at 500 ° C. to 600 ° C.

According to another aspect of the present invention, a method of manufacturing a semiconductor device includes forming a silicon insulating film on a substrate using a silicon precursor having molecules of a Si- (CH ₂ ) _n -Si structure. Forming at least one wiring in the silicon insulating film, n is an integer of 1 or 2, and the silicon precursor bonds to any one of Si atoms in its molecule It has a porogen group, and the silicon precursor has, in its molecule, two or more (C1-C5) alkoxy groups bonded to Si atoms, and the porogen group is (C3-C10) alkenyl, (C3) -C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl , (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3-C10) heterocycloalkyl (C1-C10) ) Alkyl.

The silicon insulating film has a ratio of Si-CH ₃ bonding unit / Si-O bonding unit of 0.5 to 5.

  The silicon insulating film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.

  The silicon insulating layer may have a dielectric constant of 2.2 to 3 and a Young's modulus of 6 to 15 Gpa.

  Forming the at least one wiring includes patterning the silicon insulating film to form the at least one wiring hole in the silicon insulating film, and forming a conductive film filling the at least one wiring hole. Can be included.

  Forming the at least one wire can further include forming a barrier film filling the at least one wire hole.

  The method for forming a low dielectric film according to the present invention can form a dielectric film having a low dielectric constant and high mechanical strength using a novel silicon precursor. The silicon precursor of the present invention has excellent thermal stability and can form many pores in the dielectric film. When the interconnection is formed inside the low dielectric film according to the present invention, the interconnection can be supported with high mechanical strength of the dielectric film, and the capacitance can be reduced between the interconnections by the low dielectric constant of the dielectric film.

It is sectional drawing which shows the formation method of the low dielectric film which concerns on embodiment of this invention. FIG. 1B is a cross-sectional view of a chamber in which the deposition process shown in FIG. 1A is performed. It is sectional drawing which shows the formation method of the low dielectric film which concerns on embodiment of this invention. It is a top view for explaining the method of manufacturing the semiconductor device concerning the embodiment of the present invention. It is sectional drawing in alignment with the I-I 'line | wire of FIG. It is sectional drawing in alignment with the II-II 'line | wire of FIG. It is a top view for explaining the method of manufacturing the semiconductor device concerning the embodiment of the present invention. It is sectional drawing in alignment with the I-I 'line | wire of FIG. It is sectional drawing in alignment with the II-II 'line | wire of FIG. It is a top view for explaining the method of manufacturing the semiconductor device concerning the embodiment of the present invention. It is sectional drawing in alignment with the I-I 'line | wire of FIG. It is sectional drawing in alignment with the II-II 'line | wire of FIG. It is the graph which showed the vapor pressure of the silicon precursor concerning the embodiment of the present invention. It is the graph which showed pore size distribution of the dielectric film concerning the embodiment of the present invention.

  DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to fully understand the configuration and effects of the present invention, preferred embodiments of the present invention will be described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be embodied in various forms and can be variously modified. The disclosure of the present invention is completed only by the description of the present embodiment, and is provided so that those skilled in the art to which the present invention belongs can fully understand the scope of the present invention.

  In the present specification, when it is mentioned that any component is on another component, it is formed directly on the other component, or a third component is interposed between them. It also means that you can do it. Also, in the drawings, the size of the components is exaggerated for the purpose of effectively explaining the technical content. The parts denoted by the same reference numerals throughout the specification indicate the same components.

  The embodiments described herein will be described with reference to the cross-sectional and / or plan views which are ideal illustrations of the present invention. In the drawings, the size of the membranes and regions are exaggerated for the purpose of effectively explaining the technical content. Therefore, the area illustrated as illustrated has schematic attributes, and the pattern of the illustrated area as illustrated is to illustrate the specific form of the area of the element, and to limit the scope of the invention. is not. Although the terms first, second, third, etc. are used to describe various components in various embodiments herein, the membranes of these components are limited by such terms. It must not be. These terms are only used to distinguish one component from another. The embodiments described and illustrated herein also include their complementary embodiments.

  The terms used herein are for the purpose of describing the embodiments and are not intended to limit the present invention. As used herein, the singular forms also include the plural unless the context specifically refers to the same. As used herein, 'comprises' and / or 'comprising' are components, steps, operations and / or elements mentioned one or more other components, steps, operations And / or do not exclude the presence or addition of elements.

  1A and 2 are cross-sectional views showing a method of forming a low dielectric film according to an embodiment of the present invention. FIG. 1B is a cross-sectional view of a chamber in which the deposition process shown in FIG. 1A is performed.

  Referring to FIGS. 1A and 1B, a preliminary dielectric film PDL is formed on a substrate 100. The substrate 100 is a semiconductor substrate containing silicon, germanium, silicon-germanium or the like, or a compound semiconductor substrate.

First, a silicon precursor for forming the preliminary dielectric film PDL is prepared. Silicon precursors include molecules having porogen groups. The porogen group bonds directly to the Si atom. Specifically, the silicon precursor is Si- _{(CH 2)} comprises molecules of n -Si structure (n is an integer of 1 or 2), porogen group is directly bonded to a Si atom in the molecule. For example, the silicon precursor comprises a compound of Formula 1 below.

前記化学式１で、ｎは１又は２の整数である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも２つは−Ｏ−Ｒ_７であり、残りは各々独立して水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル又は（Ｃ１−Ｃ１０）アルコキシである。ここで、Ｒ_７は水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル又は（Ｃ３−Ｃ１０）アルキニルである。一例として、Ｒ_２及びＲ_３が各々−Ｏ−Ｒ_７である場合、化合物は下記の化学式２で表示されることができる。

In Formula 1, n is an integer of 1 or 2. Among R ₁ , R ₂ , R ₃ , R ₅ and R ₆ , at least two are —O—R ₇ and the rest are each independently hydrogen, (C 1 -C 10) alkyl, (C 3 -C 10) Alkenyl, (C3-C10) alkynyl or (C1-C10) alkoxy. Wherein, _{R 7} is hydrogen, (C1-C10) alkyl, (C3-C10) alkenyl or (C3-C10) alkynyl. As an example, if R ₂ and R ₃ are each -O-R _7, the compound can be represented by the following chemical formula 2.

望ましくは、化学式２で、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも２つは（Ｃ１−Ｃ５）アルコキシである。−Ｏ−Ｒ_７でＲ_７は（Ｃ１−Ｃ５）アルキルである。さらに具体的に、前記Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも３つはメトキシである。ここで、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で残りは（Ｃ１−Ｃ５）アルキルである。この場合、化合物は一例として下記の化学式３で表示されることができる。

Desirably, in Formula 2, at least two of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are (C 1 -C 5) alkoxy. _{R 7} in _{-O-R 7} is (C1-C5) alkyl. More specifically, at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are methoxy. Here, the remaining of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ is (C 1 -C 5) alkyl. In this case, the compound may be represented by the following Chemical Formula 3 as an example.

前記化学式３で、Ｒ_４は前記ポロゲン基である。具体的に、Ｒ_４は（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、（Ｃ３−Ｃ１０）アリール、（Ｃ３−Ｃ１０）ヘテロアリール、（Ｃ３−Ｃ１０）シクロアルキル、（Ｃ３−Ｃ１０）シクロアルケニル、（Ｃ３−Ｃ１０）シクロアルキニル、（Ｃ３−Ｃ１０）ヘテロシクロアルキル、（Ｃ３−Ｃ１０）アリール（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）シクロアルキル（Ｃ１−Ｃ１０）アルキル又は（Ｃ３−Ｃ１０）ヘテロシクロアルキル（Ｃ１−Ｃ１０）アルキルである。

In Formula 3, R ₄ is the porogen group. Specifically, R ₄ is (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cyclo Alkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl or (C3-C10) ) Heterocycloalkyl (C1-C10) alkyl.

Here, aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkynyl and heterocycloalkyl are unsubstituted or each independently (C1-C10) alkyl, (C3-C10) alkenyl, (C3-C10) alkynyl And may be substituted with one or more selected from the group consisting of (C1-C10) alkoxy, halogen, cyano, nitro and hydroxyl. Furthermore, heteroaryl and heterocycloalkyl NR 8 each independently is _-, - can include one or more heteroatoms selected from the group consisting of O- and -S-. Here, R ₈ is hydrogen or (C 1 -C 10) alkyl.

For example, R ₄ is 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1- Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group , 4-hexenyl group, 5-hexenyl group, phenyl group, xylene group, cyclopropyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group, cyclo Heptaden group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, pentene And an oxide group, a terpinene group, a limonene group, butadiene oxide, styrene or fulvene.

Desirably, R ₄ has a cyclic hydrocarbon structure. Specifically, _{R 4} is (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3- C10) Aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl or (C3-C10) heterocycloalkyl (C1-C10) alkyl. In this case, relatively many micropores are formed in the dielectric film described later.

  The compound of Formula 1 has a molecular weight of 100 to 500. The compound of Formula 1 has a vapor pressure of 0.1 Torr to 100 Torr at 100 ° C. That is, the compound of Formula 1 has a relatively high vapor pressure, and thus is more stable in process when performing a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process. The compound of Formula 1 is thermally decomposed at a temperature of 100 ° C. to 500 ° C. That is, since the compound of Formula 1 is not easily decomposed even at high temperature, it is relatively excellent in thermal stability.

  For example, the compound of Formula 1 is at least one of the following compounds.

予備誘電膜ＰＤＬはシリコン前駆体をソースガスＳＧとする蒸着工程ＤＰを通じて形成される。蒸着工程ＤＰは化学気相蒸着（ＣＶＤ）又は原子層蒸着（ＡＬＤ）を含む。一例として、化学気相蒸着はプラズマ強化化学気相蒸着（Ｐｌａｓｍａ Ｅｎｈａｎｃｅｄ ＣＶＤ）であり、原子層蒸着はプラズマ強化原子層蒸着（Ｐｌａｓｍａ Ｅｎｈａｎｃｅｄ ＡＬＤ）である。

The preliminary dielectric film PDL is formed through a deposition process DP using a silicon precursor as a source gas SG. The deposition process DP includes chemical vapor deposition (CVD) or atomic layer deposition (ALD). As an example, chemical vapor deposition is plasma enhanced chemical vapor deposition (Plasma Enhanced CVD) and atomic layer deposition is plasma enhanced atomic layer deposition (Plasma Enhanced ALD).

  Specifically, referring again to FIG. 1B, a substrate is disposed within the chamber 200. As one example, the chamber 200 is a plasma chamber. The substrate is disposed on a plate 210, and the substrate is heated using the plate 210. As an example, the plate 210 is also used as a lower electrode. During heating, the temperature of the substrate is 0 ° C. to 500 ° C., and as an example, the temperature of the substrate is about 200 ° C.

The source gas SG and the reaction gas SG are charged into the chamber 200. The source gas SG is a silicon precursor, and the reaction gas SG is an oxidant. As an example, the reaction gas SG is O ₂ , O ₃ , N ₂ O, CO ₂ or a combination thereof. Specifically, the silicon precursor phase-changes to a source gas SG which is a gas in the evaporator. The silicon precursor in the evaporator is heated to change the phase of the silicon precursor into a gaseous source gas SG.

  As described above, since the silicon precursor has a relatively high vapor pressure, a relatively large amount of the silicon precursor changes into the gaseous source gas SG under a specific temperature of the evaporator. Accordingly, a relatively large amount of source gas SG may be easily introduced into the chamber 200, and the deposition process DP may be efficiently and stably performed through the relatively high amount of source gas SG.

  Furthermore, depending on the process conditions of the vapor deposition process DP, a relatively large amount of source gas SG may be required. It may be necessary to increase the pressure of the source gas SG introduced into the chamber 200. For this purpose, the specific temperature of the evaporator is increased. On the other hand, since the silicon precursor is relatively excellent in thermal stability, its chemical structure does not easily change even at a relatively high specific temperature (for example, 200 ° C. to 500 ° C.). Therefore, the preliminary dielectric film PDL can be formed without any process defect.

  The source gas SG is introduced into the chamber 200 together with the carrier gas flowing into the evaporator. The carrier gas is an inert gas, such as helium, neon, argon, krypton, xenon or radon. The flow rate of the carrier gas is 100 cc / min to 800 cc / min, and the flow rate of the reaction gas SG is 5 cc / min to 100 cc / min.

  During the deposition process DP, the pressure in the chamber 200 is 0.1 Torr to 10 Torr. The upper electrode 220 in the chamber 200 is connected to a high frequency generator (RF generator) 230 and a high frequency of 5 MHz to 20 MHz is applied to the upper electrode 220 through the high frequency generator 230 at a power of 1 W to 1000 W during the deposition process DP. Be done.

  The preliminary dielectric film PDL formed using the silicon precursor as a source contains a porogen group in its inside.

  Referring to FIG. 2, an energy process ET is performed on the preliminary dielectric film PDL to form a dielectric film DL. The energy processing ET includes applying various forms of energy, such as thermal energy or light energy, on the pre-dielectric film PDL to cure the pre-dielectric film PDL. For example, the energy treatment ET is a heat treatment or UV curing treatment.

  The heat treatment is performed on the substrate for 10 minutes to 240 minutes at 200 ° C. to 800 ° C. through the heat treatment chamber. Preferably, the heat treatment is performed at about 500 ° C. to about 600 ° C. The UV curing process is performed on the substrate for 0.1 to 120 minutes by applying a power of 10 W to 200 W to the UV lamp. At this time, the temperature of the substrate is 0 ° C. to 700 ° C.

During the energy processing ET, porogen groups present in the pre-dielectric film PDL are removed. Specifically, the Si-R ₄ bond in the preliminary dielectric film PDL is cut through the energy processing ET, and the porogen group (R ₄ ) is volatilized and removed. Thus, the dielectric film DL includes fine pores formed at positions where the porogen groups have been removed. The dielectric film DL is a porous thin film.

  The porosity of the dielectric layer DL is 8% to 35%. The total volume of the pores of the dielectric film DL is 8% to 35% of the total volume of the dielectric film DL. The average diameter of the pores of the dielectric film DL is 0.5 nm to 5 nm. The pore size (diameter) distribution of the dielectric film DL is 0.1 nm to 2.5 nm. In the distribution curve of pore size (diameter), the full width at half maximum is 0.1 nm to 2.5 nm (see FIG. 10).

The dielectric film DL is a low dielectric film and has a dielectric constant of 2.2 to 3. The dielectric layer DL has a Young's modulus of 6 GPa to 15 GPa. Although the dielectric film DL is porous, it has high mechanical strength. On the other hand, when at least three of R ₁ , R ₂ , R ₃ , R ₅ , and R _{6 in} the chemical formula 1 are methoxy, the dielectric film DL has a Young's modulus of 6 GPa to 15 GPa, preferably 8 GPa to 15 GPa. It has Young's modulus.

The dielectric film DL contains SiOCH. At this time, the carbon content of the dielectric film DL is 1 at% to 40 at%. The dielectric film DL has a ratio of Si—CH ₃ bonding units / Si—O bonding units of 0.5 to 5. Preferably, the dielectric film DL has a ratio of Si-CH ₃ bonding units / Si-O bonding units 1 to 4. That is, the dielectric film DL includes relatively many Si-CH ₃ bonds inside. The Si—CH ₃ bond helps to form a Si—O cage structure inside the dielectric film DL. The Si-O cage structure has nanovoids at the center of the structure by arranging Si-O in a three-dimensional determined structure. As a result, the porosity of the dielectric film DL can be further increased to further lower the dielectric constant. Furthermore, as the ratio of Si—CH ₃ bonding units / Si—O bonding units is relatively high, relatively more Si—CH ₃ bonds in the thin film exist. This can reduce the damage to the dielectric film DL due to plasma at the time of the wiring formation process in the dielectric film DL to be described later. That is, plasma induced damage can be improved.

The silicon-based structure forming the dielectric layer DL includes a Si-O network structure and the Si-O cage structure. The Si-O network structure has a complex network form in which Si-O bonding units are randomly arranged. The dielectric film DL has excellent mechanical strength due to the Si-O network structure. As an example, the peak area of the Si-O network structure (ca. to 1040 cm ^-1 ) shown in the data graph according to Fourier transform infrared spectroscopy (FT-IR) is 13 to 16, and the Si-O cage structure (ca Peak area of 7 to 12 cm ⁻¹ . At this time, the ratio of Si-O cage structure / Si-O network structure is 0.5 to 1. More specifically, the ratio of Si-O cage structure / Si-O network structure is 0.6 to 1. That is, by forming the Si—O network structure and the Si—O cage structure in the dielectric film DL in a ratio to each other, excellent mechanical strength and low dielectric constant can be simultaneously achieved.

Hereinafter, specific experimental examples of the silicon precursor and the dielectric film described above with reference to FIGS. 1A and 2 will be described. The compounds prepared through specific embodiments described below were analyzed using nuclear magnetic resonance spectroscopy ( ₁ H Nuclear Magnetic Resonance, NMR).

EXAMPLE 1 Preparation of 1-((Bicycloheptenyl) diethoxysilyl) -2- (methyldiethoxysilyl) methane Step 1. Preparation of 1- (trichlorosilyl) -2- (methyldichlorosilyl) methane Into a flame-dried 5000 mL Schlenk flask was added 1500 mL of acetonitrile and 500 g (3.06 mol, 1.0 equivalent) of (chloromethyl) dichloromethylsilane. Then, the temperature was raised to 70.degree. After 340.37 g (3.36 mol, 1.1 equivalents) of triethylamine was added to the reaction solution, 455.61 g (3.36 mol, 1.1 equivalents) of trichlorosilane was slowly added while maintaining 70 ° C. The reaction solution was stirred at 70 ° C. for 5 hours, filtered, and washed four times with 1500 mL of n-pentane to work-up. The solution was treated under reduced pressure to remove the solvent and purified at 28 ° C./1.01 Torr to obtain 160.54 g of MeCl ₂ Si—CH ₂ —SiCl _{3 as} a colorless liquid (yield: 20%).

₁ H-NMR (C ₆ D ₆ ) δ-0.38 (3H), 0.69 (2H).
Stage 2 Preparation of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) methane 1- (trichlorosilyl) prepared in step 1 with 3000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After adding 160.54 g (0.61 mol, 1.0 equivalent) of -2- (methyldichlorosilyl) methane, 330.84 g (7.34 mol, 12.0 equivalents) of diethylamine was added while maintaining 0 ° C. Added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 3 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, purified at 78 ° C. and 0.8 Torr, and colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ —Si (NMe ₂ ) ₂ Cl 163.48 g was obtained (yield: 90%).

₁ H-NMR (C ₆ D ₆ ) δ-0.18 (3H), 0.30 (2H), 2.43 to 2.47 (24H).
Step 3. Preparation of 1- (bis (dimethylamino) silyl) -2- (bis (dimethylamino) methylsilyl) methane Add 7.31 g (0.19 mol, 0.35 equivalents) of LiAlH ₄ to a flame-dried 1000 mL Schlenk flask After that, 300 mL of THF was slowly added while maintaining -30.degree. While maintaining the temperature of the reaction solution at -30 ° C, 163.48 g (0.55 mol, 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) methane produced in Step 2 .0 equivalents) was added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, purified at 56 ° C. and 0.5 Torr, and colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ —Si (NMe ₂ ) ₂ H 108.38 g was obtained (yield: 75%).

₁ H-NMR (C ₆ D ₆ ) δ -0.04 (2H), 0.16 (3H), 2.44 to 2.48 (24H), 4.48 (1H).
Step 4. Preparation of 1- (diethoxysilyl) -2- (diethoxy (methyl) silyl) methane 1- (bis (dimethylamino) silyl) prepared in step 3 with 1000 mL n-pentane in a flame-dried 3000 mL Schlenk flask After the addition of 108.38 g (0.41 mol, 1.0 equivalent) of -2- (bis (dimethylamino) methylsilyl) methane, the ethanol 76.07 g (1.65 mol, 4.0) was maintained while maintaining 0 ° C. ) Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, and purified at 46 ° C. and 0.6 Torr to obtain a colorless liquid Me (EtO) ₂ Si—CH ₂ —Si (OEt) ₂ H 99. Obtained 01 g (yield: 90%).

₁ H-NMR (C ₆ D ₆ ) δ-0.12 (2 H), 0.25 (3 H), 1.15 (12 H), 3.78 (8 H), 4.92 (1 H).
Step 5. Preparation of 1-((bicycloheptenyl) diethoxysilyl) -2- (methyldiethoxysilyl) methane 1- (diethoxysilyl) -2- (prepared in step 4 in a flame-dried 1000 mL Schlenk flask 99.01 g (0.37 mol, 1.0 equivalent) of diethoxy (methyl) silyl) methane and the catalyst dichloro (1,5-cyclooctadiene) platinum (II) were added. The temperature of the reaction solution was raised to 60 ° C., and then 34.23 g (0.37 mol, 1.0 equivalent) of norbornadiene was slowly added. The solution was stirred at 60 ° C. for 5 hours and then purified at 90 ° C. and 0.27 Torr to obtain 99.93 g of a compound of the following chemical formula (yield: 75%) as a colorless liquid.

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．００４（ｅｘｏ、２Ｈ）、０．０５（ｅｎｄｏ、２Ｈ）、０．１６（ｅｘｏ、３Ｈ）、０．２４（ｅｎｄｏ、３Ｈ）、１．１３（ｅｘｏ、ｅｎｄｏ、１８Ｈ）、３．５７〜３．６７（ｅｘｏ、ｅｎｄｏ、１２Ｈ）、１．３４〜１．８０、２．７８〜２．８８、５．９１〜６．１９（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例２：１−（（ビシクロヘプテニル）ジエトキシシリル）−２−（メチルジエトキシシリル）エタンの製造
段階１． １−（トリクロロシリル）−２−（メチルジクロロシリル）エタンの製造
炎で乾燥された３０００ｍＬシュレンクフラスコにトリクロロビニールシラン ２００ｇ（１．２４ｍｏｌ、１．０当量）と触媒としてヘキサクロロ白金（Ｈ_２Ｃｌ_６Ｐｔ_６Ｈ_２Ｏ）とを添加した後、反応溶液を６０℃に昇温した。反応溶液にジクロロメチルシラン １５６．７ｇ（１．３６ｍｏｌ、１．１当量）をゆっくり添加した。この混合溶液を８時間還流してＭｅＣｌ_２Ｓｉ−ＣＨ_２ＣＨ_２−ＳｉＣｌ_３ ３８４．８１ｇを得た（収率：９８％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.004 (exo, 2H), 0.05 (endo, 2H), 0.16 (exo, 3H), 0.24 (endo, 3H), 13 (exo, endo, 18H), 3.57 to 3.67 (exo, endo, 12H), 1.34 to 1.80, 2.78 to 2.88, 591 to 6.19 (bicycloheptenyl, 9H).
EXAMPLE 2 Preparation of 1-((Bicycloheptenyl) diethoxysilyl) -2- (methyldiethoxysilyl) ethane Step 1. Preparation of 1- (trichlorosilyl) -2- (methyldichlorosilyl) ethane 200 g (1.24 mol, 1.0 equivalents) of trichlorovinylsilane in a flame-dried 3000 mL Schlenk flask and hexachloroplatinum (H ₂ Cl ₆ ) as a catalyst After adding Pt ₆ H ₂ O), the reaction solution was heated to 60 ° C. To the reaction solution, 156.7 g (1.36 mol, 1.1 equivalents) of dichloromethylsilane was slowly added. This mixed solution was refluxed for 8 hours to obtain a _{MeCl 2 Si-CH 2 CH 2} -SiCl 3 384.81g ( yield: 98%).

₁ H-NMR (C ₆ D ₆ ) δ-0.21 (3H), 0.86 (2H), 1.06 (2H).
Stage 2 Preparation of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) ethane 1- (trichlorosilyl) prepared in step 1 with 3000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After adding 384.81 g (1.39 mol, 1.0 equivalent) of -2- (methyl dichloro silyl) ethane, and maintaining 0 ° C, 501.87 g (11.13 mol, 8.0 equivalents) of dimethylamine Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 3 hours. The reaction solution was filtered and treated under reduced pressure to remove the solvent to obtain 367.88 g of colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ CH ₂ —Si (NMe ₂ ) ₂ Cl ₂ (yield : 85%).

₁ H-NMR (C ₆ D ₆ ) δ -0.07 (3H), 0.78 to 0.91 (4H), 2.45 (24H).
Step 3. Preparation of 1- (bis (dimethylamino) silyl) -2- (bis (dimethylamino) methylsilyl) ethane Add 15.71 g (0.41 mol, 0.35 equivalents) of LiAlH ₄ to a flame-dried 2000 mL Schlenk flask After that, 500 mL of THF was slowly added while maintaining -30.degree. While maintaining the reaction solution at -30 ° C, 357.88 g (1.18 mol, 1.0 of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) ethane prepared in Step 2 ) Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered, treated under reduced pressure to remove the solvent, and purified at 73 ° C. and 1.66 Torr to obtain Me (NMe ₂ ) ₂ Si—CH ₂ CH ₂ —Si (NMe ₂ ) ₂ which is a colorless liquid. There were obtained 245.36 g of H (yield: 75%).

₁ H-NMR (C ₆ D ₆ ) δ − 0.10 (3 H), 0.69 (4 H), 2.47 (12 H), 2.52 (12 H), 4.59 (1 H).
Step 4. Preparation of 1- (diethoxysilyl) -2- (diethoxy (methyl) silyl) ethane 1- (bis (dimethylamino) silyl) prepared in step 3 with 1000 mL n-pentane in a flame-dried 3000 mL Schlenk flask After adding 245.36 g (0.89 mol, 1.0 equivalent) of -2- (bis (dimethylamino) methylsilyl) ethane, 163.48 g (3.55 mol, 4.0) of ethanol was maintained while maintaining 0 ° C. ) Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution was filtered and treated under reduced pressure to remove the solvent, and 218.99 g of colorless liquid Me (EtO) ₂ Si—CH ₂ CH ₂ —Si (OEt) ₂ H was obtained (yield: 88%).

₁ H-NMR (C ₆ D ₆ ) δ-0.11 (3H), 0.81 (4H), 1.10 to 1.14 (12H), 3.64 to 3.66 (4H), 71 to 3.73 (4H), 4.80 (1 H).
Step 5. Preparation of 1-((2-Cycloheptenyl) diethoxysilyl) -2- (methyldiethoxysilyl) ethane 1- (diethoxysilyl) -2- (prepared in Step 4 in a flame-dried 1000 mL Schlenk flask 218.99 g (0.78 mol, 1.0 equivalent) of diethoxy (methyl) silyl) ethane and dichloro (1,5-cyclooctadiene) platinum (II) as a catalyst were added. The temperature of the reaction solution was raised to 60 ° C., and 71.93 g (0.78 mol, 1.0 equivalent) of norbornadiene was slowly added. The mixed solution was stirred at 60 ° C. for 5 hours and then purified at 95 ° C. and 0.18 Torr to obtain 203.65 g of a compound of the following chemical formula as a colorless liquid (yield: 70%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．１６（３Ｈ）、０．８４（４Ｈ）、１．１５（１２Ｈ）、３．７０（８Ｈ）、０．６〜３．０５、５．９１〜６．１２（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例３：１−（フェニルエトキシメチルシリル）−２−（メチルジエトキシシリル）エタンの製造
段階１． ジエチルアミノメチルフェニルクロロシランの製造
炎で乾燥された５０００ｍＬシュレンクフラスコにペンタン １５００ｍＬとジクロロメチルフェニルシラン １５０ｇ（０．７９ｍｏｌ、１．０当量）とを添加した後、０℃に維持したまま、ジエチルアミン １１４．８ｇ（１．５７ｍｏｌ、２．０当量）をゆっくり添加した。反応溶液を室温（２０℃）まで昇温して１２時間攪拌した。反応溶液を濾過した後、減圧処理して溶媒を除去した後、ジエチルアミノメチルフェニルクロロシラン １５９．１２ｇを得た（収率：８９％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.16 (3 H), 0.84 (4 H), 1.15 (12 H), 3.70 (8 H), 0.6 to 3.05, 5. 91 to 6.12 (bicycloheptenyl, 9H).
Example 3 Preparation of 1- (phenylethoxymethylsilyl) -2- (methyldiethoxysilyl) ethane Step 1. Preparation of Diethylaminomethylphenylchlorosilane After adding 1500 mL of pentane and 150 g (0.79 mol, 1.0 equivalent) of dichloromethylphenylsilane to a flame-dried 5000 mL Schlenk flask, 114.8 g of diethylamine maintained at 0 ° C. (1.57 mol, 2.0 equivalents) was added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 12 hours. The reaction solution was filtered and treated under reduced pressure to remove the solvent to obtain 159.12 g of diethylaminomethylphenylchlorosilane (yield: 89%).

₁ H-NMR (C ₆ D ₆ ) δ-0.5 (3 H), 0.89 (6 H), 2.75 (4 H), 7.16 (3 H), 7.78 (2 H).
Stage 2 Preparation of Diethylaminomethylsilane 7.42 g (0.2 mol, 0.28 equivalents) of LiAlH ₄ was added to a flame-dried 3000 mL Schlenk flask, and 1500 mL of THF was added while maintaining −10 ° C. To the solution was slowly added 159 g (0.70 mol, 1.0 equivalents) of ethylaminomethylphenylchlorosilane produced in step 1. The reaction solution was slowly heated to 70 ° C. and stirred for 12 hours. The reaction solution was treated under reduced pressure to remove the solvent, and 1000 mL of hexane was added. The reaction solution was stirred for 30 minutes, filtered, and treated under reduced pressure to remove the solvent to obtain 67.53 g of diethylaminomethylsilane (yield: 50%).

₁ H-NMR (C ₆ D ₆ ) δ-0.31 (3H), 0.97 (6H), 2.79 (4H), 5.13 (1H), 7.28 (3H), 7.63 (2H).
Step 3. Preparation of Ethoxymethylsilane After adding 1500 mL of n-pentane and 67.53 g (0.35 mol, 1.0 equivalent) of diethylaminosilane prepared in step 2 to a flame-dried 5000 mL Schlenk flask, maintain at 0 ° C. As it was, 32.18 g (0.7 mol, 2.0 equivalents) of ethanol was slowly added. The reaction solution was warmed to room temperature and stirred for 12 hours, and after filtration, the solvent was removed under reduced pressure to obtain 40.65 g of ethoxymethylsilane (yield: 70%).

₁ H-NMR (C ₆ D ₆ ) δ-0.33 (3 H), 1.12 (3 H), 3.58 (2 H), 5.21 (1 H), 7.2 (3 H), 7.53 (2H).
Step 4. Preparation of diethoxymethyl (vinyl) silane After adding 1500 mL of n-pentane and 50 g (0.35 mol, 1.0 equivalent) of dichloromethyl (vinyl) silane to a flame-dried 3000 mL Schlenk flask, maintain at 0 ° C. As it was, 73.52 g (0.73 mol, 2.05 equivalents) of triethylamine was slowly added. Subsequently, 33.47 g (0.73 mol, 2.05 equivalents) of ethanol was slowly added to the solution. The reaction solution was warmed to room temperature and stirred for 12 hours, filtered, and then the solvent was removed under reduced pressure to obtain 39 g of diethoxymethyl (vinyl) silane (yield: 68%).

₁ H-NMR (C ₆ D ₆ ) δ-0.18 (3H), 1.13 (6H), 3.71 (4H), 5.8-6.3 (3H).
Step 5. Preparation of 1- (phenylethoxymethylsilyl) -2- (diethoxymethylsilyl) ethane 40.65 g (0.24 mol, 1.0 equivalents) of ethoxymethylsilane prepared in step 3 in a flame-dried 5000 mL Schlenk flask ) And hexachloroplatinum (H ₂ Cl ₆ Pt ₆ H ₂ O) as a catalyst. The reaction solution was heated to 60 ° C., and 39 g (0.24 mol, 1.0 equivalent) of diethoxymethyl (vinyl) silane prepared in step 4 was slowly added. The solution was refluxed for 8 hours to obtain 75 g of a compound of the following chemical formula (yield: 94%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．１１（３Ｈ）、０．３４（３Ｈ）、０．９６（２Ｈ）、０．９９（２Ｈ）、１．１１（９Ｈ）、３．６１（２Ｈ）、３．６６（４Ｈ）、７．２１（３Ｈ）、７．５９（２Ｈ）．
実施例４：１−（（ビシクロヘプテニル）エトキシメチルシリル）−２−（トリメチルシリル）メタンの製造
段階１． １−（メチルクロロシリル）−２−（トリクロロシリル）メタンの製造
炎で乾燥された５０００ｍＬシュレンクフラスコにマグネシウム（Ｍｇ） ３４．３７ｇ（１．４１ｍｏｌ、１．３当量）とＴＨＦ １００ｍＬとを添加した後、６０℃に昇温した。反応溶液に（クロロメチル）トリクロロシラン ２００ｇ（１．０９ｍｏｌ、１．０当量）とジクロロメチルシラン １８７．６３ｇ（１．６３ｍｏｌ、１．５当量）との混合溶液をゆっくり添加した。反応溶液を６０℃で１０時間攪拌し、濾過した後、ｎ−ペンタン １５００ｍＬで４回洗浄してワークアップした。溶液を減圧処理して溶媒を除去し、３８℃及び０．８Ｔｏｒｒで精製して、無色の液体であるＣｌ_３Ｓｉ−ＣＨ_２−ＳｉＭｅＣｌ（Ｈ） ９９．２０ｇを得た（収率：４０％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.11 (3H), 0.34 (3H), 0.96 (2H), 0.99 (2H), 1.11 (9H), 3.61 (2H), 3.66 (4H), 7.21 (3H), 7.59 (2H).
Example 4: Preparation of 1-((bicycloheptenyl) ethoxymethylsilyl) -2- (trimethylsilyl) methane Step 1. Preparation of 1- (methylchlorosilyl) -2- (trichlorosilyl) methane To a flame-dried 5000 mL Schlenk flask was added 34.37 g (1.41 mol, 1.3 equivalents) of magnesium (Mg) and 100 mL of THF. Thereafter, the temperature was raised to 60.degree. A mixed solution of 200 g (1.09 mol, 1.0 equivalent) of (chloromethyl) trichlorosilane and 187.63 g (1.63 mol, 1.5 equivalents) of dichloromethylsilane was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C. for 10 hours, filtered and worked up by washing four times with 1500 mL of n-pentane. The solution was treated under reduced pressure to remove the solvent, and purified at 38 ° C. and 0.8 Torr to obtain 99.20 g of a colorless liquid, Cl ₃ Si—CH ₂ —SiMeCl (H) (yield: 40%) ).

₁ H-NMR (C ₆ D ₆ ) δ-0.12 (3 H), 0.41 to 0.58 (2 H), 4.78 (1 H).
Stage 2 Preparation of 1- (Ethoxy (methyl) chlorosilyl) -2- (trimethylsilyl) methane 1- (methylchlorosilyl) -2- (trichloro) prepared in 2000 with 2000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After addition of 99.20 g (0.44 mol, 1.0 equivalent) of silyl) methane, while maintaining at 0 ° C., 220.07 g (2.18 mol, 5.0 equivalents) of triethylamine and 100.20 g of ethanol (2 .18 mol, 5.0 equivalents) were slowly added. The reaction solution was heated to room temperature (20 ° C.) and then stirred for 5 hours. The reaction solution is filtered, treated under reduced pressure to remove the solvent, and purified at 42 ° C. and 0.4 Torr to obtain 104.32 g of (EtO) ₃ Si-CH ₂ -SiMe (OEt) (H) which is a colorless liquid. (Yield: 90%).

₁ H-NMR (C ₆ D ₆ ) δ -0.08 to 0.11 (2H), 0.42 (3H), 1.09 to 1.18 (12H), 3.57 to 3.65 (2H) ), 3.71-3.84 (6H), 4.98 (1H).
Step 3. Preparation of 1-((bicycloheptenyl) ethoxymethylsilyl) -2- (trimethylsilyl) methane 1- (Ethoxy (methyl) chlorosilyl) -2- (trimethylsilyl) prepared in step 2 in a flame-dried 1000 mL Schlenk flask ) Methane 104.32 g (0.39 mol, 1.0 equivalent) and dichloro (1,5-cyclooctadiene) platinum (II) as catalyst were added. The temperature of the reaction solution was raised to 60 ° C., and 36.07 g (0.39 mol, 1.0 equivalent) of norbornadiene was slowly added. The solution was stirred at 60 ° C. for 5 hours and then purified at 90 ° C. and 0.23 Torr to obtain 105.29 g of a compound of the following chemical formula as a colorless liquid (yield: 75%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．０１（ｅｘｏ、２Ｈ）、０．０５（ｅｎｄｏ、２Ｈ）、０．２４（ｅｘｏ、３Ｈ）、０．３４（ｅｎｄｏ、３Ｈ）、１．１６〜１．４２（ｅｘｏ、ｅｎｄｏ、２４Ｈ）、３．６５〜３．７９（ｅｘｏ、ｅｎｄｏ、１６Ｈ）、１．１８〜２．１７、２．８０〜３．１２、５．９４〜６．２２（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例５：１−（（２−シクロヘプテニル）エトキシメチルシリル）−２−（メチルジエトキシシリル）メタンの製造
段階１． １−（メチルクロロシリル）−２−（ジクロロメチルシリル）メタンの製造
炎で乾燥された５０００ｍＬシュレンクフラスコにマグネシウム（Ｍｇ） ２８．９９ｇ（１．１９ｍｏｌ、１．３当量）とＴＨＦ １００ｍＬとを添加した後、６０℃に昇温した。反応溶液に（クロロメチル）ジクロロメチルシラン １５０ｇ（０．９２ｍｏｌ、１．０当量）とジクロロメチルシラン １５８．２９ｇ（１．３８ｍｏｌ、１．５当量）との混合溶液をゆっくり添加した。反応溶液を６０℃で１０時間攪拌し、濾過した後、ｎ−ペンタン １５００ｍＬで４回洗浄してワークアップした。溶液を減圧処理して溶媒を除去し、４０℃及び２．８Ｔｏｒｒで精製して無色の液体、ＭｅＣｌ_２Ｓｉ−ＣＨ_２−ＳｉＭｅＣｌ（Ｈ） １２３．８２ｇを得た（収率：６５％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.01 (exo, 2H), 0.05 (endo, 2H), 0.24 (exo, 3H), 0.34 (endo, 3H), 16 to 1.42 (exo, endo, 24H), 3.65 to 3.79 (exo, endo, 16H), 1.18 to 2.17, 2.80 to 3.12, 5.94 to 6. 22 (bicycloheptenyl, 9H).
Example 5 Preparation of 1-((2-Cycloheptenyl) ethoxymethylsilyl) -2- (methyldiethoxysilyl) methane Step 1. Preparation of 1- (methylchlorosilyl) -2- (dichloromethylsilyl) methane To a flame-dried 5000 mL Schlenk flask was added 28.99 g (1.19 mol, 1.3 equivalents) of magnesium (Mg) and 100 mL of THF. After heating, the temperature was raised to 60.degree. A mixed solution of 150 g (0.92 mol, 1.0 equivalent) of (chloromethyl) dichloromethylsilane and 158.29 g (1.38 mol, 1.5 equivalents) of dichloromethyl silane was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C. for 10 hours, filtered and worked up by washing four times with 1500 mL of n-pentane. The solution was treated under reduced pressure to remove the solvent and purified at 40 ° C. and 2.8 Torr to obtain 123.82 g of MeCl ₂ Si—CH ₂ —SiMeCl (H) as a colorless liquid (yield: 65%).

₁ H-NMR (C ₆ D ₆ ) δ-0.18 (3 H), 0.37 (2 H), 0.47 (3 H), 4.83 (1 H).
Stage 2 Preparation of 1- (Ethoxy (methyl) chlorosilyl) -2- (diethoxymethylsilyl) methane 1- (Methylchlorosilyl) -2 prepared in Step 1 with 2000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After the addition of 123.82 g (0.60 mol, 1.0 equivalent) of-(dichloromethylsilyl) methane, 187.05 g (1.85 mol, 3.1 equivalents) of triethylamine and ethanol were maintained while maintaining at 0 ° C. .16 g (1.85 mol, 3.1 equivalents) were slowly added. The reaction solution was heated to room temperature (20 ° C.) and then stirred for 5 hours. The reaction solution was filtered, vacuum treatment to remove the solvent, 76 ° C. and is a colorless liquid was purified by _{0.24Torr Me (EtO) 2 Si-} CH 2 -SiMe (OEt) (H) 119. 85 g were obtained (yield: 85%).

₁ H-NMR (C ₆ D ₆ ) δ-0.08 (2H), 0.17 (3H), 0.38 (3H), 1.13 (12H), 3.61-3.83 (8H) , 4.68 (1 H).
Step 3. Preparation of 1-((2-Cycloheptenyl) ethoxymethylsilyl) -2- (diethoxymethylsilyl) methane 1- (Ethoxy (methyl) chlorosilyl) -2 prepared in step 2 in a flame-dried 1000 mL Schlenk flask 119.85 g (0.51 mol, 1.0 equivalents) of (diethoxymethylsilyl) methane and dichloro (1,5-cyclooctadiene) platinum (II) as catalyst were added. The temperature of the reaction solution was raised to 60 ° C., and 46.70 g (0.51 mol, 1.0 equivalent) of norbornadiene was slowly added. The solution was stirred at 60 ° C. for 5 hours and then purified at 88 ° C. and 0.18 Torr to obtain 116.58 g of a colorless liquid of the following chemical formula (yield: 70%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．０４（ｅｘｏ、２Ｈ）、０．０６（ｅｎｄｏ、２Ｈ）、０．１７（ｅｘｏ、３Ｈ）、０．２５（ｅｎｄｏ、３Ｈ）、１．１４（ｅｘｏ、ｅｎｄｏ、１８Ｈ）、３．５７〜３．６９（ｅｘｏ、ｅｎｄｏ、１２Ｈ）、０．５４、１．７０〜１．８２、２．７９〜２．９４、５．９５〜６．１９（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例６乃至１０：シリコン前駆体（実施例１乃至５）を利用する誘電膜の製造
プラズマ強化化学気相蒸着用チャンバー内に基板を配置した。配置された基板の温度が２００℃になるように昇温し、蒸着工程が終了される時まで基板の温度を２００℃に維持した。実施例１乃至５で製造された化合物を各々シリコン前駆体として使用して、アルゴン（キャリヤーガス、４００ｓｃｃｍ）と共に４７５ｃｃ／ｍｉｎの流量でチャンバー内に供給した。また、反応ガス（酸化剤）として酸素を前記チャンバー内に供給した。酸素は２０ｃｃ／ｍｉｎの流量で供給された。チャンバーの上部電極に１３．５６ＭＨｚ及び５０ＷのＲＦパワーを印加した。チャンバー内の圧力は０．８ｔｏｒｒに調節した。チャンバー内で、予備誘電膜が基板上に蒸着された。

₁ H-NMR (C ₆ D ₆ ) δ-0.04 (exo, 2H), 0.06 (endo, 2H), 0.17 (exo, 3H), 0.25 (endo, 3H), 14 (exo, endo, 18 H), 3.57 to 3.69 (exo, endo, 12 H), 0.54, 1.70 to 1.82, 2.79 to 2.94, 5.95 to 6. 19 (bicycloheptenyl, 9H).
Examples 6 to 10: Fabrication of dielectric film using silicon precursor (Examples 1 to 5) A substrate was placed in a plasma enhanced chemical vapor deposition chamber. The temperature of the disposed substrate was raised to 200 ° C., and the temperature of the substrate was maintained at 200 ° C. until the end of the deposition process. The compounds prepared in Examples 1 to 5 were each supplied as a silicon precursor into a chamber at a flow rate of 475 cc / min with argon (carrier gas, 400 sccm). Further, oxygen was supplied into the chamber as a reaction gas (oxidant). Oxygen was supplied at a flow rate of 20 cc / min. 13.56 MHz and 50 W RF power was applied to the upper electrode of the chamber. The pressure in the chamber was adjusted to 0.8 torr. In the chamber, a preliminary dielectric film was deposited on the substrate.

The substrate on which the preliminary dielectric film was formed was heat-treated at 500 ° C. for 2 hours (N ₂ , 15 SLM), or the temperature of the substrate was raised to 400 ° C., followed by UV curing treatment for 10 minutes. Porogen groups in the pre-dielectric film were removed through such energy processing to produce a porous dielectric film.

  The dielectric constant and the Young's modulus of each of the dielectric films (Examples 6 to 10) manufactured using the compounds manufactured in Examples 1 to 5 were measured. Furthermore, the chemical structure of the dielectric film (Examples 6 to 10) was analyzed using an infrared spectrophotometer. In the infrared spectrophotometer analysis, the thickness of the dielectric films (Examples 6 to 10) are all similarly adjusted to 400 nm, and the thickness of the dielectric films (Examples 6 to 10) uses an Ellipsometer. Measured. In addition, the carbon content of the dielectric films (Examples 6 to 10) was measured using X-ray photoelectron spectroscopy (XPS).

  The first dielectric film (Example 6) manufactured using the silicon precursor of Example 1 was confirmed to have a dielectric constant of 2.32 and a Young's modulus of 8.59 GPa. The carbon content of the first dielectric film was 25 at%, the average size of the pores was 1.4 nm, the full width at half maximum of the pore size distribution was 0.45 nm, and the porosity was 22%.

  The second dielectric film (Example 7) manufactured using the silicon precursor of Example 2 was confirmed to have a dielectric constant of 2.38 and a Young's modulus of 7.95 GPa. The carbon content of the second dielectric film was 30 at%, the average size of the pores was 1.8 nm, the full width at half maximum of the pore size distribution was 0.65 nm, and the porosity was 28%.

  The third dielectric film (Example 8) manufactured using the silicon precursor of Example 3 was confirmed to have a dielectric constant of 2.40 and a Young's modulus of 7.86 GPa. The carbon content of the third dielectric film was 20 at%, the average size of the pores was 1.2 nm, the full width at half maximum of the pore size distribution was 0.55 nm, and the porosity was 17%.

  Furthermore, the pore size distribution for the third dielectric film (Example 8) was measured and is shown in FIG. Referring to FIG. 10, the full width at half maximum of the pore size distribution curve was about 0.55 nm. That is, it can be confirmed that very small and uniform pores are formed in the third dielectric film.

  The fourth dielectric film (Example 9) manufactured using the silicon precursor of Example 4 was confirmed to have a dielectric constant of 2.35 and a Young's modulus of 9.85 GPa. The carbon content of the fourth dielectric film was 27 at%, the average size of the pores was 1 nm, the full width at half maximum of the pore size distribution was 0.35 nm, and the porosity was 25%.

The fifth dielectric film (Example 10) manufactured using the silicon precursor of Example 5 was confirmed to have a dielectric constant of 2.41 and a Young's modulus of 7.75 GPa. The carbon content of the fifth dielectric film was 20 at%, the average size of the pores was 1.5 nm, the full width at half maximum of the pore size distribution was 0.55 nm, and the porosity was 20%.
On the other hand, the infrared spectrophotometer analysis results of the first to fifth dielectric films (Examples 6 to 10) are shown in Table 1 below.

表１に示したように、本発明の実施形態に係る誘電膜（実施例６乃至１０）の場合、熱処理又は紫外線硬化処理を通じて予備誘電膜の分子内のポロゲン基が除去されることによって、高い気孔率及び低い誘電率を有することを確認した。特に実施例６の誘電膜の場合、低誘電特性及び機械的強度が最も優れていることを確認することができた。これは、実施例１のシリコン前駆体の分子がブリッジカーボン（−ＣＨ_２−）と４つのアルコキシグループとを含み、これによって誘電膜内にＳｉ−Ｏネットワーク構造が相対的に多く形成されることができることによる。したがって、実施例６の誘電膜は高い機械的強度を有することができる。さらに、実施例６の誘電膜はＳｉ−ＣＨ_３結合単位の含量が相対的に高いので、これによるＳｉ−Ｏケージ構造が相対的に多く形成されることができる。したがって、実施例６の誘電膜は低い誘電率を有することができる。

As shown in Table 1, in the case of the dielectric film according to the embodiment of the present invention (Examples 6 to 10), the porogen group in the molecule of the predielectric film is removed through the heat treatment or the ultraviolet curing treatment, so that it is high. It was confirmed to have porosity and low dielectric constant. In particular, in the case of the dielectric film of Example 6, it could be confirmed that the low dielectric characteristics and the mechanical strength were the best. This is because the molecule of the silicon precursor of Example 1 contains bridged carbon (-CH _2- ) and four alkoxy groups, thereby relatively many Si-O network structures are formed in the dielectric film. Depends on what you can do. Therefore, the dielectric film of Example 6 can have high mechanical strength. Further, the dielectric film of Example 6, since a relatively high content of Si-CH ₃ bond units, can be Si-O cage structure by this is relatively much formed. Therefore, the dielectric film of Example 6 can have a low dielectric constant.

In the case of the dielectric film according to the embodiment of the present invention, the content of carbon atoms and oxygen atoms inside is high. That is, in the preliminary dielectric film deposition process can be Si-CH ₃ bond unit is often formed in the preliminary dielectric lining. Si-CH ₃ bond units by cutting the Si-O network structure formed from Si-O bond unit, it is possible to form a nanovoids inside the structure. That is, the Si—O cage structure can be formed while the Si—O network structure is broken by the Si—CH ₃ bonding unit.

Further, the dielectric film according to an embodiment of the present invention is relatively high proportion of Si-CH ₃ bond units / Si-O bond unit. The relatively higher ratio of Si-CH ₃ bonding units / Si-O bonding units results in relatively more Si-CH ₃ bonds in the dielectric film. Therefore, plasma damage is relatively less when forming dielectric interconnections. That is, plasma induced damage can be improved.

The silicon precursor according to the embodiment of the present invention contains a porogen group in its molecule, and can form many Si—O cage structures in the dielectric film. Therefore, a porous dielectric film can be provided without adding an additional pore-forming substance in the dielectric film formation process. Furthermore, the silicon precursor according to the embodiment of the present invention is improved because it has a bridged carbon bond (-(CH ₂ ) _n- ) in its molecule and contains an alkoxy group instead of a plurality of alkyl groups. It can have good thermal stability.

  As a result, the dielectric film manufactured using the silicon precursor of the present invention can have high mechanical strength which can be applied at the same time in the wiring formation process while having a relatively low dielectric constant.

Example 11 Preparation of 1-((bicycloheptenyl) methylmethoxysilyl) -2- (trimethoxysilyl) methane Step 1. Preparation of 1- (methylchlorosilyl) -2- (trichlorosilyl) methane To a flame-dried 5000 mL Schlenk flask was added 34.37 g (1.41 mol, 1.3 equivalents) of magnesium (Mg) and 100 mL of THF. Thereafter, the temperature was raised to 60.degree. A mixed solution of 200 g (1.09 mol, 1.0 equivalent) of (chloromethyl) trichlorosilane and 187.63 g (1.63 mol, 1.5 equivalents) of dichloromethylsilane was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C. for 10 hours, filtered and worked up by washing four times with 1500 mL of n-pentane. The solution was treated under reduced pressure to remove the solvent, and purified at 38 ° C. and 0.8 Torr to obtain 99.20 g of a colorless liquid, Cl ₃ Si—CH ₂ —SiMeCl (H) (yield: 40%) ).

₁ H-NMR (C ₆ D ₆ ) δ-0.12 (3 H), 0.41 to 0.58 (2 H), 4.78 (1 H).
Stage 2 Preparation of 1- (Methoxy (methyl) chlorosilyl) -2- (trimethoxysilyl) methane 1- (methylchlorosilyl) -2-one prepared in step 1 with 2000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After adding 99.20 g (0.44 mol, 1.0 equivalent) of (trichlorosilyl) methane, keeping the temperature at 0 ° C., 220.07 g (2.18 mol, 5.0 equivalents) of triethylamine and 69.85 g of methanol (2.18 mol, 5.0 equivalents) was slowly added. The reaction solution was heated to room temperature (20 ° C.) and then stirred for 5 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, purified at 30 ° C. and 0.46 Torr and the colorless liquid (MeO) ₃ Si-CH ₂ -SiMe (OMe) (H) 82.38 g (Yield: 89%).

₁ H-NMR (C ₆ D ₆ ) δ-0.05 to 0.09 (2 H), 0.31 (3 H), 3.33 to 3.42 (12 H), 4.96 (1 H).
Step 3. Preparation of 1-((bicycloheptenyl) methoxymethylsilyl) -2- (trimethoxysilyl) methane 1- (Methoxy (methyl) chlorosilyl) -2- 2 prepared in step 2 in a flame-dried 1000 mL Schlenk flask 82.38 g (0.39 mol, 1.0 equivalent) of (trimethoxysilyl) methane and dichloro (1,5-cyclooctadiene) platinum (II) as a catalyst were added. The temperature of the reaction solution was raised to 60 ° C., and 36.07 g (0.39 mol, 1.0 equivalent) of norbornadiene was slowly added. The solution was stirred at 60 ° C. for 5 hours and then purified at 64 ° C. and 0.52 Torr to obtain 88.85 g of a compound of the following chemical formula as a colorless liquid (yield: 75%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．０１（ｅｘｏ、ｅｎｄｏ、２Ｈ）、０．２２〜０．３１（ｅｘｏ、ｅｎｄｏ、３Ｈ）、３．３６〜３．４７（ｅｘｏ、ｅｎｄｏ、９Ｈ）、１．０６〜１．９２、２．７８〜２．９８、５．９２〜５．９７（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例１２：１−（（ビシクロヘプテニル）メチルメトキシシリル）−２−（トリメトキシシリル）エタンの製造
段階１． １−（トリクロロシリル）−２−（メチルジクロロシリル）エタンの製造
炎で乾燥された３０００ｍＬシュレンクフラスコにトリクロロビニールシラン ２００ｇ（１．２４ｍｏｌ、１．０当量）と触媒としてヘキサクロロ白金（Ｈ_２Ｃｌ_６Ｐｔ_６Ｈ_２Ｏ）とを添加した後、反応溶液を６０℃に昇温した。反応溶液にジクロロメチルシラン １５６．７ｇ（１．３６ｍｏｌ、１．１当量）をゆっくり添加した。この混合溶液を８時間還流してＭｅＣｌ_２Ｓｉ−ＣＨ_２ＣＨ_２−ＳｉＣｌ_３ ３８４．８１ｇを得た（収率：９８％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.01 (exo, endo, 2H), 0.22 to 0.31 (exo, endo, 3H), 3.36 to 3.47 (exo, endo, 9H), 1.06 to 1.92, 2.78 to 2.98, 5.95 to 5.97 (bicycloheptenyl, 9H).
Example 12 Preparation of 1-((Bicycloheptenyl) methylmethoxysilyl) -2- (trimethoxysilyl) ethane Step 1. Preparation of 1- (trichlorosilyl) -2- (methyldichlorosilyl) ethane 200 g (1.24 mol, 1.0 equivalents) of trichlorovinylsilane in a flame-dried 3000 mL Schlenk flask and hexachloroplatinum (H ₂ Cl ₆ ) as a catalyst After adding Pt ₆ H ₂ O), the reaction solution was heated to 60 ° C. To the reaction solution, 156.7 g (1.36 mol, 1.1 equivalents) of dichloromethylsilane was slowly added. This mixed solution was refluxed for 8 hours to obtain a _{MeCl 2 Si-CH 2 CH 2} -SiCl 3 384.81g ( yield: 98%).

₁ H-NMR (C ₆ D ₆ ) δ-0.21 (3H), 0.86 (2H), 1.06 (2H).
Stage 2 Preparation of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) ethane 1- (trichlorosilyl) prepared in step 1 with 3000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After adding 384.81 g (1.39 mol, 1.0 equivalent) of -2- (methyl dichloro silyl) ethane, and maintaining 0 ° C, 501.87 g (11.13 mol, 8.0 equivalents) of dimethylamine Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 3 hours. The reaction solution was filtered and treated under reduced pressure to remove the solvent to obtain 367.88 g of colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ CH ₂ —Si (NMe ₂ ) ₂ Cl ₂ (yield : 85%).

₁ H-NMR (C ₆ D ₆ ) δ -0.07 (3H), 0.78 to 0.91 (4H), 2.45 (24H).
Step 3. Preparation of 1- (bis (dimethylamino) silyl) -2- (bis (dimethylamino) methylsilyl) ethane Add 15.71 g (0.41 mol, 0.35 equivalents) of LiAlH ₄ to a flame-dried 2000 mL Schlenk flask After that, 500 mL of THF was slowly added while maintaining -30.degree. While maintaining the reaction solution at -30 ° C, 357.88 g (1.18 mol, 1.0 of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) ethane prepared in Step 2 ) Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered, treated under reduced pressure to remove the solvent, and purified at 73 ° C. and 1.66 Torr to obtain Me (NMe ₂ ) ₂ Si—CH ₂ CH ₂ —Si (NMe ₂ ) ₂ which is a colorless liquid. There were obtained 245.36 g of H (yield: 75%).

₁ H-NMR (C ₆ D ₆ ) δ − 0.10 (3 H), 0.69 (4 H), 2.47 (12 H), 2.52 (12 H), 4.59 (1 H).
Step 4. Preparation of 1- (diethoxysilyl) -2- (diethoxy (methyl) silyl) ethane 1- (bis (dimethylamino) silyl) prepared in step 3 with 1000 mL n-pentane in a flame-dried 3000 mL Schlenk flask After the addition of 245.36 g (0.89 mol, 1.0 equivalent) of -2- (bis (dimethylamino) methylsilyl) ethane, 113.7 g (3.55 mol, 4.0) of methanol was maintained while maintaining 0 ° C. ) Was slowly added. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution was filtered, the solvent was removed under reduced pressure treatment to obtain a colorless liquid _{Me (MeO) 2 Si-CH} 2 CH 2 -Si (OMe) 2 H 104.16g ( yield: 87%).

₁ H-NMR (C ₆ D ₆ ) δ -0.08 (3 H), 0.80 (4 H), 3.48 to 3.68 (12 H), 4.78 (1 H).
Step 5. Preparation of 1-((2-Cycloheptenyl) dimethoxysilyl) -2- (methyldimethoxysilyl) ethane 1- (Dimethoxysilyl) -2- (dimethoxy (methyl) prepared in step 4 in a flame-dried 1000 mL Schlenk flask ) Silyl) ethane 104.16 g (0.46 mol, 1.0 eq.) And dichloro (1,5-cyclooctadiene) platinum (II) as catalyst were added. The temperature of the reaction solution was raised to 60 ° C., and 42.77 g (0.46 mol, 1.0 equivalent) of norbornadiene was slowly added. The mixed solution was stirred at 60 ° C. for 5 hours and then purified at 88 ° C. and 0.18 Torr to obtain 104.84 g of a compound of the following chemical formula (yield: 72%) as a colorless liquid.

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．０８（３Ｈ）、０．８５〜０．９２（４Ｈ）、３．６６〜３．７５（１２Ｈ）、０．５２〜３．１２、５．８８〜６．１０（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実施例１３：１−（（ビシクロヘプテニル）ジメトキシシリル）−２−（メチルジメトキシシリル）メタンの製造
段階１． １−（トリクロロシリル）−２−（メチルジクロロシリル）メタンの製造
炎で乾燥された５０００ｍＬシュレンクフラスコにアセトニトリル（Ａｃｅｔｏｎｉｔｒｉｌｅ）１５００ｍＬと（クロロメチル）ジクロロメチルシラン ５００ｇ（３．０６ｍｏｌ、１．０当量）とを添加した後、７０℃に昇温した。反応溶液にトリエチルアミン ３４０．３７ｇ（３．３６ｍｏｌ、１．１当量）とを添加した後、７０℃を維持したまま、トリクロロシラン ４５５．６１ｇ（３．３６ｍｏｌ、１．１当量）をゆっくり添加した。反応溶液を７０℃で５時間攪拌し、濾過した後、ｎ−ペンタン １５００ｍＬで４回洗浄してワークアップした。溶液を減圧処理して溶媒を除去し、２８℃／１．０１Ｔｏｒｒで精製して、無色の液体であるＭｅＣｌ_２Ｓｉ−ＣＨ_２−ＳｉＣｌ_３ １６０．５４ｇを得た（収率：２０％）。

₁ H-NMR (C ₆ D ₆ ) δ-0.08 (3H), 0.85 to 0.92 (4H), 3.66 to 3.75 (12H), 0.52 to 3.12, 5 88 to 6.10 (bicycloheptenyl, 9H).
Example 13 Preparation of 1-((Bicycloheptenyl) dimethoxysilyl) -2- (methyldimethoxysilyl) methane Step 1. Preparation of 1- (trichlorosilyl) -2- (methyldichlorosilyl) methane 1500 mL of acetonitrile (Acetonitrile) and 500 g (3.06 mol, 1.0 equivalents) of (chloromethyl) dichloromethylsilane in a flame-dried 5000 mL Schlenk flask And the temperature was raised to 70.degree. After 340.37 g (3.36 mol, 1.1 equivalents) of triethylamine was added to the reaction solution, 455.61 g (3.36 mol, 1.1 equivalents) of trichlorosilane was slowly added while maintaining 70 ° C. The reaction solution was stirred at 70 ° C. for 5 hours, filtered and worked up by washing four times with 1500 mL of n-pentane. The solution was treated under reduced pressure to remove the solvent and purified at 28 ° C./1.01 Torr to obtain 160.54 g of MeCl ₂ Si—CH ₂ —SiCl _{3 as} a colorless liquid (yield: 20%).

₁ H-NMR (C ₆ D ₆ ) δ-0.38 (3H), 0.69 (2H).
Stage 2 Preparation of 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) methane 1- (trichlorosilyl) prepared in step 1 with 3000 mL n-pentane in a flame-dried 5000 mL Schlenk flask After adding 160.54 g (0.61 mol, 1.0 equivalent) of -2- (methyldichlorosilyl) methane, 330.84 g (7.34 mol, 12.0 equivalents) of diethylamine was added while maintaining 0 ° C. Added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 3 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, purified at 78 ° C. and 0.8 Torr, and colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ —Si (NMe ₂ ) ₂ Cl 163.48 g was obtained (yield: 90%).

₁ H-NMR (C ₆ D ₆ ) δ-0.18 (3H), 0.30 (2H), 2.43 to 2.47 (24H).
Step 3. Preparation of 1- (bis (dimethylamino) silyl) -2- (bis (dimethylamino) methylsilyl) methane Add 7.31 g (0.19 mol, 0.35 equivalents) of LiAlH ₄ to a flame-dried 1000 mL Schlenk flask After that, 300 mL of THF was slowly added while maintaining -30.degree. While maintaining the temperature of the reaction solution at -30 ° C, 163.48 g (0.55 mol, 1- (bis (dimethylamino) chlorosilyl) -2- (bis (dimethylamino) methylsilyl) methane produced in Step 2 .0 equivalents) was added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, purified at 56 ° C. and 0.5 Torr, and colorless liquid Me (NMe ₂ ) ₂ Si—CH ₂ —Si (NMe ₂ ) ₂ H 108.38 g was obtained (yield: 75%).

₁ H-NMR (C ₆ D ₆ ) δ -0.04 (2H), 0.16 (3H), 2.44 to 2.48 (24H), 4.48 (1H).
Step 4. Preparation of 1- (Dimethoxysilyl) -2- (dimethoxy (methyl) silyl) methane 1- (Bis (dimethylamino) silyl)-prepared in step 3 with 1000 mL n-pentane in a flame-dried 3000 mL Schlenk flask After adding 108.38 g (0.41 mol, 1.0 equivalent) of 2- (bis (dimethylamino) methylsilyl) methane, 52.87 g (1.65 mol, 4.0 equivalents) of methanol was maintained while maintaining 0 ° C. ) Was added slowly. The reaction solution was warmed to room temperature (20 ° C.) and stirred for 5 hours. The reaction solution is filtered and treated under reduced pressure to remove the solvent, and purified at 46 ° C. and 0.48 Torr to obtain Me (MeO) ₂ Si—CH ₂ —Si (OMe) ₂ H 78. which is a colorless liquid. 49 g were obtained (yield: 91%).

₁ H-NMR (C ₆ D ₆ ) δ -0.07 (2H), 0.21 (3H), 3.35 to 3.38 (9H), 4.82 (1H).
Step 5. Preparation of 1-((bicycloheptenyl) dimethoxysilyl) -2- (methyldimethoxysilyl) methane 1- (Dimethoxysilyl) -2- (dimethoxy (methyl) prepared in step 4 in a flame-dried 1000 mL Schlenk flask ) Silyl) methane 78.49 g (0.37 mol, 1.0 equivalent) and the catalyst dichloro (1,5-cyclooctadiene) platinum (II) were added. After the reaction solution was heated to 60 ° C., 34.38 g (0.37 mol, 1.0 equivalent) of norbornadiene was slowly added. The solution was stirred at 60 ° C. for 5 hours and then purified at 93 ° C. and 0.56 Torr to obtain 87.30 g of a compound of the following chemical formula as a colorless liquid (yield: 78%).

_１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ−０．０４（ｅｘｏ、ｅｎｄｏ、２Ｈ）、０．２５〜０．２７（ｅｘｏ、ｅｎｄｏ、３Ｈ）、３．３４〜３．４０（ｅｘｏ、ｅｎｄｏ、９Ｈ）、０．６１〜１．８９、２．７８〜３．０８、５．９５〜６．１６（ｂｉｃｙｃｌｏｈｅｐｔｅｎｙｌ、９Ｈ）．
実験例１
実施例４で製造された化合物と実施例１１で製造された化合物の蒸気圧を測定して、図９に示した。

₁ H-NMR (C ₆ D ₆ ) δ-0.04 (exo, endo, 2H), 0.25 to 0.27 (exo, endo, 3H), 3.34 to 3.40 (exo, endo, 9H), 0.61 to 1.89, 2.78 to 3.08, 5.95 to 6.16 (bicycloheptenyl, 9H).
Experimental Example 1
The vapor pressures of the compound produced in Example 4 and the compound produced in Example 11 were measured and are shown in FIG.

  Referring to FIG. 9, it is confirmed that the compound of Example 11 in which the alkoxy group in the molecule is a methoxy group has a vapor pressure higher than the compound of Example 4 in which the alkoxy group in the molecule is an ethoxy group. be able to. That is, when the alkoxy group in the silicon precursor is a methoxy group, the vapor pressure is relatively high, so it was confirmed that the dielectric film deposition step is more chemically stable.

Examples 14 to 16: Preparation of dielectric film using silicon precursor (Example 11) Except using the compound prepared in Example 11 as a silicon precursor, the same procedure as in Examples 6 to 10 was made. The dielectric film was manufactured in the same manner as described. On the other hand, in the case of energy treatment, heat treatment was performed for 2 hours. Here, the temperature of the heat treatment was changed to 500 ° C. (Example 14), 550 ° C. (Example 15), and 600 ° C. (Example 16) to manufacture each dielectric film.

  The dielectric film of Example 14 was confirmed to have a ratio of Si-O cage / Si-O network of 0.61. Furthermore, the dielectric film of Example 14 was confirmed to have a dielectric constant of 2.46 and a Young's modulus of 6.87 GPa.

  The dielectric film of Example 15 was confirmed to have a ratio of Si-O cage / Si-O network of 0.65. Furthermore, it was confirmed that the dielectric film of Example 15 had a dielectric constant of 2.25 and a Young's modulus of 11.2 GPa.

  The dielectric film of Example 16 was confirmed to have a ratio of Si-O cage / Si-O network of 0.75. Furthermore, it was confirmed that the dielectric film of Example 16 has a dielectric constant of 2.3 and a Young's modulus of 12.5 GPa.

  In the silicon precursor of Example 11, the alkoxy group in the molecule is a methoxy group. As can be confirmed in Examples 14 to 16, when the dielectric film is manufactured using a silicon precursor containing a methoxy group, the higher the heat treatment temperature, the more the Si--O cage / Si--O in the dielectric film. It can be confirmed that the ratio of the network increases. In particular, it can be confirmed that the heat treatment temperature of 550 ° C. exhibits the most excellent dielectric strength and the excellent mechanical strength (Example 15).

Experimental Example 2
The dielectric film (Example 9) using the silicon precursor of Example 4 is shown in Table 2 below in comparison with Example 15. The silicon precursor of Example 11 contains a methoxy group instead of an ethoxy group as compared to the silicon precursor of Example 4. On the other hand, the carbon, oxygen and silicon contents of the dielectric films (Examples 9 and 11) were measured using X-ray photoelectron spectroscopy (XPS) and the results are shown in Table 3 below.

表２を参照すると、メトキシ基を有する実施例１１のシリコン前駆体を利用する場合、エトキシ基を有する実施例４のシリコン前駆体を利用する場合より、誘電膜内Ｓｉ−Ｏケージ／Ｓｉ−Ｏネットワークの比率がさらに高いことを確認することができる。先に説明したように、Ｓｉ−Ｏケージはその内部にナノボイドを含むので、その比率が高いほど、低い誘電率を達成することができる。

Referring to Table 2, when the silicon precursor of Example 11 having a methoxy group is used, Si--O cage / Si--O in the dielectric film is used compared to the case of using the silicon precursor of Example 4 having an ethoxy group. It can be confirmed that the ratio of the network is higher. As explained above, since the Si-O cage contains nanovoids inside, the higher the ratio, the lower dielectric constant can be achieved.

  The silicon precursor of Example 11 having a methoxy group has a lower carbon content than the silicon precursor of Example 4 having an ethoxy group. However, referring to Table 3, the carbon content of the dielectric film using the silicon precursor of Example 11 (Example 15) is higher than that of the dielectric film using the silicon precursor of Example 4 (Example 9). Can be confirmed. Therefore, the dielectric film of Example 15 can achieve lower dielectric constant and higher mechanical strength than the dielectric film of Example 9.

Examples 17-19 Preparation of dielectric film using silicon precursor (Example 13) A substrate was placed in a chamber for plasma enhanced chemical vapor deposition. The temperature of the substrate placed was raised to 250 ° C., and the temperature of the substrate was maintained at 250 ° C. until the end of the deposition process. The compound prepared in Example 13 was used as a silicon precursor and supplied into the chamber at a flow rate of 475 cc / min with argon (carrier gas, 400 sccm). In addition, oxygen was supplied into the chamber as a reaction gas (oxidant). Oxygen was supplied at a flow rate of 30 cc / min. 13.56 MHz and 50 W RF power was applied to the upper electrode of the chamber. The pressure in the chamber was adjusted to 1 Torr. In the chamber, a preliminary dielectric film was deposited on the substrate. The substrate on which the preliminary dielectric film was formed was heat-treated at 550 ° C. for 2 hours (N ₂ , 15 SLM) to produce a porous dielectric film (Example 17).

  At the time of preliminary dielectric film deposition, the temperature of the substrate is 180 ° C., the flow rate of reaction gas oxygen is 25 cc / min, and the pressure of the chamber is 1.5 Torr, as described in Example 17 above. A porous dielectric film (Example 18) was prepared in the same manner as that described above.

  At the time of preliminary dielectric film deposition, the flow rate of reactive gas oxygen is 25 cc / min, and the pressure of the chamber is 1.5 Torr, the porosity is the same as that described in Example 17 above. A dielectric film (Example 19) was produced.

  At the time of preliminary dielectric film deposition, the temperature of the substrate is 200 ° C., the flow rate of reaction gas oxygen is 25 cc / min, and at the time of energy processing, the temperature of the substrate is raised to 400 ° C. A porous dielectric film (Example 20) was prepared in the same manner as described above in Example 17 with the exception of utilizing.

  The dielectric film of Example 17 was confirmed to have a ratio of Si-O cage / Si-O network of 0.75. Furthermore, it was confirmed that the dielectric film of Example 17 has a dielectric constant of 2.3 and a Young's modulus of 11.0 GPa.

  The dielectric film of Example 18 was confirmed to have a ratio of Si-O cage / Si-O network of 0.8. Furthermore, the dielectric film of Example 18 was confirmed to have a dielectric constant of 2.4 and a Young's modulus of 15 GPa.

  The dielectric film of Example 19 was confirmed to have a ratio of Si-O cage / Si-O network of 0.82. Furthermore, the dielectric film of Example 19 was confirmed to have a dielectric constant of 2.4 and a Young's modulus of 14 GPa.

  The dielectric film of Example 20 was confirmed to have a ratio of Si-O cage / Si-O network of 0.85. Furthermore, the dielectric film of Example 20 was confirmed to have a dielectric constant of 2.2 and a Young's modulus of 12.3 GPa.

  FIGS. 3, 5, and 7 are plan views for explaining a method of manufacturing a semiconductor device according to an embodiment of the present invention. 4A, 6A, and 8A are cross-sectional views taken along the line II 'of FIGS. 3, 5, and 7, respectively, and FIGS. 4B, 6B, and 8B are FIG. It is sectional drawing in alignment with the II-II 'line | wire of FIG.

  Referring to FIGS. 3, 4A and 4B, an integrated circuit IC is formed on a substrate 100. The substrate 100 is a semiconductor substrate containing silicon, germanium, silicon-germanium or the like, or a compound semiconductor substrate.

  Forming an integrated circuit IC includes forming a plurality of transistors TR. Specifically, the element isolation film ST defining the active region is formed. A capping pattern CP is formed on the active region to cover the gate electrode GE, the gate dielectric film GI interposed between the gate electrode GE and the substrate 100, and the top surface of the gate electrode GE. Impurity regions DR are formed on both sides of the gate electrode GE. The impurity region DR is formed by doping the substrate 100 with an impurity.

  Subsequently, the first insulating film 110 and the second insulating film 120 covering the transistor TR are formed on the entire surface of the substrate 100. The second insulating film 120 directly covers the first insulating film 110. The second insulating film 120 may be formed using the method for forming a low dielectric film according to the embodiment of the present invention described above with reference to FIGS. 1A and 2. Therefore, the second insulating film 120 is a porous SiOCH film. The first insulating film 110 is also a porous SiOCH film formed using the method described above with reference to FIGS. 1A and 2. Alternatively, the first insulating film 110 may be a silicon oxide film formed using another known silicon precursor.

  Referring to FIGS. 5, 6A and 6B, the second insulating layer 120 is patterned to form a wiring hole IH extended in the second direction D2. At least one wiring hole IH includes a vertically extending hole VPH extended toward the substrate 100. That is, when the second insulating film 120 is patterned, a part of the first insulating film 110 is patterned together. As an example, the vertical extension holes VPH penetrate the first insulating film 110 to expose a part of the impurity region DR. As another example, the vertical extension holes VPH may penetrate the first insulating layer 110 to expose a portion of the top surface of the gate electrode GE.

  The second insulating film 120 according to an embodiment of the present invention may have relatively high mechanical strength. Therefore, the second insulating film 120 does not collapse during the patterning process of the wiring holes IH having a high pattern density, and the structure can be maintained.

  Referring to FIGS. 7, 8A and 8B, interconnections ML filling interconnection holes IH are respectively formed. Specifically, first, a barrier film filling the wiring holes IH is formed on the entire surface of the substrate 100. The barrier film fills only a part of the wiring hole IH. The barrier film can comprise Ti, TiN, or a combination thereof.

  Subsequently, a conductive film is formed on the entire surface of the substrate 100 on the barrier film. The conductive film completely fills the wiring hole IH. The conductive film is formed using a metal such as copper (Cu) or tungsten (W). As one example, the conductive film is formed in a plating process. First, a seed layer (not shown) is formed on the barrier film. The conductive film is plated using the seed layer as a seed.

  The conductive film and the barrier film are planarized to form the interconnection ML and the barrier pattern BP in the interconnection hole IH. Therefore, the upper surface of the wiring ML is coplanar with the upper surface of the second insulating film 120.

  Since interconnection ML has a relatively high pattern density, high parasitic capacitance occurs between them. The larger the parasitic capacitance between the interconnections ML, the larger the RC delay (delay) of the semiconductor device. On the other hand, the second insulating film 120 according to the embodiment of the present invention has a low dielectric constant which is a porous film. Therefore, the parasitic capacitance generated between interconnections ML can be effectively reduced.

  Although not shown, additional insulating films and wires may be stacked on the second insulating film 120, but this is not particularly limited.

Hereinafter, the embodiments will be specifically listed.
(1) containing a silicon precursor having a compound of the following chemical formula 1,
Composition for forming a low dielectric film wherein the ratio of Si-CH ₃ bonding units / Si-O bonding units is 0.5 to 5:

前記化学式１で、ｎは、１又は２の整数であり、
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_５、及びＲ_６の中で少なくとも２つは、−Ｏ−Ｒ_７であり、残りは、各々独立して水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、又は（Ｃ１−Ｃ１０）アルコキシであり、
Ｒ_７は、水素、（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）アルケニル又は（Ｃ３−Ｃ１０）アルキニルであり、
Ｒ_４は、ポロゲン基（ｐｏｒｏｇｅｎ ｇｒｏｕｐ）であり、（Ｃ３−Ｃ１０）アルケニル、（Ｃ３−Ｃ１０）アルキニル、（Ｃ３−Ｃ１０）アリール、（Ｃ３−Ｃ１０）ヘテロアリール、（Ｃ３−Ｃ１０）シクロアルキル、（Ｃ３−Ｃ１０）シクロアルケニル、（Ｃ３−Ｃ１０）シクロアルキニル、（Ｃ３−Ｃ１０）ヘテロシクロアルキル、（Ｃ３−Ｃ１０）アリール（Ｃ１−Ｃ１０）アルキル、（Ｃ３−Ｃ１０）シクロアルキル（Ｃ１−Ｃ１０）アルキル又は（Ｃ３−Ｃ１０）ヘテロシクロアルキル（Ｃ１−Ｃ１０）アルキルである、
組成物。

In the above Chemical Formula 1, n is an integer of 1 or 2,
At least two of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are —O—R ₇ and the rest are each independently hydrogen, (C 1 -C 10) alkyl, (C 3 -C 10) C10) alkenyl, (C3-C10) alkynyl, or (C1-C10) alkoxy,
R ₇ is hydrogen, (C 1 -C 10) alkyl, (C 3 -C 10) alkenyl or (C 3 -C 10) alkynyl,
R ₄ is a porogen group and is (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) Alkyl or (C 3 -C 10) heterocycloalkyl (C 1 -C 10) alkyl,
Composition.

  (2) The aryl, the heteroaryl, the cycloalkyl, the cycloalkenyl, the cycloalkynyl and the heterocycloalkyl are each unsubstituted or independently (C1-C10) alkyl, (C3-C10) The composition according to (1), which is substituted with one or more selected from the group consisting of alkenyl, (C3-C10) alkynyl, (C1-C10) alkoxy, halogen, cyano, nitro and hydroxyl.

(3) wherein said heteroaryl and said heterocycloalkyl, NR 8 each independently _-, - include O- and one or more heteroatoms selected from the group consisting of -S-, R ₈ is hydrogen or The composition as described in (1) or (2) which is (C1-C10) alkyl.

(4) at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are (C 1 -C 5) alkoxy, and the remainder is (C 1 -C 5) alkyl, (1) The composition as described in any one of-(3).

(5) At least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are methoxy, and the remainder is (C 1 -C 5) alkyl, of (1) to (4) The composition according to any one.

(6) R ₄ is 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3- Hexenyl group, 4-hexenyl group, 5-hexenyl group, phenyl group, xylene group, cyclopropyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group , Cycloheptaden group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, pentene The composition according to any one of (1) to (5), which is an oxide group, a terpinene group, a limonene group, butadiene oxide, styrene or fulvene.

(7) The composition according to any one of (1) to (6), wherein the vapor pressure of the compound is 0.1 Torr to 100 Torr at 100 ° C.
(8) The composition according to any one of claims 1 to 7, wherein the carbon content of the low dielectric film is 1 at% to 40 at%.
(9) The composition according to any one of (1) to (8), wherein the average diameter of the pores of the low dielectric film is 0.5 nm to 5 nm.
(10) The composition according to any one of (1) to (9), wherein the total volume of pores of the low dielectric film is 8% to 35% of the total volume of the low dielectric film.
(11) The composition according to any one of (1) to (10), wherein the pore diameter distribution of the low dielectric film has a full width at half maximum of 0.1 nm to 2.5 nm. object.
(12) The composition according to any one of (1) to (11), wherein the low dielectric film has a dielectric constant of 2.2 to 3.
(13) The composition according to any one of (1) to (12), wherein the low dielectric film has a Young's modulus of 6 GPa to 15 GPa.
(14) The composition according to any one of (1) to (13), wherein the low dielectric film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.

(15) forming a silicon insulating film on a substrate using a silicon precursor having a molecule of Si— (CH ₂ ) _n —Si structure;
Forming at least one wire in the silicon insulating film,
N is an integer of 1 or 2;
The silicon precursor has, in its molecule, a porogen group which bonds to any one of Si atoms,
The silicon precursor has, in its molecule, two or more (C1-C5) alkoxy groups bonded to Si atoms,
The porogen group is (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3-C10) The manufacturing method of the semiconductor element which is heterocycloalkyl (C1-C10) alkyl.

(16) The method for producing a semiconductor device according to (15), wherein the silicon insulating film has a ratio of Si—CH ₃ bonding unit / Si—O bonding unit of 0.5 to 5.
(17) The method for manufacturing a semiconductor device according to (15) or (16), wherein the silicon insulating film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.
(18) The method for manufacturing a semiconductor device according to any one of (15) to (17), wherein the silicon insulating film has a dielectric constant of 2.2 to 3 and a Young's modulus of 6 GPa to 15 GPa.

(19) Forming the at least one wire is:
Patterning the silicon insulating film to form at least one wiring hole in the silicon insulating film;
Forming a conductive film filling the at least one wiring hole,
The manufacturing method of the semiconductor element as described in any one of (15)-(18).
(20) The method of manufacturing a semiconductor device according to (19), wherein forming the at least one wiring further includes forming a barrier film that fills the at least one wiring hole.

100 substrate 110 first insulating film 120 second insulating film 200 chamber 210 plate 220 upper electrode 230 high frequency generator DL dielectric film DP vapor deposition step DR impurity region ET energy processing GE gate electrode PDL preliminary dielectric film SG source gas ST element isolation film

Claims (20)

Comprising a silicon precursor having a compound of Formula 1
Composition for forming a low dielectric film wherein the ratio of Si-CH ₃ bonding units / Si-O bonding units is 0.5 to 5:

In the above Chemical Formula 1, n is an integer of 1 or 2,
At least two of R ₁ , R ₂ , R ₃ , R ₅ , and R ₆ are —O—R ₇ and the rest are each independently hydrogen, (C 1 -C 10) alkyl, (C 3 -C 10) C10) alkenyl, (C3-C10) alkynyl, or (C1-C10) alkoxy,
R ₇ is hydrogen, (C 1 -C 10) alkyl, (C 3 -C 10) alkenyl or (C 3 -C 10) alkynyl,
R ₄ is a porogen group and is (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) Alkyl or (C 3 -C 10) heterocycloalkyl (C 1 -C 10) alkyl,
Composition.   The aryl, the heteroaryl, the cycloalkyl, the cycloalkenyl, the cycloalkynyl and the heterocycloalkyl are each unsubstituted or each independently (C1-C10) alkyl, (C3-C10) alkenyl, The composition according to claim 1, which is substituted by one or more selected from the group consisting of C3-C10) alkynyl, (C1-C10) alkoxy, halogen, cyano, nitro and hydroxyl. Wherein said heteroaryl and said heterocycloalkyl, NR 8 each independently _-, - include O- and one or more heteroatoms selected from the group consisting of -S-, R ₈ is hydrogen or (C1- The composition according to claim 1 or 2, which is C10) alkyl. 4. At _{least two of} R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are (C 1 -C 5) alkoxy, and the remainder is (C 1 -C 5) alkyl. The composition according to any one of the preceding claims. The compound according to any one of claims 1 to 4, wherein at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are methoxy and the remainder is (C 1 -C 5) alkyl. Composition as described. R ₄ represents 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group Group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, phenyl group, xylene group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group, cyclohepta group Den group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, pentenoxy The composition according to any one of claims 1 to 5, which is a do group, a terpinene group, a limonene group, butadiene oxide, styrene or fulvene.   The composition according to any one of claims 1 to 6, wherein the vapor pressure of the compound is 0.1 Torr to 100 Torr at 100C.   The composition according to any one of claims 1 to 7, wherein the carbon content of the low dielectric film is 1 at% to 40 at%.   The composition according to any one of claims 1 to 8, wherein an average diameter of pores of the low dielectric film is 0.5 nm to 5 nm.   The composition according to any one of claims 1 to 9, wherein the total volume of pores of the low dielectric film is 8% to 35% of the total volume of the low dielectric film.   The composition according to any one of claims 1 to 10, wherein the diameter distribution of the pores of the low dielectric film has a full width at half maximum of 0.1 nm to 2.5 nm.   The composition according to any one of claims 1 to 11, wherein the low dielectric film has a dielectric constant of 2.2 to 3.   The composition according to any one of claims 1 to 12, wherein the low dielectric film has a Young's modulus of 6 GPa to 15 GPa.   The composition according to any one of claims 1 to 13, wherein the low dielectric film has a ratio of Si-O cage structure / Si-O network structure of 0.5 to 1. Forming a silicon insulating film on a substrate using a silicon precursor having molecules of Si— (CH ₂ ) _n —Si structure;
Forming at least one wire in the silicon insulating film,
N is an integer of 1 or 2;
The silicon precursor has, in its molecule, a porogen group which bonds to any one of Si atoms,
The silicon precursor has, in its molecule, two or more (C1-C5) alkoxy groups bonded to Si atoms,
The porogen group is (C3-C10) alkenyl, (C3-C10) alkynyl, (C3-C10) aryl, (C3-C10) heteroaryl, (C3-C10) cycloalkyl, (C3-C10) cycloalkenyl, (C3-C10) cycloalkynyl, (C3-C10) heterocycloalkyl, (C3-C10) aryl (C1-C10) alkyl, (C3-C10) cycloalkyl (C1-C10) alkyl, or (C3-C10) Heterocycloalkyl (C 1 -C 10) alkyl,
Method of manufacturing a semiconductor device The silicon insulating film, the ratio of Si-CH ₃ bond units / Si-O bond units is 0.5 to 5, The method according to claim 15.   17. The method of claim 15, wherein the silicon insulating film has a ratio of Si—O cage structure / Si—O network structure of 0.5 to 1.   The method for manufacturing a semiconductor device according to any one of claims 15 to 17, wherein the silicon insulating film has a dielectric constant of 2.2 to 3 and a Young's modulus of 6 to 15 GPa. Forming the at least one wire is:
Patterning the silicon insulating film to form at least one wiring hole in the silicon insulating film;
Forming a conductive film filling the at least one wiring hole,
The manufacturing method of the semiconductor element as described in any one of Claims 15-18.   The method of claim 19, wherein forming the at least one wire further comprises forming a barrier film filling the at least one wire hole.

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