KR101780977B1 - Silicon precursor, method for Preparation of the Same, and a silicon-containing dielectric film manufactured thereby - Google Patents

Abstract

The present invention relates to a silicon precursor, a process for producing the same, and a process for producing a silicon-containing dielectric film using the silicon precursor. The silicon precursor has high volatility and exhibits excellent cohesion and high deposition rate even at low temperatures, And more particularly, to a method for producing a silicon-containing dielectric film having remarkably improved mechanical strength and dielectric constant.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon precursor, a method of manufacturing the same, and a method of manufacturing a silicon-containing dielectric film using the silicon precursor,

The present invention relates to a silicon precursor, a process for producing the silicon precursor, and a process for producing a silicon-containing dielectric film using the same.

The demand for high speed and high integration of semiconductor devices has led to a rapid decrease in the wiring line width of semiconductor devices. However, the decrease in the wiring line width in such an ultra large scale integrated circuit semiconductor device leads to an increase in the RC delay represented by the capacitance (C) between the metal lines and the resistance (R) of the line metal, There is a problem of lowering the speed. To solve this problem, there was an effort to replace aluminum, which was a conventional wiring metal, with a material having a lower resistivity. In 1997, IBM released a microprocessor using copper as a wiring material, thereby solving the resistance problem of the wiring metal. However, in the case of capacitance, a silicon oxide film, which is a conventional insulator, has a dielectric constant of about 4.0, which can not prevent mutual interference between wirings due to an increase in capacitance due to a decrease in wiring width. It has been progressed.

In order to apply such an interlayer insulating material to an actual semiconductor process, it is necessary to satisfy not only low permittivity but also many integration characteristics. It is necessary to satisfy the requirements for electrical isotropy for ease of wiring design and process, low reactivity with metal wiring material, low ionic conductivity, and chemical mechanical polishing (CMP). With regard to the thermal characteristics, the copper wiring process requires thermal conductivity close to the thermal conductivity (12.0 mW / cm ° C) of the silicon oxide film in order to maintain thermal stability at temperatures up to 400 ° C and to facilitate heat emission during operation of the device , And should have a low thermal expansion coefficient (< 10 ppm / DEG C) that can suppress the change of the film with temperature change.

In addition, electrical characteristics require low leakage current and high dielectric breakdown voltage. They must have adhesive strength and crack resistance that minimizes various stress and peeling that may occur at the interface with other materials, and hygroscopicity Should be low. In unit process suitability, polishability should be maintained during the CMP process with moderate strength. Among these properties, the development of ultra-low dielectric constant films with high modulus of 5 to 6 GPa or more, which can withstand these processes, has been an issue with regard to the suitability for mechanical polishing processes such as CMP process. When the porosity is lowered, the mechanical strength is lower than 5 GPa.

Research and development and commercialization of Dow Chemical, Applied Materials, Rohm & Haas, JSR Micro, ASM, Allied Signal, etc. have been proceeding with the necessity of development of ultra low dielectric material mentioned above. Of these, Dow Chemical's SiLK ™ has been developed over the years, and SilKTM has exceeded 50 ppm / ° C coefficient of thermal expansion (CTE) in addition to its mechanical strength. . Dow Chemical has continued to develop the SiLK series that improved the CTE since IBM abandoned the process due to the CTE problem of SiLKTM. Recently, SiLKTM, a so-called SilK Y resin with a pore size of about 1.8 nm and a dielectric constant of 2.2 . However, the porous SiLKTM has a low modulus of elasticity of 3.0 GPa and the thermal expansion coefficient of the film is still as high as 40 ppm / ° C.

However, Fujitsu, Sony and Toshiba in Japan are known to mass-produce SiLKTM thin films, and these companies adopt a hybrid structure of CVD and SOD films for integration. Most other companies are developing low-k materials by changing their structure to MSQ (methylsilsesquioxane) based materials. Rohm and Haas, JSR Micro, Allied Signal, etc., And has a modulus of elasticity of 3 GPa in a range of dielectric constant 2.1 to 2.3. In the case of the CVD method, Applied Materials' Black Diamond (CDO) material and the Aurora RULK with a dielectric constant of 2.6 ~ 2.7 are mentioned, and all have elastic modulus between 8 GPa. In Korea, an ultra-low dielectric film using cyclodextrin having an alkyl or acetyl group at the terminal of Samsung type was prepared, and an organosilicate matrix was prepared by LG Chem to manufacture a nanoporous organosilicate. However, recently, There is little research on this.

In this regard, the present inventors have completed the present invention to provide a novel silicon precursor, a method for producing the same, and a method for producing a porous low-k dielectric film having remarkably improved mechanical strength and dielectric constant using the silicon precursor.

Korean Patent No. 589123 Korean Patent No. 595526 Korean Patent No. 672905

An object of the present invention is to provide a silicon precursor having high volatility and excellent cohesion and a high deposition rate even at a low temperature and a method for producing the same.

It is another object of the present invention to provide a method for producing a silicon-containing dielectric film in which mechanical strength and dielectric constant are remarkably improved by using the silicon precursor.

The present invention provides a silicon precursor represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

And n is an integer of 2 or 3.]

According to an embodiment of the present invention, the silicon precursor may be represented by the following general formula (2).

(2)

[In the formula (2)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

And n is an integer of 2 or 3.]

According to one embodiment of the present invention, each of R ₂ to R ₄ may independently be (C 1 -C ₂ ) alkyl.

According to an embodiment of the present invention, the formula (1) may be selected from the following structures.

The present invention provides a process for preparing a compound represented by the following formula (5): a) reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) And b) reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (1); Containing precursor. &Lt; RTI ID = 0.0 &gt; A &lt; / RTI &gt;

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

HOR ₂

(7)

M (OR ₂ )

[Chemical Formula 1]

[In the formulas (1) and (3) to (7)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

X is halogen;

M is Li, Na or K;

M is an integer of 0 or 1;

And n is an integer of 2 or 3.]

The present invention relates to a process for preparing a compound represented by the following formula (A): A) reacting a compound represented by the following formula (3) with a compound represented by the following formula (6) or a compound represented by the following formula (7) B) reacting a compound represented by the following formula (4) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (9) And C) reacting a compound represented by the following formula (8) with a compound represented by the following formula (9) to prepare a compound represented by the following formula (1); Wherein the silicon precursor is a silicon precursor.

(3)

[Chemical Formula 4]

[Chemical Formula 6]

HOR ₂

(7)

M (OR ₂ )

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 1]

[In the formulas (1), (3), (4) and (6) to (9)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

X is halogen;

M is Li, Na or K;

M is an integer of 0 or 1;

And n is an integer of 2 or 3.]

Said step a) according to an embodiment of the present invention is carried out in the presence of a catalyst, wherein the catalyst is _{H 2 PtCl 6, PdCl 2 (} NC-C 4 H 9) 2, Pt [P (C 4 H 9) 3 ] ₄ , Rh (acac) ₃ , Co ₂ (CO) ₈ , Ni ⁰ or Cr (CO) ₆ .

The present invention provides a method for producing a silicon-containing dielectric film using the silicon precursor.

In accordance with an embodiment of the present invention, the silicon-containing dielectric layer may be deposited using a plasma enhanced chemical vapor deposition process.

According to one embodiment of the present invention, the energy of the plasma enhanced chemical vapor deposition process is selected from the group consisting of plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, and remote plasma Lt; / RTI &gt;

According to an embodiment of the present invention, the deposition conditions include a Si compound at a flow rate of 10 to 1000 cc / min, a porogen flow rate of 0 to 1000 cc / min, an oxidant flow rate of 1 to 1000 cc / min, a pressure of 0.5 to 10 torr, A power of 30 to 1000 W and a substrate temperature of 200 to 400 캜.

According to an embodiment of the present invention, the silicon-containing dielectric layer may be formed by a curing process after deposition to remove porogen and form a porous dielectric layer.

According to an embodiment of the present invention, the curing process may be performed by UV light irradiation, e-beam irradiation, heat treatment, or a combination thereof.

According to one embodiment of the present invention, the porous dielectric layer may have a dielectric constant in the range of 2.0 to 5.0.

The present invention provides a silicon-containing dielectric film produced by the above-described method for producing a silicon-containing dielectric film.

The silicon precursor according to the present invention is advantageous in that it has excellent thermal stability, high volatility and high reactivity, has a rapid deposition rate and is easy to deposit, and has excellent cohesion and excellent step coverage.

The silicon-containing dielectric film produced using the silicon precursor according to the present invention has high purity and excellent physical and electrical characteristics.

In addition, the silicon-containing dielectric film has both mechanical strength and low thermal expansion coefficient while maintaining a low dielectric constant.

1 is a thermogravimetric analysis (TGA) of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane, Me ₂ (EtO) SiCH ₂ CH ₂ Si (OEt) ₂ Ph prepared in Example 1, Fig.
2 is a graph showing a vapor pressure curve of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane, Me ₂ (EtO) SiCH ₂ CH ₂ Si (OEt) ₂ Ph prepared in Example 1 to be.

Hereinafter, a silicon precursor according to the present invention, a method for producing the same, and a method for producing a silicon-containing dielectric film using the same will be described in detail. Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

The present invention provides a silicon precursor represented by the following general formula (1), which has excellent volatility and has a high cohesive strength and a high deposition rate even at a low temperature.

[Chemical Formula 1]

[In the above formula (1)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

And n is an integer of 2 or 3.]

&Quot; Alkyl &quot;, &quot; alkenyl &quot; and &quot; alkynyl &quot;, as used in the present invention, are hydrocarbons including both linear and branched forms. The term &quot; alkenyl &quot; means a hydrocarbon containing at least one double bond, and the term &quot; alkynyl &quot; means a hydrocarbon containing at least one triple bond.

The silicon precursor includes a structure of - (CH ₂ ) _n -, so that the mechanical strength of the silicon-containing dielectric film employing the structure can be improved. Further, by controlling the kind of the substituent of the phenyl group, it is possible to produce a porous low dielectric film having excellent pore characteristics.

In terms of having a low thermal expansion coefficient in the above formula (1), preferably, each of R ₂ to R ₄ may independently be (C 1 -C ₂ ) alkyl.

The silicon precursor may be a silicon precursor represented by the following general formula (2).

(2)

[In the formula (2)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

And n is an integer of 2 or 3.]

The silicon precursor represented by Formula 2 has high thermal stability and low activation energy, and is excellent in reactivity and does not generate non-volatile byproducts. A silicon-containing thin film having a high purity and a silicon-containing dielectric film can be easily formed.

 The silicon precursor represented by Formula 1 may be selected from the following structures in order to have high thermal stability and reactivity, but is not limited thereto.

The present invention provides a process for preparing a compound represented by the following formula (5): a) reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) And b) reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (1); Containing precursor. &Lt; RTI ID = 0.0 &gt; A &lt; / RTI &gt;

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

HOR ₂

(7)

M (OR ₂ )

[Chemical Formula 1]

[In the formulas (1) and (3) to (7)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

X is halogen;

M is Li, Na or K;

M is an integer of 0 or 1;

And n is an integer of 2 or 3.]

The a) step is carried out in the presence of a catalyst, wherein the catalyst is _{H 2 PtCl 6, PdCl 2 (} NC-C 4 H 9) 2, Pt [P (C 4 H 9) 3] 4, Rh (acac) 3, Co ₂ (CO) ₈ , Ni ^0, or Cr (CO) ₆ , preferably H ₂ PtCl ₆ (hexachloroplatinum).

The silicon-containing precursor represented by formula (1) according to the present invention can be obtained by reacting a compound represented by the following formula (3) with a compound represented by the following formula (6) or a compound represented by the following formula (7) Producing; B) reacting a compound represented by the following formula (4) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (9) And C) reacting a compound represented by the following formula (8) with a compound represented by the following formula (9) to prepare a compound represented by the following formula (1); Wherein the silicon precursor is a silicon precursor.

(3)

[Chemical Formula 4]

[Chemical Formula 6]

HOR ₂

(7)

M (OR ₂ )

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 1]

[In the formulas (1), (3), (4) and (6) to (9)

R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;

X is halogen;

M is Li, Na or K;

M is an integer of 0 or 1;

And n is an integer of 2 or 3.]

The C) step is carried out in the presence of a catalyst, wherein the catalyst is _{H 2 PtCl 6, PdCl 2 (} NC-C 4 H 9) 2, Pt [P (C 4 H 9) 3] 4, Rh (acac) 3, Co ₂ (CO) ₈ , Ni ^0, or Cr (CO) ₆ , preferably H ₂ PtCl ₆ (hexachloroplatinum).

The present invention also provides a method for producing a silicon-containing dielectric film using the silicon precursor. By using the silicon precursor according to the present invention having excellent thermal stability and high volatility, a silicon-containing dielectric film can be manufactured quickly and easily. At this time, it is preferable that the silicon-containing dielectric film is deposited using a plasma enhanced chemical vapor deposition (CVD) method, and the energy of the plasma enhanced chemical vapor deposition method is plasma, pulsed plasma, helicon plasma, high density plasma, A plasma, and a remote plasma.

The conditions for the deposition may include a Si compound at a flow rate of 10 to 1000 cc / min, a porogen flow rate of 0 to 1000 cc / min, an oxidant flow rate of 1 to 1000 cc / min, and a pressure of 0.5 to 1000 cc / min depending on the type or characteristics of the silicon- 10 Torr, RF power 30 to 1000 W, or substrate temperature 200 to 400 占 폚.

The silicon-containing dielectric layer may include the silicon precursor, the oxidizing agent and the porogen uniformly distributed on the substrate.

At this time, the substrate may be a substrate including at least one semiconductor material of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP, a silicon on insulator (SOI) substrate, a quartz substrate, The substrate may be a rigid substrate or may be formed of a material such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC) , Polyethersulfone (PES), and polyester (Polyester), but the present invention is not limited thereto. In addition, the silicon-containing dielectric layer may be formed with a plurality of conductive layers, a dielectric layer, or an insulating layer between the substrate and the dielectric layer, in addition to forming a dielectric layer directly on the substrate.

Also, the oxidizing agent may be O ₂ , O ₃ , N ₂ O, CO ₂ or a mixture thereof, and the porogen means a material capable of forming pores on the substrate. Specific examples of the porogen include an epoxy group Cyclohexane, toluene, norbornene, terpinene, xylene and branched poly (p-xylene), which are non-linear hydrocarbon compounds, Linear polybutadiene, branched polyethylene, poly (ethylene terephthalate) ("PET"), Polyamide-6,6 "Nylon 6/6 &quot;, syndiotactic polystyrene (PS-syn), polycaprolactone (PCL), poly (propylene oxide) poly (propylene oxide): "PPO"), polycarbonates, poly (phenyl polyamideimide ("PAI"), polyphthalamide ("PPA", "Amodel"), polymethylstyrene ("PMS"), polyetheretherketone polyetheretherketone ("PEEK"), poly (ether sulfone) "PES", poly (etherketone) "PEK", polyoxymethylene " ), Poly (butylene terephthalate): "PBT"), polystyrene ("PS"), poly (norbornene), cetyltrimethylammonium bromide "PEO-b-PPO-b-PEO"), poly (ethylene oxide-b-propylene oxide-b-ethylene oxide) And cyclodextrin ("CD"), but is not limited thereto.

The silicon-containing dielectric layer containing the porogen can form pores by removing the porogen through a curing process, and the dielectric constant can be lowered by the pores. The curing process may be performed by UV light irradiation, e-beam irradiation, heat treatment, or a combination thereof. The curing process may be appropriately controlled depending on the type and characteristics of the dielectric layer. In order to improve the dielectric characteristics, the curing process is preferably performed by a heat treatment. In this case, the heat treatment may be performed at a temperature of 200 to 700 ° C. In order to optimize the low dielectric constant and mechanical strength characteristics of the thin film, 600 &lt; 0 &gt; C.

The dielectric constant and modulus of elasticity of the silicon-containing dielectric film can be appropriately adjusted according to the substrate temperature during deposition according to an embodiment of the present invention, and a silicon-containing low dielectric constant film having a uniform thickness can be formed even at a substrate temperature of 300 ° C or lower And more preferably 200 to 300 ° C.

That is, the dielectric film from which porogen is removed by the above method can be converted into a porous low dielectric film. The dielectric constant of the porous low-k film may range from 2.0 to 5.0, preferably 2.0 to 3.0.

The present invention provides a silicon-containing dielectric film produced by the above-described method for producing a silicon-containing dielectric film. At this time, the silicon-containing dielectric film may be a low dielectric film having a dielectric constant in the range of 2.0 to 5.0.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto.

All compound examples below were carried out in an inert argon or nitrogen atmosphere using a glove box or a Schlenk line and the product was analyzed by ¹ H Nuclear Magnetic Resonance (NMR) and thermogravimetric analysis, TGA).

[Example 1] Preparation of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane

(a) Preparation of 1- (Dichlorophenylsilyl) -2- (dimethylchlorosilyl) ethane

After adding 100 g (0.5 mol, 1.0 equivalent) of dichlorophenylsilane and hexachloroplatinum (H ₂ Cl ₆ Pt ₆ H ₂ O) as a catalyst to a flame-dried 3000 mL Schlenk flask, the reaction solution was heated to 60 ° C., 71.53 g (0.59 mol, 1.05 eq) of chlorovinylsilane was slowly added. This mixed solution was refluxed for 8 hours to obtain 159.7 g (yield: 95%) of 1- (dichlorophenylsilyl) -2- (dimethylchlorosilyl) ethane.

^{_{1 H NMR (C 6 D 6}} ): δ 0.09 (6H), 0.82 (2H), 1.21 (2H), 7.11 (3H), 7.15 (2H).

(b) Preparation of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane

To a flame-dried 5000 mL Schlenk flask, 3000 mL of pentane and 159.7 (0.54 mol, 1.0 equivalent) of 1- (dichlorophenylsilyl) -2- (dimethylchlorosilyl) ethane obtained were added thereto, g (1.64 mol, 3.05 eq.) was added thereto. After 75.4 g (0.54 mol, 3.05 eq.) of ethanol was slowly added, the reaction solution was slowly warmed to room temperature and stirred for 12 hours. The solvent was removed from the reaction solution under reduced pressure and then purified at 114 ° C / 0.9 torr to obtain 105 g of a colorless liquid, Me ₂ (OEt) SiCH ₂ CH ₂ Si (OEt) ₂ Ph (yield: 60%).

¹ H NMR (C ₆ D ₆ ):? 0.03 (6H), 0.73 (2H), 0.94 (2H), 1.13 (3H), 1.62 (6H), 3.47 , 7.79 (2H).

1 shows the thermogravimetric analysis (TGA) of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane (Me ₂ (EtO) SiCH ₂ CH ₂ Si (OEt) ₂ Ph) prepared in Example 1 (Diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane (Me ₂ (EtO) SiCH ₂ CH (CH 3) 2) prepared in Example 1 was confirmed to have high thermal stability as shown in FIG. ₂ Si (OEt) ₂ Ph), the vapor pressure of the silicon precursor prepared by the above method was confirmed to be high.

[Example 2] Preparation of 1- (diethoxyphenylsilyl) -2- (dimethylethoxysilyl) ethane

A) In a flame-dried 3000 mL Schlenk flask, 1500 mL of pentane and 100 g (0.83 mol, 1.0 equivalent) of dimethylchlorovinylsilane were added and 68.8 g (0.87 mol, 1.05 equivalent) of pyridine was added 40.1 g (0.87 mol, 1.05 eq) of ethanol are slowly added. The reaction solution was heated to room temperature, stirred for 12 hours, and then purified at 100 ° C to obtain 75.6 g (yield: 70%) of a colorless liquid, Me ₂ Si (OEt) (CHCH ₂ ).

^{_{1 H NMR (C 6 D 6}} ): δ 0.14 (6H), 1.22 (3H), 3.83 (2H), 5.1 ~ 5.4 (3H).

B) To a flame-dried 3000 mL Schlenk flask, 1500 mL of pentane and 100 g (0.56 mol, 1.0 equivalent) of dichlorophenylsilane were added and 90.8 g (1.148 mol, 2.05 equivalent) of pyridine was added 52.9 g (1.148 mol, 2.05 eq) of ethanol were slowly added. The reaction solution was heated to room temperature, stirred for 12 hours, and then the solvent was removed under reduced pressure. The solvent was then purified at 198 ° C to obtain 76.96 g of a colorless liquid, HSi (OEt) ₂ Ph (yield: 70%).

^{_{1 H NMR (C 6 D 6}} ): δ 1.12 (6H), 3.75 (4H), 5.18 (1H), 7.19 (3H), 7.72 (2H).

C) a catalyst to the flame-dried 3000 mL Herr Lenk flask hexachloro-platinum (diethoxy phenyl silane, HSi (OEt) arid then obtained followed by the addition of _{H 2 Cl 6 Pt6H 2 O)} 2 Ph 76.96 g (0.39 mol, 1 After the temperature was raised to 60 ° C, 51.06 g (0.39 mol, 1 equivalent) of dimethylethoxyvinylsilane, Me ₂ Si (OEt) (CHCH ₂ ) was added slowly. The mixed solution was refluxed for 8 hours and the reaction solution was purified at 14 ° C / 0.9 torr to obtain a colorless liquid, Me ₂ (OEt) SiCH ₂ CH ₂ Si (OEt) ₂ Ph, 1- (diethoxyphenylsilyl) - (dimethylethoxysilyl) ethane (yield: 99.7%).

¹ H NMR (C ₆ D ₆ ):? 0.03 (6H), 0.73 (2H), 0.94 (2H), 1.13 (3H), 1.62 (6H), 3.47 , 7.79 (2H).

[Example 3] Production of silicon-containing dielectric film

A chamber for plasma enhanced chemical vapor deposition (CVD) was used to form the silicon-containing dielectric film. After the substrate was supplied into the chamber, the temperature of the substrate was raised to 200 占 폚, and maintained at 200 占 폚 until the reaction was completed. After supplying the substrate, the silicon precursor (Me ₂ (OEt) SiCH ₂ CH ₂ Si (OEt) ₂ Ph) prepared in Example 1 of the present invention as an organic silicon precursor was mixed with argon (100 sccm) at 400 cc / min Was fed into the chamber at a flow rate.

The silicon precursor (Me ₂ (OEt) SiCH ₂ CH ₂ Si (OEt) ₂ Ph) prepared in Example 1 of the present invention was supplied and a 50 W plasma was supplied. O ₂ was used as the oxidizing agent, the supply flow rate of O ₂ was 25 cc / min, and the chamber pressure of Example 1 was 0.8 torr.

The deposited dielectric film was annealed at 500 ° C for 2 hours (N ₂ , 15 SLM) to remove the porogen, thereby preparing a porous low dielectric film.

The dielectric constant of the porous low-k dielectric film prepared in Example 1 is 2.47 and the modulus of elasticity (E) is 5.59 GPa.

[Example 4] Production of silicon-containing dielectric film

A porous low-k film was prepared in the same manner as in Example 3, except that the substrate temperature was changed to 250 ° C in Example 3.

The dielectric constant of the porous low-k dielectric film prepared in Example 4 is 2.65 and the modulus of elasticity (E) is 6.10 GPa.

[Example 5] Production of silicon-containing dielectric film

A porous low dielectric film was prepared in the same manner as in Example 3, except that the substrate temperature was changed to 300 ° C in Example 3.

The dielectric constant of the porous low-k dielectric film prepared in Example 5 is 2.89 and the modulus of elasticity (E) is 6.05 GPa.

That is, when a silicon-containing dielectric film is manufactured using the silicon precursor according to the present invention, excellent mechanical strength and low dielectric characteristics can be effectively achieved even at a low temperature of 200 to 300 ° C., It is possible to confirm that it has a dielectric property.

Claims (15)

1. A silicon precursor represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;
And n is an integer of 2 or 3.] The method according to claim 1,
A silicon precursor represented by the following formula (2).
(2)

[In the formula (2)
R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;
And n is an integer of 2 or 3.] The method according to claim 1,
Wherein each of R ₂ to R ₄ is independently (C 1 -C ₂ ) alkyl. The method according to claim 1,
Wherein said formula (1) is selected from the following structures.

a) reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And
b) reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (1); &Lt; / RTI &gt;
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]
HOR ₂
(7)
M (OR ₂ )
[Chemical Formula 1]

[In the formulas (1) and (3) to (7)
R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;
X is halogen;
M is Li, Na or K;
M is an integer of 0 or 1;
And n is an integer of 2 or 3.] A) reacting a compound represented by the following formula (3) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (8)
B) reacting a compound represented by the following formula (4) with a compound represented by the following formula (6) or a compound represented by the following formula (7) to prepare a compound represented by the following formula (9) And
C) reacting a compound represented by the following formula (8) with a compound represented by the following formula (9) to prepare a compound represented by the following formula (1); &Lt; / RTI &gt;
(3)

[Chemical Formula 4]

[Chemical Formula 6]
HOR ₂
(7)
M (OR ₂ )
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 1]

[In the formulas (1), (3), (4) and (6) to (9)
R ₁ to R ₆ are each independently hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkenyl or (C 1 -C 10) alkynyl;
X is halogen;
M is Li, Na or K;
M is an integer of 0 or 1;
And n is an integer of 2 or 3.] 7. A compound according to any one of claims 5 and 6,
The step a) or C) step is carried out in the presence of a catalyst, wherein the catalyst is _{H 2 PtCl 6, PdCl 2 (} NC-C 4 H 9) 2, Pt [P (C 4 H 9) 3] 4, Rh ( acac) ₃ , Co ₂ (CO) ₈ , Ni ^0, or Cr (CO) ₆ . A process for producing a silicon-containing dielectric film produced by using the silicon precursor according to claim 1. 9. The method of claim 8,
Wherein the silicon-containing dielectric film is deposited using a plasma enhanced chemical vapor deposition process. 10. The method of claim 9,
Wherein the energy of the plasma enhanced chemical vapor deposition process is selected from the group consisting of plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, and remote plasma. 10. The method of claim 9,
The conditions for the deposition are as follows: a Si compound is introduced at a flow rate of 10 to 1000 cc / min, a flow rate of a porogen of 10 to 1000 cc / min, an oxidant flow rate of 1 to 1000 cc / min, a pressure of 0.5 to 10 torr, To &lt; RTI ID = 0.0 &gt; 400 C. &lt; / RTI &gt; 9. The method of claim 8,
Wherein the silicon-containing dielectric layer has a porosity removal and a porous dielectric layer through a curing process after deposition. 13. The method of claim 12,
Wherein the curing process is performed by UV light irradiation, e-beam irradiation, heat treatment, or a combination thereof. 13. The method of claim 12,
Wherein the porous dielectric film is a porous low dielectric film having a dielectric constant in the range of 2.0 to 5.0. delete

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