KR101144497B1 - Modifier for low dielectric constant film, and method for production thereof - Google Patents

Modifier for low dielectric constant film, and method for production thereof Download PDF

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KR101144497B1
KR101144497B1 KR1020097018100A KR20097018100A KR101144497B1 KR 101144497 B1 KR101144497 B1 KR 101144497B1 KR 1020097018100 A KR1020097018100 A KR 1020097018100A KR 20097018100 A KR20097018100 A KR 20097018100A KR 101144497 B1 KR101144497 B1 KR 101144497B1
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dielectric constant
low dielectric
modifier
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KR20090105977A (en
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쯔요시 오가와
미쯔야 오하시
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샌트랄 글래스 컴퍼니 리미티드
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Abstract

본 발명의 저유전율막의 개질제는, 반도체 디바이스에 사용되는 저유전율막의 비유전율을 저하시키기 위한 개질제로서, 식(1) The modifier of the low dielectric constant film of the present invention is a modifier for lowering the dielectric constant of a low dielectric constant film used in a semiconductor device, and is represented by the formula (1).

Figure 112009053248476-pct00005
Figure 112009053248476-pct00005

(R은 C1~C4의 알킬기, n은 0~3의 정수)로 표시되는 규소 화합물을 유효성분으로서 함유하는 것을 특징으로 한다.It is characterized by containing the silicon compound represented by (R is a C1-C4 alkyl group, n is an integer of 0-3) as an active ingredient.

Description

저유전율막의 개질제 및 제조방법{Modifier for low dielectric constant film, and method for production thereof}Modifier for low dielectric constant film, and method for production

본 발명은 반도체 디바이스에 사용되는 저유전율막에 있어서, 저유전율막의 비유전율을 저하시키기 위해 사용되는 저유전율막의 개질제 및 개질된 저유전율막의 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low dielectric constant film modifier and a method for producing a modified low dielectric constant film in a low dielectric constant film used in a semiconductor device.

최근의 고집적화된 반도체에 있어서는, 디바이스 내의 신호 지연 문제를 해소하여, 보다 고속이며 전력절약의 디바이스를 제조하기 위해, 층간 절연막으로서 저유전율막이 사용되고 있다. 저유전율막에는, 유기계, 무기계를 포함하여, 수많은 종류가 있지만, 현재, 가장 일반적인 것은, 실리카막에 탄소를 첨가한 SiOC막이다. 향후, 반도체 디바이스가 더욱 미세화되면, SiOC막에 있어서도 충분한 저유전율 특성이 얻어지지 않는 점에서, 층간 절연막에는 다공질화된 SiOC막이 사용될 전망이다.In the recent highly integrated semiconductor, a low dielectric constant film is used as an interlayer insulating film in order to solve the signal delay problem in the device and to manufacture a device having a higher speed and power saving. There are many kinds of low dielectric constant films, including organic and inorganic, but at present, the most common are SiOC films in which carbon is added to silica films. In the future, when the semiconductor device is further miniaturized, a porous SiOC film is expected to be used for the interlayer insulating film because sufficient low dielectric constant characteristics are not obtained even in the SiOC film.

그러나 SiOC막은 성막 후부터 막 중의 Si-C 결합이나 Si-H 결합이 절단되어, 실란올(Si-OH)이 발생하고, 막의 비유전율이 상승한다는 문제가 있다. 이와 같은 문제를 해소하기 위해, SiOC막에 HMDS(헥사메틸디실라잔)와 같은 실란커플링제를 막의 개질제로서 작용시켜, 실란올을 화학적으로 실릴화하여, 막의 비유전율을 저 하시키는 방법이 공지로 되어 있다. 또한, 최근에는, HMDS 대신에, TMS-Cl(트리메틸클로로실란)이나 TMSDMA(트리메틸실릴디메틸아민) 등을 사용한 방법도 보고되어 있다(특허문헌 1). 그러나, 어느 방법에 있어서도, 얻어지는 막의 비유전율은 만족되지 않았다.However, since the SiOC film | membrane cut | disconnects Si-C bond and Si-H bond in a film | membrane after film-forming, silanol (Si-OH) generate | occur | produces and there exists a problem that the dielectric constant of a film rises. In order to solve such a problem, a method is known in which a silane coupling agent such as HMDS (hexamethyldisilazane) is acted on the SiOC film as a film modifier to chemically silylate the silanol to lower the dielectric constant of the film. It is. In recent years, a method using TMS-Cl (trimethylchlorosilane), TMSDMA (trimethylsilyldimethylamine) or the like instead of HMDS has also been reported (Patent Document 1). However, in either method, the dielectric constant of the obtained film was not satisfied.

따라서, SiOC막과 같은 저유전율막에 대해, 막 중의 실란올을 가능한 한 화학적으로 실릴화하여, 만족되는 막의 비유전율까지 저하시키도록 개질할 수 있는 화합물이 요망되고 있다.Therefore, for low dielectric constant films such as SiOC films, there is a demand for compounds that can be modified such that silanol in the film is chemically silylated as much as possible to reduce the relative dielectric constant of the film to be satisfied.

특허문헌 1: 일본국 특허공개 제2006-179913호 공보Patent Document 1: Japanese Patent Application Laid-Open No. 2006-179913

발명의 개요Summary of the Invention

본 발명은 반도체 디바이스에 사용되는 저유전율막에 대해, 막 중의 실란올을 화학적으로 실릴화하여, 막의 비유전율이 저하되도록 개질할 수 있는 개질제를 제공하는 것을 목적으로 하고 있다.An object of the present invention is to provide a modifier capable of chemically silylating silanol in a film and reducing the relative dielectric constant of the film to a low dielectric constant film used in a semiconductor device.

더 나아가서는, 개질제에 의해 비유전율을 저하시킨 저유전율막의 제조방법을 제공하는 것을 목적으로 하고 있다.Furthermore, it aims at providing the manufacturing method of the low dielectric constant film by which the dielectric constant was reduced by the modifier.

본 발명자들은 상기 목적을 달성하기 위해 예의 검토를 거듭한 결과, 저유전율막에, 분자 내에 아지드기를 갖는 규소 화합물을 유효성분으로서 함유한 개질제와 접촉시킴으로써, 저유전율막 중의 실란올이 화학적으로 실릴화되어, 막의 비유전율이 저하되도록 개질할 수 있는 것을 발견하고, 본 발명에 도달한 것이다.MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, as a result, silanol in a low dielectric constant film is chemically silicided by contacting a low dielectric constant film with the modifier which contains the silicon compound which has an azide group in a molecule as an active ingredient. The present invention has been found to be capable of being modified so that the relative dielectric constant of a film is lowered.

즉, 본 발명은 반도체 디바이스에 사용되는 저유전율막의 비유전율을 저하시키기 위한 개질제로서, 식(1)That is, the present invention is formula (1) as a modifier for lowering the dielectric constant of a low dielectric constant film used in a semiconductor device.

Figure 112009053248476-pct00001
Figure 112009053248476-pct00001

(R은 C1~C4의 알킬기, n은 0~3의 정수)로 표시되는 규소 화합물을 유효성분으로서 함유하는 것을 특징으로 하는 저유전율막의 개질제를 제공하는 것이다.It is to provide the modifier of the low dielectric constant film characterized by containing the silicon compound represented by (R is a C1-C4 alkyl group, n is an integer of 0-3) as an active ingredient.

더 나아가서는, 반도체 디바이스에 사용되는 저유전율막에 대해, 상기의 식(1)로 표시되는 규소 화합물을 함유하는 개질제를 20℃~300℃의 범위 내에서 접촉시킴으로써 되는 개질된 저유전율막의 제조방법을 제공하는 것이다.Furthermore, the manufacturing method of the modified low dielectric constant film formed by making the low dielectric constant film used for a semiconductor device contact the modifier containing the silicon compound represented by said Formula (1) within 20 degreeC-300 degreeC. To provide.

상세한 설명details

본 발명에 의하면, 저유전율막 중의 실란올을 화학적으로 실릴화하여, 저유전율막의 비유전율을 저하시켜, 막을 개질시킬 수 있다. 또한 본 발명의 방법에 의하면, 비유전율이 저하된 개질된 저유전율막을 제조할 수 있다.According to the present invention, silanol in the low dielectric constant film can be chemically silylated to lower the relative dielectric constant of the low dielectric constant film to modify the film. In addition, according to the method of the present invention, a modified low dielectric constant film having a lower dielectric constant can be produced.

이하, 본 발명을 더욱 상세하게 기술한다. 본 발명에서 저유전율막의 개질제 중에 유효성분으로서 포함되는 규소 화합물은, 식(1)Hereinafter, the present invention will be described in more detail. The silicon compound contained as an active ingredient in the modifier of a low dielectric constant film in this invention is Formula (1).

Figure 112009053248476-pct00002
Figure 112009053248476-pct00002

(R은 C1~C4의 알킬기, n은 0~3의 정수)로 표시되는 화합물이다. 본 발명에 있어서 C1~C4의 알킬기란, 구체적으로는, 메틸기, 에틸기, n-프로필기, i-프로필기, n-부틸기, i-부틸기, s-부틸기, t-부틸기 등이다. R이 복수 존재하는 경우에는, 이들이 서로 동일한 것이어도 되고, 상이한 것이 혼재된 것이어도 된다. 그러나 최근의 저유전율막은 다공질화가 진행되고 있어, 개질제를 막 중의 공공(空孔) 내로 침투시키기 위해서도, 이들 화합물의 분자 직경은 작은 편이 바람직하고, R로서는 특히 메틸기가 바람직하다.(R is a C1-C4 alkyl group, n is an integer of 0-3). In this invention, a C1-C4 alkyl group is specifically a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, etc. . In the case where a plurality of R's are present, these may be the same as or different from each other. However, in recent years, the low dielectric constant membrane is porous, and in order to infiltrate the modifier into the vacancy in the membrane, the molecular diameter of these compounds is preferably smaller, and R is particularly preferably methyl.

본 발명에 있어서 저유전율막의 비유전율 저하의 메커니즘을 상세하게 기술한다. 저유전율막 중에 실란올이 발생하면, 막의 비유전율이 상승한다. 여기서, 개질제 중에 포함되는 식(1)로 표시되는 화합물은, 식(2)에 나타내는 반응식과 같이, 실란올의 활성수소 부분에 대해, 실릴화 반응을 행한다.In the present invention, the mechanism of lowering the dielectric constant of the low dielectric constant film will be described in detail. When silanol is generated in the low dielectric constant film, the dielectric constant of the film increases. Here, the compound represented by Formula (1) contained in a modifier performs a silylation reaction with respect to the active hydrogen part of silanol like the reaction formula shown in Formula (2).

Figure 112009053248476-pct00003
Figure 112009053248476-pct00003

(Si’는 막을 구성하는 Si와 구별하기 위한 표기로, 식(1)의 Si에 상당하는 것이다.) (Si 'is a notation for distinguishing it from Si constituting the film, which corresponds to Si in Formula (1).)

그 결과, 막 중의 실란올이 감소하여, 막의 비유전율이 저하된다. 반응 후에는 아지드화 수소(HN3)가 발생하기 때문에, 이것을 계(系)외로 배출한다. 아지드화 수소는 유해하여, 적당한 제해(除害)처리를 행한 후에 폐기한다.As a result, silanol in a film | membrane decreases and the dielectric constant of a film | membrane falls. Since hydrogen azide (HN 3 ) is generated after the reaction, this is discharged out of the system. Hydrogen azide is harmful and disposed of after proper decontamination treatment.

식(1)로 표시되는 개질제의 유효성분은, 단일성분 또는 치환기가 상이한 복수의 성분을 조합시킨 상태로 사용해도 된다. 예를 들면, 아지도트리메틸실란((CH3)3SiN3)과 아지도트리에틸실란((CH3CH2)3SiN3)을 임의의 비율로 혼합시켜, 그들을 사용해도 된다. 또한 이들을 유효성분으로 하는 개질제는, 기존의 실란커플링제와 임의의 비율로 혼합시킨 상태로 사용해도 된다. 기존의 실란커플링제로서는, HMDS(헥사메틸디실라잔), TMDS(테트라메틸디실라잔), TMSDMA(트리메틸실릴디메틸아민), DMSDMA(디메틸실릴디메틸아민), TMSDEA(트리메틸실릴디에틸아민), B[DMA]MS(비스디메틸아미노메틸실란), B[DMA]DS(비스디메틸아미노디메틸실란), TMS-Cl(트리메틸클로로실란), TMMOS(트리메틸메톡시실란) 등을 들 수 있다. 더 나아가서는 헬륨 등의 불활성 가스로 희석해서 사용해도 된다. 어느 경우에도, 개질제 중에 식(1)로 표시되는 화합물을 일정 농도 이상 함유해 둘 필요가 있고, 그 농도로서는 1 vol%~100 vol%, 바람직하게는 50 vol%~100 vol%, 더욱 바람직하게는 95 vol%~100 vol%이다.You may use the active ingredient of the modifier represented by Formula (1) in the state which combined the several component from which a single component or a substituent differs. For example, azidotrimethylsilane ((CH 3 ) 3 SiN 3 ) and azidotriethylsilane ((CH 3 CH 2 ) 3 SiN 3 ) may be mixed at any ratio and used. Moreover, you may use the modifier which uses these as an active ingredient in the state mixed with the existing silane coupling agent in arbitrary ratios. Existing silane coupling agents include HMDS (hexamethyldisilazane), TMDS (tetramethyldisilazane), TMSDMA (trimethylsilyldimethylamine), DMSDMA (dimethylsilyldimethylamine), TMSDEA (trimethylsilyldiethylamine), B [DMA] MS (bisdimethylaminomethylsilane), B [DMA] DS (bisdimethylaminodimethylsilane), TMS-Cl (trimethylchlorosilane), TMMOS (trimethylmethoxysilane), etc. are mentioned. Furthermore, you may dilute and use with inert gas, such as helium. In any case, it is necessary to contain the compound represented by Formula (1) or more in a modifier at a constant concentration or more, and as the concentration, 1 vol% to 100 vol%, preferably 50 vol% to 100 vol%, more preferably Is 95 vol%-100 vol%.

개질제를 저유전율막에 접촉시킬 때의 온도로서는 20℃~300℃의 범위 내가 바람직하고, 특히 60℃~200℃가 바람직하다. 온도가 20℃ 미만이 되면, 개질제 중의 유효성분과 실란올의 반응속도가 매우 느려지고, 또한, 부반응으로서 실란올의 아지드화 반응도 진행되기 때문에 바람직하지 않다. 한편, 온도가 300℃를 초과하면, 개질제 중의 유효성분의 분해가 우선적으로 발생하기 때문에 바람직하지 않다.As temperature at the time of making a modifier contact a low dielectric constant film, the inside of the range of 20 to 300 degreeC is preferable, and 60 to 200 degreeC is especially preferable. When the temperature is less than 20 ° C, the reaction rate between the active ingredient and the silanol in the modifier becomes very slow, and the azide reaction of silanol also proceeds as a side reaction, which is not preferable. On the other hand, when the temperature exceeds 300 ° C, decomposition of the active ingredient in the modifier occurs preferentially, which is not preferable.

개질제를 저유전율막에 접촉시킬 때, 개질제는 가스상, 액상 중 어느 상태로도 사용할 수 있다. 가스상으로 사용하는 경우는, 저유전율막에 대해 직접 접촉시키면 되고, 액상으로 사용하는 경우는, 저유전율막에 대해 스핀코트시키는 방법이 바람직하다. 어느 방법에 있어서도, 대기에 폭로하지 않고 실시할 필요가 있다.When the modifier is brought into contact with the low dielectric constant film, the modifier may be used in any of a gaseous state and a liquid state. When using in gas phase, what is necessary is just to directly contact a low dielectric constant film, and when using in a liquid phase, the method of spin-coating with respect to a low dielectric constant film is preferable. In either method, it is necessary to carry out without exposing to the atmosphere.

개질제를 저유전율막에 접촉시킬 때의 시간으로서는 특별히 한정되지는 않는다. 그러나, 반도체 디바이스의 제조시간을 단축화시키기 위해서도 10~120초의 접촉이 바람직하다.It does not specifically limit as time when a modifier contacts a low dielectric constant film. However, in order to shorten the manufacturing time of a semiconductor device, the contact of 10 to 120 second is preferable.

개질제를 저유전율막에 접촉시킨 후에는, 장치 내를 감압으로 함으로써, 미반응의 개질제 및 반응생성물을 제거할 수 있다. 이때, 장치 내를 가온하여, 제거효율을 올려서 실시해도 된다.After the modifier is brought into contact with the low dielectric constant film, the inside of the apparatus is reduced in pressure, whereby unreacted modifier and reaction product can be removed. At this time, the inside of the apparatus may be heated to increase the removal efficiency.

본 발명에 있어서의 저유전율막은, 막 중에 공공(空孔)이 존재하고 있는 것도 포함된다. 그러나, 이들 막의 형성방법에 대해서는 특별히 한정되는 것은 아니다. 막의 형성방법으로서는, 예를 들면, 플라즈마 CVD법이나 스핀온글래스법 등을 들 수 있다.The low dielectric constant film in the present invention includes those in which voids exist in the film. However, the method for forming these films is not particularly limited. As a film formation method, plasma CVD method, spin-on glass method, etc. are mentioned, for example.

이하, 실시예에 의해 본 발명을 구체적으로 설명한다.Hereinafter, an Example demonstrates this invention concretely.

실시예 1Example 1

실리콘 웨이퍼 상에 MSQ(메틸실세스퀴옥산) 용액을 스핀 도포한 후, 100℃에서 30분간, 200℃에서 1시간 베이크하여, MSQ막을 형성하였다. 얻어진 MSQ막의 비유전율을 구하기 위해, 증착법으로, 막 상에 Al 전극을 형성하여, 1 MHz에 있어서의 막의 정전용량(靜電容量)을 측정하였다. 정전용량값, 막두께, 전극면적으로부터, MSQ막의 비유전율을 산출한 바, 3.6이었다. 다음으로 MSQ막을 개질하기 위해서, 밀폐 가능한 SUS제 용기를 준비하고, MSQ막을 용기 내로 옮겼다. 용기 내를 10 Pa까지 감압으로 하고, 150℃까지 가온한 후, 개질제로서 아지도트리메틸실란((CH3)3SiN3)의 증기를 10 kPa 도입하였다. 실릴화처리는 60초간 행하였다. 개질 후의 MSQ막의 비유전율을 측정한 바, 3.2였다.After spin-coating an MSQ (methylsilsesquioxane) solution on a silicon wafer, it baked for 30 minutes at 100 degreeC, and 200 degreeC for 1 hour, and formed the MSQ film | membrane. In order to determine the relative dielectric constant of the obtained MSQ film, an Al electrode was formed on the film by the vapor deposition method, and the capacitance of the film at 1 MHz was measured. It was 3.6 when the dielectric constant of the MSQ film was calculated from the capacitance value, the film thickness, and the electrode area. Next, in order to modify the MSQ membrane, a hermetic container made of SUS was prepared, and the MSQ membrane was transferred into the vessel. The inside of the vessel was reduced to 10 Pa, and heated to 150 ° C., and then 10 kPa of azidotrimethylsilane ((CH 3 ) 3 SiN 3 ) was introduced as a modifier. The silylation treatment was performed for 60 seconds. It was 3.2 when the dielectric constant of the MSQ membrane after modification was measured.

실시예 2Example 2

MSQ막의 개질제를 아지도트리에틸실란((CH3CH2)3SiN3)으로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.3이었다.The modification was carried out in the same manner as in Example 1, except that the modifier of the MSQ film was azidotriethylsilane ((CH 3 CH 2 ) 3 SiN 3 ). The dielectric constant of the MSQ membrane after modification was 3.3.

실시예 3Example 3

MSQ막의 개질제를 아지도디메틸실란((CH3)2HSiN3)으로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.2였다.The modification was carried out in the same manner as in Example 1 except that the modifier of the MSQ membrane was azidodimethylsilane ((CH 3 ) 2 HSiN 3 ). The dielectric constant of the MSQ membrane after modification was 3.2.

실시예 4Example 4

개질제 도입시의 온도를 70℃로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.3이었다.It carried out by the method similar to Example 1 except having made the temperature at the time of introducing a modifier 70 degreeC. The dielectric constant of the MSQ membrane after modification was 3.3.

실시예 5Example 5

MSQ막의 개질제를 아지도트리메틸실란((CH3)3SiN3)과 HMDS(헥사메틸디실라잔)의 혼합물(혼합비 1:1)로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.3이었다.The modification of the MSQ film was carried out in the same manner as in Example 1, except that a modifier of azidotrimethylsilane ((CH 3 ) 3 SiN 3 ) and HMDS (hexamethyldisilazane) (mixing ratio 1: 1) was used. The dielectric constant of the MSQ membrane after modification was 3.3.

[비교예 1]Comparative Example 1

MSQ막의 개질제를 HMDS(헥사메틸디실라잔)로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.4였다.The modification was carried out in the same manner as in Example 1 except that the modifier of the MSQ membrane was HMDS (hexamethyldisilazane). The relative dielectric constant of the modified MSQ film was 3.4.

[비교예 2]Comparative Example 2

개질제 도입시의 온도를 450℃로 한 것 이외에는, 실시예 1과 동일한 방법으로 실시하였다. 개질 후의 MSQ막의 비유전율은 3.8로, 비유전율의 저하는 인정되지 않았다.It carried out by the method similar to Example 1 except having set the temperature at the time of introducing a modifier at 450 degreeC. The relative dielectric constant of the modified MSQ film was 3.8, and no decrease in relative dielectric constant was observed.

Claims (7)

반도체 디바이스에 사용되는 저유전율막의 비유전율을 저하시키기 위한 개질제로서, 식(1)Formula (1) as a modifier for lowering the dielectric constant of a low dielectric constant film used in a semiconductor device
Figure 112009053248476-pct00004
Figure 112009053248476-pct00004
(R은 C1~C4의 알킬기, n은 0~3의 정수)로 표시되는 규소 화합물을 유효성분으로서 함유하는, 저유전율막의 개질제.The modifier of the low dielectric constant film containing the silicon compound represented by (R is a C1-C4 alkyl group, n is an integer of 0-3) as an active ingredient.
제1항에 있어서,The method of claim 1, 식(1)의 R이 메틸기인 저유전율막의 개질제.The modifier of the low dielectric constant film whose R of Formula (1) is a methyl group. 제1항에 있어서,The method of claim 1, 상기 규소 화합물이 아지도트리메틸실란((CH3)3SiN3), 아지도트리에틸실란((CH3CH2)3SiN3), 또는 아지도디메틸실란((CH3)2HSiN3)인 저유전율막의 개질제.The silicon compound is azidotrimethylsilane ((CH 3 ) 3 SiN 3 ), azidotriethylsilane ((CH 3 CH 2 ) 3 SiN 3 ), or azidodimethylsilane ((CH 3 ) 2 HSiN 3 ) Modifiers of low dielectric constant membranes. 제1항 내지 제3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 추가적으로, 실란커플링제를 함유하는 저유전율막의 개질제.In addition, a modifier of a low dielectric constant film containing a silane coupling agent. 반도체 디바이스에 사용되는 저유전율막에 대해, 제1항의 식(1)로 표시되는 규소 화합물을 함유하는 개질제를 20℃~300℃의 온도범위 내에서 접촉시키는 것을 포함하는, 개질된 저유전율막의 제조방법.Preparation of the modified low dielectric constant film containing contacting the modifier containing the silicon compound represented by Formula (1) of Claim 1 within the temperature range of 20 degreeC-300 degreeC with respect to the low dielectric constant film used for a semiconductor device. Way. 제5항에 있어서,The method of claim 5, 상기 온도범위가 60℃~200℃인 개질된 저유전율막의 제조방법.The temperature range is 60 ℃ ~ 200 ℃ A method for producing a modified low dielectric constant film. 제5항 또는 제6항에 있어서,The method according to claim 5 or 6, 상기 접촉시키는 것을 대기에 폭로하지 않고 행하는 개질된 저유전율막의 제조방법.A method for producing a modified low dielectric constant film, wherein the contacting is performed without exposing to the atmosphere.
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