JP2012138614A - Method for forming interlayer dielectric film, semiconductor device and apparatus for producing semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reliability of a device by suppressing change with time in an interlayer dielectric film in a semiconductor device.SOLUTION: A residence time of gas molecules in a chamber is shortened to prevent depositing of monomer decomposition products to a film surface at the end of film formation. Also, the monomer decomposition products deposited on the surface are removed by treating the surface with inactive gas plasma.

Description

  The present invention relates to an interlayer insulating film forming method, an interlayer insulating film, a semiconductor device, and a semiconductor manufacturing apparatus, and more particularly to an interlayer insulating film forming method with little change with time and an interlayer insulating film formed by the method.

  Conventionally, silica (SiO 2) has been widely used as an interlayer insulating film material used for a copper wiring layer of a semiconductor device. However, with the progress of miniaturization and speeding up of semiconductor devices, a low dielectric constant film having a lower dielectric constant has been used as an interlayer insulating film in order to suppress signal transmission delay and power consumption in wiring. It was. In general, pores or hydrocarbons are introduced to lower the dielectric constant, and plasma CVD or spin coating is used as the production method. Several interlayer insulation films with a relative dielectric constant of 2.4 or less have been reported by these methods, but due to the decrease in mechanical strength of the interlayer insulation film due to the increase in vacancies and hydrocarbons, it is due to delamination within the semiconductor process. Declining reliability is a problem.

  Therefore, from the viewpoint of mechanical strength, a plasma CVD method is often used for forming an interlayer insulating film. In the case of interlayer insulation film growth by many plasma CVD methods, a carrier gas composed of an inert gas, a mixed gas of an organic silane source gas and an oxidizing gas is introduced into the reactor, and the oxidation reaction between the source gas and the oxidizing gas is performed in the plasma. The interlayer insulating film is grown by promoting.

Increases in pores and hydrocarbons cause not only a decrease in mechanical strength but also a problem of adsorption of moisture in the atmosphere. When moisture is adsorbed in the pores, there is a concern about an increase in dielectric constant. Also, the adsorbed moisture induces decomposition of the hydrocarbon, which also contributes to an increase in dielectric constant. In particular, when a film is formed by the plasma CVD method, the decomposition product of the raw material due to the plasma reaction is not terminated and may become a site for moisture adsorption. In particular, since an increase in dielectric constant due to moisture adsorption is remarkable in an interlayer insulating film containing fluorine, Patent Document 1 introduces an attempt to obtain a stable film by introducing hydrogen during film formation. On the other hand, Patent Document 2 describes a method of removing reaction products by purging with an inert gas before film formation.
JP 11-330070 A JP 2006-253290 A

  However, when the technique described in Patent Document 1 is used, film formation using a hydrogen reaction is difficult to control because it induces the complexity of the system by introducing two kinds of gases and the reduction of the film itself. In addition, as described in Patent Document 2, even if purging with an inert gas is performed before film formation, it is impossible to remove reaction products at the time of subsequent interlayer insulation film formation. As a result, a change in the dielectric constant over time is caused. Such a change with time in the dielectric constant of the film becomes remarkable in the plasma polymerization method or the plasma copolymerization method. The plasma polymerization method is a common name for one embodiment of the plasma CVD method, and without using an oxidizing gas, a mixed gas of an inert gas and a monomer having an unsaturated hydrocarbon is activated in the plasma, This is a plasma CVD method for growing an interlayer insulating film having a monomer as a part of the skeleton. The plasma copolymerization method is a method of growing an interlayer insulating film using a plurality of raw material monomers and an inert gas without adding an oxidizing gas. In forming an interlayer insulating film using such a plasma reaction, there is a demand for a simple method with little change in dielectric constant with time.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an interlayer insulating film that suppresses changes over time of the interlayer insulating film and realizes long-term stability, a semiconductor device using the same, and a method of manufacturing the same. And

  In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon, purging is performed with an inert gas immediately after the high-frequency power supply for film formation is turned off. Alternatively, in a method for forming an interlayer insulating film by a plasma CVD method using a monomer having an unsaturated hydrocarbon, a surface treatment is performed with an inert gas plasma after the film formation, and then a purge is performed with the inert gas. Alternatively, in the method of forming an interlayer insulating film by plasma CVD using monomers having unsaturated hydrocarbons, the supply of raw materials was stopped before turning off the high-frequency power supply during film formation, and plasma treatment was performed only with a carrier gas. After that, the high frequency power supply is turned off and purged with an inert gas.

  As a result, the monomer decomposition product that could not contribute to film formation in the chamber at the end of film formation is prevented from being adsorbed on the surface of the interlayer insulating film. Since the monomer decomposition product is in a state in which the bond is not cut and terminated, it is highly active and easily adsorbs moisture in the atmosphere. For this reason, when the monomer decomposition product is adsorbed on the surface of the insulator, moisture absorption starts from this point, and residence in the pores or decomposition of the hydrocarbon component begins. As a result, the dielectric constant of the interlayer insulating film increases with time. Such a phenomenon is likely to occur in a process in which only the raw material monomer and carrier gas or only the raw material monomer, carrier gas and inert gas are introduced into the reactor during film formation. This is because the decomposed monomer has a large number of dangling bonds of oxygen and can easily adsorb moisture in the atmosphere.

  The present invention has been made in view of these events, and is a method for suppressing adsorption of monomer decomposition products onto the surface of an interlayer insulating film made of a monomer having an unsaturated hydrocarbon. When the high frequency power supply is turned off, monomer decomposition products that did not contribute to film formation exist in the film formation chamber. The decomposition product is discharged out of the chamber at a high speed with an inert gas, whereby adsorption to the surface of the interlayer insulating film can be suppressed. In addition, the adsorbed decomposition products can be removed by performing a surface treatment with an inert gas plasma after film formation. In addition, the decomposition product can be removed by stopping the supply of the raw material monomer at the time of film formation and performing the surface treatment with the plasma of only the carrier gas.

By using the interlayer insulating film manufacturing method, the interlayer insulating film, the semiconductor device, and the semiconductor manufacturing apparatus of the present invention, it is possible to suppress degradation of long-term reliability of wiring, so that high speed and low power consumption LSI can be formed. It becomes.

1 is a schematic diagram of a semiconductor device deposition apparatus according to a first embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The chamber schematic diagram of the semiconductor device film-forming apparatus of Embodiment 1 of this invention. The figure which showed the relationship between the residence time in this invention, and a time-dependent change of a dielectric constant. The figure which showed the relationship between the residence time in this invention, and presence of the deposit | attachment of the outermost surface. The figure which showed the stay time and TDS analysis result in this invention. The figure which showed the film-forming process of 1st Embodiment in this invention. The figure which showed the film-forming process of 2nd Embodiment in this invention. The figure which showed the film-forming process of 3rd Embodiment in this invention.

(First embodiment)
Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  The interlayer insulating film is formed using a monomer having an unsaturated hydrocarbon as a raw material. Monomers having unsaturated hydrocarbons include monomers having a 3-membered ring structure of SiO (Formula 1), monomers having a 4-membered ring structure of SiO (Formula 5), and monomers having a linear structure (Formula 10). .

式１に示す前記３員環構造を持つ不飽和炭化水素を持つモノマーは、Ｒ１は不飽和炭素化合物、Ｒ２飽和炭素化合物であり、Ｒ１はビニル基、またはアリル基、Ｒ２はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかである。

The monomer having an unsaturated hydrocarbon having the three-membered ring structure shown in Formula 1 is R1 is an unsaturated carbon compound or R2 saturated carbon compound, R1 is a vinyl group or an allyl group, R2 is a methyl group, an ethyl group , A propyl group, an isopropyl group, or a butyl group.

  In the monomer having an unsaturated hydrocarbon having the 4-membered ring structure shown in Formula 5, R3 is an unsaturated carbon compound, R4 is a saturated carbon compound, R1 is a vinyl group or an allyl group, R2 is a methyl group, ethyl Group, propyl group, isopropyl group, or butyl group.

  In the linear monomer represented by Formula 10, R5 is an unsaturated carbon compound, R6, R7, and R8 are saturated carbon compounds, R5 is a vinyl group or an allyl group, R6, R7, and R8 are a methyl group, an ethyl group, One of propyl group, isopropyl group and butyl group.

  A plasma CVD apparatus used for film formation is shown in FIG.

  The monomer reservoir 2 is a raw material supply unit. The pressurized gas 3 is a gas for discharging the raw material monomer from the monomer reservoir 1. The liquid mass flow 4 is a device that controls the flow rate of the raw material monomer 1 discharged from the monomer reservoir 1. The vaporizer 5 is a device that vaporizes the raw material monomer 1. The carrier gas 6 is a gas that transports the vaporized raw material monomer. The mass flow 7 is a device that controls the flow rate of the carrier gas 6. The reactor 8 is a chamber for forming a film by plasma CVD. The RF unit 9 is a device that applies RF in order to generate plasma. The exhaust pump 10 is an apparatus for discharging the vaporized gas of the raw material monomer 1 and the carrier gas 6 introduced into the reactor 8. The inert gas 11 is a purge gas.

  FIG. 2 shows the reactor 8 in more detail.

  The upper electrode 12 and the lower electrode 13 are portions where a bias is applied from the RF unit 9 to generate plasma. The substrate 14 is a wafer on which film formation is performed. The decomposition product 15 is the raw material monomer 1 decomposed by plasma. Film formation is performed by the following method. The raw material monomer 1 filled in the monomer reservoir 2 is discharged by the pressurized gas 3, and the flow rate of the raw material monomer 1 is controlled by the liquid mass flow 4. The raw material monomer 1 whose flow rate is controlled is vaporized by receiving heat from a heater (not shown) in the vaporizer 5. The vaporized gas is mixed with the carrier gas 6 whose flow rate is controlled by the mass flow 7 in the vaporizer 5 and sent to the reactor 8. The vaporized gas of the raw material monomer 1 and the carrier gas 6 sent to the reactor 8 become plasma between the upper electrode 12 and the lower electrode 13 by the power supplied from the RF unit 9. At this time, an interlayer insulating film is formed on the substrate 14 by the CVD reaction. The decomposition product 15 of the raw material monomer 1 exists between the upper electrode 12 and the lower electrode 13 when the high frequency power supply is turned off.

  Since only the raw material monomer and carrier gas, or the raw material monomer, carrier gas and inert gas are introduced into the reactor 8 at the time of film formation, there is no termination of oxygen dangling bonds of these decomposition products. When exposed to water, adsorption of moisture and the like is likely to occur. Therefore, it is necessary to shorten the residence time of the decomposition product and to discharge it outside the reactor before adsorption.

Example 1
Next, Example 1 using the first embodiment will be described with reference to the drawings. The following raw materials can be used for the formation of the interlayer insulating film. As the monomer having a SiO3 member ring structure, monomers represented by (Formula 2) to (Formula 4) can be used.

またＳｉＯ４員環構造のモノマーとしては（式６）〜（式９）に示すものを原料として使用することができる。

Moreover, as a monomer of SiO4 member ring structure, those shown in (Formula 6) to (Formula 9) can be used as raw materials.

また直鎖状モノマーとしては（式１１）に示す構造の原料を用いることが出来る。

As the linear monomer, a raw material having a structure shown in (Formula 11) can be used.

モノマーリザーバー２に満たされた上記原料モノマー１を圧送ガス３により排出し、液体マスフロー４により原料モノマー１の流量制御を行う。流量制御された原料モノマー１は気化器５内のヒータ（図示せず）から熱をもらい気化する。この気化したガスは、マスフロー７により流量制御されたキャリアガス６と気化器５内で混合しリアクタ８に送られる。リアクタ８に送られた原料モノマー１の気化ガスとキャリアガス６は、ＲＦユニット９より供給された電力により、上部電極１２と下部電極１３の間でプラズマとなる。図３に示す成膜装置では原料供給ラインが２系統あり、１原料のみを使ったプラズマ重合法、あるいは２原料によるプラズマ共重合反応により成膜が可能である。これら手法により基板１４上に層間絶縁膜が形成される。高周波電源ＯＦＦ時には上部電極１２と下部電極１３の間には原料モノマー１の分解生成物１５が存在する。図５に第一の実施の形態の成膜プロセスを示す。高周波電源ＯＦＦと同時に原料モノマーの供給を停止する。ここで同時とは高周波電源ＯＦＦと原料供給バルブ（図示せず）を閉じるタイミングが同時であることを意味しており、リアクタ内の状態は数秒のタイムラグが発生している。この分解生成物１５を排出し基板１４に吸着させないために不活性ガス１１を導入しリアクタ８内をパージする。このときリアクタ８内に気体分子（分解生成物）が滞在する平均滞在時間τは以下の式により求めることが出来る。なお、式１２は、電気書院発刊岡本幸雄著「プラズマプロセッシングの基礎」ｐ．１６に記載されている。

The raw material monomer 1 filled in the monomer reservoir 2 is discharged by the pressurized gas 3 and the flow rate of the raw material monomer 1 is controlled by the liquid mass flow 4. The raw material monomer 1 whose flow rate is controlled is vaporized by receiving heat from a heater (not shown) in the vaporizer 5. The vaporized gas is mixed with the carrier gas 6 whose flow rate is controlled by the mass flow 7 in the vaporizer 5 and sent to the reactor 8. The vaporized gas of the raw material monomer 1 and the carrier gas 6 sent to the reactor 8 become plasma between the upper electrode 12 and the lower electrode 13 by the power supplied from the RF unit 9. In the film forming apparatus shown in FIG. 3, there are two raw material supply lines, and film formation is possible by a plasma polymerization method using only one raw material or a plasma copolymerization reaction using two raw materials. By these methods, an interlayer insulating film is formed on the substrate 14. The decomposition product 15 of the raw material monomer 1 exists between the upper electrode 12 and the lower electrode 13 when the high frequency power supply is turned off. FIG. 5 shows a film forming process of the first embodiment. The supply of the raw material monomer is stopped simultaneously with turning off the high frequency power supply. Here, simultaneous means that the high-frequency power supply is turned off and the timing of closing the raw material supply valve (not shown) is simultaneous, and the state in the reactor has a time lag of several seconds. In order to discharge the decomposition product 15 and prevent the decomposition product 15 from being adsorbed on the substrate 14, an inert gas 11 is introduced to purge the inside of the reactor 8. At this time, the average residence time τ during which gas molecules (decomposition products) stay in the reactor 8 can be obtained by the following equation. Note that Equation 12 is based on Yukio Okamoto, published by Denki Shoin, “Fundamentals of Plasma Processing” p. 16.

τ = pV / pS (12)
Where τ is the average residence time (seconds), p is the reactor pressure (Torr), V is the reactor volume (L), and S is the exhaust velocity (L / sec). Further, although the exhaust speed S cannot be directly stopped, the displacement Q can be expressed by the product of p and S, so (Equation 12) can be modified as follows.

τ = pV / Q (Equation 13)
When purging the reactor from Equation 14, if the reactor pressure is constant, the exhaust amount Q becomes equal to the purge gas introduction amount. If the amount of purge gas introduced is increased, the average residence time τ can be shortened and can be discharged before the decomposition product 15 is adsorbed on the substrate. A mixed gas of helium and nitrogen was used as the inert gas. FIG. 3 is a diagram showing the change with time of the relative dielectric constant of the interlayer insulating film. From this figure, it was found that the relative permittivity increased drastically when the purge was performed so that the average residence time τ disappeared.

  Therefore, a sample having a stay time τ of 1 second and a sample outermost surface having a stay time of 0.05 seconds were analyzed by TOF-SIMS, and the result of analyzing the difference in the surface state is shown in FIG. From this figure, it was found that the surface of the film purged so as to increase the residence time contains a large amount of substances containing oxygen such as carboxylic acid. This carboxylic acid originates from decomposition products adsorbed on the substrate surface.

  Next, TDS analysis was performed to analyze organic substances released from the surface. As a result, in the sample that was purged with a short residence time, organic matter was not released unless it was overheated at 400 ° C. or higher. On the other hand, it was found that the organic substance was released at around 120 ° C. in the sample that was purged with a long residence time. It is thought that this is because moisture and the like are adsorbed by the decomposition product adsorbed on the surface, the hydrocarbon is decomposed, and is easily released at a low temperature.

(Second Embodiment)
Next, a second embodiment for carrying out the present invention will be described with reference to the drawings.

  As in the first embodiment, an interlayer insulating film was formed on the substrate 14, and then an inert gas was introduced to perform plasma treatment on the surface of the interlayer insulating film. This process is illustrated in FIG. After the film formation, the introduction of the raw material monomer and the carrier gas was stopped at the same time, the inert gas was introduced and stabilized, and then plasma was generated to perform the treatment. He was used as the inert gas, and the treatment was performed at a reactor pressure of 800 Pa and an RF power of 400 W for 10 to 60 seconds. The processing conditions vary depending on the reactor size, the inert gas species, and the raw material monomer species, and are not uniquely determined. After the plasma treatment with the inert gas, purging was performed under the condition that the residence time of the gas molecules was 0.8 seconds. As a result, it is possible to suppress the change in the relative dielectric constant with time of the interlayer insulating film, as in the case where the stay time of the purge gas in the first embodiment is short.

(Third embodiment)
Next, a third embodiment for carrying out the present invention will be described with reference to the drawings.

  As in the first embodiment, an interlayer insulating film is formed on the substrate 14 and the supply of the raw material monomer is stopped before the application of RF power is stopped. This process is illustrated in FIG. As a result, plasma is generated only by the carrier gas in the reactor. He was used as a carrier gas to treat the surface of the interlayer insulating film. The surface treatment conditions were the same as the film formation except that the introduction of raw materials was stopped, and the treatment was performed for 10 to 60 seconds. After the plasma treatment with the carrier gas, purging was performed under the condition that the residence time of the gas molecules was 0.6 seconds. As a result, it is possible to suppress the change in the relative dielectric constant with time of the interlayer insulating film, as in the case where the stay time of the purge gas in the first embodiment is short.

DESCRIPTION OF SYMBOLS 1 ... Raw material monomer 2 ... Monomer reservoir 3 ... Pressure feed gas 4 ... Liquid mass flow 5 ... Vaporizer 6 ... Carrier gas 7 ... Mass flow 8 ... Reactor 9 ... RF unit 10 ... exhaust pump 11 ... inert gas 12 ... upper electrode 13 ... lower electrode 14 ... substrate 15 ... decomposition product

（付記９）
前記ＳｉＯの３員環構造を持つ不飽和炭化水素を持つモノマーが、下記式２、３、４に示す構造のうち少なくともいずれかの１つであることを特徴とする付記７に記載の層間絶縁膜形成方法。

（付記１０）
前記ＳｉＯの４員環構造を持つ不飽和炭化水素を持つモノマーが、下記式５に示す構造であり、Ｒ３は不飽和炭素化合物、Ｒ４飽和炭素化合物であり、Ｒ１はビニル基またはアリル基、Ｒ２はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかであることを特徴とする付記７に記載の層間絶縁膜形成方法。

（付記１１）
前記ＳｉＯの４員環構造を持つ不飽和炭化水素を持つモノマーが下記式６、７、８、９に示す構造のうち少なくともいずれかの１つであることを特徴とする付記７に記載の層間絶縁膜形成方法。

（付記１２）
前記ＳｉＯの直鎖構造を持つ不飽和炭化水素を持つモノマーが、下記式１０に示す構造であり、Ｒ５は不飽和炭素化合物、Ｒ６、Ｒ７、Ｒ８は飽和炭素化合物であり、Ｒ５はビニル基またはアリル基、Ｒ６、Ｒ７、Ｒ８はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかであることを特徴とする付記７に記載の層間絶縁膜形成方法。

（付記１３）
前記ＳｉＯの直鎖構造を持つ不飽和炭化水素を持つモノマーが下記式１１に示す構造であることを特徴とする付記７に記載の層間絶縁膜形成方法。

（付記１４）
前記不活性ガスが原料供給ラインとは異なった経路で供給されることを特徴とする付記１乃至４のいずれか一つに記載の層間絶縁膜形成方法。
（付記１５）
前記キャリアガスが、ヘリウム、窒素、アルゴンのいずれか１種類以上含むことを特徴とする付記３記載の層間絶縁膜形成方法。
（付記１６）
付記１乃至１５のいずれか一つに記載の層間絶縁膜形成方法であって、原料となる不飽和炭化水素を持つモノマーが１種であるプラズマ重合反応、もしくは２種であるプラズマ重合反応を用いることを特徴とする層間絶縁膜形成方法。
（付記１７）
前記付記１乃至１６のいずれか一つに記載の層間絶縁膜形成方法によって形成された層間絶縁膜であって、ＴＤＳ分析より１２０℃で放出される有機物がないことを特徴とする層間絶縁膜。
（付記１８）
付記１乃至１６のいずれか一つに記載の層間絶縁膜形成方法によって形成された層間絶縁膜を具備することを特徴とする半導体デバイス。
（付記１９）
付記１乃至１６のいずれか一つに記載の層間絶縁膜形成方法によって層間絶縁膜を成膜する半導体製造装置。

As in the first embodiment, an interlayer insulating film is formed on the substrate 14 and the supply of the raw material monomer is stopped before the application of RF power is stopped. This process is illustrated in FIG. As a result, plasma is generated only by the carrier gas in the reactor. He was used as a carrier gas to treat the surface of the interlayer insulating film. The surface treatment conditions were the same as the film formation except that the introduction of raw materials was stopped, and the treatment was performed for 10 to 60 seconds. After the plasma treatment with the carrier gas, purging was performed under the condition that the residence time of the gas molecules was 0.6 seconds. As a result, it is possible to suppress the change in the relative dielectric constant with time of the interlayer insulating film, as in the case where the stay time of the purge gas in the first embodiment is short.
In any of the above-described embodiments, the following invention is disclosed.
(Appendix 1)
In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method of forming an interlayer insulating film, characterized by purging with an inert gas simultaneously with turning off the high-frequency power supply for film formation.
(Appendix 2)
In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method for forming an interlayer insulating film, characterized by performing a surface treatment with an inert gas plasma after film formation and then purging with an inert gas.
(Appendix 3)
In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method of forming an interlayer insulating film, characterized in that the supply of raw materials is stopped before turning off the high frequency power supply during film formation, the plasma treatment is performed only with the carrier gas, the high frequency power supply is turned off, and the inert gas is purged.
(Appendix 4)
In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
The interlayer insulating film forming method according to any one of appendices 1 to 3, wherein only the raw material monomer and the carrier gas or only the raw material monomer, the carrier gas and the inert gas are supplied into the reactor during the film formation. .
(Appendix 5)
The method for forming an interlayer insulating film according to any one of appendices 1 to 4, wherein the inert gas includes one or more of helium, nitrogen, and argon.
(Appendix 6)
The interlayer insulating film according to any one of appendices 1 to 5, wherein the flow rate during the purging with the inert gas is such that the residence time in the deposition chamber is 0.8 seconds or less. Forming method.
(Appendix 7)
The interlayer insulating film forming method according to any one of appendices 1 to 6, wherein the monomer having an unsaturated hydrocarbon has a three-membered ring structure, a four-membered ring structure, or a straight chain structure of SiO.
(Appendix 8)
The monomer having an unsaturated hydrocarbon having a three-membered ring structure of SiO is a structure represented by the following formula 1, R1 is an unsaturated carbon compound, an R2 saturated carbon compound, R1 is a vinyl group or an allyl group, The interlayer insulating film forming method according to appendix 7, wherein R2 is any one of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

(Appendix 9)
The interlayer insulation according to appendix 7, wherein the monomer having an unsaturated hydrocarbon having a three-membered ring structure of SiO is at least one of the structures represented by the following formulas 2, 3, and 4: Film forming method.

(Appendix 10)
The monomer having an unsaturated hydrocarbon having a 4-membered ring structure of SiO has a structure represented by the following formula 5, wherein R3 is an unsaturated carbon compound or an R4 saturated carbon compound, R1 is a vinyl group or an allyl group, R2 The method for forming an interlayer insulating film according to appendix 7, wherein any one of methyl group, ethyl group, propyl group, isopropyl group, and butyl group is used.

(Appendix 11)
The interlayer according to appendix 7, wherein the monomer having an unsaturated hydrocarbon having a 4-membered ring structure of SiO is at least one of structures represented by the following formulas 6, 7, 8, and 9: Insulating film forming method.

(Appendix 12)
The monomer having an unsaturated hydrocarbon having a straight chain structure of SiO is a structure represented by the following formula 10, R5 is an unsaturated carbon compound, R6, R7, and R8 are saturated carbon compounds, and R5 is a vinyl group or 8. The method for forming an interlayer insulating film according to appendix 7, wherein allyl group, R6, R7, and R8 are any of methyl group, ethyl group, propyl group, isopropyl group, and butyl group.

(Appendix 13)
The interlayer insulating film forming method according to appendix 7, wherein the monomer having an unsaturated hydrocarbon having a linear structure of SiO has a structure represented by the following formula 11.

(Appendix 14)
The method for forming an interlayer insulating film according to any one of appendices 1 to 4, wherein the inert gas is supplied through a path different from that of the raw material supply line.
(Appendix 15)
The method for forming an interlayer insulating film according to appendix 3, wherein the carrier gas contains one or more of helium, nitrogen, and argon.
(Appendix 16)
The method for forming an interlayer insulating film according to any one of appendices 1 to 15, wherein a plasma polymerization reaction in which a monomer having an unsaturated hydrocarbon as a raw material is one type or a plasma polymerization reaction in which two types are used is used. An interlayer insulating film forming method characterized by the above.
(Appendix 17)
An interlayer insulating film formed by the method for forming an interlayer insulating film according to any one of Appendices 1 to 16, wherein no organic material is released at 120 ° C. by TDS analysis.
(Appendix 18)
A semiconductor device comprising an interlayer insulating film formed by the method for forming an interlayer insulating film according to any one of appendices 1 to 16.
(Appendix 19)
A semiconductor manufacturing apparatus for forming an interlayer insulating film by the interlayer insulating film forming method according to any one of appendices 1 to 16.

Claims (19)

In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method of forming an interlayer insulating film, characterized by purging with an inert gas simultaneously with turning off the high-frequency power supply for film formation. In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method for forming an interlayer insulating film, characterized by performing a surface treatment with an inert gas plasma after film formation and then purging with an inert gas. In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
A method of forming an interlayer insulating film, characterized in that the supply of raw materials is stopped before turning off the high frequency power supply during film formation, the plasma treatment is performed only with the carrier gas, the high frequency power supply is turned off, and the inert gas is purged. In the method of forming an interlayer insulating film by plasma CVD using a monomer having an unsaturated hydrocarbon,
4. The interlayer insulating film formation according to claim 1, wherein only the raw material monomer and the carrier gas, or only the raw material monomer, the carrier gas, and the inert gas are supplied into the reactor during the film formation. Method.   5. The method for forming an interlayer insulating film according to claim 1, wherein the inert gas is one or more of helium, nitrogen, and argon.   The interlayer insulation according to any one of claims 1 to 5, wherein a flow rate during the purging with the inert gas is set so that a residence time in the film forming chamber is 0.8 seconds or less. Film forming method.   The method for forming an interlayer insulating film according to claim 1, wherein the monomer having an unsaturated hydrocarbon has a three-membered ring structure, a four-membered ring structure, or a straight chain structure of SiO. The monomer having an unsaturated hydrocarbon having a three-membered ring structure of SiO is a structure represented by the following formula 1, R1 is an unsaturated carbon compound, an R2 saturated carbon compound, R1 is a vinyl group or an allyl group, 8. The method for forming an interlayer insulating film according to claim 7, wherein R2 is any one of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

The interlayer monomer according to claim 7, wherein the monomer having an unsaturated hydrocarbon having a three-membered ring structure of SiO is at least one of structures represented by the following formulas 2, 3, and 4. Insulating film forming method.

The monomer having an unsaturated hydrocarbon having a 4-membered ring structure of SiO has a structure represented by the following formula 5, wherein R3 is an unsaturated carbon compound or an R4 saturated carbon compound, R1 is a vinyl group or an allyl group, R2 8. The method for forming an interlayer insulating film according to claim 7, wherein is one of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

The monomer having an unsaturated hydrocarbon having a 4-membered ring structure of SiO is at least one of structures represented by the following formulas 6, 7, 8, and 9. Interlayer insulating film forming method.

The monomer having an unsaturated hydrocarbon having a straight chain structure of SiO is a structure represented by the following formula 10, R5 is an unsaturated carbon compound, R6, R7, and R8 are saturated carbon compounds, and R5 is a vinyl group or 8. The method for forming an interlayer insulating film according to claim 7, wherein allyl group, R6, R7, and R8 are any one of methyl group, ethyl group, propyl group, isopropyl group, and butyl group.

8. The method for forming an interlayer insulating film according to claim 7, wherein the monomer having an unsaturated hydrocarbon having a linear structure of SiO has a structure represented by the following formula 11.

  5. The method of forming an interlayer insulating film according to claim 1, wherein the inert gas is supplied through a path different from that of the raw material supply line.   4. The method for forming an interlayer insulating film according to claim 3, wherein the carrier gas contains one or more of helium, nitrogen, and argon.   The interlayer insulating film forming method according to any one of claims 1 to 15, wherein a plasma polymerization reaction in which a monomer having an unsaturated hydrocarbon as a raw material is one type or a plasma polymerization reaction in which two types are used. A method for forming an interlayer insulating film, comprising using the method.   The interlayer insulating film formed by the interlayer insulating film forming method according to any one of claims 1 to 16, wherein there is no organic substance released at 120 ° C by TDS analysis. .   17. A semiconductor device comprising an interlayer insulating film formed by the interlayer insulating film forming method according to claim 1.   17. A semiconductor manufacturing apparatus for forming an interlayer insulating film by the interlayer insulating film forming method according to claim 1.

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