JP5040162B2 - Si-containing film forming material comprising alkenyl group-containing organosilane compound and use thereof - Google Patents

Description

  The present invention relates to a Si-containing film-forming material composed of an organosilane compound, its use, and the like. In particular, the present invention relates to a material suitable for forming a low dielectric constant interlayer insulating film used in multilayer wiring technology in logic ULSI.

  In the manufacturing technology of the integrated circuit field of the electronics industry, there is an increasing demand for high integration and high speed. In silicon ULSIs, especially logic ULSIs, the performance of wiring connecting them is a problem rather than the performance due to miniaturization of MOSFETs. That is, in order to solve the wiring delay problem associated with the multilayer wiring, it is required to reduce the wiring resistance and between the wirings and the interlayer capacitance.

  For these reasons, it is essential to introduce copper wiring with lower electrical resistance and migration resistance instead of aluminum wiring, which is currently used in most integrated circuits. Sputtering or chemical vapor deposition A process of performing copper plating after seed formation by the (hereinafter abbreviated as CVD) method is being put into practical use.

There are various proposals for low dielectric constant interlayer insulating film materials. As the prior art, silicon dioxide (SiO ₂ ), silicon nitride, phosphosilicate glass has been used for inorganic systems, and polyimide has been used for organic systems. Recently, however, a tetralayer has been previously prepared for the purpose of obtaining a more uniform interlayer insulating film. Hydrolysis of ethoxysilane monomer, that is, polycondensation to obtain SiO ₂ and proposal to use it as a coating material called Spin on Glass (inorganic SOG), or polysiloxane obtained by polycondensation of organic alkoxysilane monomer to organic SOG There is a proposal to use as.

  Also, as an insulating film forming method, an insulating film polymer solution is applied by spin coating or the like, and a coating type is used, and PECVD (Plasma Enhanced Chemical Vapor Deposition) is mainly formed by plasma polymerization in a plasma CVD apparatus. There are two methods.

  As a proposal of the PECVD method, for example, in Patent Document 1, a method of forming a trimethylsilane oxide thin film from a trimethylsilane and oxygen by PECVD is used, and in Patent Document 2, straight lines such as methyl, ethyl, and n-propyl are used. There has been proposed a method of forming an alkyl oxysilane thin film by an PECVD method from an alkoxysilane having an alkynyl and aryl group such as chain alkyl, vinyl, and phenyl. Insulating films formed of these conventional PECVD methods have good adhesion to barrier metal and copper wiring material as wiring material, but there are cases where uniformity of the film becomes a problem. In addition, the film formation requires high plasma power in order to realize a high film formation rate, and high power high frequency power supply of several thousand watts (watt) or quartz or the like in the chamber for film formation. Expensive materials had to be used, and there were economic problems. Furthermore, since the film is formed with a high plasma power, it is difficult to control the structure of the thin film polymer to be produced, and the relative dielectric constant may be insufficient. Patent Document 3 proposes a method of depositing a silicon carbide layer using divinyldimethylsilane on a substrate. However, this material may be polymerized in a vaporizer that is in a high temperature condition and block the vaporizer piping, which may make it difficult to stably operate the PECVD apparatus.

  Therefore, there is a demand for a material that can form a low dielectric constant insulating film with a low plasma power, a high film formation rate, and can be stably vaporized using an inexpensive apparatus.

  On the other hand, as a coating type proposal, although the uniformity of the film is good, three steps of coating, solvent removal, and heat treatment are necessary, which is economically disadvantageous than CVD materials, and barrier metal, wiring In many cases, adhesion to the copper wiring material, which is the material, and uniform application of the coating liquid to the miniaturized substrate structure itself are problems.

Moreover, in the coating type material, the method of using a porous material in order to implement | achieve the Ultra Low-k material whose relative dielectric constant is 2.5 or less and also 2.0 or less is proposed. Organic or inorganic material matrix readily disperse the thermally decomposed organic component particles in the method of heat treating and pore formation, silicon and oxygen by evaporating SiO ₂ ultrafine particles formed by evaporation in a gas, SiO ₂ than There is a method of forming a fine particle thin film.

  However, although these porous methods are effective for lowering the dielectric constant, the mechanical strength decreases, chemical mechanical polishing (CMP) becomes difficult, and the dielectric constant increases due to moisture absorption. And wiring corrosion could be caused.

  Therefore, the market further seeks well-balanced materials that satisfy all the required performance such as low dielectric constant, sufficient mechanical strength, adhesion to barrier metal, copper diffusion prevention, plasma ashing resistance, moisture absorption resistance, etc. . As a method for balancing these required performances to some extent, a material having an intermediate characteristic between an organic polymer and an inorganic polymer has been proposed in an organic silane material by increasing the carbon ratio of the organic substituent to silane.

  For example, in Patent Document 4, a coating solution obtained by hydrolyzing and condensing a silicon compound having an adamantyl group by a sol-gel method in the presence of an acidic aqueous solution is used, and an interlayer having a relative dielectric constant of 2.4 or less without being made porous. A method for obtaining an insulating film is proposed. However, this material is a coating type material, and still has the problem of the film forming method using the coating type as described above.

JP 2002-110670 A JP-A-11-288931 JP 2005-64518 A JP 2000-302791 A

  An object of the present invention is to provide a novel Si-containing film forming material, particularly an Si-containing film forming material comprising an alkenyl group-containing organosilane compound suitable for a PECVD apparatus.

  The present inventors have found that an organosilane compound having an alkenyl group is particularly suitable as a low dielectric constant interlayer insulating film material for a semiconductor device, and have completed the present invention.

  That is, the present invention provides the following general formula (1)

（式中、Ｒ^１，Ｒ^２は、炭素数１〜２０の炭化水素基または水素原子を表し、ｎは０〜３の整数を表す。）で表される有機シラン化合物から成ることを特徴とする、Ｓｉ含有膜形成材料である。

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and n represents an integer of 0 to 3). Si-containing film forming material.

  Moreover, this invention is a formation method of Si containing film characterized by using the above-mentioned Si containing film forming material.

  Furthermore, the present invention is a Si-containing film obtained by the above-described method.

  In addition, the present invention is a Si-containing film obtained by treating the above-mentioned Si-containing film under conditions where a bond between a carbon atom and a silicon atom is broken.

  Furthermore, the present invention is an insulating film characterized by comprising the above-mentioned Si-containing film.

  The present invention also provides a semiconductor device using the above-described insulating film. Details of the present invention will be described below.

In the general formula (1), R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R ¹ and R ² may be the same or different. The hydrocarbon group at this time may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In consideration of stable use in a CVD apparatus, R ¹ and R ² are particularly preferably hydrocarbon groups having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, the vapor pressure of the organosilane compound represented by the general formula (1) becomes low, and it may take time to use in the PECVD apparatus.

The hydrocarbon group of R ¹ and R ² has 1 to 20 carbon atoms, and preferably includes an alkyl group, aryl group, arylalkyl group, and alkylaryl group having 1 to 10 carbon atoms.

  For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, n-pentyl, tert. -Amyl, n-hexyl, cyclohexyl and the like can be mentioned.

  As unsaturated hydrocarbon groups, alkenyl such as vinyl, 1-propenyl, 1-butenyl and 2-butenyl, alkadienyl such as 1,3-butadienyl, 1,3-pentadienyl and 1,3-hexadienyl, ethynyl, 1- Examples thereof include alkynyl such as propynyl, 1-butynyl and 2-butynyl, aryl such as phenyl, and alkylaryl such as toluyl.

Among these, R ¹ is preferably a primary hydrocarbon group, and more preferably a methyl group. On the other hand, R ² is preferably a hydrogen atom.

  N in the general formula (1) is an integer of 0 to 3, but preferably n is an integer of 0 to 2, and in this case, the general formula (1) represents a polyalkenylsilane.

As a specific example of the organosilane compound represented by the general formula (1),
Tetraallylsilane, tetraisobutenylsilane,
Methyltriallylsilane, ethyltriallylsilane, isopropyltriallylsilane, sec-butyltriallylsilane, tert. -Butyltriallylsilane, phenyltriallylsilane,
Methyltriisobutenylsilane, ethyltriisobutenylsilane, isopropyltriisobutenylsilane, sec-butyltriisobutenylsilane, tert. -Butyl triisobutenyl silane, phenyl triisobutenyl silane and the like.

Further, dimethyldiallylsilane, diethyldiallylsilane, diisopropyldiallylsilane, disec-butyldiallylsilane, ditert. -Butyl diallyl silane, diphenyl diallyl silane,
Dimethyldiisobutenylsilane, diethyldiisobutenylsilane, diisopropyldiisobutenylsilane, disec-butyldiisobutenylsilane, ditert. -Butyl diisobutenyl silane, diphenyl diisobutenyl silane,
Trimethylallylsilane, triethylallylsilane, triisopropylallylsilane, trisec-butylallylsilane, tritert. -Butyl allyl silane, triphenyl allyl silane and the like.

Further, trimethylisobutenylsilane, triethylisobutenylsilane, triisopropylisobutenylsilane, trisec-butylisobutenylsilane, tritert. -Butyl isobutenyl silane, triphenyl isobutenyl silane,
tert. -Butyldimethylallylsilane, tert. -Butylmethyldiallylsilane, tert. -Butylethyldiallylsilane,
tert. -Butyldimethylisobutenylsilane, tert. -Butylmethyldiisobutenylsilane, tert. -Butyl ethyl diisobutenyl silane etc. can be mentioned.

  Among these, tetraallylsilane, methyltriallylsilane, or dimethyldiallylsilane is preferable.

  Although the manufacturing method of the organosilane compound represented by the said General formula (1) is not specifically limited, For example, following General formula (2)

（式中、Ｒ^１及びｎは、上記一般式（１）に同じ。Ｘは、フッ素原子、塩素原子、臭素原子、沃素原子、または炭素数１〜４のアルコキシ基を表す。）で表される化合物と、下記一般式（３）

(Wherein, R ¹ and n are the same as those in the general formula (1). X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkoxy group having 1 to 4 carbon atoms). And the following general formula (3)

（式中、Ｒ^２は、上記一般式（１）に同じ。Ｍは、Ｌｉ、ＭｇＣｌ、ＭｇＢｒ、またはＭｇＩを表す。）で表されるアルケニル金属化合物とを反応させ、製造することができる。

(Wherein R ² is the same as in the general formula (1). M represents Li, MgCl, MgBr, or MgI) and can be produced by reacting with an alkenyl metal compound.

  For example, the following general formula (4)

（式中、Ｒ^２及びｎは、上記一般式（１）に同じ。Ｘは、フッ素原子、塩素原子、臭素原子、沃素原子、または炭素数１〜４のアルコキシ基を表す。）で表されるアルケニル基置換ハロゲン化シラン化合物と、下記一般式（５）

(In the formula, R ² and n are the same as those in the general formula (1). X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkoxy group having 1 to 4 carbon atoms). An alkenyl group-substituted halogenated silane compound and the following general formula (5)

（式中、Ｒ^１は、上記一般式（１）に同じ。Ｍは、上記一般式（３）に同じ。）で表される化合物とを反応させ、製造することもできる。

(In the formula, R ¹ is the same as in the general formula (1). M is the same as in the general formula (3)).

  In this production method, the formation of by-products is suppressed, and an organic silane compound represented by the general formula (1) with high yield and high purity is obtained.

  Reaction conditions of the compound represented by the general formula (2) and the alkenyl metal compound represented by the general formula (3), and the alkenyl group-substituted halogenated silane compound represented by the general formula (4) and the general The reaction conditions with the compound represented by formula (5) are not particularly limited, and are usually in the range of −100 to 200 ° C., preferably −85 to 150 ° C., which is an industrially used temperature. Preferably it is done. The pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.

  The solvent used in the above reaction is not particularly limited as long as it is used in the technical field. For example, n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, n- Saturated hydrocarbons such as decane, unsaturated hydrocarbons such as toluene, xylene and decene-1, diethyl ether, dipropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, and cyclopentyl methyl ether can be used. Moreover, these mixed solvents can also be used.

  In the production, the method in the organometallic compound synthesis field is followed. That is, the dehydration and deoxygenation is performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification are preferably subjected to dehydration operations in advance. It is also preferable to remove impurities such as metal residues and particles.

  About the purification method of the organosilane compound represented by the above general formula (1) obtained by the above method, the moisture content is less than 50 ppm useful for use as an insulating film material, and elements other than silicon, carbon, oxygen and hydrogen It is preferable to make the content of less than 10 ppb. For this purpose, by-product lithium salt, magnesium salt, or alkali metal salt is filtered using glass filter, sintered porous body, etc., atmospheric pressure or vacuum distillation or silica. It may be removed by means such as column separation and purification using alumina or polymer gel. At this time, these means may be used in combination as necessary.

  The alkenyl metal compound represented by the general formula (3) and the compound represented by the general formula (5) used in the production are represented by the following general formula (6).

（式中、Ｒ^３は、アルケニル基を含む炭素数１〜２０の炭化水素基を表し、Ｘは、上記に同じ。）で表される化合物と、金属リチウムまたは金属マグネシウムとを反応させて製造することができる。

(Wherein R ³ represents a hydrocarbon group having 1 to 20 carbon atoms including an alkenyl group, and X is the same as described above) and produced by reacting lithium metal or magnesium metal can do.

  Although the reaction conditions of the compound represented by the general formula (6) and metallic lithium or metallic magnesium are not particularly limited, an example is shown below.

  As the metallic lithium to be used, lithium wire, lithium ribbon, lithium shot, lithium particles, and the like can be used. From the viewpoint of reaction efficiency, it is preferable to use lithium fine particles having a particle size of 500 μm or less.

  As the metallic magnesium to be used, magnesium ribbon, magnesium particles, magnesium powder and the like can be used.

  The solvent used in the above reaction is not particularly limited as long as it is used in the technical field, and the solvent exemplified in the production of the organosilane compound represented by the general formula (1) is used. be able to. Moreover, those mixed solvents can also be used.

  About reaction temperature in said reaction, it is preferable to carry out in the temperature range which the organic lithium compound or organic magnesium compound to produce | generate does not decompose | disassemble. Usually, it is carried out in the range of −100 to 200 ° C., preferably −85 to 150 ° C., which is a temperature used industrially. The pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.

  The synthesized alkenyl metal compound represented by the general formula (3) and the compound represented by the general formula (5) can be used as they are after the synthesis, and are represented by the unreacted general formula (6). It can also be used after removing the compound, metal lithium or metal magnesium, or the reaction by-product lithium halide or magnesium halide.

  Since the Si-containing film forming material of the present invention preferably has less impurities and moisture when producing a Si-containing film, the content of elements other than silicon, carbon, oxygen and hydrogen is less than 10 ppb. The water content is preferably less than 50 ppm.

  According to the present invention, a Si-containing film can be formed by using the Si-containing film forming material as described above. Although there is no particular limitation on the formation method at this time, it is preferable to form a film by a CVD method, and it is more preferable to form a film by a PECVD method.

  The organosilane compound represented by the general formula (1) has at least one alkenyl group, and the details of its mechanism of operation are unknown, but the film formation rate is higher than that of conventional organosilane compounds. Thus, it is possible to form a Si-containing film.

  The Si-containing film is preferably formed in the presence of a compound having at least one oxygen atom. Thereby, the Si-containing film obtained can be made porous. Examples of the compound having at least one oxygen atom include oxygen, ozone, dinitrogen monoxide, water, hydrogen peroxide, alkoxysilane compounds, carbon dioxide, carbon monoxide, carboxylic acid, carboxylic acid peroxide, or carboxylic acid. Examples thereof include peroxide esters.

  In the case of forming a film by PECVD, the type of PECVD and the apparatus used are not particularly limited. For example, this PECVD is generally used in the technical field such as the semiconductor manufacturing field and the liquid crystal display manufacturing field. Is used.

  For example, in a PECVD apparatus, the Si-containing film forming material of the present invention is vaporized by a vaporizer and introduced into a film forming chamber, and is applied to an electrode in the film forming chamber by a high frequency power source to generate plasma. A plasma CVD thin film can be formed on a silicon substrate or the like. At this time, a gas such as argon or helium, or an oxidant such as oxygen or nitrous oxide may be introduced for the purpose of generating plasma.

  The plasma generation method of the PECVD apparatus is not particularly limited, and inductively coupled plasma, capacitively coupled plasma, ECR plasma, microwave plasma, or the like used in the art can be used. Inductively coupled plasma and capacitively coupled plasma are preferable. As the plasma generation source, various types such as a parallel plate type and an antenna type can be used. As the inert gas supplied to the chamber of the PECVD apparatus, helium, argon, krypton, neon used in the technical field. Xenon, etc. can be used.

  As an example of the PECVD apparatus, FIG. 1 shows a parallel plate capacitively coupled PECVD apparatus. A parallel plate capacitively coupled PECVD apparatus 1 shown in FIG. 1 includes a showerhead upper electrode and a lower electrode capable of controlling the temperature of the substrate in the PECVD apparatus chamber, a vaporizer apparatus for supplying the Si-containing film forming material to the chamber, and a high frequency. It consists of a plasma generator consisting of a power supply and a matching circuit, and an exhaust system consisting of a vacuum pump.

  Specifically, this PECVD apparatus 1 is provided with a PECVD chamber 2, an upper electrode 3 having a shower head for uniformly supplying a Si-containing film forming material into the chamber, and a thin film forming substrate 5 such as a Si substrate. Lower electrode 4 having temperature control device 8 for vaporization, vaporization devices 9 to 15 for vaporizing Si-containing film forming material, matching circuit 6 and RF power source 7 which are plasma generation sources, unreacted substances and by-products in the chamber It comprises an exhaust device 16 for exhausting the air. Reference numerals 17 and 18 denote grounds.

  The matching circuit 6 and the RF power source 7 which are plasma generation sources are connected to the upper electrode 3 and generate plasma by discharge. The standard of the RF power source 7 is not particularly limited, but the power used in the technical field is 1 W to 2000 W, preferably 10 W to 1000 W, the frequency is 50 kHz to 2.5 GHz, preferably 100 kHz to 100 MHz, particularly preferably 200 kHz. An RF power source of ˜50 MHz can be used.

  The substrate temperature is not particularly limited, but is −90 to 1,000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with the Si-containing film forming material 13 and includes a container 12 having a dip pipe and a pipe 15 that is pressurized with the inert gas, a liquid flow rate control apparatus 10 that controls the flow rate of the Si-containing film forming material 13, It comprises a vaporizer 9 for vaporizing the Si-containing film forming material 13, a pipe 14 for supplying the inert gas into the PECVD apparatus chamber via the vaporizer, and a gas flow rate controller 11 for controlling the flow rate thereof. This vaporizer is connected by piping from the vaporizer 9 to the upper electrode 3 having a shower head.

  As an example of a PECVD apparatus, FIG. 2 shows an inductively coupled remote PECVD apparatus. The inductively coupled remote PECVD apparatus 19 shown in FIG. 2 is represented by a plasma generating part wound in a coil around the quartz at the upper part of the PECVD apparatus chamber, a temperature-controllable substrate setting part, and a Si-containing film forming material. It consists of a vaporizer device for vaporizing the compound into the chamber, a plasma generator comprising a high frequency power source and a matching circuit, and an exhaust system comprising a vacuum pump.

  Specifically, the PECVD apparatus 19 includes a PECVD chamber 20, a coil 21 that is a plasma generation unit and a quartz tube 22, a heater unit 23 for installing a thin film forming substrate 24 such as a Si substrate, and a temperature control unit 27, It comprises vaporizers 28 to 35 for vaporizing the Si-containing film forming material, a matching circuit 25 and an RF power source 26 as a plasma generation source, and an exhaust device 36 for exhausting unreacted substances and by-products in the chamber. 37 is a ground.

  A coil around quartz, which is a plasma generation unit, is connected to the matching circuit 25 and is discharged in the quartz tube by an antenna current magnetic field by RF current to generate plasma. Although it does not specifically limit about the specification of RF power supply 26, The electric power used in the said technical field is 1W-2000W, Preferably it is 10W-1000W, A frequency is 50 kHz-2.5 GHz, Preferably it is 100 kHz-100 MHz, Most preferably, it is 200 kHz- A 50 MHz RF power supply can be used.

  The substrate temperature is not particularly limited, but is −90 to 1,000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with the Si-containing film forming material 33, and includes a container 32 having a dip pipe and a pipe 35 that is pressurized with the inert gas, a liquid flow rate control device 29 that controls the flow rate of the Si-containing film forming material 33, A vaporizer 28 for vaporizing the Si-containing film forming material 33, a pipe 34 for supplying the inert gas to the PECVD apparatus chamber via the vaporizer, a gas flow rate controller 30 for controlling the flow rate, an inert gas and a gas It comprises a shower head 31 for uniformly supplying the formed Si-containing film forming material 33 into the chamber.

  The Si-containing film forming material is gasified using the PECVD apparatus exemplified above, and is supplied into the chamber together with an inert gas as necessary, and is formed by PECVD. The pressure in the chamber at this time is not particularly limited, but is 0.1 Pa to 10000 Pa, preferably 1 Pa to 5000 Pa.

The Si-containing film obtained by the present invention is further made porous or mechanically treated by, for example, heat treatment, ultraviolet irradiation treatment, or electron beam treatment, under the condition that the bond between carbon atoms and silicon atoms is broken. A Si-containing film with improved mechanical strength can be obtained. The Si-containing film obtained by the present invention may have a low relative dielectric constant, and depending on conditions, a film having a relative dielectric constant of 2.0 or less can be obtained. These can be used as an insulating film for a semiconductor device. It is particularly suitable for the manufacture of ULSI using multilayer wiring.

  By forming a film using the Si-containing film forming material composed of the organosilane compound represented by the general formula (1), it is possible to obtain a Si-containing film at a high film formation rate. This film has a low relative dielectric constant. Therefore, it can be used as an interlayer insulating film for semiconductor devices.

  Examples are shown below, but the present invention is not limited to these Examples.

Example 1
[Synthesis of allylmagnesium chloride]
Under a nitrogen atmosphere, 214 g (8.80 mol) of magnesium and 2883 g (3.2 L) of tetrahydrofuran were charged into a 5 L four-necked flask reactor equipped with a reflux condenser, a dropping funnel and a stirrer, and the reactor was ice-cooled. 612 g (8.00 mol) of allyl chloride was added dropwise over 3 hours. After dropwise addition of allyl chloride, the mixture was further stirred at room temperature for 16 hours to obtain a tetrahydrofuran solution of allyl magnesium chloride.

[Synthesis of dimethyldiallylsilane]
The 5 L four-necked flask reactor in which the tetrahydrofuran solution of allylmagnesium chloride was prepared was ice-cooled again, and 516 g (4.00 mol) of dimethyldichlorosilane was dropped into the reactor over 3 hours. After dropwise addition of dimethyldichlorosilane, the mixture was further stirred overnight at room temperature. After stirring, 911 g of water was added dropwise over 2 hours, and a mixture of 184 g of sulfuric acid and 900 g of water was added dropwise over 40 minutes. After dropping, a reaction mixture solution (organic layer) was obtained by a liquid separation operation. After drying with 371 g of molecular sieves, tetrahydrofuran was distilled off, and the target product, dimethyldiallylsilane, was isolated by distillation under reduced pressure.

The yield was 179 g (1.27 mol), corresponding to a yield of 31.9%. The results of analyzing the isolated dimethyldiallylsilane by ¹ H-NMR and GC-MS were as follows.

¹ H-NMR; 0.003 ppm (s, 6H), 1.541 ppm (d, 4H), 4.845 ppm (m, 4H), 5.773 ppm (m, 2H)
GC-MS; Mw = 140.

Example 2 [Plasma CVD film formation of dimethyldiallylsilane]
The dimethyldiallylsilane synthesized in Example 1 was formed on a silicon substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG.

The film formation conditions were as follows: argon gas as an inert gas at 10 sccm, oxygen at 0.1 sccm, vaporized dimethyldiallylsilane was continuously supplied so that the internal pressure of the chamber was 10 Pa, the substrate temperature was 150 ° C., the RF power source The film was formed under the conditions of power 30 W and RF power supply frequency 13.56 MHz. As a result, the film formation rate was 20.7 nm / min. Met. The infrared absorption spectrum of the obtained thin film is shown in FIG. In the figure, a represents absorption of an alkyl chain, b represents absorption of Si—CH ₃ , c represents absorption of Si—O, and d represents absorption of Si—C.

It is a figure which shows a parallel plate capacitive coupling type PECVD apparatus. It is a figure which shows an inductively coupled remote PECVD apparatus. 6 is a diagram showing an infrared absorption spectrum obtained in Example 2. FIG.

Explanation of symbols

1. PECVD apparatus 2. PECVD chamber Upper electrode 4. Lower electrode 5. 5. Substrate for thin film formation 6. Matching circuit RF power supply 8. Temperature controller 9. Vaporizer 10. Liquid flow controller 11. Gas flow control device 12. Container 13. Si-containing film forming material 14. Piping 15. Piping 16. Exhaust device 17. Earth 18. Earth 19. PECVD apparatus 20. PECVD chamber 21. Coil 22. Quartz tube 23. Heater section 24. Thin film forming substrate 25. Matching circuit 26. RF power supply 27. Temperature controller 28. Vaporizer 29. Liquid flow control device 30. Gas flow control device 31. Shower head 32. Container 33. Si-containing film forming material 34. Piping 35. Piping 36. Exhaust device 37. Earth

Claims (11)

The following general formula (1)

(Wherein, R ¹ represents a primary hydrocarbon group, R ² represents a hydrogen atom, n represents represents. 1 or 2) Ri consists organosilane compounds represented by silicon, carbon, other than oxygen and hydrogen A Si-containing film-forming material for chemical vapor deposition, characterized in that the content of the element is less than 10 ppb and the water content is less than 50 ppm . The Si-containing film forming material according to claim 1, wherein R ¹ is a methyl group. The Si-containing film forming material according to claim 1, wherein the organosilane compound represented by the general formula (1) is methyltriallylsilane or dimethyldiallylsilane. A method for forming a Si-containing film, wherein the Si-containing film forming material according to any one of claims 1 to 3 is used to form a film by chemical vapor deposition. The method for forming a Si-containing film according to claim 4 , wherein the film is formed by plasma enhanced chemical vapor deposition. 6. The method for forming a Si-containing film according to claim 4, wherein the film is formed in the presence of a compound having at least one oxygen atom. The compound having at least one oxygen atom is oxygen, ozone, dinitrogen monoxide, water, hydrogen peroxide, alkoxysilane compound, carbon dioxide, carbon monoxide, carboxylic acid, carboxylic acid peroxide, or carboxylic acid peroxidation. The method according to claim 6 , wherein the method is a product ester. A Si-containing film obtained by the method according to claim 4 . A Si-containing film obtained by treating the Si-containing film according to claim 8 under a condition in which a bond between a carbon atom and a silicon atom is broken. An insulating film comprising the Si-containing film according to claim 8 . A semiconductor device comprising the insulating film according to claim 10 .

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