TW202323260A - Precursor for low-k silicon-containing film deposition, deposition method of low-k silicon-containing film and semiconductor device of the same - Google Patents

Precursor for low-k silicon-containing film deposition, deposition method of low-k silicon-containing film and semiconductor device of the same Download PDF

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TW202323260A
TW202323260A TW111145349A TW111145349A TW202323260A TW 202323260 A TW202323260 A TW 202323260A TW 111145349 A TW111145349 A TW 111145349A TW 111145349 A TW111145349 A TW 111145349A TW 202323260 A TW202323260 A TW 202323260A
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silicon
dielectric constant
thin film
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朴鍾律
姜兌衡
朴容主
金相鎬
黃仁天
李相京
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南韓商思科特利肯股份有限公司
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Abstract

The present invention relates to a precursor for low-K silicon-containing film deposition, which is characterized by comprising a silicon-containing compound represented by chemical formula 1, a deposition method of low-K silicon-containing film using the same, and a semiconductor device, characterized by comprising a low-K silicon-containing film produced by the deposition method of the film. In the chemical formula 1, R is independently a hydrogen atom, or a C1-C6 linear, branched or cyclic alkyl group, an acrylic group containing a C1-C6 linear, branched or cyclic functional group, a vinyl group containing a C1-C6 linear, branched or cyclic functional group, an alkoxy or a primary amine or a secondary amine group containing a C1-C6 linear, branched or cyclic functional group, or a phenyl group containing a C1-C6 functional group, L is a linking group selected from a linear, branched or cyclic alkyl group or an aryl group.

Description

低介電常數含矽薄膜形成用前驅體、利用所述前驅體的低介電常數含矽薄膜形成方法以及包含所述低介電常數含矽薄膜的半導體器件Precursor for forming low dielectric constant silicon-containing thin film, method for forming low dielectric constant silicon-containing thin film using said precursor, and semiconductor device including said low dielectric constant silicon-containing thin film

本發明係有關一種含矽薄膜形成用前驅體、利用所述前驅體的含矽薄膜形成方法以及包含所述含矽薄膜的半導體器件，尤指一種可以利用二醇鹽橋接的乙矽烷結構（Dialkoxide-bridged disilane）的含矽化合物形成低介電常數薄膜的前驅體、利用所述前驅體的含矽薄膜形成方法以及包含所述金屬薄膜的半導體器件。The present invention relates to a precursor for forming a silicon-containing thin film, a method for forming a silicon-containing thin film using the precursor, and a semiconductor device comprising the silicon-containing thin film, especially a disilane structure (Dialkoxide) that can be bridged by a dialkoxide -bridged disilane) silicon-containing compound to form a low dielectric constant thin film precursor, a method for forming a silicon-containing thin film using the precursor, and a semiconductor device including the metal thin film.

伴隨著半導體器件的小型化以及高集成化，寄生電容也隨之增加並因此導致響應速度的延遲（RC delay），從而正在積極開展旨在解決所述問題的研發活動。形成所述寄生電容的主要原因在於，因為金屬佈線與金屬佈線之間的距離過於接近，因此所述金屬佈線之間的配置會形成與電容器相同的結構，而為了減少如上所述的現象，需要利用低介電常數的絕緣物質形成在所述金屬部件之間形成的層間絕緣膜。With the miniaturization and high integration of semiconductor devices, the parasitic capacitance increases, which causes a delay in response speed (RC delay), and R&D activities to solve this problem are being actively carried out. The main reason for the formation of the parasitic capacitance is that because the distance between the metal wiring and the metal wiring is too close, the configuration between the metal wiring will form the same structure as the capacitor, and in order to reduce the above-mentioned phenomenon, it is necessary to The interlayer insulating film formed between the metal parts is formed using an insulating substance with a low dielectric constant.

所述低介電常數的絕緣物質可以通過旋塗絕緣介質（SOD，spin-on dielectric）方式以及化學氣相沉積（Chemical vapor deposition，以下簡稱為CVD）方式形成，作為相關示例，可以以氟化矽酸鹽玻璃膜（Fluorinated Silicate Glass，以下簡稱為FSG膜）以及碳氧化矽（SiOC）膜為例。The low dielectric constant insulating material can be formed by spin-on dielectric (SOD, spin-on dielectric) and chemical vapor deposition (Chemical vapor deposition, hereinafter referred to as CVD). As a related example, fluorinated Silicate glass film (Fluorinated Silicate Glass, hereinafter referred to as FSG film) and silicon oxycarbide (SiOC) film are examples.

作為目前為了形成低介電常數薄膜而使用的前驅體，可以以如八甲基環四矽氧烷（OMCTS）、二乙氧基甲基矽烷（DEMS）以及四乙氧基原矽酸鹽（TEOS）等為例。所述前驅體為液態，有利於沉積工程中的汽化，但是在所形成的薄膜中難以實現足夠的硬度，因此其適用範圍比較受限。As the precursors currently used to form low dielectric constant films, octamethylcyclotetrasiloxane (OMCTS), diethoxymethylsilane (DEMS) and tetraethoxyorthosilicate ( TEOS) etc. as an example. The precursor is in a liquid state, which is beneficial to vaporization in the deposition process, but it is difficult to achieve sufficient hardness in the formed film, so its application range is relatively limited.

例如，在大韓民國公開專利公報第10-2006-0029762號中，在使用SiH4以及SiF4氣體形成絕緣膜的工程商作為有機矽氧烷源氣體使用如甲基乙氧基矽烷（MTES）、二乙氧基甲基矽烷（DEMS）、二甲氧基甲基矽烷（DMOMS）、四甲基環四矽氧烷（TOMCATS）、二甲基二甲氧基矽烷（DMDMOS）、二甲基二氧甲矽烷基環己烷（DMDOSH）以及三甲基矽烷（Z3MS）等，但是所述有機矽氧烷源只是附加添加到前驅體中，在降低介電常數方面比較受限，而且在將所述有機矽氧烷源作為前驅體使用的情況下，還會造成硬度降低的問題，因此在薄膜形成工程中使用時比較受限。For example, in the Republic of Korea Laid-Open Patent Publication No. 10-2006-0029762, engineers who use SiH4 and SiF4 gases to form insulating films use such as methyl ethoxy silane (MTES), diethoxy Dimethoxymethylsilane (DEMS), Dimethoxymethylsilane (DMOMS), Tetramethylcyclotetrasiloxane (TOMCATS), Dimethyldimethoxysilane (DMDMOS), Dimethyldioxysilane Cyclohexane (DMDOSH) and trimethylsilane (Z3MS), etc., but the organosiloxane source is only added to the precursor, which is relatively limited in reducing the dielectric constant, and the organosilicon When an oxane source is used as a precursor, it also causes the problem of a decrease in hardness, so its use in thin film formation processes is relatively limited.

先前技術文獻prior art literature

專利文獻patent documents

大韓民國公開專利公報第10-2006-0029762號Republic of Korea Patent Publication No. 10-2006-0029762

本發明旨在解決如上所述之先前技術中存在的問題，其目的在於提供一種利用可以通過在薄膜形成工程中施加能量而輕易地發生分解的化學結構的含矽化合物輕易地對分子內的碳含量比進行調節並對所形成的薄膜的硬度進行改善的低介電常數含矽薄膜形成用前驅體。The present invention aims to solve the problems in the prior art as described above, and its object is to provide a silicon-containing compound with a chemical structure that can be easily decomposed by applying energy in the film formation process to easily decompose the carbon in the molecule. A precursor for forming a low dielectric constant silicon-containing thin film that adjusts the content ratio and improves the hardness of the formed thin film.

此外，其目的在於提供一種可以通過使用所述低介電常數含矽薄膜形成用前驅體而形成低介電常數含矽薄膜的方法。In addition, it aims to provide a method capable of forming a low dielectric constant silicon-containing thin film by using the precursor for forming a low dielectric constant silicon-containing thin film.

此外，其目的在於提供一種包含所述低介電常數含矽薄膜的半導體器件。In addition, it aims to provide a semiconductor device including the low dielectric constant silicon-containing thin film.

為了達成如上所述之目的，本發明的低介電常數含矽薄膜形成用前驅體，其特徵在於：包含以下述化學式1表示的含矽化合物。 [化學式1]

Figure 02_image004
In order to achieve the above object, the precursor for forming a low dielectric constant silicon-containing thin film of the present invention is characterized in that it contains a silicon-containing compound represented by the following chemical formula 1. [chemical formula 1]
Figure 02_image004

在所述化學式1中，R各自獨立地為氫原子、或C 1-C 6的直鏈型或支鏈型或環型烷基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的烯丙基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的乙烯基、包含C 1-C 6的支鏈型後支鏈型或環型官能團的烷氧基、伯胺或仲胺基團、或包含C 1-C 6的官能團的苯基，L為從直鏈型、支鏈型、環型烷基或芳基中選擇的連接基團。 In the chemical formula 1, each R is independently a hydrogen atom, or a C 1 -C 6 linear or branched or cyclic alkyl group, a C 1 -C 6 linear or branched or Allyl of cyclic functional groups, vinyl containing C 1 -C 6 linear or branched or cyclic functional groups, alkyl containing C 1 -C 6 branched or cyclic functional groups An oxy group, a primary or secondary amine group, or a phenyl group containing a C 1 -C 6 functional group, and L is a linking group selected from linear, branched, cyclic alkyl or aryl.

具體來講，以所述化學式1表示的含矽化合物，可以為以下述化學式2至化學式4中的任一個表示的含矽化合物。 [化學式2]

Figure 02_image006
[化學式3]
Figure 02_image008
[化學式4]
Figure 02_image010
Specifically, the silicon-containing compound represented by Chemical Formula 1 may be a silicon-containing compound represented by any one of Chemical Formula 2 to Chemical Formula 4 below. [chemical formula 2]
Figure 02_image006
[chemical formula 3]
Figure 02_image008
[chemical formula 4]
Figure 02_image010

在所述化學式2至化學式4中，R各自獨立地為氫原子、或C 1-C 6的直鏈型或支鏈型或環型烷基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的烯丙基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的乙烯基、包含C 1-C 6的支鏈型或支鏈型或環型官能團的烷氧基、伯胺或仲胺基團、或包含C 1-C 6的官能團的苯基，n為1至8的整數。 In the chemical formulas 2 to 4, each R is independently a hydrogen atom, or a C 1 -C 6 linear or branched or cyclic alkyl group, or a C 1 -C 6 linear or branched alkyl group. Allyl with chain or cyclic functional group, vinyl with C 1 -C 6 linear or branched or cyclic functional group, branched or branched or cyclic with C 1 -C 6 An alkoxy group of a functional group, a primary or secondary amine group, or a phenyl group containing a C 1 -C 6 functional group, n is an integer of 1 to 8.

此外，所述前驅體可以進一步包含溶劑。此時，所述溶劑可以為C 1-C 16的飽和或不飽和烴、酮、醚、乙二醇二甲醚、酯、四氫呋喃以及叔胺中的任一個或多個，相對於所述低介電常數含矽薄膜形成用前驅體的總重量可以包含1至99重量%。 In addition, the precursor may further include a solvent. At this time, the solvent may be any one or more of C 1 -C 16 saturated or unsaturated hydrocarbons, ketones, ethers, ethylene glycol dimethyl ether, esters, tetrahydrofuran, and tertiary amines. The total weight of the precursor for forming a silicon-containing thin film with a dielectric constant may include 1 to 99% by weight.

此外，本發明的低介電常數含矽薄膜形成方法，包括：利用所述低介電常數含矽薄膜形成用前驅體在基板上形成薄膜的步驟。In addition, the method for forming a low dielectric constant silicon-containing thin film of the present invention includes: using the precursor for forming a low dielectric constant silicon-containing thin film to form a thin film on a substrate.

此外，所述低介電常數含矽薄膜，可以通過旋塗絕緣介質（spin-on dielectric，SOD）工程、高密度等離子體化學氣相沉積（High Density Plasma-Chemical Vapor Deposition，HDPCVD）工程或原子層沉積（Atomic Layer Deposition，ALD）工程形成。In addition, the silicon-containing thin film with low dielectric constant can be processed by spin-on dielectric (SOD) engineering, high density plasma chemical vapor deposition (High Density Plasma-Chemical Vapor Deposition, HDPCVD) engineering or atomic Layer deposition (Atomic Layer Deposition, ALD) engineering formation.

此外，可以包括：將所述低介電常數含矽薄膜形成用前驅體通過直接液體注入（DLI，Direct Liquid Injection）移送到腔室內部的步驟。In addition, it may include: a step of transferring the precursor for forming the silicon-containing thin film with low dielectric constant to the inside of the chamber through direct liquid injection (DLI, Direct Liquid Injection).

此外，可以包括：將所述低介電常數含矽薄膜形成用前驅體供應到基板上並通過生成等離子體而形成薄膜的步驟。In addition, it may include a step of supplying the precursor for forming a low dielectric constant silicon-containing thin film onto a substrate and forming a thin film by generating plasma.

此外，本發明的半導體器件可以通過所述低介電常數含矽薄膜形成方法進行製造。In addition, the semiconductor device of the present invention can be manufactured by the method for forming a thin film containing silicon with a low dielectric constant.

根據本發明的前驅體係以可以通過在薄膜形成工程中施加能量而輕易地發生分解的化學結構構成，因此在適用於低介電常數含矽薄膜的形成工程時，可以達成輕易地對分子內的碳含量比進行調節並對所形成的薄膜的硬度進行改善的效果。The precursor system according to the present invention is composed of a chemical structure that can be easily decomposed by applying energy in the film formation process. Therefore, when it is suitable for the formation process of low dielectric constant silicon-containing films, it can easily achieve molecular The effect of adjusting the carbon content ratio and improving the hardness of the formed film.

此外，通過使用所述前驅體，可以製造出低介電常數含矽薄膜以及包含所述低介電常數含矽薄膜的半導體器件。In addition, by using the precursor, a low dielectric constant silicon-containing film and a semiconductor device including the low dielectric constant silicon-containing film can be manufactured.

接下來，將對本發明進行更為詳細的說明。在說明書以及發明申請專利範圍中所使用的術語或單詞並不應該限定於一般或詞典上的含義做出解釋，而是應該立足於發明人可以為了以最佳的方式對自己的發明進行說明而對術語的概念做出適當定義的原則，以符合本發明之技術思想的含義以及概念做出解釋。Next, the present invention will be described in more detail. The terms or words used in the description and the patent scope of the invention application should not be limited to the general or dictionary meanings, but should be based on the inventor's ability to describe his invention in the best way. The principle of properly defining the concepts of terms is explained in order to comply with the meanings and concepts of the technical ideas of the present invention.

根據本發明的低介電常數含矽薄膜形成用前驅體，其特徵在於：包含以下述化學式1表示的含矽化合物。 [化學式1]

Figure 02_image004
The precursor for forming a low dielectric constant silicon-containing thin film according to the present invention is characterized in that it contains a silicon-containing compound represented by the following chemical formula 1. [chemical formula 1]
Figure 02_image004

在所述化學式1中，R各自獨立地為氫原子、或C 1-C 6的直鏈型或支鏈型或環型烷基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的烯丙基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的乙烯基、包含C 1-C 6的支鏈型後支鏈型或環型官能團的烷氧基、伯胺或仲胺基團、或包含C 1-C 6的官能團的苯基，L為從直鏈型、支鏈型、環型烷基或芳基中選擇的連接基團。 In the chemical formula 1, each R is independently a hydrogen atom, or a C 1 -C 6 linear or branched or cyclic alkyl group, a C 1 -C 6 linear or branched or Allyl of cyclic functional groups, vinyl containing C 1 -C 6 linear or branched or cyclic functional groups, alkyl containing C 1 -C 6 branched or cyclic functional groups An oxy group, a primary or secondary amine group, or a phenyl group containing a C 1 -C 6 functional group, and L is a linking group selected from linear, branched, cyclic alkyl or aryl.

在以所述化學式1表示的含矽化合物中，因為兩個矽烷化合物係以對稱的形態鍵合，因此在作為薄膜形成工程的前驅體使用時，可以獲得最佳的沉積效率。In the silicon-containing compound represented by the chemical formula 1, since two silane compounds are bonded in a symmetrical form, the best deposition efficiency can be obtained when used as a precursor of a thin film forming process.

以將如圖1所示的結構的含矽化合物適用於包膜形成工程的情況為例進行說明，因為對兩個矽烷化合物進行連接的烷氧基具有較低的鍵合能而很容發生斷裂（break-up），因此在施加等離子體時將分解成在氧原子上形成自由基的中間體。藉此，將形成具有反映區域的兩個矽單體，從而可以大幅提升形成薄膜的速度。此外，因為所述反映區域與薄膜表面的反應基團可以氣密鍵合，因此可以提升所形成的薄膜的硬度。此外，因為在所述化學式1中R與矽原子鍵合，因此在被吸附到薄膜表面之後會在薄膜內形成Si-C鍵。通過如上所述的表面吸附過程，可以降低所形成的含矽薄膜的介電常數。The case where a silicon-containing compound with the structure shown in Figure 1 is applied to the coating formation process is explained as an example, because the alkoxy group connecting two silane compounds has low bonding energy and is prone to breakage (break-up), and thus will decompose into intermediates that form free radicals on oxygen atoms when plasma is applied. In this way, two silicon monomers with reflecting regions will be formed, so that the speed of forming thin films can be greatly increased. In addition, since the reactive groups on the surface of the film can be airtightly bonded between the reflection region and the surface of the film, the hardness of the formed film can be improved. In addition, since R is bonded to a silicon atom in the chemical formula 1, a Si—C bond is formed in the film after being adsorbed to the surface of the film. Through the surface adsorption process as described above, the dielectric constant of the formed silicon-containing film can be reduced.

以所述化學式1表示的含矽化合物的連接基團為結合到矽原子的烷氧基之間的連接並以在施加能量時可以輕易地發生分解的結構構成，如上所述，可以從直鏈型、支鏈型、環型烷基或芳基中選擇。The linking group of the silicon-containing compound represented by the above chemical formula 1 is a link between alkoxy groups bonded to silicon atoms and has a structure that can easily decompose when energy is applied. Type, branched, cyclic alkyl or aryl.

具體來講，在所述連接基團為直鏈型或支鏈型烷基的情況下，以所述化學式1表示的含矽化合物可以為以下述化學式2表示的化合物。 [化學式2]

Figure 02_image006
Specifically, when the linking group is a linear or branched alkyl group, the silicon-containing compound represented by the chemical formula 1 may be a compound represented by the following chemical formula 2. [chemical formula 2]
Figure 02_image006

對所述R的定義與化學式1相同，所述n為1至8的整數，在所述兩個烷氧基之間可以結合各種形態的烷基。The definition of R is the same as in Chemical Formula 1, the n is an integer from 1 to 8, and various forms of alkyl groups can be combined between the two alkoxy groups.

此外，在所述連接基團為環型烷基的情況下，可以形成如下述化學式3所示的化學結構的化合物。 [化學式3]

Figure 02_image008
In addition, in the case where the linking group is a cyclic alkyl group, a compound having a chemical structure shown in Chemical Formula 3 below may be formed. [chemical formula 3]
Figure 02_image008

對所述R的定義與化學式1相同，所述n為1至8的整數，在所述兩個烷氧基之間可以結合各種形態的環型烷基。The definition of R is the same as in Chemical Formula 1, the n is an integer from 1 to 8, and various forms of cycloalkyl groups can be combined between the two alkoxy groups.

此外，在所述連接基團為芳基的情況下，可以形成如下述化學式4所示的化學結構的化合物。 [化學式4]

Figure 02_image010
In addition, in the case where the linking group is an aryl group, a compound having a chemical structure shown in Chemical Formula 4 below may be formed. [chemical formula 4]
Figure 02_image010

對所述R的定義與化學式1相同，在所述化學結構中，當有能量照射時芳基與氧之間可以發生斷裂並形成自由基。此外，以如上所述的方式形成的芳基可以提升薄膜內的碳含量。The definition of R is the same as that of Chemical Formula 1. In the chemical structure, aryl and oxygen can be broken and free radicals can be formed when energy is irradiated. In addition, the aryl group formed in the manner described above can increase the carbon content in the film.

此外，本發明的前驅體可以進一步包含溶劑。作為所述溶劑，可以使用C 1-C 16的飽和或不飽和烴、酮、醚、乙二醇二甲醚、酯、四氫呋喃以及叔胺中的任一個或所述之混合物。作為所述C 1-C 16的飽和或不飽和烴的實例，可以以甲苯以及庚烷等為例，而作為叔胺可以以二甲基乙胺為例。 In addition, the precursor of the present invention may further contain a solvent. As the solvent, any one of C 1 -C 16 saturated or unsaturated hydrocarbons, ketones, ethers, ethylene glycol dimethyl ether, esters, tetrahydrofuran and tertiary amines or a mixture thereof can be used. Examples of the C 1 -C 16 saturated or unsaturated hydrocarbons include toluene and heptane, and examples of tertiary amines include dimethylethylamine.

尤其是，在含矽化合物在室溫下為固體狀態的情況下，包含可以對其進行溶解的溶劑為宜。即，在包含所述溶劑的情況下，以可對所述含矽化合物進行溶解的含量包含可對所述含矽化合物進行溶解的溶劑，相對於所述含矽薄膜形成用前驅體的總重量包含1至99重量%為宜。In particular, when the silicon-containing compound is in a solid state at room temperature, it is preferable to include a solvent that can dissolve it. That is, when the solvent is included, the solvent that can dissolve the silicon-containing compound is contained in an amount that can dissolve the silicon-containing compound, relative to the total weight of the precursor for forming a silicon-containing thin film It is suitable to contain 1 to 99% by weight.

因為包含或不包含所述溶劑的前驅體可以被汽化，因此可以以前驅體氣體的形態供應到腔室內部。因此，根據含矽化合物的類型，當在室溫下以液態存在且可以輕易地發生汽化時，也可以在沒有單獨的溶劑的情況下執行薄膜成型工程。Since the precursor including or not including the solvent can be vaporized, it can be supplied to the inside of the chamber in the form of precursor gas. Therefore, depending on the type of silicon-containing compound, when it exists in a liquid state at room temperature and can easily vaporize, it is also possible to perform thin film formation without a separate solvent.

此外，在使用所述含矽化合物形成低介電常數含矽薄膜時，可以利用旋塗絕緣介質（spin-on dielectric，SOD）工程、高密度等離子體化學氣相沉積（High Density Plasma-Chemical Vapor Deposition，HDP-CVD）工程或原子層沉積（Atomic Layer Deposition，ALD）工程形成薄膜。In addition, when using the silicon-containing compound to form a low dielectric constant silicon-containing film, spin-on dielectric (SOD) engineering, high density plasma chemical vapor deposition (High Density Plasma-Chemical Vapor Deposition, HDP-CVD) engineering or atomic layer deposition (Atomic Layer Deposition, ALD) engineering to form thin films.

例如，在適用高密度等離子體化學氣相沉積（HDP-CVD）工程的情況下，因為與常壓化學氣相沉積（AP-CVD）工程、低壓化學氣相沉積（LP-CVD）工程或等離子體強化化學氣相沉積（PE-CVD）工程相比可以在高真空以及高功率條件下執行，因此可以形成結構緻密且機械特性優秀的薄膜。For example, in the case of high-density plasma chemical vapor deposition (HDP-CVD) engineering, because it is different from atmospheric pressure chemical vapor deposition (AP-CVD) engineering, low pressure chemical vapor deposition (LP-CVD) engineering or plasma Compared with the bulk enhanced chemical vapor deposition (PE-CVD) process, it can be performed under high vacuum and high power conditions, so it can form a thin film with a dense structure and excellent mechanical properties.

為此，形成薄膜的工程，包括：將所述低介電常數含矽薄膜形成用前驅體通過直接液體注入（DLI，Direct Liquid Injection）移送到腔室內部的步驟；以及，通過在將與移送到所述腔室內部的所述前驅體不同的源氣體供應到基板上的狀態下施加等離子體而形成薄膜的步驟。For this reason, the process of forming the thin film includes: the step of transferring the precursor for forming the low dielectric constant silicon-containing thin film to the interior of the chamber through direct liquid injection (DLI, Direct Liquid Injection); A step of forming a thin film by applying plasma in a state in which a source gas different from the precursor is supplied to the substrate inside the chamber.

例如，通過向形成有金屬佈線圖案的基板供應所述低介電常數含矽薄膜形成用前驅體氣體、氧氣以及作為運載氣體的氫氣並在其中生成等離子體，可以形成對在所述基板上形成的金屬佈線圖案之間的縫隙進行填充的低介電常數的層間絕緣膜。此外，在需要形成氟化矽絕緣膜的情況下，也可以以同時供應氟源氣體的方式形成薄膜。For example, by supplying the precursor gas for forming a low dielectric constant silicon-containing thin film, oxygen gas, and hydrogen gas as a carrier gas to a substrate on which a metal wiring pattern is formed, and generating plasma therein, a pair formed on the substrate can be formed. The gaps between the metal wiring patterns are filled with a low dielectric constant interlayer insulating film. In addition, when it is necessary to form a silicon fluoride insulating film, the thin film can also be formed by simultaneously supplying a fluorine source gas.

此外，根據層間絕緣膜的類型，通過在向基板供應矽源氣體、氟源氣體、氧氣以及含碳氣體的同時供應運載氣體即氫氣並生成等離子體，可以形成對基板上的金屬佈線圖案之間的縫隙進行填充的低介電常數的絕緣膜。In addition, depending on the type of interlayer insulating film, by supplying silicon source gas, fluorine source gas, oxygen gas, and carbon-containing gas to the substrate and simultaneously supplying hydrogen gas as a carrier gas and generating plasma, it is possible to form a gap between metal wiring patterns on the substrate. The gap is filled with a low dielectric constant insulating film.

作為所述氟源，可以使用通常所使用的SiF 4，而作為包含碳的氣體，可以使用如CH 4、C 2H 4、C 2H 6、C 2H 2以及C 6H 6等烴氣體，或使用如甲基乙氧基矽烷（MTES）、二乙氧基甲基矽烷（DEMS）、二甲氧基甲基矽烷（DMOMS）、四甲基環四矽氧烷（TOMCATS）、二甲基二甲氧基矽烷（DMDMOS）、二甲基二氧甲矽烷基環己烷（DMDOSH）以及三甲基矽烷等有機矽氧烷源氣體。 As the fluorine source, generally used SiF 4 can be used, and as the carbon-containing gas, hydrocarbon gases such as CH 4 , C 2 H 4 , C 2 H 6 , C 2 H 2 , and C 6 H 6 can be used. , or use such as methylethoxysilane (MTES), diethoxymethylsilane (DEMS), dimethoxymethylsilane (DMOMS), tetramethylcyclotetrasiloxane (TOMCATS), dimethyl Organosiloxane source gases such as dimethoxysilane (DMDMOS), dimethyldioxysilylcyclohexane (DMDOSH) and trimethylsilane.

用於形成所述薄膜的工程，可以在1至1000mTorr的腔室內壓力條件下執行。此外，用於在所述腔室內生成等離子體的源功率為500至9,000W為宜，而偏置功率為0至5,000W為宜。此外，在一部分情況下也可以不施加所述偏置功率。The process for forming the thin film can be performed under the pressure condition in the chamber of 1 to 1000 mTorr. In addition, the source power for generating plasma in the chamber is preferably 500 to 9,000W, and the bias power is preferably 0 to 5,000W. In addition, the bias power may not be applied in some cases.

在所述薄膜形成工程中，因為在本發明中使用的含矽化合物的結構特性，在形成層間絕緣膜時將同時形成微細的空隙。通過形成如上所述的空隙，可以進一步降低所述層間絕緣膜的介電常數，從而達成與目前的層間絕緣膜相比更低的介電常數。In the thin film formation process, because of the structural characteristics of the silicon-containing compound used in the present invention, fine voids are formed at the same time when the interlayer insulating film is formed. By forming the void as described above, the dielectric constant of the interlayer insulating film can be further lowered, thereby achieving a lower dielectric constant than the conventional interlayer insulating film.

此外，因為可以提升含矽化合物與薄膜表面之間的結合力，因此可以提升所形成的薄膜的機械特性。In addition, since the bonding force between the silicon-containing compound and the surface of the film can be improved, the mechanical properties of the formed film can be improved.

此外，因為可以藉助於所述氫氣的流入而提升縫隙填充能力，因此可以在所述金屬佈線之間形成沒有無效區（void）的層間絕緣膜，從而防止可能會因為所述無效區而導致的工程不良下良。In addition, since the gap-filling capability can be improved by the inflow of the hydrogen gas, an interlayer insulating film without voids can be formed between the metal wirings, thereby preventing damage that may be caused by the voids. Bad engineering goes bad.

此外，通過適用所述薄膜形成工程，可以製造出包含低介電常數含矽薄膜的半導體器件。此時，所述低介電常數含矽薄膜將作為層間絕緣膜形成氟化矽酸鹽玻璃（FSG，Fluarinated Silicate Glass）或有機矽酸鹽玻璃（OSG，Organo Silicate Glass）膜，藉此減少半導體器件的佈線之間的寄生電容器並形成高品質的半導體器件。In addition, by applying the above thin film formation process, it is possible to manufacture a semiconductor device including a low dielectric constant silicon-containing thin film. At this time, the low dielectric constant silicon-containing film will be used as an interlayer insulating film to form a fluorinated silicate glass (FSG, Fluarinated Silicate Glass) or organic silicate glass (OSG, Organo Silicate Glass) film, thereby reducing the Parasitic capacitors between the wiring of the device and form a high-quality semiconductor device.

接下來，將參閱實施例對本發明的效果進行說明。Next, effects of the present invention will be described with reference to Examples.

實施例1：4,4,6,7,9,9-六甲基-3,5,8,10-四氧雜-4,9-二矽雜十二烷（4,4,6,7,9,9-hexamethyl-3,5,8,10-tetraoxa-4,9-disiladodecane）的製造Example 1: 4,4,6,7,9,9-hexamethyl-3,5,8,10-tetraoxa-4,9-disilazadodecane (4,4,6,7 ,9,9-hexamethyl-3,5,8,10-tetraoxa-4,9-disiladodecane) manufacture

在將利用5L的己烷溶解200g（1.55mol）的二氯二甲基矽烷的溶液冷卻至低溫（約為0℃）狀態之後，依次緩緩添加90.4mL（1.55mol）的乙醇以及215mL（1.55mol）的三乙胺，然後在室溫下進行大約6小時的攪拌。在將反應物重新冷卻至低溫（約為0℃）狀態之後，添加70.7mL（0.77mol）的2,3-丁二醇和259mL（1.86mol）的三乙胺以及1L的己烷的混合物，接下來在室溫下進行大約12小時的攪拌。對最終反應物進行過濾並將過濾液在減壓條件下去除溶劑，從而獲得無色液體。對所獲得的液體進行減壓提純(70℃（bath基準）@0.2torr)，從而獲得159.5g的無色液體即4,4,6,7,9,9-六甲基-3,5,8,10-四氧雜-4,9-二矽雜十二烷(4,4,6,7,9,9-hexamethyl-3,5,8,10-tetraoxa-4,9-disiladodecane)（產率：70%）。After cooling the solution of 200 g (1.55 mol) of dichlorodimethylsilane dissolved in 5 L of hexane to a low temperature (about 0°C), 90.4 mL (1.55 mol) of ethanol and 215 mL (1.55 mol) of triethylamine, followed by stirring at room temperature for about 6 hours. After recooling the reactant to a low temperature (about 0°C), a mixture of 70.7 mL (0.77 mol) of 2,3-butanediol and 259 mL (1.86 mol) of triethylamine and 1 L of hexane was added, followed by Come down and stir at room temperature for about 12 hours. The final reaction was filtered and the filtrate was freed of solvent under reduced pressure to obtain a colorless liquid. Purify the obtained liquid under reduced pressure (70°C (bath basis) @0.2torr) to obtain 159.5 g of a colorless liquid, namely 4,4,6,7,9,9-hexamethyl-3,5,8 ,10-tetraoxa-4,9-disiladodecane (4,4,6,7,9,9-hexamethyl-3,5,8,10-tetraoxa-4,9-disiladodecane) (produced rate: 70%).

生成物的核磁共振（NMR）分析結構如圖2所示，其特徵峰值如下。 1H-NMR(C 6D 6)：δ 0.16 [s, 12H, -Si(OCH 2CH 3)(CH 3) 2], 1.15 [t, J=7.0 Hz, 6H, meso-Si(OCH 2CH 3)(CH 3) 2], 1.22-1.25 [m, 6.8H, dl -Si(OCH 2CH 3)(CH 3) 2and -OCH(CH 3)], 3.65-3.72 [m, 4H, meso and dl -Si(OCH 2CH 3)(CH 3) 2], 3.79-3.86 [m, 1.7H, meso -OCH(CH 3)], 3.95-4.02 [m, 0.5H, dl -OCH(CH 3)] The nuclear magnetic resonance (NMR) analysis structure of the product is shown in Figure 2, and its characteristic peaks are as follows. 1 H-NMR(C 6 D 6 ): δ 0.16 [s, 12H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.15 [t, J=7.0 Hz, 6H, meso-Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.22-1.25 [m, 6.8H, dl -Si(OCH 2 CH 3 )(CH 3 ) 2 and -OCH(CH 3 )], 3.65-3.72 [m, 4H, meso and dl -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 3.79-3.86 [m, 1.7H, meso -OCH(CH 3 )], 3.95-4.02 [m, 0.5H, dl -OCH(CH 3 )]

實施例2：1,2-雙((乙氧基二甲基甲矽烷基)氧基)環己烷（1,2-bis((ethoxydimethylsilyl)oxy)cyclohexane）的製造Example 2: Production of 1,2-bis((ethoxydimethylsilyl)oxy)cyclohexane (1,2-bis((ethoxydimethylsilyl)oxy)cyclohexane)

在將利用500mL的己烷溶解20g（0.15mol）的二氯二甲基矽烷的溶液冷卻至低溫（約為0℃）狀態之後，依次緩緩添加9mL（0.15mol）的乙醇以及21.5mL（0.15mol）的三乙胺，然後在室溫下進行大約6小時的攪拌。在將反應物重新冷卻至低溫（約為0℃）狀態之後，添加8.9g（0.07mol）的1,2-环己二醇和26mL（0.18mol）的三乙胺以及100mL的四氫呋喃的混合物，接下來在室溫下進行大約12小時的攪拌。對最終反應物進行過濾並將過濾液在減壓條件下去除溶劑，從而獲得無色液體。對所獲得的液體進行減壓提純(100℃（bath基準）@0.2torr)，從而獲得13.2g的無色液體即1,2-雙((乙氧基二甲基甲矽烷基)氧基)環己烷(1,2-bis((ethoxydimethylsilyl)oxy)cyclohexane)（產率：53%）。After cooling the solution of 20 g (0.15 mol) of dichlorodimethylsilane dissolved in 500 mL of hexane to a low temperature (about 0°C), 9 mL (0.15 mol) of ethanol and 21.5 mL (0.15 mol) of triethylamine, followed by stirring at room temperature for about 6 hours. After recooling the reactant to a low temperature (about 0°C), a mixture of 8.9 g (0.07 mol) of 1,2-cyclohexanediol, 26 mL (0.18 mol) of triethylamine and 100 mL of tetrahydrofuran was added, followed by Come down and stir at room temperature for about 12 hours. The final reaction was filtered and the filtrate was freed of solvent under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure (100°C (bath basis)@0.2torr) to obtain 13.2 g of a colorless liquid, 1,2-bis((ethoxydimethylsilyl)oxy)cyclo Hexane (1,2-bis((ethoxydimethylsilyl)oxy)cyclohexane) (Yield: 53%).

生成物的核磁共振（NMR）分析結構如圖3所示，其特徵峰值如下。 1H-NMR(C 6D 6)：δ 0.21-0.24 [m, 12H, -Si(OCH 2CH 3)(CH 3) 2], 1.16-1.20 [m, 7.3H, -Si(OCH 2CH 3)(CH 3) 2], 1.36-1.46 [m, 2.8H, cycle-(CHCH 2-CH 2)-], 1.51-1.57 [m, 1.1H, cycle-(CHCH 2-CH 2)-], 1.64-1.72 [m, 1.5H, cycle-(CHCH 2-CH 2)-], 1.86-1.94 [m, 1.6H, cycle-(CHCH 2-CH 2)-], 1.96-2.03 [m, 1.1H, cycle-(CHCH 2-CH 2)-], 3.70-3.76 [m, 4.9H, cycle-(CHCH 2-CH 2)- and -Si(OCH 2CH 3)(CH 3) 2], 3.86-3.88 [m, 1.1H, cycle-(CHCH 2-CH 2)-] The nuclear magnetic resonance (NMR) analysis structure of the product is shown in Figure 3, and its characteristic peaks are as follows. 1 H-NMR (C 6 D 6 ): δ 0.21-0.24 [m, 12H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.16-1.20 [m, 7.3H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.36-1.46 [m, 2.8H, cycle-(CHCH 2 -CH 2 )-], 1.51-1.57 [m, 1.1H, cycle-(CHCH 2 -CH 2 )-] , 1.64-1.72 [m, 1.5H, cycle-(CHCH 2 -CH 2 )-], 1.86-1.94 [m, 1.6H, cycle-(CHCH 2 -CH 2 )-], 1.96-2.03 [m, 1.1 H, cycle-(CHCH 2 -CH 2 )-], 3.70-3.76 [m, 4.9H, cycle-(CHCH 2 -CH 2 )- and -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 3.86 -3.88 [m, 1.1H, cycle-(CHCH 2 -CH 2 )-]

實施例3：1,4-雙((乙氧基二甲基甲矽烷基)氧基)環己烷（1,4-bis((ethoxydimethylsilyl)oxy)cyclohexane）的製造Example 3: Production of 1,4-bis((ethoxydimethylsilyl)oxy)cyclohexane (1,4-bis((ethoxydimethylsilyl)oxy)cyclohexane)

在將利用500mL的己烷溶解10g（0.08mol）的二氯二甲基矽烷的溶液冷卻至低溫（約為0℃）狀態之後，依次緩緩添加4.5mL（0.08mol）的乙醇以及10.8mL（0.08mol）的三乙胺，然後在室溫下進行大約6小時的攪拌。在將反應物重新冷卻至低溫（約為0℃）狀態之後，添加4.5g（0.04mol）的1,4-环己二醇和11.8mL（0.09mol）的三乙胺以及100mL的四氫呋喃的混合物，接下來在室溫下進行大約12小時的攪拌。對最終反應物進行過濾並將過濾液在減壓條件下去除溶劑，從而獲得無色液體。對所獲得的液體進行減壓提純(100℃（bath基準）@0.6torr)，從而獲得7.9g的無色液體即1,4-雙((乙氧基二甲基甲矽烷基)氧基)環己烷(1,4-bis((ethoxydimethylsilyl)oxy)cyclohexane)（產率：62%）。After cooling the solution of 10g (0.08mol) of dichlorodimethylsilane dissolved in 500mL of hexane to a low temperature (about 0°C), 4.5mL (0.08mol) of ethanol and 10.8mL ( 0.08mol) of triethylamine, and then stirred at room temperature for about 6 hours. After recooling the reactant to a low temperature (about 0°C), a mixture of 4.5 g (0.04 mol) of 1,4-cyclohexanediol, 11.8 mL (0.09 mol) of triethylamine and 100 mL of tetrahydrofuran was added, Stirring is then carried out at room temperature for about 12 hours. The final reaction was filtered and the filtrate was freed of solvent under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure (100° C. (bath basis) @ 0.6 torr) to obtain 7.9 g of a colorless liquid, 1,4-bis((ethoxydimethylsilyl)oxy)cyclo Hexane (1,4-bis((ethoxydimethylsilyl)oxy)cyclohexane) (Yield: 62%).

生成物的核磁共振（NMR）分析結構如圖4所示，其特徵峰值如下。 1H-NMR(C 6D 6)：δ 0.15 [d, 12H, J=6.0 Hz -Si(OCH 2CH 3)(CH 3) 2], 1.14 [t, J=7.0 Hz, 5.6H, -Si(OCH 2CH 3)(CH 3) 2], 1.46-1.55, 1.91-2.00 [m, 4.3H, cycle-CH(CH 2-CH 2)CH-], 1.91-2.00 [m, 4.3H, cycle-CH(CH 2-CH 2)CH-], 3.67 [q, 3.9H, -Si(OCH 2CH 3)(CH 3) 2], 3.82-3.89 [m, 2.1H, cycle-CH(CH 2-CH 2)CH-] The nuclear magnetic resonance (NMR) analysis structure of the product is shown in Figure 4, and its characteristic peaks are as follows. 1 H-NMR (C 6 D 6 ): δ 0.15 [d, 12H, J=6.0 Hz -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.14 [t, J=7.0 Hz, 5.6H, - Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.46-1.55, 1.91-2.00 [m, 4.3H, cycle-CH(CH 2 -CH 2 )CH-], 1.91-2.00 [m, 4.3H, cycle-CH(CH 2 -CH 2 )CH-], 3.67 [q, 3.9H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 3.82-3.89 [m, 2.1H, cycle-CH(CH 2 -CH 2 )CH-]

實施例4：1,2-雙((乙氧基二甲基甲矽烷基)氧基)苯（1,4-bis((ethoxydimethylsilyl)oxy)benzene）的製造Example 4: Production of 1,2-bis((ethoxydimethylsilyl)oxy)benzene (1,4-bis((ethoxydimethylsilyl)oxy)benzene)

在將利用500mL的己烷溶解10g（0.08mol）的二氯二甲基矽烷的溶液冷卻至低溫（約為0℃）狀態之後，依次緩緩添加4.5mL（0.08mol）的乙醇以及10.8mL（0.08mol）的三乙胺，然後在室溫下進行大約6小時的攪拌。在將反應物重新冷卻至低溫（約為0℃）狀態之後，添加4.2g（0.04mol）的1,2-二羥基苯和11.8mL（0.09mol）的三乙胺以及100mL的四氫呋喃的混合物，接下來在室溫下進行大約12小時的攪拌。對最終反應物進行過濾並將過濾液在減壓條件下去除溶劑，從而獲得無色液體。對所獲得的液體進行減壓提純(175℃（bath基準）@0.4torr)，從而獲得3.2g的無色液體即1,2-雙((乙氧基二甲基甲矽烷基)氧基)苯(1,2-bis((ethoxydimethylsilyl)oxy)benzene)（產率：25%）。After cooling the solution of 10g (0.08mol) of dichlorodimethylsilane dissolved in 500mL of hexane to a low temperature (about 0°C), 4.5mL (0.08mol) of ethanol and 10.8mL ( 0.08mol) of triethylamine, and then stirred at room temperature for about 6 hours. After recooling the reactant to a low temperature (about 0°C), a mixture of 4.2 g (0.04 mol) of 1,2-dihydroxybenzene, 11.8 mL (0.09 mol) of triethylamine and 100 mL of tetrahydrofuran was added, Stirring is then carried out at room temperature for about 12 hours. The final reaction was filtered and the filtrate was freed of solvent under reduced pressure to obtain a colorless liquid. The obtained liquid was purified under reduced pressure (175°C (bath basis)@0.4torr) to obtain 3.2 g of a colorless liquid, namely 1,2-bis((ethoxydimethylsilyl)oxy)benzene (1,2-bis((ethoxydimethylsilyl)oxy)benzene) (Yield: 25%).

生成物的核磁共振（NMR）分析結構如圖5所示，其特徵峰值如下。 1H-NMR(C 6D 6)：δ 0.26 [s, 12H, -Si(OCH 2CH 3)(CH 3) 2], 1.13 [t, 6.5H, J=7.0 Hz, -Si(OCH 2CH 3)(CH 3) 2], 3.74 [q, 4.3H, -Si(OCH 2CH 3)(CH 3) 2], 6.79-6.83 [m, 2.5H, aromatic-C(CH=CH)-], 7.09-7.13 [m, 2.2H, aromatic-C(CH=CH)-] The nuclear magnetic resonance (NMR) analysis structure of the product is shown in Figure 5, and its characteristic peaks are as follows. 1 H-NMR(C 6 D 6 ): δ 0.26 [s, 12H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 1.13 [t, 6.5H, J=7.0 Hz, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 3.74 [q, 4.3H, -Si(OCH 2 CH 3 )(CH 3 ) 2 ], 6.79-6.83 [m, 2.5H, aromatic-C(CH=CH)- ], 7.09-7.13 [m, 2.2H, aromatic-C(CH=CH)-]

此外，對實施例1至實施例4的化合物進行熱重分析儀（TGA）分析的結果如圖6所示，在100至200℃的區域內觀察到重量損失。通過如上所述的結果可以確認，可以在相對較低的溫度下進行沉積。Furthermore, as a result of thermogravimetric analysis (TGA) analysis of the compounds of Examples 1 to 4, as shown in FIG. 6 , weight loss was observed in the region of 100 to 200°C. From the results as described above, it was confirmed that deposition can be performed at a relatively low temperature.

按照如下所述的方式，執行了通過利用實施例1至實施例4的化合物的沉積工程形成薄膜的試驗評估。Experimental evaluations of forming thin films by deposition processes using the compounds of Examples 1 to 4 were performed in the manner described below.

製造例Manufacturing example

為了執行低介電常數含矽薄膜的沉積工程，在反應腔室內安裝6英吋p-型Si晶圓並利用氬（Ar）氣體對方反應腔室內部進行吹掃。在120℃的汽化器（vaporizer）中，以0.4g/min的速度以及400sccm的運載氣體的條件將前驅體供應到施加400W的等離子體的腔室，並對350至400℃的工程溫度以及2至10sccm的氧氣（O 2）注入量下通過***（split）沉積的低介電常數含矽薄膜的沉積率（GPC）進行測定，其結果如下述表1所示。 In order to perform the deposition process of low dielectric constant silicon-containing thin films, a 6-inch p-type Si wafer is installed in the reaction chamber and the inside of the reaction chamber is purged with argon (Ar) gas. In a vaporizer (vaporizer) at 120°C, the precursor was supplied to the chamber applying a 400W plasma at a rate of 0.4g/min and a carrier gas of 400sccm, and the engineering temperature of 350 to 400°C and 2 to The deposition rate (GPC) of the low-dielectric-constant silicon-containing film deposited by split deposition under the oxygen (O 2 ) injection amount of 10 sccm was measured, and the results are shown in Table 1 below.

表1 工程條件 工程溫度（℃） O 2氣流（Gas Flow，sccm） 沉積率（GPC，Å/min） 1 350 2 113 2 350 10 142 3 400 2 96 4 400 10 122 Table 1 Engineering conditions Engineering temperature (°C) O2 gas flow (Gas Flow, sccm) Deposition rate (GPC, Å/min) 1 350 2 113 2 350 10 142 3 400 2 96 4 400 10 122

通過所沉積的薄膜的X射線光電子能譜（XPS）分析而對薄膜內的矽、氧以及碳的含量進行測定的結果如下述表2所示。The results of measuring the contents of silicon, oxygen and carbon in the thin film by X-ray photoelectron spectroscopy (XPS) analysis of the deposited thin film are shown in Table 2 below.

表2 工程條件 Si O C 組成比 （Si : O : C） 1 36.8 43.3 20 1 : 1.18 : 0.54 2 36.7 49.5 13.8 1 : 1.35 : 0.38 3 37.7 42.9 19.5 1 : 1.14 : 0.52 4 37.2 49.5 13.4 1 : 1.33 : 0.36 Table 2 Engineering conditions Si o C Composition ratio (Si : O : C) 1 36.8 43.3 20 1 : 1.18 : 0.54 2 36.7 49.5 13.8 1 : 1.35 : 0.38 3 37.7 42.9 19.5 1 : 1.14 : 0.52 4 37.2 49.5 13.4 1 : 1.33 : 0.36

此外，對所沉積的薄膜的k值以及模數（modulus）進行測定的結果如下述表3所示。In addition, the results of measuring the k value and modulus of the deposited thin film are shown in Table 3 below.

表3 工程條件 k 模數（Modulus，GPa） 1 1.94 31.1 2 2.46 28 3 1.80 42 4 2.27 38.4 table 3 Engineering conditions k Modulus (Modulus, GPa) 1 1.94 31.1 2 2.46 28 3 1.80 42 4 2.27 38.4

通過表3中的結果可以確認，所沉積的薄膜在具有低介電常數的同時呈現出較高的機械物性。這表明使用本發明的含矽薄膜形成用前驅體可以形成高品質的低介電常數薄膜。From the results in Table 3, it can be confirmed that the deposited films exhibit high mechanical properties while having a low dielectric constant. This shows that a high-quality low dielectric constant film can be formed using the silicon-containing film-forming precursor of the present invention.

在上述內容中參閱較佳的實施形態對本發明進行了說明，但是本發明並不限定於所述實施形態，具有本發明所屬技術領域之一般知識的人員可以在不脫離本發明之要旨的範圍內進行各種變形以及變更。如上所述的變形例以及變更例都應該解釋為包含在本發明以及所附的發明申請專利範圍之內。In the above content, the present invention has been described with reference to preferred embodiments, but the present invention is not limited to the described embodiments, and those with general knowledge in the technical field to which the present invention belongs can understand the present invention without departing from the gist of the present invention. Various modifications and changes are made. The above-mentioned modified examples and modified examples should be interpreted as being included in the scope of the present invention and the appended patent application.

無none

圖1係對由以化學式1表示的含矽化合物構成的前驅體在施加等離子體時形成反應區域的過程進行圖示的概念圖。 圖2係根據實施例1的含矽化合物的核磁共振氫谱（ 1H-NMR）分析結果； 圖3係根據實施例2的含矽化合物的核磁共振氫谱（ 1H-NMR）分析結果； 圖4係根據實施例3的含矽化合物的核磁共振氫谱（ 1H-NMR）分析結果； 圖5係根據實施例4的含矽化合物的核磁共振氫谱（ 1H-NMR）分析結果； 圖6係根據實施例1至4的含矽化合物的熱重分析儀（TGA）分析結果。 1 is a conceptual diagram illustrating a process in which a precursor composed of a silicon-containing compound represented by Chemical Formula 1 forms a reaction region when plasma is applied. Fig. 2 is the hydrogen nuclear magnetic resonance spectrum ( 1 H-NMR) analysis result of the silicon-containing compound according to Example 1; Fig. 3 is the hydrogen nuclear magnetic resonance spectrum ( 1 H-NMR) analysis result of the silicon-containing compound according to Example 2; Fig. 4 is the proton nuclear magnetic resonance ( 1 H-NMR) analysis result of the silicon-containing compound according to Example 3; Fig. 5 is the proton nuclear magnetic resonance ( 1 H-NMR) analysis result of the silicon-containing compound according to Example 4; FIG. 6 shows the thermogravimetric analysis (TGA) analysis results of silicon-containing compounds according to Examples 1 to 4. FIG.

Figure 111145349-A0101-11-0002-2
Figure 111145349-A0101-11-0002-2

Claims (10)

一種低介電常數含矽薄膜形成用前驅體，其包含以下述化學式表示的含矽化合物： [化學式1]
Figure 03_image004
在該化學式1中，R各自獨立地為氫原子、或C 1-C 6的直鏈型或支鏈型或環型烷基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的烯丙基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的乙烯基、包含C 1-C 6的支鏈型後支鏈型或環型官能團的烷氧基、伯胺或仲胺基團、或包含C 1-C 6的官能團的苯基，L為從直鏈型、支鏈型、環型烷基或芳基中選擇的連接基團。 A precursor for forming a silicon-containing thin film with a low dielectric constant, comprising a silicon-containing compound represented by the following chemical formula: [Chemical Formula 1]
Figure 03_image004
In the chemical formula 1, each R is independently a hydrogen atom, or a C 1 -C 6 linear or branched or cyclic alkyl group, a C 1 -C 6 linear or branched or cyclic alkyl group Allyl group with C 1 -C 6 linear or branched or cyclic functional group, vinyl with C 1 -C 6 branched or cyclic functional group, alkoxy group with C 1 -C 6 branched or cyclic functional group A group, a primary or secondary amine group, or a phenyl group containing a C 1 -C 6 functional group, L is a linking group selected from linear, branched, cyclic alkyl or aryl. 如請求項1所述之低介電常數含矽薄膜形成用前驅體，其中以該化學式1表示的含矽化合物，係以下述化學式2至化學式4中的任一個表示的含矽化合物： [化學式2]
Figure 03_image006
[化學式3]
Figure 03_image008
[化學式4]
Figure 03_image010
在該化學式2至化學式4中，R各自獨立地為氫原子、或C 1-C 6的直鏈型或支鏈型或環型烷基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的烯丙基、包含C 1-C 6的直鏈型或支鏈型或環型官能團的乙烯基、包含C 1-C 6的支鏈型或支鏈型或環型官能團的烷氧基、伯胺或仲胺基團、或包含C 1-C 6的官能團的苯基，n為1至8的整數。 The precursor for forming a low dielectric constant silicon-containing thin film as described in Claim 1, wherein the silicon-containing compound represented by the chemical formula 1 is a silicon-containing compound represented by any one of the following chemical formula 2 to chemical formula 4: 2]
Figure 03_image006
[chemical formula 3]
Figure 03_image008
[chemical formula 4]
Figure 03_image010
In the chemical formula 2 to chemical formula 4, each R is independently a hydrogen atom, or a C 1 -C 6 linear or branched or cyclic alkyl group, including a C 1 -C 6 linear or branched Allyl group with C 1 -C 6 linear or branched or cyclic functional group, Vinyl with C 1 -C 6 linear or branched or cyclic functional group, C 1 -C 6 branched or branched or cyclic functional group alkoxy, primary or secondary amine groups, or phenyl groups containing C 1 -C 6 functional groups, n is an integer from 1 to 8. 如請求項1所述之低介電常數含矽薄膜形成用前驅體，其進一步包含溶劑。The precursor for forming a low dielectric constant silicon-containing thin film according to claim 1, further comprising a solvent. 如請求項3所述之低介電常數含矽薄膜形成用前驅體，其中該溶劑為C 1-C 16的飽和或不飽和烴、酮、醚、乙二醇二甲醚、酯、四氫呋喃以及叔胺中的任一個或多個。 The precursor for forming a silicon-containing thin film with a low dielectric constant as described in Claim 3, wherein the solvent is a C 1 -C 16 saturated or unsaturated hydrocarbon, ketone, ether, ethylene glycol dimethyl ether, ester, tetrahydrofuran and Any one or more of tertiary amines. 如請求項3所述之低介電常數含矽薄膜形成用前驅體，其中該溶劑相對於該低介電常數含矽薄膜形成用前驅體的總重量包含1至99重量%。The precursor for forming a low dielectric constant silicon-containing thin film according to claim 3, wherein the solvent contains 1 to 99% by weight relative to the total weight of the precursor for forming a low dielectric constant silicon-containing thin film. 一種低介電常數含矽薄膜形成方法，其包括： 利用如請求項1或請求項3中任一項所述的低介電常數含矽薄膜形成用前驅體在一基板上形成薄膜的步驟。 A method for forming a silicon-containing film with a low dielectric constant, comprising: A step of forming a thin film on a substrate by using the precursor for forming a low dielectric constant silicon-containing thin film according to any one of Claim 1 or Claim 3. 如請求項6所述之低介電常數含矽薄膜形成方法，其中該低介電常數含矽薄膜，通過旋塗絕緣介質（spin-on dielectric，SOD）工程、高密度等離子體化學氣相沉積（High Density Plasma-Chemical Vapor Deposition，HDP-CVD）工程或原子層沉積（Atomic Layer Deposition，ALD）工程形成。The method for forming a low dielectric constant silicon-containing film as described in Claim 6, wherein the low dielectric constant silicon-containing film is deposited by spin-on dielectric (SOD) engineering, high-density plasma chemical vapor deposition (High Density Plasma-Chemical Vapor Deposition, HDP-CVD) engineering or atomic layer deposition (Atomic Layer Deposition, ALD) engineering formation. 如請求項6所述之低介電常數含矽薄膜形成方法，其包括將該低介電常數含矽薄膜形成用前驅體通過直接液體注入（DLI，Direct Liquid Injection）移送到腔室內部的步驟。The method for forming a low dielectric constant silicon-containing thin film according to Claim 6, which includes the step of transferring the precursor for forming the low dielectric constant silicon-containing thin film to the interior of the chamber by direct liquid injection (DLI, Direct Liquid Injection) . 如請求項6所述之低介電常數含矽薄膜形成方法，其包括將該低介電常數含矽薄膜形成用前驅體供應到該基板上並通過生成等離子體而形成薄膜的步驟。The method for forming a low dielectric constant silicon-containing thin film according to claim 6, comprising the steps of supplying the precursor for forming a low dielectric constant silicon-containing thin film onto the substrate and forming a thin film by generating plasma. 一種半導體器件，其包括： 一低介電常數含矽薄膜，其通過如請求項6所述之低介電常數含矽薄膜形成方法進行製造。 A semiconductor device comprising: A low dielectric constant silicon-containing thin film manufactured by the method for forming a low dielectric constant silicon-containing thin film as described in Claim 6.
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