TW201833368A - Methods of forming a dielectric layer and methods of fabricating a semiconductor device - Google Patents

Abstract

A method of forming a dielectric layer includes forming a preliminary dielectric layer on a substrate using a silicon precursor and performing an energy treatment on the preliminary dielectric layer to form a dielectric layer. In the dielectric layer, a ratio of Si-CH3 bonding unit to Si-O bonding unit ranges from 0.5 to 5.

Description

Method of forming dielectric layer and method of manufacturing semiconductor device

Some example embodiments of the present invention are directed to a semiconductor device and a method of fabricating the same, and more particularly to a method of forming a low-k dielectric layer using a hafnium precursor and a method of fabricating a semiconductor device using the method.

Semiconductor devices are an important component in the electronics industry due to their relatively small size, versatility, and/or relatively low cost characteristics. Generally, a semiconductor device is classified into a memory device for storing data, a logic device for processing data, and a hybrid device for performing various functions.

With the development of the electronics industry, there is an increasing demand for semiconductor devices having higher buckling density and higher performance. In order to meet this demand, it is necessary to reduce the process margin (for example, in the lithography process). Although many studies have been conducted to overcome this difficulty, reducing the process margin has caused several difficulties in the manufacture of semiconductor devices.

Some example embodiments of the inventive concept provide a method of forming a low-k dielectric layer having a relatively low dielectric constant and relatively high mechanical strength.

Some example embodiments of the inventive concept provide a method of fabricating a semiconductor device configured such that a parasitic capacitance of its interconnect line is relatively low.

According to some example embodiments of the inventive concepts, a method of forming a dielectric layer includes forming an initial dielectric layer on a substrate using a hafnium precursor containing a compound represented by the following Chemical Formula 1 and performing energy treatment on the initial dielectric layer to form Dielectric layer. In the dielectric layer, the ratio of the Si-CH ₃ bonding unit to the Si-O bonding unit is in the range of 0.5 to 5. [Chemical Formula 1]

Wherein in Chemical Formula 1, n is 1 or 2, at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are -OR ₇ and the others are each independently hydrogen, (C ₁ -C ₁₀ ) One of an alkyl group, a (C ₃ -C ₁₀ )alkenyl group, a (C ₃ -C ₁₀ )alkynyl group, and a (C ₁ -C ₁₀ ) alkoxy group, R ₇ is hydrogen, (C ₁ -C ₁₀ )alkyl , (C ₃ -C ₁₀ )alkenyl and one of (C ₃ -C ₁₀ )alkynyl, and R ₄ is a porogen group, including (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ Alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl ( One of C ₁ -C ₁₀ )alkyl and (C ₃ -C ₁₀ )heterocycloalkyl(C ₁ -C ₁₀ )alkyl.

According to some example embodiments of the inventive concepts, a method of forming a dielectric layer includes forming a dielectric layer on a substrate using a hafnium precursor containing a compound represented by the following Chemical Formula 1, [Chemical Formula 1]

Wherein, in Chemical Formula 1, n is 1 or 2, at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are -OR ₇ and the others are each independently hydrogen, (C ₁ -C ₁₀ Alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl and one of (C ₁ -C ₁₀ )alkoxy, R ₇ is hydrogen, (C ₁ -C ₁₀ ) alkane a group of (C ₃ -C ₁₀ )alkenyl and (C ₃ -C ₁₀ )alkynyl, and R ₄ is a porogen group, including (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ ) heteroaryl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl ( C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl(C ₁ -C ₁₀ )alkyl, and (C ₃ -C ₁₀ )heterocycloalkyl(C ₁ -C ₁₀ )alkyl One.

According to some example embodiments of the inventive concepts, a method of forming a dielectric layer includes forming an initial dielectric layer on a substrate using a hafnium precursor containing a compound represented by the following Chemical Formula 1 and performing energy treatment on the initial dielectric layer to form Dielectric layer. The dielectric layer has a Young's modulus in the range of 6 GPa to 15 GPa. [Chemical Formula 1]

Wherein, in Chemical Formula 1, n is 1 or 2, and at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are a methoxy group and the others are each independently hydrogen, (C ₁ - C ₁₀ Alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, and (C ₁ -C ₁₀ )alkoxy, and R ₄ is a porogen group, including (C) _3- C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl (C ₁ -C ₁₀ ) One of an alkyl group, a (C ₃ -C ₁₀ )cycloalkyl (C ₁ -C ₁₀ )alkyl group, and a (C ₃ -C ₁₀ )heterocycloalkyl group (C ₁ -C ₁₀ )alkyl group.

According to some example embodiments of the inventive concepts, a method of fabricating a semiconductor device includes forming a germanium insulating layer on a substrate using a hafnium precursor, the germanium precursor comprising a molecule having a Si—(CH ₂ )n—Si structure, and At least one interconnect line is formed in the tantalum insulating layer. Here, n is 1 or 2, the ruthenium precursor contains a porogen group configured to combine with at least one Si atom in the molecule, and at least two are configured to combine with the Si atom in the molecule (C ₁ -C ₅ ) alkoxy group. The porogen group comprises (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl(C ₁ -C ₁₀ )alkyl, and (C ₃ -C ₁₀ )heterocycloalkyl(C ₁ -C ₁₀ )alkane One of the bases.

According to some example embodiments of the inventive concepts, a method of forming a dielectric layer includes forming a dielectric layer using a hafnium precursor containing a compound represented by the following Chemical Formula 1: [Chemical Formula 1]

Wherein, in Chemical Formula 1, n is 1 or 2, and at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are a methoxy group and the others are each independently hydrogen, (C ₁ - C ₁₀ Alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, and (C ₁ -C ₁₀ )alkoxy, and R ₄ is (C ₃ -C ₁₀ )alkenyl (C ₃ -C ₁₀ )alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ ) Cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl (C ₁ -C ₁₀ ) one of an alkyl group and a (C ₃ -C ₁₀ )heterocycloalkyl (C ₁ -C ₁₀ )alkyl group.

1A and 2 are cross-sectional views illustrating a method of forming a low-k dielectric layer in accordance with example embodiments of the inventive concepts. FIG. 1B is a cross-sectional view schematically illustrating a chamber configured to perform the deposition process of FIG. 1A.

Referring to FIGS. 1A and 1B, an initial dielectric layer PDL may be formed on the substrate 100. The substrate 100 may be a semiconductor substrate formed of or comprising at least one of ruthenium, osmium, iridium-ruthenium or a compound semiconductor material.

First, a hafnium precursor for forming the initial dielectric layer PDL can be prepared. The ruthenium precursor may contain molecules having porogen groups. The porogen group can be combined directly with the ruthenium atom. In detail, the ruthenium precursor may contain a molecule having a structure of Si-(CH ₂ ) _n -Si (where n is 1 or 2), and the porogen group may be directly combined with a ruthenium atom in such a molecule. For example, the ruthenium precursor may contain at least one compound represented by the following Chemical Formula 1. [Chemical Formula 1]

Where n is 1 or 2. At least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are -OR ₇ and the others are independently hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ ) alkene A (C ₃ -C ₁₀ ) alkynyl group or a (C ₁ -C ₁₀ ) alkoxy group. Here, R ₇ is hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )alkenyl or (C ₃ -C ₁₀ )alkynyl. For example, in the case where R ₂ and R _{3 are} each -OR ₇ , the compound can be represented by the following Chemical Formula 2. [Chemical Formula 2]

In Chemical Formula 2, at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are (C ₁ -C ₅ ) alkoxy groups. In other words, in -OR ₇ , R ₇ is (C ₁ -C ₅ )alkyl. In more detail, at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are a methoxy group. Here, the other of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ is (C ₁ -C ₅ )alkyl. In this case, the compound can be represented by the following Chemical Formula 3. [Chemical Formula 3]

In Chemical Formula 3, R ₄ is a porogen group. In detail, R ₄ is (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C _3- C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ ) Aryl (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl(C ₁ -C ₁₀ )alkyl, or (C ₃ -C ₁₀ )heterocycloalkyl (C ₁ -C ₁₀ )alkyl.

Herein, the aryl, heteroaryl, cycloalkyl, cycloalkenyl, cycloalkynyl and heterocycloalkyl are unsubstituted or each independently substituted with one or more selected from the group consisting of: (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, (C ₁ -C ₁₀ )alkoxy, halogen, cyano, nitro and hydroxy. Further, the heteroaryl group and the heterocycloalkyl group each independently comprise one or more hetero atoms selected from the group consisting of -NR ₈ -, -O-, and -S-. Here, R ₈ is hydrogen or (C ₁ -C ₁₀ )alkyl.

For example, R ₄ is 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl- 2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl , 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, phenyl, xylyl, cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, bicycloheptyl, bicycloheptenyl, epoxycyclohexane, Epoxycyclopentyl, terpineyl, limonyl, epoxybutene, styrene or fulvene.

R ₄ may have a cyclic hydrocarbon structure. In detail, R ₄ is (C ₃ -C ₁₀ ) aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl(C ₁ -C ₁₀ )alkyl Or (C ₃ -C ₁₀ )heterocycloalkyl(C ₁ -C ₁₀ )alkyl. In this case, the number of voids formed in the dielectric layer can be increased as will be described below.

The compound of Chemical Formula 1 may have a molecular weight in the range of 100 to 500. The compound of Chemical Formula 1 may have a vapor pressure of from 0.1 Torr to 100 Torr at 100 °C. In other words, the compound of Chemical Formula 1 can have a relatively high vapor pressure, and this makes it possible to perform a chemical vapor deposition (CVD) or an atomic layer deposition (ALD) process more stably. The compound of Chemical Formula 1 can be pyrolyzed under a process condition of from 100 ° C to 500 ° C. In other words, the compound of Chemical Formula 1 does not readily decompose at relatively high temperatures. That is, the compound of Chemical Formula 1 has improved thermal stability.

In an example embodiment, the compound of Chemical Formula 1 may be at least one of the following compounds.

The initial dielectric layer PDL can be formed by a deposition process DP using a hafnium precursor as the source gas SG. The deposition process DP may comprise a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. For example, the CVD process can be a plasma enhanced CVD (PE-CVD) process, and the ALD process can be a plasma enhanced ALD (PE-ALD) process.

In detail, referring back to FIG. 1B, a substrate may be disposed in the chamber 200. For example, chamber 200 can be a plasma chamber. The substrate can be loaded on the sheet 210. In an example embodiment, the sheet 210 can be used as a lower electrode. The sheet 210 can be used to heat the substrate to a temperature of between about 0 °C and 500 °C. For example, the substrate can be heated to a temperature of about 200 °C.

The source gas SG and the reaction gas RG may be supplied into the chamber 200. Here, the source gas SG may be or contain a ruthenium precursor, and the reaction gas RG may be or contain an oxidant. For example, the reaction gas RG may contain at least one of O ₂ , O ₃ , N ₂ O, or CO ₂ . In an example embodiment, the hafnium precursor may be vaporized into a vapor phase in an evaporator, thereby forming a source gas SG. For example, the source gas SG can be formed by heating a ruthenium precursor in an evaporator.

Since the ruthenium precursor has a relatively high vapor pressure as described above, a relatively large amount of ruthenium precursor can be converted to the source gas SG at a predetermined evaporator temperature. Accordingly, a relatively large amount of source gas SG can be easily supplied into the chamber 200, and this can perform the deposition process DP efficiently and stably.

At the same time, the amount of the source gas SG can be changed according to the process conditions of the deposition process DP. For example, in order to increase the amount of the source gas SG, it is necessary to increase the pressure of the source gas SG supplied into the chamber 200. In this regard, the temperature of the evaporator can be increased. In this case, since the thermal stability of the ruthenium precursor is relatively improved, it is possible to substantially suppress or prevent the change in the chemical structure of the ruthenium precursor by increasing the evaporator temperature (for example, increasing to 200 ° C to 500 ° C). Therefore, this can make the initial dielectric layer PDL have a defect-free structure.

The source gas SG may be supplied into the chamber 200 together with a carrier gas supplied to the evaporator. The carrier gas may comprise at least one inert gas (e.g., helium, neon, argon, helium, neon or xenon). The flow rate of the carrier gas can range from 100 cc/min to 800 cc/min, and the flow rate of the reaction gas RG can range from 5 cc/min to 100 cc/min.

During the deposition process DP, the chamber 200 can be controlled to have an internal pressure of 0.1 Torr to 10 Torr. The upper electrode 220 in the chamber 200 can be connected to the RF generator 230. During the deposition process DP, the RF generator 230 can be configured to apply electrical power (eg, 1 W-1000 W power and 5 MHz-20 MHz frequency) to the upper electrode 220.

In the case where the ruthenium precursor is used to form the initial dielectric layer PDL, a porogen group may be present in the initial dielectric layer PDL.

Referring to FIG. 2, the initial dielectric layer PDL may be subjected to energy processing ET to form a dielectric layer DL. The energy treatment ET can include curing the initial dielectric layer PDL using various types of energy, such as thermal or optical energy. For example, the energy treatment ET can be performed using a thermal annealing process or an ultraviolet (UV) curing process.

A thermal annealing process can be performed to heat the substrate in a heat treatment chamber of about 200 ° C to 800 ° C for about 10 minutes to 240 minutes. The thermal annealing process can be carried out at a temperature ranging from about 500 ° C to about 600 ° C. The UV curing process can be performed on the substrate using a UV lamp (applying a power of about 10 W to 200 W) for 0.1 minute to 120 minutes. Here, the temperature of the substrate may range from 0 °C to 700 °C.

The energy treatment ET can remove the porogen groups from the initial dielectric layer PDL. In detail, energy treatment ET may be performed to break the Si-R ₄ bond in the initial dielectric layer PDL, and thereby the porogen group (R ₄ ) may be volatilized and removed from the initial dielectric layer PDL. Removal of the porogen groups can form pores in the dielectric layer DL. In other words, pores may be formed at the position of the porogen group, and thus, the dielectric layer DL may have a porous structure.

A dielectric layer DL having a porosity of 8% to 35% can be formed. Here, the porosity is defined as the ratio of the pore volume to the total volume in the dielectric layer DL. In the dielectric layer DL, pores having an average diameter of about 0.5 nm to 5 nm can be formed. Additionally, the radius profile of the pores may have a Full-Width-at-Half-Maximum (FWHM) selected from the range of about 0.1 nm to 2.5 nm, as shown in FIG. It means that the difference in pore size between the relatively large pores and the relatively small pores may be selected from the range of about 0.1 nm to 2.5 nm. In other words, the pores in the dielectric layer DL may have a uniform size.

The dielectric layer DL may be a low-k dielectric layer having a dielectric constant of 2.2-3. The dielectric layer DL may also have a Young's modulus of about 6 GPa to 15 GPa. In other words, the dielectric layer DL can have not only a porous structure but also high mechanical strength. Meanwhile, in the case where at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ in Chemical Formula 1 are a methoxy group, the dielectric layer DL may have about 6 GPa to 15 GPa (for example, about 8) Young's modulus of GPa-15 GPa).

The dielectric layer DL may contain SiOCH. In this case, the dielectric layer DL may have a carbon content ranging from 1 atomic percent (at%) to 40 at%. The dielectric layer DL may be formed in such a manner that the ratio of the Si—CH ₃ bonding unit to the Si—O bonding unit is in the range of 0.5 to 5. The dielectric layer DL may be formed in such a manner that the ratio of the Si—CH ₃ bonding unit to the Si—O bonding unit is in the range of 1 to 4. In other words, a dielectric layer DL containing a relatively large amount of Si-CH ₃ bonds can be formed. The presence of a Si-CH ₃ bond can contribute to the formation of a Si-O cage structure in the dielectric layer DL. The Si-O cage structure may be a crystal structure containing Si-O bonds arranged in three dimensions around the nanovoids located at the center of the structure. Here, the higher the porosity of the dielectric layer DL, the lower the dielectric constant of the dielectric layer DL. Further, the higher the ratio of the Si—CH ₃ bonding unit to the Si—O bonding unit, the larger the number or density of Si—CH ₃ bonds in the dielectric layer DL. These characteristics of the dielectric layer DL make it possible to prevent or suppress damage to the dielectric layer DL by plasma, which can be used in the process of forming an interconnect structure in the dielectric layer DL. In other words, it is possible to suppress the occurrence of plasma-induced damage in the dielectric layer DL.

In addition to the Si-O cage structure, the anthrone-based structure in the dielectric layer DL may further comprise a Si-O network structure. The Si-O network structure may be a complex network structure containing randomly arranged Si-O bonding units. The presence of the Si-O network structure can contribute to an increase in the mechanical strength of the dielectric layer DL. According to the experimental results obtained by Fourier transform infrared spectroscopy (FT-IR), the peak area of the Si-O network structure (about 1040 cm ^-1 ) is 13 to 16, and the Si-O cage The peak area of the type structure (about 1140 cm ^-1 ) is 7 to 12. Here, the ratio of the Si-O cage structure to the Si-O network structure may be in the range of 0.5 to 1. In more detail, the ratio of the Si-O cage structure to the Si-O network structure may be in the range of 0.6 to 1. In this case, the dielectric layer DL can have both high mechanical strength and low dielectric constant.

Hereinafter, the tantalum precursor and the dielectric layer described with reference to FIGS. 1A and 2 will be described with reference to detailed experimental examples. The compounds in the experimental examples below were analyzed using ₁ H nuclear magnetic resonance (NMR) spectroscopy.

Instance 1 :preparation 1-(( Bicycloheptenyl ) Diethoxydecyl )-2-( Methyldiethoxydecyl ) Methane

Step 1. Preparation of 1-(trichlorodecylalkyl)-2-(methyldichloroindolyl)methane

Acetonitrile (1500 mL) and (chloromethyl)dichloromethylnonane (500 g, 3.06 mol, 1.0 eq.) were added to a flame dried 5000 mL Schlenk flask and heated to 70 °C. Triethylamine (340.37 g, 3.36 mol, 1.1 equivalent) was added to the reaction solution, and then trichloromethane (455.61 g, 3.36 mol, 1.1 eq.) was slowly added to the flask while maintaining the temperature at 70 °C. The reaction solution was stirred at 70 ° C for 5 hours, filtered, and then treated with n-pentane (1500 mL) four times. (: 20% 160.54 g, yield) and the resulting solution to remove the solvent and purified (28 ℃ and at 1.01 torr) to give a colorless MeCl ₂ Si-CH ₂ -SiCl ₃ liquid under reduced pressure.

₁ H-NMR (C ₆ D ₆ ) δ 0.38 (3H), 0.69 (2H).

Step 2. Preparation of 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)methane

3000 mL of n-pentane and 1-(trichlorodecyl)-2-(methyldichlorodecylalkyl)methane (160.54 g, 0.61 mol, 1.0 eq.) prepared in Step 1 were added to the flame dried 5000 In a mL Schlenk bottle, diethylamine (330.84 g, 7.34 mol, 12.0 equivalents) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 3 hours. The reaction solution was filtered under reduced pressure to remove the solvent, and purified at 78 deg.] C and 0.8 torr in the obtained colorless _{Me (NMe 2) 2 Si-} CH 2 -Si (NMe 2) 2 Cl liquid (163.48 g, yield: 90 %).

₁ H-NMR (C ₆ D ₆ ) δ 0.18 (3H), 0.30 (2H), 2.43-2.47 (24H).

Step 3. Preparation of 1-(bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)methane

LiAlH ₄ (7.31 g, 0.19 mol, 0.35 eq.) was added to a flame dried 1000 mL Schlenk bottle, and THF (300 mL) was slowly added to the flask while maintaining the temperature at -30 °C. 1-(Bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)methane (163.48 g, 0.55 mol, 1.0 eq.) prepared in Step 2 was slowly added. Into the flask while maintaining the temperature at -30 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered under reduced pressure to remove the solvent, and purification at 0.5 torr and at 56 ℃ obtain colorless _{Me (NMe 2) 2 Si-} CH 2 -Si (NMe 2) 2 H liquid (108.38 g, yield: 75 %).

₁ H-NMR (C ₆ D ₆ ) δ 0.04 (2H), 0.16 (3H), 2.44-2.48 (24H), 4.48 (1H).

Step 4. Preparation of 1-(diethoxydecyl)-2-(diethoxy(methyl)decylalkyl)methane

1-(Bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)methane (108.38 g, 0.41 mol, 1.0 eq.) and n-pentane prepared in the step 3 Alkane (1000 mL) was added to a flame dried 3000 mL Schlenk bottle, and ethanol (76.07 g, 1.65 mol, 4.0 eq.) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and purified at 46 ° C and 0.6 Torr to obtain a colorless Me(EtO) ₂ Si-CH ₂ -Si(OEt) ₂ H liquid (99.01 g, yield: 90%) .

₁ H-NMR (C ₆ D ₆ ) δ 0.12 (2H), 0.25 (3H), 1.15 (12H), 3.78 (8H), 4.92 (1H).

Step 5. Preparation of 1-((bicycloheptenyl)diethoxydecyl)-2-(methyldiethoxydecyl)methane

1-(Diethoxydecyl)-2-(diethoxy(methyl)decylalkyl)methane (99.01 g, 0.37 mol, 1.0 eq.) prepared in Step 4 and dichloride as a catalyst ( 1,5-cyclooctadiene)platinum (II) was added to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C, and then norbornadiene (34.23 g, 0.37 mol, 1.0 equivalent) was slowly added to the flask. The reaction solution was stirred at 60 ° C for 5 hours and purified at 90 ° C and 0.27 Torr to obtain a colorless liquid compound (99.93 g, yield: 75%) represented by the following formula.

₁ H-NMR(C ₆ D ₆ )δ -0.004 (external, 2H), 0.05 (inner, 2H), 0.16 (external, 3H), 0.24 (inner, 3H), 1.13 (outside, in, 18H), 3.57 -3.67 (outside, inner, 12H), 1.34-1.80, 2.78-2.88, 5.91-6.19 (bicycloheptenyl, 9H).

Instance 2 :preparation 1-(( Bicycloheptenyl ) Diethoxydecyl )-2-( Methyldiethoxydecyl ) Ethane

Step 1. Preparation of 1-(trichlorodecylalkyl)-2-(methyldichlorodecylalkyl)ethane

Trichlorovinyl decane (200 g, 1.24 mol, 1.0 eq.) and chloroplatinic acid (H ₂ Cl ₆ Pt·6H ₂ O) as a catalyst were added to a flame dried 3000 mL Schlenk bottle, and then The reaction solution was heated to 60 °C. Dichloromethyl decane (156.7 g, 1.36 mol, 1.1 equivalent) was slowly added to the reaction solution. The mixed solution was refluxed for 8 hours to obtain MeCl ₂ Si-CH ₂ CH ₂ -SiCl ₃ (384.81 g, yield: 98%).

₁ H-NMR (C ₆ D ₆ ) δ 0.21 (3H), 0.86 (2H), 1.06 (2H).

Step 2. Preparation of 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)ethane

Add 1-(trichloroindolyl)-2-(methyldichlorodecylalkyl)ethane (384.81 g, 1.39 mol, 1.0 eq.) and n-pentane (3000 mL) prepared in Step 1 to a flame. In a dry 5000 mL Schlenk bottle, dimethylamine (501.87 g, 11.13 mol, 8.0 equivalents) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 3 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and then a colorless Me(NMe ₂ ) ₂ Si-CH ₂ CH ₂ -Si(NMe ₂ ) ₂ Cl liquid (367.88 g, yield: 85%) was obtained.

₁ H-NMR (C ₆ D ₆ ) δ 0.07 (3H), 0.78-0.91 (4H), 2.45 (24H).

Step 3. Preparation of 1-(bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)ethane

LiAlH ₄ (15.71 g, 0.41 mol, 0.35 eq.) was added to a flame dried 2000 mL Schlenk bottle, and then THF (500 mL) was slowly added to the flask while maintaining the temperature at -30 °C. 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)ethane (357.88 g, 1.18 mol, 1.0 eq.) prepared in step 2 was slowly Add to the flask while maintaining the temperature at -30 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure, and purified at 73 ° C and 1.66 Torr to give a colorless liquid Me(NMe ₂ ) ₂ Si-CH ₂ CH ₂ -Si(NMe ₂ ) ₂ H (245.36 g, yield: 75%).

₁ H-NMR (C ₆ D ₆ ) δ 0.10 (3H), 0.69 (4H), 2.47 (12H), 2.52 (12H), 4.59 (1H).

Step 4. Preparation of 1-(diethoxydecyl)-2-(diethoxy(methyl)decylalkyl)ethane

1-(Bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)ethane prepared in Step 3 (245.36 g, 0.89 mol, 1.0 eq.) and Pentane (1000 mL) was added to a flame dried 3000 mL Schlenk bottle, and then ethanol (163.48 g, 3.55 mol, 4.0 eq.) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and then a colorless product of Me(EtO) ₂ Si-CH ₂ CH ₂ -Si(OEt) ₂ H (218.99 g, yield: 88%) was obtained.

_{1 H-NMR (C 6 D} 6) δ 0.11 (3H), 0.81 (4H), 1.10-1.14 (12H), 3.64-3.66 (4H), 3.71-3.73 (4H), 4.80 (1H).

Step 5. Preparation of 1-((2-cycloheptenyl)diethoxydecylalkyl)-2-(methyldiethoxydecyl)ethane

1-(Diethoxydecylalkyl)-2-(diethoxy(methyl)decylalkyl)ethane prepared in Step 4 (218.99 g, 0.78 mol, 1.0 equivalent) and dichloride as a catalyst (1,5-cyclooctadiene)platinum (II) was added to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C, and then norbornadiene (71.93 g, 0.78 mol, 1.0 equivalent) was slowly added to the flask. The mixed solution was stirred at 60 ° C for 5 hours, and purified at 95 ° C and 0.18 Torr to obtain a colorless liquid compound (203.65 g, yield: 70%) represented by the following chemical formula.

₁ H-NMR (C ₆ D ₆ ) δ 0.16 (3H), 0.84 (4H), 1.15 (12H), 3.70 (8H), 0.6-3.05, 5.91-6.12 (bicycloheptenyl, 9H).

Instance 3 : preparation 1-( Phenyl ethoxylate Methyl decyl )-2-( Methyldiethoxydecyl ) Ethane

Step 1. Preparation of diethylaminomethylphenylchlorodecane

Pentane (1500 mL) and dichloromethylphenyl decane (150 g, 0.79 mol, 1.0 eq.) were added to a flame dried 5000 mL Schlenk bottle, and diethylamine was slowly added to the flask (114.8) g, 1.57 mol, 2.0 eq.) while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 12 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and then diethylaminomethylphenylchloromethane (159.12 g, yield: 89%) was obtained.

₁ H-NMR (C ₆ D ₆ ) δ 0.5 (3H), 0.89 (6H), 2.75 (4H), 7.16 (3H), 7.78 (2H).

Step 2. Preparation of diethylaminomethyl decane

LiAlH ₄ (7.42 g, 0.2 mol, 0.28 equivalent) was added to a flame dried 3000 mL Schlenk bottle, and THF (1500 mL) was added to the flask while maintaining the temperature at -10 °C. Ethylaminomethylphenylchloromethane (159 g, 0.70 mol, 1.0 equivalent) prepared in the step 1 was slowly added to the reaction solution. The reaction solution was slowly heated to room temperature (70 ° C) and stirred for 12 hours. The resulting solution was depressurized to remove the solvent and hexane (1000 mL) was added. The resulting solution was stirred for 30 minutes, filtered, and the solvent was evaporated under reduced pressure, and then diethylaminomethyl decane (67.53 g, 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 ethoxymethyl decane

Diethylaminononane (67.53 g, 0.35 mol, 1.0 eq.) and n-pentane (1500 mL) prepared in Step 2 were added to a flame dried 5000 mL Schlenk bottle and slowly added to the flask. Ethanol (32.18 g, 0.7 mol, 2.0 eq.) while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature, stirred for 12 hours, filtered, and the solvent was removed under reduced pressure, and then ethoxymethyl decane (40.65 g, yield: 70%) was obtained.

₁ H-NMR (C ₆ D ₆ ) δ 0.33 (3H), 1.12 (3H), 3.58 (2H), 5.21 (1H), 7.2 (3H), 7.53 (2H).

Step 4. Preparation of diethoxymethyl (vinyl) decane

Dichloromethyl(vinyl)decane (50 g, 0.35 mol, 1.0 eq.) and n-pentane (1500 mL) were added to a flame dried 3000 mL Schlenk bottle, and then three were slowly added to the flask. Ethylamine (73.52 g, 0.73 mol, 2.05 eq.) while maintaining the temperature at 0 °C. Subsequently, ethanol (33.47 g, 0.73 mol, 2.05 equivalent) was slowly added to the reaction solution. The reaction solution was heated to room temperature, stirred for 12 hours, filtered, and the solvent was removed under reduced pressure, and then diethoxymethyl(vinyl) decane (39 g, yield: 68%) was obtained.

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-(phenylethoxymethyl decyl)-2-(diethoxymethyl decyl) ethane

Ethoxymethyl decane (40.65 g, 0.24 mol, 1.0 eq.) prepared in the step 3 and chloroplatinic acid (H ₂ Cl ₆ Pt·6H ₂ O) as a catalyst were added to the flame-dried 5000 mL shu In the bottle of Lenk. The reaction solution was heated to 60 ° C, and diethoxymethyl(vinyl)decane (39 g, 0.24 mol, 1.0 equivalent) prepared in Step 4 was slowly added to the flask. The reaction solution was refluxed for 8 hours to obtain a compound represented by the following chemical formula (75 g, yield: 94%).

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).

Instance 4 :preparation 1-(( Bicycloheptenyl ) Ethoxygen Methyl decyl )-2-( Triethoxydecyl ) Methane

Step 1. Preparation of 1-(methylchloroindolyl)-2-(trichlorodecanealkyl)methane

Magnesium (Mg) (34.37 g, 1.41 mol, 1.3 equivalents) and 100 mL of THF were added to a flame dried 5000 mL Schlenk bottle and heated to 60 °C. To the reaction solution, a mixed solution of (chloromethyl)trichloromethane (200 g, 1.09 mol, 1.0 equivalent) and dichloromethylnonane (187.63 g, 1.63 mol, 1.5 equivalent) was slowly added. The reaction solution was stirred at 60 ° C for 10 hours, filtered, and then treated with n-pentane (1500 mL) four times. The solution was depressurized to remove the solvent and purified (at 38 ° C and 0.8 Torr) to obtain a colorless Cl ₃ Si-CH ₂ -SiMeCl (H) liquid (99.20 g, yield: 40%).

₁ H-NMR (C ₆ D ₆ ) δ 0.12 (3H), 0.41 - 0.58 (2H), 4.78 (1H).

Step 2. Preparation of 1-(ethoxy(methyl)chloroindolyl)-2-(triethoxydecyl)methane

Add n-pentane (2000 mL) and 1-(methylchloroindolyl)-2-(trichlorodecanealkyl)methane (99.20 g, 0.44 mol, 1.0 eq.) prepared in Step 1 to flame dried In a 5000 mL Schlenk bottle, triethylamine (220.07 g, 2.18 mol, 5.0 equivalents) and ethanol (100.20 g, 2.18 mol, 5.0 equivalents) were slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure, and, at 42 ° C and 0.4 Torr, a colorless (EtO) ₃ Si-CH ₂ -SiMe (OEt) (H) liquid (104.32 g, yield: 90%) was obtained.

₁ H-NMR (C ₆ D ₆ ) δ 0.08-0.11 (2H), 0.42 (3H), 1.09-1.18 (12H), 3.57-3.65 (2H), 3.71-3.84 (6H), 4.98 (1H).

Step 3. Preparation of 1-((bicycloheptenyl)ethoxymethyldecyl)-2-(triethoxydecyl)methane

1-(ethoxy(methyl)chloroindolyl)-2-(triethoxydecylalkyl)methane (104.32 g, 0.39 mol, 1.0 eq.) prepared in Step 2 together with dichloride as catalyst ( 1,5-cyclooctadiene)platinum (II) was added together to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C and norbornadiene (36.07 g, 0.39 mol, 1.0 equivalent) was slowly added. The solution was stirred at 60 ° C for 5 hours and at 90 ° C and 0.23 Torr to obtain a colorless liquid compound (105.29 g, yield: 75%) represented by the following chemical formula.

₁ H-NMR (C ₆ D ₆ ) δ 0.01 (external, 2H), 0.05 (inner, 2H), 0.24 (external, 3H), 0.34 (inner, 3H), 1.16-1.42 (outside, in, 24H), 3.65-3.79 (outer, inner, 16H), 1.18-2.17, 2.80-3.12, 5.94-6.22 (bicycloheptenyl, 9H).

Instance 5 :preparation 1-((2- Cycloheptenyl ) Ethoxygen Methyl decyl )-2-( Methyldiethoxydecyl ) Methane

Step 1. Preparation of 1-(methylchloroindolyl)-2-(dichloromethylindolyl)methane

Magnesium (Mg) (28.99 g, 1.19 mol, 1.3 equivalents) and THF (100 mL) were added to a flame dried 5000 mL Schlenk bottle and the reaction solution was heated to 60 °C. A mixed solution of (chloromethyl)dichloromethylnonane (150 g, 0.92 mol, 1.0 equivalent) and dichloromethylnonane (158.29 g, 1.38 mol, 1.5 equivalent) was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C for 10 hours, filtered, and then treated with n-pentane (1500 mL) four times. The solution was depressurized to remove the solvent and purified (at 40 ° C and 2.8 Torr) to give a colorless MeCl ₂ Si-CH ₂ -SiMeCl (H) liquid (123.82 g, yield: 65%).

₁ H-NMR (C ₆ D ₆ ) δ 0.18 (3H), 0.37 (2H), 0.47 (3H), 4.83 (1H).

Step 2. Preparation of 1-(ethoxy(methyl)chloroindolyl)-2-(diethoxymethyldecyl)methane

Add 1-(methylchloroindolyl)-2-(dichloromethylindenyl)methane (123.82 g, 0.60 mol, 1.0 eq.) and n-pentane (2000 mL) prepared in Step 1 to a flame. In a dry 5000 mL Schlenk bottle, triethylamine (187.05 g, 1.85 mol, 3.1 eq.) and ethanol (85.16 g, 1.85 mol, 3.1 eq.) were slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and purified at 76 ° C and 0.24 Torr to obtain a colorless Me(EtO) ₂ Si-CH ₂ -SiMe(OEt)(H) liquid (119.85 g, 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 (1H).

Step 3. Preparation of 1-((2-cycloheptenyl)ethoxymethyldecyl)-2-(diethoxymethyldecyl)methane

1-(ethoxy(methyl)chloroindolyl)-2-(diethoxymethyldecyl)methane (119.85 g, 0.51 mol, 1.0 equivalent) prepared in the step 2 and as a catalyst Chloro(1,5-cyclooctadiene)platinum (II) was added to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C, and then norbornadiene (46.70 g, 0.51 mol, 1.0 equivalent) was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C for 5 hours and purified at 88 ° C and 0.18 Torr to obtain a colorless liquid compound (116.58 g, yield: 70%) represented by the following formula.

₁ H-NMR (C ₆ D ₆ ) δ 0.04 (external, 2H), 0.06 (inner, 2H), 0.17 (outside, 3H), 0.25 (inner, 3H), 1.14 (outside, in, 18H), 3.57 -3.69 (outer, inner, 12H), 0.54, 1.70-1.82, 2.79-2.94, 5.95-6.19 (bicycloheptenyl, 9H).

Instance 6 To instance 10 : use case 1 To 5 矽 precursor forms a dielectric layer

The substrate is placed in a PE-CVD chamber. The substrate was heated to 200 ° C and maintained at 200 ° C until the deposition process was completed. The ruthenium precursor is supplied to the chamber together with a carrier gas (for example, 400 sccm of argon gas) at a flow rate of 475 cc/min, and here, the compound prepared using each of Examples 1 to 5 is used as a ruthenium precursor. . In addition, oxygen (for example, an oxidant) as a reaction gas is supplied into the chamber. Oxygen was supplied at a flow rate of 20 cc/min. 13.56 MHz and 50 W of RF power were applied to the upper electrode in the chamber. The internal pressure of the chamber was controlled at 0.8 Torr. Thereby an initial dielectric layer is deposited on the substrate.

The substrate having the initial dielectric layer is subjected to a thermal annealing process (N ₂ , 15 SLM) or a UV curing process. The thermal annealing process was performed at a temperature of 500 ° C for 2 hours. A UV curing process was performed on the substrate heated to 400 ° C for 10 minutes. The porogen groups are removed from the initial dielectric layer by such energy treatment to form a porous dielectric layer.

A dielectric layer (Example 6 to Example 10) was formed using the compounds of Examples 1 to 5, respectively, and then the dielectric constant and Young's modulus were measured. The chemical structure of the dielectric layers (Examples 6 to 10) was analyzed using an infrared spectrometer. In the analysis using an infrared spectrometer, the dielectric layers (Examples 6 to 10) were controlled to have the same thickness of 400 nm, and the thickness of the dielectric layers (Examples 6 to 10) was measured using an ellipsometer. In addition, the carbon content of the dielectric layers (Examples 6 to 10) was measured using an X-ray photoelectron spectroscopy (XPS) system.

The first dielectric layer (Example 6) formed using the ruthenium precursor of Example 1 had a dielectric constant of 2.32 and a Young's modulus of 8.59 GPa. The first dielectric layer has a carbon content of 25 at%, an average pore diameter of 1.4 nm, a FWHM (pore radius distribution) of 0.45 nm, and a porosity of 22%.

The second dielectric layer (Example 7) formed using the hafnium precursor of Example 2 had a dielectric constant of 2.38 and a Young's modulus of 7.95 GPa. The second dielectric layer has a carbon content of 30 at%, an average pore diameter of 1.8 nm, a FWHM (pore radius distribution) of 0.65 nm, and a porosity of 28%.

The third dielectric layer (Example 8) formed using the hafnium precursor of Example 3 had a dielectric constant of 2.40 and a Young's modulus of 7.86 GPa. The third dielectric layer has a carbon content of 20 at%, an average pore diameter of 1.2 nm, and a porosity of 17%.

The pore radius in the third dielectric layer (Example 8) was measured, and FIG. 10 depicts the measured pore radius distribution. In the pore radius distribution curve shown in Fig. 10, the FWHM is about 0.55 nm. This result means that uniform small-sized pores are formed in the third dielectric layer.

The fourth dielectric layer (Example 9) formed using the ruthenium precursor of Example 4 had a dielectric constant of 2.35 and a Young's modulus of 9.85 GPa. The fourth dielectric layer has a carbon content of 27 at%, an average pore diameter of 1 nm, a FWHM (pore radius distribution) of 0.35 nm, and a porosity of 25%.

The fifth dielectric layer (Example 10) formed using the ruthenium precursor of Example 5 had a dielectric constant of 2.41 and a Young's modulus of 7.75 GPa. The fifth dielectric layer has a carbon content of 20 at%, an average pore diameter of 1.5 nm, a FWHM (pore radius distribution) of 0.55 nm, and a porosity of 20%.

Table 1 below shows analytical data of the first to fifth dielectric layers (Examples 6 to 10) measured by an infrared spectrometer.

[Table 1]

Since the porogen groups are removed from the initial dielectric layer molecules as a thermal annealing process or a UV curing process, the dielectric layers of Examples 6 to 10 having high porosity and low dielectric constant are formed, as shown in Table 1. Show. Specifically, the dielectric layer of Example 6 has the lowest dielectric constant and the highest mechanical strength. Since the molecular structure of the ruthenium precursor of Example 1 contained bridge carbon (-CH ₂ -) and four alkoxy groups, the dielectric layer of Example 6 was formed to have a relatively large amount of Si-O network structure. Thus, the dielectric layer of Example 6 has a high mechanical strength as described above. In addition, the dielectric layer of Example 6 was formed to have a relatively high content of Si-CH ₃ bonding units, and therefore, it had a relatively large amount of Si-O cage structure. Thus, the dielectric layer of Example 6 has a low dielectric constant as described above.

According to an example embodiment of the inventive concept, a dielectric layer having a high carbon content and an oxygen atom content may be formed. For example, during an initial deposition process of the dielectric layer, the dielectric layer may initially form a plurality of Si-CH ₃ bond unit. The Si-O network structure composed of Si-O bonding units can be interrupted by Si-CH ₃ bonding units, and thus nanovoids can be formed in the structure. In other words, the Si-O network structure fracture caused by the Si-CH ₃ bonding unit can form a Si-O cage structure.

In addition, the ratio of the Si—CH ₃ bonding unit to the Si—O bonding unit in the dielectric layer according to example embodiments of the inventive concepts is relatively high. The higher the ratio of Si-CH ₃ bonding units to Si-O bonding units, the greater the number of Si-CH ₃ bonds in each dielectric layer. In the process of forming interconnections in the dielectric layer, this may cause damage to the plasma. That is, it is possible to suppress plasma-induced damage.

The ruthenium precursor according to example embodiments of the inventive concepts may have a molecular structure containing a porogen group, and this may cause a plurality of Si-O cage structures to be formed in the dielectric layer. Therefore, in the case where a germanium precursor is used to form a dielectric layer, a porous dielectric layer can be formed without using an additional step of supplying a pore-generating material. In addition, the ruthenium precursor according to an example embodiment of the inventive concept may have a molecular structure containing a bridge carbon bond (-(CH ₂ ) _n -) and may contain an alkoxy group instead of a plurality of alkyl groups, and thus, a ruthenium precursor The material can have improved thermal stability.

Therefore, in the case where a germanium precursor according to an example embodiment of the inventive concept is used to form a dielectric layer, the dielectric layer can be formed to have a relatively low dielectric constant and high mechanical strength suitable for the interconnect structure. .

Instance 11 :preparation 1-(( Bicycloheptenyl ) Methylmethoxyalkyl -2-( Trimethoxydecyl ) Methane

Step 1. Preparation of 1-(methylchloroindolyl)-2-(trichlorodecanealkyl)methane

Magnesium (Mg) (34.37 g, 1.41 mol, 1.3 equivalents) and 100 mL of THF were added to a flame dried 5000 mL Schlenk bottle and heated to 60 °C. To the reaction solution, a mixed solution of (chloromethyl)trichloromethane (200 g, 1.09 mol, 1.0 equivalent) and dichloromethylnonane (187.63 g, 1.63 mol, 1.5 equivalent) was slowly added. The reaction solution was stirred at 60 ° C for 10 hours, filtered, and then treated with n-pentane (1500 mL) four times. The solution was depressurized to remove the solvent and purified (at 38 ° C and 0.8 Torr) to obtain a colorless Cl ₃ Si-CH ₂ -SiMeCl (H) liquid (99.20 g, yield: 40%).

₁ H-NMR (C ₆ D ₆ ) δ 0.12 (3H), 0.41 - 0.58 (2H), 4.78 (1H).

Step 2. Preparation of 1-(methoxy(methyl)chloroindolyl)-2-(trimethoxydecyl)methane

Add 1-(methylchloroindolyl)-2-(trichlorodecanealkyl)methane (99.20 g, 0.44 mol, 1.0 eq.) and n-pentane (2000 mL) prepared in Step 1 to flame dried In a 5000 mL Schlenk bottle, triethylamine (220.07 g, 2.18 mol, 5.0 equivalents) and methanol (69.85 g, 2.18 mol, 5.0 equivalents) were slowly added to the reaction solution while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure, and purified at 30 ° C and 0.46 Torr to obtain a colorless (MeO) ₃ Si-CH ₂ -SiMe (OMe) (H) liquid (82.38 g, yield: 89%) .

₁ H-NMR (C ₆ D ₆ ) δ 0.05-0.09 (2H), 0.31 (3H), 3.33-3.42 (12H), 4.96 (1H).

Step 3. Preparation of 1-((bicycloheptenyl)methoxymethyldecyl-2-(trimethoxydecyl)methane

1-(Methoxy(methyl)chloroindolyl)-2-(trimethoxydecylalkyl)methane (82.38 g, 0.39 mol, 1.0 eq.) prepared in Step 2 and dichloride as a catalyst (1) , 5-cyclooctadiene)platinum (II) was added to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C and norbornadiene (36.07 g, 0.39 mol, 1.0 equivalent) was slowly added. The reaction solution was stirred at 60 ° C for 5 hours and purified at 64 ° C and 0.52 Torr to obtain a colorless liquid compound (88.85 g, yield: 75%) represented by the following formula.

₁ H-NMR(C ₆ D ₆ )δ -0.01 (outer, inner, 2H), 0.22-0.31 (outer, inner, 3H), 3.36-3.47 (outer, inner, 9H), 1.06-1.92, 2.78-2.98 , 5.92-5.97 (bicycloheptenyl, 9H).

Instance 12 :preparation 1-(( Bicycloheptenyl ) Methylmethoxyalkyl )-2-( Trimethoxydecyl ) Ethane

Step 1. Preparation of 1-(trichlorodecylalkyl)-2-(methyldichlorodecylalkyl)ethane

Silane vinyl trichlorosilane (200 g, 1.24 mol, 1.0 equiv) was added as a catalyst and chloroplatinic acid _{(H 2 Cl 6 Pt · 6H} 2 O) to a flame dried Schlenk flask, followed by 3000 mL, and then The reaction solution was heated to 60 °C. Dichloromethyl decane (156.7 g, 1.36 mol, 1.1 equivalent) was slowly added to the reaction solution. The mixed solution was refluxed for 8 hours to obtain MeCl ₂ Si-CH ₂ CH ₂ -SiCl ₃ (384.81 g, yield: 98%).

₁ H-NMR (C ₆ D ₆ ) δ 0.21 (3H), 0.86 (2H), 1.06 (2H).

Step 2. Preparation of 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)ethane

1-(Trichlorodecyl)-2-(methyldichlorodecylalkyl)ethane (384.81 g, 1.39 mol, 1.0 eq.) and 3000 mL of n-pentane prepared in Step 1 were added to the flame dried In a 5000 mL Schlenk bottle, dimethylamine (501.87 g, 11.13 mol, 8.0 equivalents) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 3 hours. The reaction solution was filtered to remove the solvent, and purified to obtain colorless _{Me (NMe 2) 2 Si-} CH 2 CH 2 -Si (NMe 2) 2 Cl pressure liquid (357.88 g, yield: 85%).

₁ H-NMR (C ₆ D ₆ ) δ 0.07 (3H), 0.78-0.91 (4H), 2.45 (24H).

Step 3. Preparation of 1-(bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)ethane

LiAlH ₄ (15.71 g, 0.41 mol, 0.35 eq.) was added to a flame dried 2000 mL Schlenk bottle, and then THF (500 mL) was slowly added to the flask while maintaining the temperature at -30 °C. 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)ethane (357.88 g, 1.18 mol, 1.0 eq.) prepared in step 2 was slowly Add to the flask while maintaining the temperature at -30 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure, and purified at 73 ° C and 1.66 Torr to obtain a colorless Me(NMe ₂ ) ₂ Si-CH ₂ CH ₂ -Si(NMe ₂ ) ₂ H liquid (245.36 g, yield :75%).

₁ H-NMR (C ₆ D ₆ ) δ 0.10 (3H), 0.69 (4H), 2.47 (12H), 2.52 (12H), 4.59 (1H).

Step 4. Preparation of 1-(diethoxydecyl)-2-(diethoxy(methyl)decylalkyl)ethane

1-(Bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)ethane prepared in Step 3 (245.36 g, 0.89 mol, 1.0 eq.) and Pentane (1000 mL) was added to a flame dried 3000 mL Schlenk bottle, and methanol (113.7 g, 3.55 mol, 4.0 eq.) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was removed under reduced pressure, and then a colorless Me(MeO) ₂ Si-CH ₂ CH ₂ -Si(OMe) ₂ H liquid (104.16 g, yield: 87%) was obtained.

₁ H-NMR (C ₆ D ₆ ) δ 0.08 (3H), 0.80 (4H), 3.48-3.68 (12H), 4.78 (1H).

Step 5. Preparation of 1-((2-cycloheptenyl)dimethoxydecyl)-2-(methyldimethoxydecyl)ethane

1-(Dimethoxydecylalkyl)-2-(dimethoxy(methyl)decylalkyl)ethane (104.16 g, 0.46 mol, 1.0 eq.) prepared in Step 4 together with dichloride as a catalyst (1,5-cyclooctadiene)platinum (II) was added together to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C and norbornadiene (42.77 g, 0.46 mol, 1.0 equivalent) was slowly added. The mixed solution was stirred at 60 ° C for 5 hours and purified at 88 ° C and 0.18 Torr to obtain a colorless liquid compound (104.84 g, yield: 72%) represented by the following chemical formula.

_{1 H-NMR (C 6 D} 6) δ 0.08 (3H), 0.85-0.92 (4H), 3.66-3.75 (12H), 0.52-3.12, 5.88-6.10 ( bicyclo heptenyl, 9H).

Instance 13 :preparation 1-(( Bicycloheptenyl ) Dimethoxydecyl )-2-( Methyldimethoxydecyl ) Methane

Step 1. Preparation of 1-(trichlorodecylalkyl)-2-(methyldichloroindolyl)methane

Acetonitrile (1500 mL) and (chloromethyl)dichloromethylnonane (500 g, 3.06 mol, 1.0 eq.) were added to a flame dried 5000 mL Schlenk bottle and heated to 70 °C. Triethylamine (340.37 g, 3.36 mol, 1.1 equivalent) was added to the reaction solution, and then trichloromethane (455.61 g, 3.36 mol, 1.1 eq.) was slowly added to the flask while maintaining the temperature at 70 °C. The reaction solution was stirred at 70 ° C for 5 hours, filtered, and then treated with n-pentane (1500 mL) four times. The solution was depressurized to remove the solvent and purified (at 28 ° C and 1.01 Torr) to obtain a colorless MeCl ₂ Si-CH ₂ -SiCl ₃ liquid (160.54 g, yield: 20%).

₁ H-NMR (C ₆ D ₆ ) δ 0.38 (3H), 0.69 (2H).

Step 2. Preparation of 1-(bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)methane

Add 1-(trichlorodecanealkyl)-2-(methyldichloroindenyl)methane (160.54 g, 0.61 mol, 1.0 eq.) and n-pentane (3000 mL) prepared in Step 1 to flame drying In a 5000 mL Schlenk bottle, diethylamine (330.84 g, 7.34 mol, 12.0 equivalents) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 3 hours. The reaction solution was filtered under reduced pressure to remove the solvent, and purified at 78 deg.] C and 0.8 torr in the obtained colorless _{Me (NMe 2) 2 Si-} CH 2 -Si (NMe 2) 2 Cl liquid (163.48 g, yield: 90 %).

₁ H-NMR (C ₆ D ₆ ) δ 0.18 (3H), 0.30 (2H), 2.43-2.47 (24H).

Step 3. Preparation of 1-(bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)methane

LiAlH ₄ (7.31 g, 0.19 mol, 0.35 eq.) was added to a flame dried 1000 mL Schlenk bottle, and then THF (300 mL) was slowly added to the flask while maintaining the temperature at -30 °C. 1-(Bis(dimethylamino)chloroindolyl)-2-(bis(dimethylamino)methyldecyl)methane (163.48 g, 0.55 mol, 1.0 eq.) prepared in Step 2 was slowly added. Into the flask while maintaining the temperature at -30 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered under reduced pressure to remove the solvent, and purification at 0.5 torr and at 56 ℃ obtain colorless _{Me (NMe 2) 2 Si-} CH 2 -Si (NMe 2) 2 H liquid (108.38 g, yield: 75 %).

₁ H-NMR (C ₆ D ₆ ) δ 0.04 (2H), 0.16 (3H), 2.44-2.48 (24H), 4.48 (1H).

Step 4. Preparation of 1-(dimethoxydecyl)-2-(dimethoxy(methyl)decylalkyl)methane

1-(Bis(dimethylamino)decyl)-2-(bis(dimethylamino)methyldecyl)methane (108.38 g, 0.41 mol, 1.0 eq.) and n-pentane prepared in the step 3 Alkane (1000 mL) was added to a flame dried 3000 mL Schlenk bottle, and then methanol (52.87 g, 1.65 mol, 4.0 eq.) was slowly added to the flask while maintaining the temperature at 0 °C. The reaction solution was heated to room temperature (20 ° C) and stirred for 5 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure, and purified at 46 ° C and 0.48 Torr to obtain a colorless Me(MeO) ₂ Si-CH ₂ -Si(OMe) ₂ H liquid (78.49 g, yield: 91%) .

₁ H-NMR (C ₆ D ₆ ) δ 0.07 (2H), 0.21 (3H), 3.35-3.38 (9H), 4.82 (1H).

Step 5. Preparation of 1-((bicycloheptenyl)dimethoxydecylalkyl)-2-(methyldimethoxydecyl)methane

1-(Dimethoxydecylalkyl)-2-(dimethoxy(methyl)decylalkyl)methane (78.49 g, 0.37 mol, 1.0 eq.) prepared in Step 4 and dichloride as a catalyst ( 1,5-cyclooctadiene)platinum (II) was added to a flame dried 1000 mL Schlenk bottle. The reaction solution was heated to 60 ° C, and then norbornadiene (34.38 g, 0.37 mol, 1.0 equivalent) was slowly added to the reaction solution. The reaction solution was stirred at 60 ° C for 5 hours and purified at 93 ° C and 0.56 Torr to obtain a colorless liquid compound (87.30 g, yield: 78%) represented by the following formula.

₁ H-NMR(C ₆ D ₆ )δ -0.04 (outer, inner, 2H), 0.25-0.27 (outer, inner, 3H), 3.34-3.40 (outer, inner, 9H), 0.61-1.89, 2.78-3.08 , 5.95-6.16 (bicycloheptenyl, 9H).

Experimental example 1

Figure 9 depicts the measured vapor pressures of the compounds prepared in Examples 4 and 11, respectively.

As shown in Figure 9, the compound of Example 11 (i.e., a molecule containing a molecule in which the alkoxy group is a methoxy group) has a vapor pressure higher than that of Example 4 (i.e., a molecule containing an alkoxy group in which an alkoxy group is an ethoxy group). Pressure. In other words, in the case where the methoxy group is used as the alkoxy group in the ruthenium precursor, the resulting compound has a relatively high vapor pressure, making it more stable in the dielectric layer deposition process.

Instance 14 To instance 16 : use case 11 Dielectric layer formed by the ruthenium precursor

The dielectric layers of Examples 14 through 16 were formed by substantially the same procedures as described with reference to Examples 6 to 10, except that the compound prepared in Example 11 was used as the ruthenium precursor of the dielectric layer. The thermal annealing process was performed as an energy treatment for 2 hours. In Examples 14 to 16, the thermal annealing process was performed at different temperatures. In Examples 14 to 16, the process temperatures were 500 ° C, 550 ° C, and 600 ° C, respectively.

In the dielectric layer of Example 14, the ratio of Si-O cage to Si-O mesh was 0.61. Additionally, the dielectric layer of Example 14 had a dielectric constant of 2.46 and a Young's modulus of 6.87 GPa.

In the dielectric layer of Example 15, the ratio of Si-O cage to Si-O mesh was 0.65. Additionally, the dielectric layer of Example 15 had a dielectric constant of 2.25 and a Young's modulus of 11.2 GPa.

In the dielectric layer of Example 16, the ratio of Si-O cage to Si-O mesh was 0.75. Additionally, the dielectric layer of Example 16 had a dielectric constant of 2.3 and a Young's modulus of 12.5 GPa.

In the molecular structure of the ruthenium precursor of Example 11, the alkoxy group may be a methoxy group. According to the results of Examples 14 to 16, in the case where a ruthenium precursor containing a methoxy group is used to form a dielectric layer, the process temperature of the thermal annealing process is increased such that Si-O cage and Si- in the dielectric layer The ratio of O nets increases. Specifically, when the thermal annealing process was performed at a temperature of 550 ° C (Example 15), the dielectric layer had the lowest dielectric constant and improved mechanical strength.

Experimental example 2

Table 2 below provides a comparison between the dielectric layer of Example 9 (i.e., the formation of the hafnium precursor of Example 4) and the dielectric layer of Example 15. The ruthenium precursor of Example 11 contained a methoxy group instead of an ethoxy group as compared to the ruthenium precursor of Example 4. Table 3 below shows the carbon, oxygen and helium contents of the dielectric layers of Examples 9 and 11 as measured by the XPS system.

[Table 2]

[table 3] ;

Referring to Table 2, in the case where the hafnium precursor of Example 11 (i.e., containing a methoxy group) is used to form a dielectric layer, a dielectric layer having a high ratio of Si-O cage to Si-O mesh is formed (compared to In the case of the ruthenium precursor of Example 4 (i.e., containing an ethoxy group). Since the nanovoids are formed in the Si-O cage structure as described above, the increase in the Si-O cage structure makes it possible to lower the dielectric constant of the dielectric layer.

The ruthenium precursor of Example 11 (i.e., containing methoxy) had a lower carbon content than the ruthenium precursor of Example 4 (i.e., contained ethoxy). However, as shown in Table 3, the carbon content of the dielectric layer of Example 15 formed using the ruthenium precursor of Example 11 was higher than the carbon content of the dielectric layer of Example 9 formed using the ruthenium precursor of Example 4. That is, the dielectric layer of Example 15 was formed to have a lower dielectric constant and higher mechanical strength than the dielectric layer of Example 9.

Instance 17 To instance 19 : use case 13 矽 precursor forms a dielectric layer

The substrate is placed in a PE-CVD chamber. The substrate was heated to 250 ° C and maintained at 250 ° C until the deposition process was completed. The ruthenium precursor was supplied to the chamber together with a carrier gas (for example, 400 sccm of argon gas) at a flow rate of 475 cc/min, and here, the compound prepared in Example 13 was used as the ruthenium precursor. In addition, oxygen (for example, an oxidant) as a reaction gas is supplied into the chamber. The flow rate of oxygen is 30 cc/min. 13.56 MHz and 50 W of RF power were applied to the upper electrode in the chamber. The internal pressure of the chamber was adjusted to 1 Torr. In the chamber, an initial dielectric layer is deposited on the substrate. A thermal annealing process (N ₂ , 15 SLM) was performed on the substrate having the initial dielectric layer for 2 hours at a temperature of 550 ° C. The porous dielectric layer of Example 17 was thus formed on the substrate.

In the case of the porous dielectric layer of Example 18, the initial dielectric layer was deposited at a substrate temperature of 180 ° C, the flow rate of reactant (ie, oxygen) oxygen was 25 cc/min, and the internal pressure of the chamber was 1.5. Trust. Except for these differences, the porous dielectric layer of Example 18 was formed using the same method as in Example 17.

In the case of the porous dielectric layer of Example 19, the flow rate of the reactant (i.e., oxygen) oxygen was 25 cc/min and the internal pressure of the chamber was 1.5 Torr. Except for these differences, the porous dielectric layer of Example 19 was formed using the same method as in Example 17.

In the case of the porous dielectric layer of Example 19, the initial dielectric layer was deposited at a substrate temperature of 200 ° C, the flow rate of the reactant (ie, oxygen) oxygen was 25 cc / min, and the substrate was heated to 400 ° C. The energy treatment was performed in a manner, and then the UV curing process was performed for 10 minutes. Except for these differences, the porous dielectric layer of Example 20 was formed using the same method as in Example 17.

In the dielectric layer of Example 17, the ratio of Si-O cage to Si-O mesh was 0.75. Additionally, the dielectric layer of Example 17 had a dielectric constant of 2.3 and a Young's modulus of 11.0 GPa.

In the dielectric layer of Example 18, the ratio of Si-O cage to Si-O mesh was 0.8. Additionally, the dielectric layer of Example 18 had a dielectric constant of 2.4 and a Young's modulus of 15 GPa.

In the dielectric layer of Example 19, the ratio of Si-O cage to Si-O mesh was 0.82. Additionally, the dielectric layer of Example 19 had a dielectric constant of 2.4 and a Young's modulus of 14 GPa.

In the dielectric layer of Example 20, the ratio of Si-O cage to Si-O mesh was 0.85. Additionally, the dielectric layer of Example 20 had a dielectric constant of 2.2 and a Young's modulus of 12.3 GPa.

3, 5, and 7 are plan views illustrating a method of fabricating a semiconductor device in accordance with example embodiments of the inventive concepts. 4A, 6A, and 8A are cross-sectional views taken along line I-I' of Figs. 3, 5, and 7, respectively, and Figs. 4B, 6B, and 8B are along Figs. 3 and 5, respectively. And a cross-sectional view taken along line II-II' of Fig. 7.

Referring to FIGS. 3, 4A, and 4B, an integrated circuit IC can be formed on the substrate 100. The substrate 100 may be a semiconductor substrate formed of at least one of tantalum, niobium, tantalum-ruthenium or a composite semiconductor material.

The integrated circuit IC may include a plurality of transistors TR. The formation of the transistor TR may include forming a device isolation layer ST defining the active region and forming a gate dielectric layer GI, a gate electrode GE, and a capping pattern CP on the active region. The gate electrode GE may be formed on the active region, the gate dielectric layer GI may be provided between the gate electrode GE and the substrate 100, and the capping pattern CP may be formed to cover the top surface of the gate electrode GE. An impurity region DR may be formed on both sides of the gate electrode GE. For example, the impurity region DR may be formed by doping the substrate 100 with impurities.

Subsequently, a first insulating layer 110 and a second insulating layer 120 may be formed on the substrate 100 to cover the transistor TR. The second insulating layer 120 may be formed to directly cover the first insulating layer 110. The second insulating layer 120 can be or comprise a low-k dielectric layer formed using the method described with reference to FIGS. 1A and 2. For example, the second insulating layer 120 may be a porous SiOCH layer. The first insulating layer 110 may also be a porous SiOCH layer formed using the method described with reference to FIGS. 1A and 2 . In an example embodiment, the first insulating layer 110 may be formed of a hafnium oxide layer or comprise a hafnium oxide layer, which may be formed using other known hafnium precursors.

Referring to FIGS. 5, 6A, and 6B, the second insulating layer 120 may be patterned to form interconnect holes IH, and here, the interconnect holes IH may each have a shape elongated in the second direction D2. At least one of the interconnecting holes IH may include a vertical through hole VPH that extends toward the substrate 100. For example, a portion of the first insulating layer 110 may be patterned by a patterning process of the second insulating layer 120. For example, a vertical through hole VPH that passes through the first insulating layer 110 and exposes a portion of the impurity region DR may be formed. As another example, a vertical through hole VPH that passes through the first insulating layer 110 and exposes a portion of the top surface of the gate electrode GE may be formed.

According to an example embodiment of the inventive concept, the second insulating layer 120 may have a relatively high mechanical strength. This can suppress or prevent the second insulating layer 120 from collapsing or maintaining the original structure of the second insulating layer 120 in the patterning process of forming the interconnect holes IH in a high pattern density.

Referring to FIG. 7, FIG. 8A, and FIG. 8B, interconnection lines ML filling the interconnection holes IH may be formed, respectively. For example, the formation of the interconnect lines ML can include forming a barrier layer on the substrate 100. The barrier layer may be formed to conformally cover the interconnect hole IH. The barrier layer may be formed of at least one of Ti or TiN or contain at least one of Ti or TiN.

Next, a conductive layer can be formed on the substrate 100. The conductive layer may be formed to fill the interconnected holes IH having the barrier layer. The conductive layer may be formed of or comprise at least one metal material such as copper (Cu) or tungsten (W). For example, the conductive layer can be formed by an electroplating process. In an example embodiment, the forming of the conductive layer may include forming a seed layer (not shown) on the barrier layer, and then performing a plating process using the seed layer.

The conductive layer and the barrier layer may be planarized to form an interconnection ML and a barrier pattern BP in each of the interconnection holes IH. In an example embodiment, the interconnect lines ML may be formed to have a top surface that is coplanar with the second insulating layer 120.

In the case where the interconnect line ML pattern density is relatively high, the semiconductor device may be disturbed by high parasitic capacitance between the interconnect lines ML. The higher the parasitic capacitance between the interconnect lines ML, the worse the RC delay characteristics of the semiconductor device. However, in the case where a porous layer having a low dielectric constant is used as the second insulating layer 120 (as described above), the parasitic capacitance between the interconnection lines ML can be effectively reduced.

Although not shown, an insulating layer and an interconnect layer may be further stacked on the second insulating layer 120.

In accordance with an example embodiment of the inventive concept, a method of forming a low-k dielectric layer using a hafnium precursor is disclosed. Using this method, the dielectric layer can have a low dielectric constant and high mechanical strength. Novel germanium precursors can have improved thermal stability and can form dielectric layers with many pores. In the case where the low-k dielectric layer is used to cover the interconnect lines, the interconnect lines can be stably supported due to its high mechanical strength, and the capacitance between the interconnect lines can be reduced due to its low dielectric constant.

While the embodiments of the present invention have been shown and described, the embodiments of the present invention

100‧‧‧Base

110‧‧‧First insulation

120‧‧‧Second insulation

200‧‧‧ chamber

210‧‧‧ plates

220‧‧‧Upper electrode

230‧‧‧RF generator

BP‧‧‧Block pattern

CP‧‧‧ cover pattern

DL‧‧‧ dielectric layer

DP‧‧‧ deposition process

DR‧‧‧ impurity area

ET‧‧‧Energy treatment

GE‧‧‧ gate electrode

GI‧‧‧ gate dielectric layer

IC‧‧‧ integrated circuit

IH‧‧‧Interconnecting holes

I-I'‧‧‧ line

II-II'‧‧‧ line

ML‧‧‧interconnect line

PDL‧‧‧ initial dielectric layer

RG‧‧‧reaction gas

SG‧‧‧ source gas

ST‧‧‧ device isolation

TR‧‧‧O crystal

VPH‧‧‧ vertical through the hole

1A and 2 are cross-sectional views illustrating a method of forming a low-k dielectric layer in accordance with example embodiments of the inventive concepts. FIG. 1B is a cross-sectional view schematically illustrating a chamber configured to perform the deposition process of FIG. 1A. 3, 5, and 7 are plan views illustrating a method of fabricating a semiconductor device in accordance with example embodiments of the inventive concepts. 4A, 6A, and 8A are cross-sectional views taken along line II' of Figs. 3, 5, and 7, respectively. 4B, 6B, and 8B are cross-sectional views taken along line II-II' of Figs. 3, 5, and 7, respectively. Figure 9 illustrates the vapor pressure of a ruthenium precursor in accordance with an example embodiment of the inventive concept. Figure 10 illustrates a pore radius distribution of a dielectric layer in accordance with an example embodiment of the inventive concept.

Claims (25)

A method of forming a dielectric layer, comprising: forming an initial dielectric layer on a substrate using a hafnium precursor containing a compound represented by the following Chemical Formula 1; and performing energy treatment on the initial dielectric layer to form a dielectric layer, [Chemical Formula 1] Wherein, in the chemical formula 1, n is 1 or 2, at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are -OR ₇ and the others are each independently hydrogen, (C ₁ - C ₁₀ ) alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl and one of (C ₁ -C ₁₀ )alkoxy, R ₇ is hydrogen, (C ₁ -C ₁₀ Alkyl, (C ₃ -C ₁₀ )alkenyl and one of (C ₃ -C ₁₀ )alkynyl, and R ₄ is a porogen group comprising (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ ) alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ )cycloalkynyl, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ ) ring One of an alkyl (C ₁ -C ₁₀ )alkyl group and a (C ₃ -C ₁₀ )heterocycloalkyl (C ₁ -C ₁₀ )alkyl group, wherein the Si—CH ₃ bonding unit and the Si—O bonding unit The ratio is in the range of 0.5 to 5. The method of forming a dielectric layer according to claim 1, wherein the aryl group, heteroaryl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group and heterocycloalkyl group in R ₄ are unsubstituted. Or each independently substituted with at least one of: (C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl, (C ₁ -C ₁₀ ) alkane Oxygen, halogen, cyano, nitro and hydroxy. The method of forming a dielectric layer according to claim 1, wherein the heteroaryl group and the heterocycloalkyl group in R ₄ each independently comprise at least one hetero atom, the hetero atom comprising -NR ₈ - And one of -O- and -S-, and R ₈ is one of hydrogen and (C ₁ -C ₁₀ )alkyl. The method of forming a dielectric layer according to claim ₁ , wherein at least two of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are (C ₁ -C ₅ ) alkoxy groups, and The other is (C ₁ -C ₅ )alkyl. The method of forming a dielectric layer according to claim 4, wherein at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are methoxy groups, and the others are (C ₁ -C) ₅ ) an alkyl group. The method of forming a dielectric layer according to claim 1, wherein R ₄ is 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2- Butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, phenyl, xylene , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, bicycloheptane One of a base, a bicycloheptenyl group, an epoxycyclohexane group, an epoxycyclopentyl group, a terpineyl group, a limonyl group, an epoxybutene, a styrene, and a fulvene. The method of forming a dielectric layer according to claim 1, wherein the compound has a vapor pressure of from 0.1 Torr to 100 Torr at 100 °C. The method of forming a dielectric layer according to claim 1, wherein the forming the initial dielectric layer is performed by chemical vapor deposition using at least one of oxygen, ozone, nitrous oxide, and carbon dioxide as a reactive gas. To form the initial dielectric layer. The method of forming a dielectric layer according to claim 1, wherein the performing the energy treatment is a thermal annealing process at a temperature ranging from 200 ° C to 800 ° C. The method of forming a dielectric layer according to claim 1, wherein the performing the energy treatment is an ultraviolet curing process, and the substrate has a temperature ranging from 0 ° C to 700 ° C. The method of forming a dielectric layer according to claim 1, wherein the dielectric layer has a carbon content ranging from 1 atomic percent to 40 atomic percent. The method of forming a dielectric layer according to claim 1, wherein the average diameter of the pores in the dielectric layer is in the range of 0.5 nm to 5 nm. The method of forming a dielectric layer according to claim 1, wherein the total volume of the voids in the dielectric layer is in the range of 8% to 35% of the total volume of the dielectric layer. The method of forming a dielectric layer according to claim 1, wherein the dielectric layer has a Young's modulus of 6 GPa to 15 GPa. The method of forming a dielectric layer according to claim 1, wherein a ratio of the Si-O cage structure to the Si-O network structure in the dielectric layer is in the range of 0.5 to 1. A method of fabricating a semiconductor device, the method comprising: forming a germanium insulating layer using a germanium precursor on a substrate, the germanium precursor comprising: a molecule having a Si-(CH ₂ ) _n -Si structure, wherein n is 1 or 2. A porogen group configured to combine with at least one Si atom in the molecule, the porogen group comprising (C ₃ -C ₁₀ )alkenyl, (C ₃ -C ₁₀ )alkynyl (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkyl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ a cycloalkynyl group, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl (C ₁ - One of C ₁₀ )alkyl and (C ₃ -C ₁₀ )heterocycloalkyl (C ₁ -C ₁₀ )alkyl, and at least two (C ₁ - configured to combine with Si atoms in the molecule a C ₅ ) alkoxy group; and at least one interconnect line is formed in the tantalum insulating layer. The method of manufacturing a semiconductor device according to claim 16, wherein a ratio of the Si—CH ₃ bonding unit to the Si—O bonding unit in the tantalum insulating layer is in a range of 0.5 to 5. The method of manufacturing a semiconductor device according to claim 16, wherein a ratio of the Si-O cage structure to the Si-O network structure in the tantalum insulating layer is in the range of 0.5 to 1. The method of manufacturing a semiconductor device according to claim 16, wherein the tantalum insulating layer has a dielectric constant of 2.2 to 3 and a Young's modulus of 6 GPa -15 GPa. The method of fabricating a semiconductor device according to claim 16, wherein the forming the at least one interconnect line comprises: patterning the tantalum insulating layer to form at least one interconnect in the tantalum insulating layer a hole; and forming a conductive layer to fill the at least one interconnected hole. The method of fabricating a semiconductor device according to claim 20, wherein the forming the at least one interconnect line further comprises forming a barrier layer covering the at least one interconnected hole before the forming the conductive layer. A method comprising: forming a dielectric layer using a ruthenium precursor containing a compound represented by the following Chemical Formula 1: [Chemical Formula 1] Wherein, in the chemical formula 1, n is 1 or 2, and at least three of R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are a methoxy group and the others are each independently hydrogen, (C ₁ -C) ₁₀ ) one of an alkyl group, a (C ₃ -C ₁₀ )alkenyl group, a (C ₃ -C ₁₀ )alkynyl group, and a (C ₁ -C ₁₀ )alkoxy group, and R ₄ is a (C ₃ -C ₁₀ ) alkene , (C ₃ -C ₁₀ )alkynyl, (C ₃ -C ₁₀ )aryl, (C ₃ -C ₁₀ )heteroaryl, (C ₃ -C ₁₀ )cycloalkenyl, (C ₃ -C ₁₀ a cycloalkynyl group, (C ₃ -C ₁₀ )heterocycloalkyl, (C ₃ -C ₁₀ )aryl(C ₁ -C ₁₀ )alkyl, (C ₃ -C ₁₀ )cycloalkyl (C ₁ - C ₁₀ ) an alkyl group and one of (C ₃ -C ₁₀ )heterocycloalkyl (C ₁ -C ₁₀ )alkyl groups. The method of forming a dielectric layer according to claim 22, wherein the forming the dielectric layer comprises: forming an initial dielectric layer using the germanium precursor on a substrate; and performing the initial dielectric layer Energy processing. The method of forming a dielectric layer according to claim 22, wherein the total pore volume in the dielectric layer is in the range of 8% to 35% of the total volume of the dielectric layer. The method of forming a dielectric layer according to claim 22, wherein a ratio of the Si-O cage structure to the Si-O network structure in the dielectric layer is in the range of 0.5 to 1.