JP6993394B2 - Silicon compounds and methods of depositing films using silicon compounds - Google Patents

Description

Cross-reference to related applications This application is a US provisional patent application No. 62 / 717,454 filed on August 10, 2018, and a US patent application No. 16 / filed on August 6, 2019. Claim the priority of No. 532,657. These disclosures are incorporated herein by reference in their entirety.

Described herein are compositions and methods for forming a dielectric film using a silicon compound as a structure-forming precursor. More specifically, described herein are compositions and methods for forming low dielectric constant films (“low k” films, or films having a dielectric constant of about 3.2 or less). There is a method used to deposit the film is a chemical vapor deposition (CVD) method. Low dielectric constant films produced by the compositions and methods described herein are, for example, insulating layers in electronic devices. Can be used as.

The electronics industry utilizes dielectric materials as insulating layers between circuits and between integrated circuit (IC) components and related electronic devices. Line dimensions are being reduced to increase the speed and memory storage capacity of microelectronic devices (eg, computer chips). As the line size decreases, the insulation requirements for interstitial dielectrics (ILDs) become significantly tighter. Shortening the interval requires a lower permittivity to minimize the RC time constant. Here, R is the resistance of the conductive wire, and C is the capacitance of the insulating dielectric intermediate layer. The capacitance (C) is inversely proportional to the spacing and proportional to the permittivity (k) of the interlayer dielectric (ILD). The dielectric constant k of a conventional silica (SiO ₂ ) CVD dielectric film made from SiH ₄ or TEOS (Si (OCH ₂ CH ₃ ) ₄ , tetraethyl orthosilicate) and O ₂ is greater than 4.0. The industry has attempted to produce silica-based CVD films with lower dielectric constants in several ways. The most successful is to dope an insulating silicon oxide film with an organic group, resulting in a dielectric constant of about 2.7 to about 3.5. The organosilica glass is typically deposited as a high density film (density of approximately 1.5 g / cm ³ ) from organosilicon precursors such as methylsilane or siloxane and oxidants such as O ₂ or N ₂ O. Organic silica glass is referred to herein as OSG. As the carbon content of OSG increases, the mechanical strength of the film, such as the hardness (H) and elastic modulus (EM) of the film, tends to decrease rapidly as the dielectric constant decreases.

A challenge recognized within the industry is that the lower the dielectric constant of a film, the lower the mechanical strength of the film. Due to the reduced mechanical strength, defects in the narrow pitch film, such as delamination, buckling, and increased electron transfer, such as conductive wire formed from copper embedded in a dielectric film with reduced mechanical properties. Will promote the increase in electron transfer as observed with respect to. Such defects can lead to premature destruction of the dielectric or void of the conductive copper wire, which results in premature failure of the device. Carbon deficiency in the OSG film is the following problem: increased dielectric constant of the film, film etching and feature boiling during the wet cleaning process, moisture absorption into the film due to loss of hydrophobicity, after pattern etching. Of the pattern crushing of fine features during the wet cleaning process and / or accumulation problems when depositing subsequent layers, eg, copper diffusion barriers such as Ta / TaN or advanced Co or MnN barrier layers. It may lead to one or more of the above.

A possible solution to one or more of these problems involves using a porous OSG film that has an increased carbon content but maintains mechanical strength. Unfortunately, the relationship between the increased Si-Me content typically results in a decrease in mechanical properties, and thus films with more Si-Me are detrimental to the mechanical strength, which is important for integration. It will affect you.

One proposed solution is to use ethylene or methylene crosslinked alkoxysilanes of the general formula R _x (RO) _3-x Si (CH ₂ ) _y SiR _z (OR) _3-z . Here, x = 0 to 3, y = 1 or 2, and z = 0 to 3. The use of cross-linked species is believed to avoid adverse effects on mechanical properties by substituting cross-linking oxygen with cross-linking carbon chains. That's because network connectivity remains the same. This arises from the idea that substituting the cross-linking oxygen with a terminal methyl group reduces the network binding property and thus the mechanical strength. In this way, by substituting one or two carbon atoms for the oxygen atom, the atomic weight percent (%) C can be increased without reducing the mechanical strength. However, these crosslinked precursors generally have a very high boiling point due to their increased molecular weight due to their two silicon groups. When the boiling point is increased, this means that the chemical precursor is delivered as a gas phase reagent into the reaction chamber without condensing it in the steam delivery line or in the process pump exhaust system. Making it difficult can adversely affect the manufacturing process.

Therefore, there is a need in the art for dielectric precursors that provide a film that has an increased carbon content during deposition and yet does not suffer from the above-mentioned drawbacks.

The methods and compositions described herein meet one or more of the above requirements. The methods and compositions described herein include at least one silicon compound, such as 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, or 2,5,5. -Trimethyl-2-ethoxy-1-oxa-2-silacyclopentane is used as a silicon precursor. This silicon precursor can be used as deposited to provide a low-k interlayer dielectric, or can be subsequently treated with a heat, plasma, or UV energy source to alter the film properties. For example, chemical cross-linking can be provided to improve mechanical strength. In addition, films deposited using the silicon compounds described herein as silicon precursors contain relatively large amounts of carbon. In addition, the silicon compounds described herein are conventional silicon precursors, eg, crosslinked precursors with higher MW and higher boiling point due to their property of having two silicon groups (eg, alkoxysilane precursors). ), Which has a lower molecular weight (Mw), thereby forming a silicon precursor having a boiling point of 250 ° C. or lower, more preferably 200 ° C. or lower. The methods and compositions described herein are more convenient, for example, for processing in mass production processes.

Described herein is a single precursor-based dielectric film that _includes a material _{represented by} the _{formula SivOwCxHYFz} . Where v + w + x + y + z = 100%, v is 10-35 atomic%, w is 10-65 atomic%, x is 5-45 atomic%, y is 10-50 atomic%, and z is 0 to 15 atomic%. The film has pores with a volume of 5.0 to 30.0%, a dielectric constant of 2.3 to 3.2, a hardness of 1.0 to 7.0 gigapascal (GPa), and an elastic modulus of 4.0 to 4.0. It has mechanical properties such as 40.0 GPa. In certain embodiments, the film contains higher carbon content (10-40%) as measured by X-ray photoelectron analysis (XPS) and is measured by examining the carbon content as determined by XPS depth profiling. It is shown that the carbon removal depth is reduced when exposed to, for example, O ₂ or NH ₃ plasma.

の構造を有するケイ素化合物を含むケイ素前駆体を含み、
Ｒ^１は水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基から成る群から選択され、そしてＲ^２は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、前記リングに結合された任意のアルキル置換基を有する状態で形成するＣ_２～Ｃ_４アルキルジラジカルであり、Ｒ^３は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、Ｃ_３～Ｃ_１０ヘテロアリール基、及びアルコキシＯＲ^４から成る群から選択され、Ｒ^４は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、及び直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、少なくとも１種の酸素源から成る群から選択され、そして、前記基体上にフィルムを堆積するために前記気体状試薬の反応を誘発するように、前記反応チャンバ内の前記気体状試薬にエネルギーを印加することを含む、誘電体フィルムを製造するための化学蒸着方法が提供される。堆積されたままのフィルムは、付加的な処理、例えば熱アニーリング、プラズマ暴露、又はＵＶ硬化なしで使用することができる。 In one embodiment, it is a chemical vapor deposition method for producing a dielectric film, wherein the substrate is provided in a reaction chamber, a gaseous reagent is introduced into the reaction chamber, and the gaseous reagent is expressed by the following formula. I, that is,

Containing a silicon precursor containing a silicon compound having the structure of
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, and R ² is A _C2 - _C4 alkyl diradyl that forms a 4-membered, 5-membered, or 6-membered saturated ring with a Si atom and an oxygen atom with any alkyl substituent attached to the ring, R ³ Is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, C ₃ to Selected from the group consisting of C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, C ₃ to C ₁₀ heteroaryl groups, and alkoxy OR ⁴ , R ⁴ is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups, at least one. Selected from the group consisting of oxygen sources and comprising applying energy to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent to deposit a film on the substrate. , A chemical vapor deposition method for producing a dielectric film is provided. The as-deposited film can be used without additional treatment, such as thermal annealing, plasma exposure, or UV curing.

を有するケイ素化合物を含み、
Ｒ^１は水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基から成る群から選択され、Ｒ^２は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、任意のＣ_１～Ｃ_６アルキル置換基を有する状態で形成するＣ_２～Ｃ_４アルキルジラジカルであり、Ｒ^３は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基、及びアルコキシＯＲ^４から成る群から選択され、Ｒ^４は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、及び直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基から成る群から選択される、誘電体フィルムの蒸着のための組成物が提供される。 A composition for vapor deposition of a dielectric film, wherein the composition is the following formula I, that is,

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 - C4} alkyl diradyl that forms a 4-membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1-C6 alkyl substituents ^, where R3 is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ Selected from the group consisting of a cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic alkyl group, a C ₅ to C ₁₀ aryl group, and a C ₃ to C ₁₀ heteroaryl group, and an alkoxy OR ⁴ , where R ⁴ is direct. Selected from the group consisting of chain or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups. A composition for vapor deposition of a dielectric film is provided.

According to another aspect, the composition is almost free of at least one impurity selected from the group consisting of halides, organic silanes, and water.

によって表されるケイ素化合物を製造する方法であって、
前記方法が、
触媒の存在において不飽和アルコールでアルコキシシランのヒドロシリル化を実施し、これに続いて７０％以上の収率で、反応式（１）又は（２）、すなわち、

に従って、溶媒がある状態又はない状態で環化を行うことを含み、
Ｒ^１は水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基から成る群から選択され、Ｒ^３は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基、及びアルコキシＯＲ^４から成る群から選択され、Ｒ^４は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、及び直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基から成る群から選択され、そしてＲ^５－８は、水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基から成る群から選択される、ケイ素化合物を製造する方法が提供される。 Equation I, i.e.

A method for producing a silicon compound represented by
The above method
Hydrosilylation of the alkoxysilane with unsaturated alcohols was carried out in the presence of the catalyst, followed by reaction equation (1) or (2), ie in yields of 70% or greater.

Including cyclization with or without solvent according to
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ³ is direct. Chained or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ rings Selected from the group consisting of formula alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, and alkoxy OR ⁴ , R ⁴ is a straight chain. Selected from the group consisting of linear or branched C ₁ to C ₁₀ alkyl groups and linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups. And R ^5-8 provides a method for producing a silicon compound selected from the group consisting of hydrogen, linear or branched C ₁ to C ₁₀ alkyl groups.

の構造を有するケイ素化合物を含むケイ素前駆体を含み、
Ｒ^１は水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基から成る群から選択され、そしてＲ^２は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、前記リングに結合された任意のアルキル置換基を有する状態で形成するＣ_２～Ｃ_４アルキルジラジカルであり、Ｒ^３は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、Ｃ_３～Ｃ_１０ヘテロアリール基、及びアルコキシＯＲ^４から成る群から選択され、Ｒ^４は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、及び直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、少なくとも１種の酸素源から成る群から選択され、そして、前記基体上にフィルムを堆積するために前記気体状試薬の反応を誘発するように、前記反応チャンバ内の前記気体状試薬にエネルギーを印加することを含む、誘電体フィルムを製造するための化学蒸着方法である。フィルムは、堆積されたままの状態で使用することができ、或いは、続いて熱エネルギー（アニール）、プラズマ暴露、及びＵＶ硬化から成る群から選択された付加的なエネルギーで処理することによって、フィルムの機械的強度を増大させ、そして３．３未満の誘電率をもたらすことにより、フィルムの化学的特性を改変することもできる。 Described herein is a chemical vapor deposition method for producing a dielectric film, wherein the substrate is provided into a reaction chamber and a gaseous reagent is introduced into the reaction chamber. , The gaseous reagent is the following formula I, that is,

Containing a silicon precursor containing a silicon compound having the structure of
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, and R ² is A _C2 - _C4 alkyl diradyl that forms a 4-membered, 5-membered, or 6-membered saturated ring with a Si atom and an oxygen atom with any alkyl substituent attached to the ring, R ³ Is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, C ₃ to Selected from the group consisting of C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, C ₃ to C ₁₀ heteroaryl groups, and alkoxy OR ⁴ , R ⁴ is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups, at least one. Selected from the group consisting of oxygen sources and comprising applying energy to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent to deposit a film on the substrate. , A chemical vapor deposition method for producing a dielectric film. The film can be used as deposited, or by subsequent treatment with additional energy selected from the group consisting of thermal energy (annealing), plasma exposure, and UV curing. The chemical properties of the film can also be modified by increasing the mechanical strength of the film and resulting in a dielectric constant of less than 3.3.

The silicon compounds described herein provide unique attributes. These attributes allow for higher carbon content in the dielectric film as compared to prior art structure forming precursors such as diethoxymethylsilane (DEMS), as well as low k dielectric films. It has little effect on mechanical properties. For example, DEMS has a mixed ligand system containing two alkoxy groups, one silicon-methyl (Si-Me), and one silicon-hydrogen compound. The mixed ligand system provides a balance of reactive sites and allows the formation of mechanically more robust films while maintaining the desired permittivity. The use of silicon compounds is that the silicon-methyl group, which tends to reduce mechanical strength, is absent in the precursor, while the carbon in the silacyclic ring provides carbon to the OSG film. This brings about the advantage of lowering the dielectric constant and imbuing the hydrophobicity.

The low k dielectric film is an organic silica glass (“OSG”) film or material. Organic silicates are candidates for low k materials. The type of organic silicon precursor has a strong influence on the structure and composition of the film, so adding the required amount of carbon to reach the desired permittivity does not produce a film that is not mechanically rigid. It is beneficial to use precursors that provide the film properties required to ensure. The methods and compositions described herein are low to improve integrated plasma damage resistance by having a desirable balance of electrical and mechanical properties, as well as other beneficial film properties, such as high carbon content. A means for producing a dielectric film is provided.

For certain embodiments of the methods and compositions described herein, the silicon-containing dielectric material layer may be a chemical vapor deposition (CVD) method or a plasma-enhanced chemical vapor deposition (PECVD) method, preferably a PECVD method. Through, a reaction chamber is employed and deposited on at least a portion of the substrate. Examples of suitable substrates are semiconductor materials such as gallium arsenide (“GaAs”), silicon, and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide (“SiO ₂ ””. ), Silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductors, integrated circuits, flat panel displays, flexible display applications. The substrate is an additional layer, such as silicon, SiO ₂ , organic silicate glass (OSG), fluorinated silicate glass (FSG), boron carbide, silicon carbide, silicon hydride, silicon nitride, hydride Silicon, silicon nitride, silicon hydride, boron nitride, organic-inorganic composites, photoresists, organic polymers, porous organic and inorganic materials and composites, metal oxides such as aluminum oxide, and germanium oxide. May have. Yet another layer may be germanium silicate, aluminosilicate, copper and aluminum, and diffusion barrier materials, eg TiN, Ti (C) N, TaN, Ta (C) N, Ta, W, or WN. good.

In certain embodiments, the silicon-containing dielectric material layer is made of a substrate by introducing a gaseous reagent containing at least one silicon precursor containing a silicon compound into the reaction chamber in the absence of a pologene precursor. At least partially deposited on top. In another embodiment, the silicon-containing dielectric material layer comprises at least one of the substrates by introducing a gaseous reagent containing at least one silicon precursor containing a silicon compound into the reaction chamber in the presence of a curing additive. It is deposited on the part.

を有するケイ素化合物を含み、
Ｒ^１は水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基から成る群から選択され、そしてＲ^２は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、前記リングに結合された任意のアルキル置換基を有する状態で形成するＣ_２～Ｃ_４アルキルジラジカルであり、Ｒ^３は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０ヘテロ環式アルキル基、Ｃ_５～Ｃ_１０アリール基、及びＣ_３～Ｃ_１０ヘテロアリール基、及びアルコキシＯＲ^４から成る群から選択され、Ｒ^４は、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基、直鎖状又は分枝状Ｃ_２～Ｃ_１０アルケニル基、及び直鎖状又は分枝状Ｃ_２～Ｃ_１０アルキニル基から成る群から選択される。 The methods and compositions described herein are:
The following formula I, that is,

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, and R ² is A _C2 - _C4 alkyl diradyl that forms a 4-membered, 5-membered, or 6-membered saturated ring with a Si atom and an oxygen atom with any alkyl substituent attached to the ring, R ³ Is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, C ₃ to Selected from the group consisting of C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, and alkoxy OR ⁴ , R ⁴ is selected. , Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups. Be selected.

In the above formula and throughout the description, the term "alkyl" means a linear or branched functional group having 1-10 carbon atoms. Examples of exemplary linear alkyl groups include methyl, ethyl, n-propyl, butyl, pentyl, and hexyl groups. Examples of exemplary branched alkyl groups include iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl, and neo-hexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto. Examples of such functional groups include alkoxy groups attached to alkyl groups such as methoxy, ethoxy, iso-propoxy, and n-propoxy, dialkylamino groups such as dimethylamino, or combinations thereof. In other embodiments, the alkyl group does not have one or more functional groups attached to it. The alkyl group may be saturated or unsaturated.

In Formula I above, and throughout the description, the term "cyclic alkyl" means a cyclic functional group having 3 to 10 carbon atoms. Examples of exemplary cyclic alkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In Formula I above, and throughout the description, the term "heterocyclic" means a C ₃ to C ₁₀ heterocyclic alkyl group, such as an epoxy group.

In Formula I above, and throughout the description, the term "alkenyl group" has one or more carbon-carbon double bonds and has 2-10, or 2-10, or 2 carbon atoms. It means a group of ~ 6.

In Formula I above, and throughout the description, the term "alkynyl group" has one or more carbon-carbon triple bonds and has 3 to 10, or 2 to 10, or 2 to carbon atoms. It means a group that is 6.

In Formula I above, and throughout the description, the term "aryl group" means an aromatic cyclic functional group having 5 to 10 carbon atoms or 6 to 10 carbon atoms. Examples of exemplary aryl groups include phenyl, benzyl, chlorobenzyl, trill, and o-kisilyl.

In Formula I above, and throughout the description, the term "hetero-aryl group" means C ₃ to C ₁₀ heterocyclic aryl groups, 1,2,3-triazolyl, pyrrolyl, and furanyl.

In formula I above, the substituent ^R2 is a C _3- to C ₁₀ alkyl diradical that forms a 4-membered, 5-membered, or 6-membered cyclic ring with a Si atom and an oxygen atom.
As will be apparent to those of skill in the art, R ² is a substituted or unsubstituted hydrocarbon chain, which links with Si and oxygen atoms to form a ring of formula I. This ring is a 4-member, 5-member, or 6-member ring. In these embodiments, the ring structure may be a saturated ring, eg, a cyclic alkyl ring. Examples of exemplary saturation rings include silacyclobutane, silacyclopentane, and silacyclohexane, preferably silacyclopentane, or alkyl, eg, methyl-substituted silacyclopentane.

Throughout the description, the term "alkoxy" means a group derived from an alcohol having at least one carbon atom. Examples of exemplary alkoxy groups include methoxy, ethoxy, iso-propoxy, normal-propoxy.

Throughout the description, the term "oxygen source" means a gas containing oxygen (O ₂ ), a mixture of oxygen and helium, a mixture of oxygen and argon, carbon dioxide, carbon monoxide, and combinations thereof.

Throughout the description, the term "dielectric film" is a film containing the composition Si _{vO w} C _{x Hy} F _z with silicon and oxygen atoms, where v + w + x + y + z = 100%, where v is from 10 to. 35 atomic%, w is 10-65 atomic%, x is 5-40 atomic%, y is 10-50 atomic%, and z is 0-15 atomic%, meaning film. do.

式Ｉを有するケイ素化合物は、例えば触媒の存在において不飽和アルコールでアルコキシシランをヒドロシリル化し、続いて、７０％以上、好ましくは８０％以上の収率で、溶媒がある状態又はない状態で５員、又は６員飽和環式リングを製造するように環化を行うことによって合成することができる（例えば反応式（１）又は（２））。合成ルートの例を以下に示す。

Ｒ^１，Ｒ^３及びＲ^４は、上述のものと同じであり、Ｒ^５－８は、水素、直鎖状又は分枝状Ｃ_１～Ｃ_１０アルキル基から成る群から選択され、好ましくは水素、又はメチルである。 In certain embodiments of formula I, R ¹ is selected from the group consisting of hydrogen, methyl, and ethyl, and R ³ is methyl, ethyl, isopropyl, n-propyl, methoxy, ethoxy, iso-propoxy, and n. -Selected from the group consisting of propoxy, and R ² forms a 4-membered, 5-membered, or 6-membered saturated cyclic ring with Si and oxygen atoms. In some embodiments, the 4-membered, 5-membered, or 6-membered saturated cyclic ring with a Si atom may have at least one alkyl substituent, such as a methyl group, on the ring structure. Examples of these embodiments are as follows.

The silicon compound having formula I hydrosilylates the alkoxysilane with an unsaturated alcohol, for example in the presence of a catalyst, followed by 5 members in a yield of 70% or higher, preferably 80% or higher, with or without solvent. , Or can be synthesized by performing cyclization to produce a 6-membered saturated cyclic ring (eg, reaction formula (1) or (2)). An example of a synthetic route is shown below.

R ¹ , R ³ and R ⁴ are the same as those described above, and R ^5-8 is selected from the group consisting of hydrogen, linear or branched C ₁ to C ₁₀ alkyl groups, preferably hydrogen. , Or methyl.

The silicon compounds described herein, as well as methods and compositions comprising these compounds, are almost free of one or more impurities, such as halide ions and water. As used herein, the term "nearly free" for each impurity is 100 parts (ppm) or less, 50 ppm or less, 10 ppm or less, 5 ppm or less, and 1 ppm or less per million copies, respectively. It means impurities, for example chloride or water.

It is preferable that the composition containing the silicon compound having the formula I according to the present invention and the silicon precursor compound having the formula I according to the present invention contains almost no halide. As used herein, halide ions (or halides), such as chlorides (ie, chloride-containing species, such as HCl, or silicon compounds with at least one Si—Cl bond), and fluorides. , Bromide, and iodide "almost free" is less than 5 ppm (weight) as measured by ICP-MS, preferably less than 3 ppm as measured by ICP-MS, and more preferably by ICP-MS. It means less than 1 ppm, and most preferably 0 ppm as measured by ICP-MS. Chloride is known to act as a decomposition catalyst for silicon compounds having formula I. Significant levels of chloride in the final product can degrade the silicon precursor compound. The gradual deterioration of the silicon compound can directly affect the film deposition process, which makes it difficult for semiconductor manufacturers to meet the film specifications. In addition, shelf life or stability is adversely affected by the higher rate of deterioration of silicon compounds having formula I, which makes it difficult to guarantee a shelf life of 1-2 years. Thus, the accelerated decomposition of silicon compounds of formula I raises safety and performance concerns associated with the formation of flammable and / or pyrophoric gaseous by-products. The silicon compound having the formula I may contain almost no metal ions such as Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ and Cr ³⁺ . preferable. As used herein, the term "nearly free" for Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr is less than 5 ppm (weight) as measured by ICP-MS. It means less than 3 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm. In some embodiments, the silicon compound having formula I or IA is a metal ion such as Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ . , Cr ³⁺ is not included. As used herein, Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, noble metals, such as volatile Ru or derived from ruthenium or platinum catalysts used during synthesis. In connection with the Pt complex, the term "free" of metal impurities means less than 1 ppm, preferably less than 0.1 ppm (weight) as measured by ICP-MS or other analytical methods for measuring metals. do. Silicon compounds having Formula I are also preferably free of water or organosilane impurities, such as alkoxysilanes derived from starting materials, or by-products derived from synthesis. The term "nearly free" with respect to water is less than 100 ppm (weight), preferably less than 50 ppm, and more preferably less than 10 ppm. The sum of all organic silane impurities, such as methyltriethoxysilane, or dimethyldiethoxysilane, is analyzed by gas chromatography (GC) to less than 1.0 wt%, preferably less than 0.5 wt%, and preferably 0.1 wt%. Less than%.

The compositions according to the invention containing little halide are (1) by reducing or eliminating chloride sources during chemical synthesis and / or (2) ensuring that the final purified product contains little chloride. In addition, it can be obtained by carrying out an effective purification process to remove chloride from the crude product. Chloride sources are reduced during synthesis by using reagents that do not contain halides such as chlorosilane, bromosilane, or iodosilane, thereby avoiding the formation of by-products containing halide ions. Can be done. In addition, the reagents described above should be free of chloride impurities so that the resulting crude product contains few chloride impurities. Similarly, synthesis should not use halide-based solvents, catalysts, or solvents containing unacceptably high levels of halide contaminants. The crude product can also be treated by various purification methods so that the final product contains few halides such as chlorides. Such methods are well described in the art and examples include purification processes such as distillation or adsorption. Distillation is commonly used to separate impurities from the desired product by taking advantage of the difference in boiling points. Adsorption can also be used to take advantage of the difference in adsorption properties of the components to cause separation so that the final product contains few halides. Adsorbents such as commercially available MgO _{- Al2O3} blends can be used to remove halides such as chlorides.

Conventional silicon-containing silicon precursors, such as DEMS, once excited in the reaction chamber, have an -O-linkage (eg, -Si-O-Si- or -Si-OC-) in the polymer backbone. Whereas the silicon compound having formula I polymerizes to form the structure it has, some of the -O-bridges in the backbone are replaced with -CH ₂ -methylene or -CH ₂ CH ₂ -ethylene bridges. It is considered to polymerize so as to form the structure to be formed. For films deposited using DEMS as a structure-forming precursor in which carbon is mainly present in the form of terminal Si-Me groups,% Si-Me (directly related to% C) and mechanical strength. When the cross-linking Si—O—Si group is replaced with two terminal Si—Me groups, the mechanical properties are deteriorated. This is because the network structure is destroyed. In the case of silicon compounds, the cyclic structure is at least a portion of the porogen precursor contained in the as-deposited film to form a SiC ₂ Si or SiC ₂ CH ₂ Si cross-linking group during the film deposition process. , Or to remove almost all) is considered to be broken during the curing process. Thus, from the viewpoint of mechanical strength, by increasing the carbon content in the film, carbon can be incorporated in the form of a cross-linking group so that the network structure is not destroyed. Although not bound by any particular theory, this attribute adds carbon to the film, which causes the film to be porous resulting from processes such as film etching, photoresist plasma ashing, and _NH3 plasma treatment of copper surfaces. It is possible to have higher resilience to carbon deficiency of quality OSG film. Carbon deficiency in OSG film can increase the dielectric constant of the film, as well as feature boeing problems during film etching and wet cleaning processes, and / or accumulation problems when depositing copper diffusion barriers. be.

In certain embodiments of the methods and compositions contained herein, the structure-forming precursor further comprises a curing additive. Hardening additives increase mechanical strength. An example of a curing additive is tetraalkoxysilane (Si (OR ⁹ )), in which R ⁹ is a linear or branched C ₁ to C ₁₀ alkyl group, linear or branched C ₂ to. C ₁₀ alkenyl group, linear or branched C ₂ to C ₁₀ alkynyl group, C ₃ to C ₁₀ cyclic alkyl group, C ₃ to C ₁₀ heterocyclic alkyl group, C ₅ to C ₁₀ aryl group, and Includes those selected from the group consisting of C ₃ to C ₁₀ hetero-aryl groups, such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMS). In embodiments where a curing additive is used, the composition of the structure forming moiety is from about 5 to about 95 weight percent with a structure forming precursor comprising an alkyl-alkoxysilacyclic compound of formula I. It contains 70 weight percent curing additives and about 40 to about 95 weight percent porogen precursors such as alpha terpinene or cyclooctane in the total precursor stream.

Although the expression "gaseous reagent" is sometimes used herein to describe a reagent, this expression is a reagent delivered directly to the reactor as a gas, vaporized liquid, sublimated. It is intended to include reagents delivered as solids and / or reagents carried into the reactor by the Inactive Carrier Gas.

In addition, the reagents can be transported into the reactor separately from the distinguishable sources or as a mixture. Reagents are preferably sent to the reactor system by any number of means using a pressurable stainless steel container with appropriate valves and fittings to allow delivery of the liquid to the process reactor. Can be delivered.

In addition to the structure-forming species (ie, compounds of formula I), additional material can be introduced into the reaction chamber before, during, and / or after the deposition reaction. Such materials are, for example, inert gases such as He, Ar, _N2 , Kr, Xe, which can be employed as carrier gases for lower volatile precursors and / or are deposited. It can accelerate the curing of the raw material and provide a more stable final film), and reactive substances such as oxygen-containing species such as O ₂ , O ₃ and N ₂ O, gaseous or liquid. It contains an organic substance, NH ₃ , H ₂ , CO ₂ , or CO. In one particular embodiment, the reaction mixture introduced into the reaction chamber is a group consisting of O ₂ , N ₂ O, NO, NO ₂ , CO ₂ , water, H ₂ O ₂ , ozone, and combinations thereof. Contains at least one oxidant selected from. In another embodiment, the reaction mixture is oxidant-free.

By applying energy to the gaseous reagent, the gas reacts to induce the formation of a film on the substrate. Such energies can be provided, for example, by plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, remote plasma, thermal filament, and thermal (ie, non-filament) methods. A secondary rf frequency source can be used to modify the plasma properties on the surface of the substrate. Preferably, the film is formed by plasma-enhanced chemical vapor deposition (“PECVD”).

The flow rate of each of the gaseous reagents is preferably 10 to 5000 sccm, more preferably 30 to 1000 sccm per 200 mm wafer. The individual velocities are selected to provide the desired amounts of silicon, carbon, and oxygen in the film. The actual flow rate required may depend on the wafer size and chamber form and is by no means limited to a 200 mm wafer or a single wafer chamber.

In some embodiments, the film is deposited at a deposition rate of about 50 nanometers (nm) per minute.

The pressure in the reaction chamber during deposition is from about 0.01 to about 600 torr or from about 1 to 15 torr.

The film is preferably deposited to a thickness of 0.002-10 microns, but the thickness can be varied as needed. The blanket film deposited on the unpatterned surface has excellent uniformity, with thickness variations greater than 1 standard deviation over the entire substrate being less than 2% with reasonable edge exclusion. Is. For example, the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity.

Preferred embodiments of the present invention have a lower dielectric constant and improved machine compared to other porous low k dielectric films deposited using other structure forming precursors known to those of skill in the art. Provided are thin film materials having physical properties, thermal stability, and chemical resistance (against oxygen and oxidizing materials). The structure-forming precursors described herein, including alkyl-alkoxycyclic compounds having formula I, have a higher carbon uptake into the film (preferably mostly organic carbon, -CH _x (preferably organic carbon, -CH x). x is provided in the form of 1 to 3). In this case, certain precursors or network-forming chemicals are used to deposit the film. In certain embodiments, most of the hydrogen in the film is bonded to carbon.

The low dielectric film deposited according to the compositions and methods described herein is (a) about 10 to about 35 atomic%, more preferably about 20 to about 30 atomic% silicon, (b) about. 10 to about 65 atomic%, more preferably about 20 to about 45 atomic% oxygen, (c) about 10 to about 50 atomic%, more preferably about 15 to about 40 atomic% hydrogen, (d) about 5 to about 5 to. It contains about 40 atomic%, more preferably about 10 to about 45 atomic% carbon. The film contains from about 0.1 to about 15 atomic%, more preferably from about 0.5 to about 7.0 atomic% fluorine in order to improve one or more of the material properties. May be good. A smaller proportion of other elements may be present within a particular film of the invention. OSG materials are considered low k materials because their dielectric constants are lower than the standard materials traditionally used in the industry, namely silica glass.

The total porosity of the film may be 0-15% or more than 15% depending on the process conditions and the desired final film properties. The density of the film of the present invention is preferably 2.3 g / ml, or less than 2.0 g / ml or less than 1.8 g / ml. The total porosity of the OSG film can be affected by post-deposition treatment, including exposure to a plasma source for thermosetting or UV curing. A preferred embodiment of the invention does not involve the addition of pologene during film deposition, but can induce porosity by post-deposition treatment, such as UV curing. For example, UV treatment can result in a porosity of about 15 to about 20%, preferably about 5 to about 10%.

The film of the present invention may contain fluorine in the form of inorganic fluorine (eg Si—F). Fluorine, when present, is preferably contained in an amount of about 0.5 to about 7 atomic%.

The film of the present invention has good chemical resistance as well as thermal stability. Specifically, the preferred average weight loss of the film after annealing is less than 1.0 wt% / hr at an isothermal temperature of 425 ° C. under _N2 . Moreover, the average weight loss of the film is preferably less than 1.0 wt% / hr at an isothermal temperature of 425 ° C. under air.

The film is suitable for various applications. The film is particularly suitable for deposition on semiconductor substrates and is particularly suitable for use as, for example, an insulating layer, an interlayer dielectric layer, and / or an intermetallic dielectric layer. The film can form a conformal coating. The mechanical properties exhibited by these films make them particularly suitable for use in Al subtractive technology and Cu damascene or dual damascene technology.

The film is compatible with chemical mechanical flattening (CMP) and anisotropic etching, and various materials such as silicon, SiO ₂ , Si _{3N 4 ,} OSG, FSG, silicon carbide, silicon nitride, silicon nitride, etc. Silicon nitride, silicon hydride, silicon nitride, silicon hydride, boron nitride, antireflection coating, photoresist, organic polymer, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers. As an example, it can be attached to TiN, Ti (C) N, TaN, Ta (C) N, Ta, W, WN, or W (C) N. It is preferable that the film can be sufficiently adhered to at least one of the above materials to pass a conventional tensile test, such as an ASTM D3359-95a tape tensile test. If there is no recognizable peeling of the film, the sample is considered to have passed the test.

Thus, in certain embodiments, the film is an insulating layer, an interlayer dielectric layer, and / or an intermetallic dielectric layer, a capping layer, a chemical mechanical flattening (CMP) or etching stop layer, a barrier layer in an integrated circuit. Or it is an adhesive layer.

Although the films described herein are uniformly deposited dielectric films, films such as those used in fully integrated structures are actually several sandwich layers, eg, deposited. It may consist of a sandwich layer with a thin layer at the bottom or top that contains little or no porogen, or the layer may be deposited under conditions where a lower porogen precursor flow ratio is present, or UV treatment. Layers may be deposited at higher plasma powers so that not all porogen precursors can be removed by. These sandwich layers can be utilized to enhance secondary integration properties such as adhesion performance, etching selectivity, or electron transfer performance.

The present invention is particularly suitable for providing a film, and although the product of the present invention is mainly described as a film, the present invention is not limited thereto. The products of the invention are used in any form that can be deposited by CVD, such as coatings, multilayer assemblies, and other types of objects that are not necessarily flat or thin, as well as in integrated circuits. It can be provided in the form of many objects that are not. Preferably, the substrate is a semiconductor.

In addition to the OSG products of the invention, the present disclosure includes processes for making the products, methods of using the products, and compounds and compositions useful for preparing the products. For example, the process of forming an integrated circuit on a semiconductor device is disclosed in US Pat. No. 6,583,049. This is incorporated herein by reference.

The compositions of the invention further include at least one addition with a suitable valve and fitting to allow delivery of, for example, a curing additive and a silicon precursor having formula I, such as DESCAP, to a process reactor. It can include a pressure-capable (preferably made of stainless steel) container. The contents of the container can be premixed. Alternatively, the curing additive and precursor can be maintained in separate containers or in a single container with separation means for keeping the curing additive and precursor separately during storage. Such a container can also have a means of mixing the porogen with the precursor, if desired.

Temporary (or as-deposited) films can be further treated by a curing step, i.e., a step of applying an additional energy source to the film. This curing step can include thermal annealing, chemical treatment, in-situ or remote plasma treatment, photocuring (eg UV) and / or microwave treatment. Other in-situ or post-deposition treatments can be used to improve material properties such as hardness, stability (against shrinkage, air exposure, etching, wet etching, etc.), integrity, uniformity, and adhesion. .. Thus, the term "post-treatment" as used herein refers to energy (eg, heat, plasma, photons, electrons, microwaves, etc.) to remove porogens and optionally improve material properties. It means treating the film with a wave, etc.) or chemicals.

The conditions under which post-processing is performed can vary significantly. For example, the post-treatment can be performed under high pressure or in a vacuum atmosphere.

UV annealing is the preferred curing method and is typically performed under the following conditions.

The environment is inert (eg, nitrogen, CO ₂ , rare gas (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg, oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, hydrocarbon nitrogen, etc.) ), Or reducing (eg, dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The pressure is preferably from about 1 Torr to about 1000 Torr, more preferably atmospheric pressure. However, a vacuum atmosphere is also possible for thermal annealing and any other post-treatment means. The temperature is preferably 200-500 ° C, and the temperature gradient is 0.1-100 deg ° C / min. The total UV annealing time is preferably 0.01 minutes to 12 hours.

The chemical treatment of the OSG film is carried out under the following conditions.

Fluorination (HF, SIF ₄ , NF ₃ , F ₂ , COF ₂ , CO ₂ F ₂ , etc.), oxygenation (H ₂ O ₂ , O ₃ , etc.), chemical drying, methylation, or the properties of the final material Use other chemical treatments to improve. The chemicals used in such treatments may be solid, liquid, gas, and / or supercritical.

A supercritical fluid post-treatment for selectively removing porogen from the organic silicate film is performed under the following conditions.

The fluid may be carbon dioxide, water, nitrous oxide, ethylene, SF ₆ , and / or other types of chemicals. Other chemicals can be added to the supercritical fluid to improve the process. Chemicals are inert (eg nitrogen, CO ₂ , rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg oxygen, ozone, hydrocarbon nitrogen, etc.), or reducing (eg, dilute or concentrated). It may be a hydrocarbon, hydrogen, a plasma containing hydrogen, etc.). The temperature is preferably an ambient temperature to 500 ° C. Chemicals can also contain larger species, such as surfactants. The total exposure time is preferably 0.01 minutes to 12 hours.

Plasma treatment is performed under the following conditions to selectively remove unstable groups and to make possible chemical modifications to the OSG film.

The environment is inert (eg, nitrogen, CO ₂ , rare gas (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg, oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, hydrocarbon nitrogen, etc.) ), Or reducing (eg, dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The plasma output is preferably 0 to 5000 W. The temperature is preferably from about ambient temperature to about 500 ° C. The pressure is preferably from 10 mtorr to atmospheric pressure. The total curing time is preferably 0.01 minutes to 12 hours.

UV curing for chemical cross-linking of organic silicate films is typically performed under the following conditions:

The environment is inert (eg, nitrogen, CO ₂ , rare gas (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg, oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, nitrogen peroxide, etc.) ), Or may be reducing (eg, dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from about ambient temperature to about 500 ° C. The output is preferably 0 to about 5000 W. The wavelength is preferably IR, visible, UV, or deep UV (wavelength <200 nm). The total curing time is preferably 0.01 minutes to 12 hours.

Microwave post-treatment of the organic silicate film is typically performed under the following conditions.

The environment is inert (eg, nitrogen, CO ₂ , rare gas (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg, oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, nitrogen peroxide, etc.) ), Or may be reducing (eg, dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from about ambient temperature to about 500 ° C. The outputs and wavelengths are diverse and can be harmonious with the specific coupling. The total curing time is preferably 0.01 minutes to 12 hours.

Electron beam post-treatment to selectively remove porogens or specific chemical species from the organic silicate film and / or improve film properties is typically performed under the following conditions:

The environment is vacuum, inert (eg nitrogen, CO ₂ , rare gas (He, Ar, Ne, Kr, Xe), etc.), oxidizing (eg oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, suboxidation). It may be nitrogen, etc.) or reducible (eg, dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from about ambient temperature to about 500 ° C. Electron densities and energies are diverse and can be harmonized with specific bonds. The total curing time is preferably 0.001 minutes to 12 hours and may be continuous or pulsed. Additional guidance on the general use of electron beams can be found in publications such as Chattopadhyay et al., Journal of Materials Science, 36 (2001) 4323-4330, G. Kloster et al., Proceedings of IITC, June 3- 5, 2002, SF, CA, and US Pat. Nos. 6,207,555, 6,204,201, and 6,132,814. By utilizing electron beam processing, pologene can be removed and the film mechanical properties can be improved through the bond forming process in the matrix.

The present invention will be described in detail with reference to the following examples. However, it goes without saying that the present invention is not considered to be limited to these examples.

Work Example 1
It is 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, and in the reaction formula (1), R ¹ = Me, R ³ = OEt, R ⁴ = Et, R ⁵ = R. ⁶ = Synthesis of what is Me

1.50 mL Karstedt in 741.0 g (8.6 mol) of 2-methyl-3-buten-2-ol heated to 50 ° C. in a 3-neck round bottom flask equipped with an internal thermocouple and a reflux condenser. 1155.0 g (8.6 mol) of diethoxymethylsilane was added in droplet form to the catalyst (2% platinum in xylene) via an additional funnel. There was heat generation and the temperature of the mixture gradually increased to 85 ° C. The heating was stopped when the temperature reached 85 ° C. The temperature was maintained at 75-85 ° C. with the addition of DEMS. When the addition was complete, the reaction was cooled to room temperature and allowed to stir overnight. Ethanol by-products were removed by distillation at ambient pressure and heating to a steam temperature of 153 ° C. The product was vacuum distilled at 93-94 ° C. under a pressure of 105-108 Torr in an amount of 1235 g with a purity of 97%. The yield was 82%.

Work Example 2
It is 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, and in the reaction formula (1), R ¹ = R ³ = Me, R ⁴ = Et, R ⁵ = R ⁶ = Me. Synthesis of what is

2.00 mL Karstedt in 1731.0 g (20.1 mol) 2-methyl-3-buten-2-ol heated to 50 ° C. in a 3-neck round bottom flask equipped with an internal thermocouple and a reflux condenser. 2095.0 g (20.1 mol) of dimethylethoxysilane was added in droplet form to the catalyst (2% platinum in xylene) via an additional funnel. There was gradual exotherm and the temperature of the mixture reached 87 ° C. After that, the temperature gradually decreased to 60 ° C. When the amount of DEMS added was increased, the temperature began to rise gradually, followed by a sudden exotherm, and the reaction mixture refluxed at 95 ° C. The second temperature spike was steeper than the first temperature spike.
After the addition was complete, the reaction was cooled to room temperature and stirred overnight. The sample was run on GC and showed a ratio of product to diethoxydimethylsilane 3: 1. Ethanol and residual 2-methyl-3-butene-2-ol starting material were removed by distillation at ambient pressure. When the steam temperature reached 107 ° C., the removal was completed. The product was distilled under ambient pressure in an amount of 566 g with 97% purity. The yield was 20%.

Work Example 3
It is 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, and in the reaction formula (1), R ¹ = Me, R ³ = isopropyl, R ⁴ = Et, R ⁵ = R. ⁶ = Synthesis of what is Me

16.0 g (186.0 mmol) of 2-methyl-3-butene-in a single-necked round-bottom flask containing 24.6 g (186.0 mmol) of isopropylethoxymethylsilane in a 350 mL mixture of hexane and THF. 2-ol was subsequently added with 0.03 mL of Karstedt catalyst (2% platinum in xylene). The reaction was stirred overnight. GC-MS showed evidence of the desired product at m / z 172.

Work Example 4 (Film Example)
PECVD of silicon-containing dielectric film using dielectric 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane

An Applied Materials Producer SE system, which simultaneously deposits films on two wafers, was used to form an exemplary film for processing 300 mm wafers via plasma-assisted CVD (PECVD). Therefore, the flow rates of the precursor and the gas correspond to the flow rates required to simultaneously deposit the film on the two wafers. Since each wafer processing station has its own independent RF output feeder, the defined PF output per wafer is accurate. Films obtained from two different chemical precursors were deposited under different process conditions. Roughly speaking, the PECVD process involved the following basic steps: initializing and stabilizing the gas flow, depositing the film on a silicon wafer substrate, and purging / exhausting the chamber prior to substrate removal. The test was carried out on a p-type Si wafer (resistivity = 8 to 12 ohm-cm).

Thickness and index of refraction were measured with SCI FilmTek 2000 reflectance. Dielectric constants were determined using Hg probe technology on medium resistivity p-type wafers (range 8-12 ohm-cm). The mechanical properties (modulus and hardness, GPa) are determined using nanoindentation technology, the carbon content (atomic%) is determined by X-ray photoelectron spectroscopy, and the seeds inside the SiO _X network are determined by infrared spectroscopy. The composition of was determined. The latter included the silicon methyl density attributable to Si (CH ₃ ) ₁ and the disilyl methylene cross-linking density (SiCH ₂ Si / SiO _x * 1 E4).

Work Example 5 (Film Example)

Under the following conditions, a low dielectric constant film was deposited using the 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane precursor. The total precursor flow rate is 2000 mg / min, the oxygen flow rate is 15 sccm, the deposition temperature is maintained at 390 ° C, the RF output is varied from 230 to 500 W, the pressure is maintained at 7.5 torr, and the electrode spacing is 380. The He carrier flow rate maintained on the mill and used to deliver the precursor to the process chamber was 1500 sccm. Table 1 below shows the film properties obtained from the 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane precursor at three different RF outputs. The deposited film has a higher mechanical strength, a higher permittivity, and a Si-CH ₂ -Si / SiOx ratio obtained from the ratio of the integrated Si-CH ₂ -Si band to the integrated Si-O band in the FTIR spectrum. It showed a higher network carbon content, as indicated by the increase. Incorporating higher network carbon densities such as Si-CH ₂ -Si reduces the depth of film damage that occurs during subsequent integration steps such as etching, ashing, flattening, and metallization. It is desirable because it does.

Work Example 6 (Film Example)
PECVD of a silicon-containing dielectric film using a dielectric using 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane

Under the following conditions, a low dielectric constant film was deposited using the 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane precursor. The total precursor flow rate is varied from 2000 to 2500 mg / min, the oxygen flow rate is 25 to 50 sccm, the deposition temperature is maintained at 390 ° C, the RF output is varied from 315 to 515 W, and the pressure is maintained at 7.5 torr. The electrode spacing was maintained at 380 mils and the He carrier flow rate used to deliver the precursor to the process chamber was 1500 sccm. Table 2 below shows the film properties obtained from the 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane precursor under three different process conditions. The deposited film showed similar mechanical strength and dielectric constant for 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, but integrated Si in the FTIR spectrum. It showed a lower network carbon content, as indicated by a decrease in the Si—CH ₂ -Si / SiOx ratio obtained from the ratio of the _−CH2 -Si band to the integrated Si—O band. Substitution of the methyl group with an ethoxy group reduced the amount of network carbon that could be incorporated into the film.

を有するケイ素化合物を含むケイ素前駆体を含み、
Ｒ ^１ は水素、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基から成る群から選択され、Ｒ ^２ は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、任意のＣ _１ ～Ｃ _６ アルキル置換基を有する状態で形成するＣ _２ ～Ｃ _４ アルキルジラジカルであり、Ｒ ^３ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基、及びアルコキシＯＲ ^４ から成る群から選択され、Ｒ ^４ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、及び直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基から成る群から選択され、そして、
前記基体上にフィルムを堆積するために前記気体状試薬の反応を誘発するように、前記反応チャンバ内の前記気体状試薬にエネルギーを印加する
ことを含む、
誘電体フィルムを製造するための化学蒸着方法。
（２）前記ケイ素前駆体がさらに硬化添加剤を含む、（１）に記載の方法。
（３）前記ケイ素化合物が、２，２，５，５－テトラメチル－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－エトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－メトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロペンタン、２，２－ジメチル－１－オキサ－２－シラシクロヘキサン、２，２，６，６－テトラメチル－１－オキサ－２－シラシクロヘキサン、２－メチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，５，５－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、及びこれらの組み合わせから成る群から選択された少なくとも１種を含む、（１）に記載の方法。
（４）前記硬化添加剤がテトラエトキシシランを含む、（２）に記載の方法。
（５）前記硬化添加剤がテトラメトキシシランを含む、（２）に記載の方法。
（６）プラズマ支援型化学蒸着方法である、（１）に記載の方法。
（７）前記気体状試薬がさらに、Ｏ _２ 、Ｎ _２ Ｏ、ＮＯ、ＮＯ _２ 、ＣＯ _２ 、ＣＯ、水、Ｈ _２ Ｏ _２ 、オゾン、及びこれらの組み合わせから成る群から選択された少なくとも１種の酸素源を含む、（１）に記載の方法。
（８）前記印加工程の前記反応チャンバが、Ｈｅ、Ａｒ、Ｎ _２ 、Ｋｒ、Ｘｅ、ＮＨ _３ 、Ｈ _２ 、ＣＯ _２ 、及びＣＯから成る群から選択された少なくとも１種の気体を含む、（１）に記載の方法。
（９）さらに前記フィルムに付加的なエネルギーを印加する工程を含む、（１）に記載の方法。
（１０）前記付加的なエネルギーが、熱処理、紫外線（ＵＶ）処理、電子ビーム処理、及びガンマ線処理から成る群から選択された少なくとも１種である、（９）に記載の方法。
（１１）前記ＵＶ処理が、前記熱処理の少なくとも一部が実施されている間に行われる、（１０）に記載の方法。
（１２）前記気体状試薬がさらにポロゲン前駆体を含み、そして、
フィルムを堆積するために前記気体状試薬にエネルギーを印加する工程が、前記基体上に犠牲ポロゲンを共堆積することを含む、
（１）に記載の方法。
（１３）誘電体フィルムを製造する堆積プロセスに際して使用するための組成物であって、前記組成物が下記式Ｉ、すなわち

を有するケイ素化合物を含み、
Ｒ ^１ は水素、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基から成る群から選択され、Ｒ ^２ は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、任意のＣ _１ ～Ｃ _６ アルキル置換基を有する状態で形成するＣ _２ ～Ｃ _４ アルキルジラジカルであり、Ｒ ^３ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基、及びアルコキシＯＲ ^４ から成る群から選択され、Ｒ ^４ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、及び直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基から成る群から選択される、
誘電体フィルムを製造する堆積プロセスに際して使用するための組成物。
（１４）前記ケイ素化合物が、２，２，５，５－テトラメチル－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－エトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－メトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロペンタン、２，２－ジメチル－１－オキサ－２－シラシクロヘキサン、２，２，６，６－テトラメチル－１－オキサ－２－シラシクロヘキサン、２－メチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，５，５－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、及びこれらの組み合わせから成る群から選択された少なくとも１種である、（１３）に記載の組成物。
（１５）式Ｉ、すなわち

によって表されるケイ素化合物を製造する方法であって、
前記方法が、
触媒の存在において不飽和アルコールでアルコキシシランのヒドロシリル化を実施し、これに続いて７０％以上の収率で、反応式（１）又は（２）、すなわち、

に従って、溶媒がある状態又はない状態で環化を行うことを含み、
Ｒ ^１ は水素、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基から成る群から選択され、Ｒ ^３ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基、及びアルコキシＯＲ ^４ から成る群から選択され、Ｒ ^４ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、及び直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基から成る群から選択され、そしてＲ ^５－８ は、水素、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基から成る群から独立して選択される、
ケイ素化合物を製造する方法。
（１６）式Ｉによって表される化合物が、２，２，５，５－テトラメチル－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－エトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－メトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロペンタン、２，２－ジメチル－１－オキサ－２－シラシクロヘキサン、２，２，６，６－テトラメチル－１－オキサ－２－シラシクロヘキサン、２－メチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，５，５－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、及びこれらの組み合わせから成る群から選択される、（１５）に記載の方法。
（１７）誘電体フィルムの蒸着のための組成物であって、下記式Ｉ、すなわち、

を有するケイ素化合物を含み、
Ｒ ^１ は水素、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基から成る群から選択され、Ｒ ^２ は、Ｓｉ原子及び酸素原子とともに４員、５員、又は６員飽和環式リングを、任意のＣ _１ ～Ｃ _６ アルキル置換基を有する状態で形成するＣ _２ ～Ｃ _４ アルキルジラジカルであり、Ｒ ^３ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基、Ｃ _３ ～Ｃ _１０ 環式アルキル基、Ｃ _３ ～Ｃ _１０ ヘテロ環式アルキル基、Ｃ _５ ～Ｃ _１０ アリール基、及びＣ _３ ～Ｃ _１０ ヘテロアリール基、及びアルコキシＯＲ ^４ から成る群から選択され、Ｒ ^４ は、直鎖状又は分枝状Ｃ _１ ～Ｃ _１０ アルキル基、直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルケニル基、及び直鎖状又は分枝状Ｃ _２ ～Ｃ _１０ アルキニル基から成る群から選択され、そして前記化合物が、ハロゲン化物、有機シラン不純物、及び水から成る群から選択された少なくとも１種の不純物をほとんど含まない、
誘電体フィルムの蒸着のための組成物。
（１８）前記ケイ素化合物が、２，２，５，５－テトラメチル－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－エトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－メトキシ－１－オキサ－２－シラシクロペンタン、２，５，５－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロペンタン、２，２－ジメチル－１－オキサ－２－シラシクロヘキサン、２，２，６，６－テトラメチル－１－オキサ－２－シラシクロヘキサン、２－メチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－エトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－メトキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－ｎ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２－メチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロポキシ－１－オキサ－２－シラシクロヘキサン、２，５，５－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロペンタン、２－メチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、２，６，６－トリメチル－２－イソ－プロピル－１－オキサ－２－シラシクロヘキサン、及びこれらの組み合わせから成る群から選択された少なくとも１種である、（１７）に記載の組成物。
（１９）前記ハロゲン化物が塩化物イオンを含む、（１７）に記載の組成物。
（２０）前記塩化物イオンが、存在するならば、５０ｐｐｍ以下の濃度で存在する、（１９）に記載の組成物。
（２１）前記塩化物イオンが、存在するならば、１０ｐｐｍ以下の濃度で存在する、（１９）に記載の組成物。
（２２）前記塩化物イオンが、存在するならば、５ｐｐｍ以下の濃度で存在する、（１９）に記載の組成物。
（２３）前記組成物が０ｐｐｍの塩化物イオンを有する、（１９）に記載の組成物。
（２４）ＧＣに基づく全ての有機シラン不純物の合計が１．０ｗｔ％以下である、（１７）に記載の組成物。
（２５）ＧＣに基づく全ての有機シラン不純物の合計が０．５ｗｔ％以下である、（１７に記載の組成物。 Although exemplified and described above in connection with certain embodiments and examples, the invention is by no means limited to the details presented. Rather, various changes may be made in detail within the scope and scope of the claims without departing from the ideas of the present invention. For example, any range broadly shown in this document is expressly intended to include any narrower range within these areas.
The present invention includes the following aspects.
(1) A chemical vapor deposition method for producing a dielectric film, wherein the method is
A gaseous reagent is introduced into the reaction chamber provided in which the substrate is provided, and the gaseous reagent is the following formula I, i.e.

Contains silicon precursors, including silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 -} C4 alkyl diradyl that forms a ₄ -membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1 -C6 alkyl substituents ^, where R3 is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ Selected from the group consisting of a cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic alkyl group, a C ₅ to C ₁₀ aryl group, and a C ₃ to C ₁₀ heteroaryl group, and an alkoxy OR ⁴ , where R ⁴ is direct. Selected from the group consisting of chain or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups. ,and,
Energy is applied to the gaseous reagent in the reaction chamber to induce the reaction of the gaseous reagent to deposit the film on the substrate.
Including that
A chemical vapor deposition method for producing a dielectric film.
(2) The method according to (1), wherein the silicon precursor further contains a curing additive.
(3) The silicon compound is 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane. , 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane, 2,2 -Dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2 , 6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1 -Oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl- 2-Iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa- 2 (1), which comprises at least one selected from the group consisting of 2-silacyclohexane, 2,6,6-trimethyl-2-iso-propyl-1-oxa-2-silacyclohexane, and combinations thereof. the method of.
(4) The method according to (2), wherein the curing additive contains tetraethoxysilane.
(5) The method according to (2), wherein the curing additive contains tetramethoxysilane.
(6) The method according to (1), which is a plasma-assisted chemical vapor deposition method.
(7) The gaseous reagent is further selected from the group consisting of O ₂ , N ₂ O, NO, NO ₂ , CO ₂ , CO, water, H ₂ O ₂ , ozone, and combinations thereof. The method according to (1), which comprises an oxygen source of.
(8) The reaction chamber of the application step comprises at least one gas selected from the group consisting of He, Ar, N ₂ , Kr, Xe, NH ₃ , H ₂ , CO ₂ and CO ((8). The method described in 1).
(9) The method according to (1), further comprising a step of applying additional energy to the film.
(10) The method according to (9), wherein the additional energy is at least one selected from the group consisting of heat treatment, ultraviolet (UV) treatment, electron beam treatment, and gamma ray treatment.
(11) The method according to (10), wherein the UV treatment is performed while at least a part of the heat treatment is performed.
(12) The gaseous reagent further comprises a pologene precursor and
The step of applying energy to the gaseous reagent to deposit the film comprises co-depositing the sacrificial porogen on the substrate.
The method according to (1).
(13) A composition for use in a deposition process for producing a dielectric film, wherein the composition is the following formula I, that is,

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 -} C4 alkyl diradyl that forms a ₄ -membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1 -C6 alkyl substituents ^, where R3 is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ Selected from the group consisting of a cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic alkyl group, a C ₅ to C ₁₀ aryl group, and a C ₃ to C ₁₀ heteroaryl group, and an alkoxy OR ⁴ , where R ⁴ is direct. Selected from the group consisting of chain or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups. ,
A composition for use in the deposition process of producing dielectric films.
(14) The silicon compound is 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane. , 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane, 2,2 -Dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2 , 6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1 -Oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl- 2-Iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa- 2-Silacyclohexane, 2,6,6-trimethyl-2-iso-propyl-1-oxa-2-silacyclohexane, and at least one selected from the group consisting of combinations thereof, according to (13). Composition.
(15) Equation I, that is,

A method for producing a silicon compound represented by
The above method
Hydrosilylation of the alkoxysilane with unsaturated alcohols was carried out in the presence of the catalyst, followed by reaction equation (1) or (2), ie in yields of 70% or greater.

Including cyclization with or without solvent according to
R ¹ is hydrogen, linear or branched C ₁ to C ₁₀ alkyl group, linear or branched C ₂ to C ₁₀ alkenyl group, linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ³ is direct. Chained or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ rings Selected from the group consisting of the formula alkyl group, the C ₃ to C ₁₀ heterocyclic alkyl group, the C ₅ to C ₁₀ aryl group, and the C ₃ to C ₁₀ heteroaryl group, and the alkoxy OR ⁴ , R ⁴ is a straight chain. Selected from the group consisting of linear or branched C ₁ to C ₁₀ alkyl groups and linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups. And R ^5-8 is independently selected from the group consisting of hydrogen, linear or branched C1 _to C10 _alkyl groups.
A method for producing a silicon compound.
The compound represented by the formula (I) is 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2. -Silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane , 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2- Silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2 -Methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2 -Silacyclohexane, 2-methyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,5 5-trimethyl-2-iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl- 1-Oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propyl-1-oxa-2-silacyclohexane, which is selected from the group consisting of, and combinations thereof, according to (15). Method.
(17) A composition for vapor deposition of a dielectric film, wherein the following formula I, that is,

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 -} C4 alkyl diradyl that forms a ₄ -membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1 -C6 alkyl substituents ^, where R3 is Linear or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, linear or branched C ₂ to C ₁₀ alkynyl groups, C ₃ to C ₁₀ Selected from the group consisting of a cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic alkyl group, a C ₅ to C ₁₀ aryl group, and a C ₃ to C ₁₀ heteroaryl group, and an alkoxy OR ⁴ , where R ⁴ is direct. Selected from the group consisting of chain or branched C ₁ to C ₁₀ alkyl groups, linear or branched C ₂ to C ₁₀ alkenyl groups, and linear or branched C ₂ to C ₁₀ alkynyl groups. And the compound contains very little of at least one impurity selected from the group consisting of halides, organic silane impurities, and water.
A composition for the deposition of dielectric films.
(18) The silicon compound is 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane. , 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane, 2,2 -Dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2 , 6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1 -Oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl- 2-Iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa-2-silacyclopentane, 2-methyl-2-iso-propyl-1-oxa- 2-Silacyclohexane, 2,6,6-trimethyl-2-iso-propyl-1-oxa-2-silacyclohexane, and at least one selected from the group consisting of combinations thereof, according to (17). Composition.
(19) The composition according to (17), wherein the halide contains chloride ions.
(20) The composition according to (19), wherein the chloride ion is present at a concentration of 50 ppm or less, if present.
(21) The composition according to (19), wherein the chloride ion is present at a concentration of 10 ppm or less, if present.
(22) The composition according to (19), wherein the chloride ion is present at a concentration of 5 ppm or less, if present.
(23) The composition according to (19), wherein the composition has 0 ppm chloride ion.
(24) The composition according to (17), wherein the total of all organic silane impurities based on GC is 1.0 wt% or less.
(25) The composition according to (17), wherein the total of all organic silane impurities based on GC is 0.5 wt% or less.

Claims (23)

A chemical vapor deposition method for producing a dielectric film, wherein the method is
A gaseous reagent is introduced into the reaction chamber provided in which the substrate is provided, and the gaseous reagent is the following formula I, i.e.

Contains silicon precursors, including silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 - C4} alkyl diradyl that forms a 4-membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1-C6 alkyl substituents ^, where R3 is Aalkoxy OR ⁴ , where R ⁴ is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, and a linear or branched C. Selected from the group consisting of ₂ to _C10 alkynyl groups, and
It comprises applying energy to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent to deposit a film on the substrate.
A chemical vapor deposition method for producing a dielectric film. The method of claim 1, wherein the silicon precursor further comprises a curing additive. The silicon compound is 2,5,5-trimethyl-2-ethoxy-1-oxa- 2 -silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2 , 5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane , 2 -methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2- Ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2 -Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-iso-propoxy Claimed to include at least one selected from the group consisting of -1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane , and combinations thereof. Item 1. The method according to Item 1. The method of claim 2, wherein the curing additive comprises tetraethoxysilane. The method of claim 2, wherein the curing additive comprises tetramethoxysilane. The method according to claim 1, which is a plasma-assisted chemical vapor deposition method. The gaseous reagent further comprises at least one oxygen source selected from the group consisting of O ₂ , N ₂ O, NO, NO ₂ , CO ₂ , CO, water, H ₂ O ₂ , ozone, and combinations thereof. The method according to claim 1, comprising the above. 1. The reaction chamber of the application step comprises at least one gas selected from the group consisting of He, Ar, N ₂ , Kr, Xe, NH ₃ , H ₂ , CO ₂ and CO. The method described. The method according to claim 1, further comprising a step of applying additional energy to the film. 9. The method of claim 9, wherein the additional energy is at least one selected from the group consisting of heat treatment, ultraviolet (UV) treatment, electron beam treatment, and gamma ray treatment. 10. The method of claim 10, wherein the UV treatment is performed while at least a portion of the heat treatment is being performed. The gaseous reagent further comprises a pologene precursor, and
The step of applying energy to the gaseous reagent to deposit the film comprises co-depositing the sacrificial porogen on the substrate.
The method according to claim 1. A composition for use in a deposition process for producing a dielectric film, wherein the composition is the following formula I, i.e.

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 - C4} alkyl diradyl that forms a 4-membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1-C6 alkyl substituents ^, where R3 is Aalkoxy OR ⁴ , where R ⁴ is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, and a linear or branched C. Selected from the group consisting of ₂ to _C10 alkynyl groups,
A composition for use in the deposition process of producing dielectric films. The silicon compound is 2,5,5-trimethyl-2-ethoxy-1-oxa- 2 -silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2 , 5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane , 2 -methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2- Ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2 -Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-iso-propoxy At least one selected from the group consisting of -1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane , and combinations thereof, claim. Item 3. The composition according to Item 13. A composition for vapor deposition of a dielectric film, wherein the following formula I, that is,

Contains silicon compounds with
R ¹ is hydrogen, a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, a linear or branched C ₂ to C ₁₀ alkynyl group, Selected from the group consisting of C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ heterocyclic alkyl groups, C ₅ to C ₁₀ aryl groups, and C ₃ to C ₁₀ heteroaryl groups, R ² is Si. A _{C2 - C4} alkyl diradyl that forms a 4-membered, 5-membered, or ₆ -membered saturated cyclic ring with an atom and an oxygen atom with any C1-C6 alkyl substituents ^, where R3 is Aalkoxy OR ⁴ , where R ⁴ is a linear or branched C ₁ to C ₁₀ alkyl group, a linear or branched C ₂ to C ₁₀ alkenyl group, and a linear or branched C. Selected from the group consisting of ₂ to _C10 alkynyl groups, and said compound contains very little of at least one impurity selected from the group consisting of halides, organic silane impurities, and water.
A composition for the deposition of dielectric films. The silicon compound is 2,5,5-trimethyl-2-ethoxy-1-oxa- 2 -silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2 , 5,5-trimethyl-2-iso-propoxy-1-oxa-2-silacyclopentane , 2 -methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2- Ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2 -Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-iso-propoxy At least one selected from the group consisting of -1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-iso-propoxy-1-oxa-2-silacyclohexane , and combinations thereof, claim. Item 5. The composition according to Item 15 . The composition according to claim 15 , wherein the halide contains chloride ions. 17. The composition of claim 17 , wherein the chloride ion, if present, is present at a concentration of 50 ppm or less. 17. The composition of claim 17 , wherein the chloride ion, if present, is present at a concentration of 10 ppm or less. 17. The composition of claim 17 , wherein the chloride ion, if present, is present at a concentration of 5 ppm or less. 17. The composition of claim 17 , wherein the composition has 0 ppm chloride ion. The composition according to claim 15 , wherein the total of all organic silane impurities based on GC is 1.0 wt% or less. The composition according to claim 15 , wherein the total of all organic silane impurities based on GC is 0.5 wt% or less.