KR100359489B1 - Method of fabricating gate dielectric for use in semiconductor device - Google Patents

Method of fabricating gate dielectric for use in semiconductor device Download PDF

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KR100359489B1
KR100359489B1 KR1020000065830A KR20000065830A KR100359489B1 KR 100359489 B1 KR100359489 B1 KR 100359489B1 KR 1020000065830 A KR1020000065830 A KR 1020000065830A KR 20000065830 A KR20000065830 A KR 20000065830A KR 100359489 B1 KR100359489 B1 KR 100359489B1
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metal oxide
zro
nitrogen
film
semiconductor device
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KR20020035986A (en
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황현상
전상훈
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광주과학기술원
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Abstract

본 발명은, 실리콘 기판 상에 금속산화물을 형성하는 단계와, 상기 금속산화물에 질소성분을 함유시키는 질화처리 단계와, 상기 질소성분이 함유된 금속산화물을 산화시키는 재산화 단계를 포함하는 것을 특징으로 한다. 여기서, 상기 금속산화물로는 ZrO2을 사용하거나 HfO2, La2O3, Al2O3또는 Ta2O5을 사용할 수 있으며, ZrSixOy, HfSixOy, LaSixOy, AlSixOy또는 TaSixOy을 사용할 수도 있다. 그리고, 상기 질화처리 단계는 상기 금속산화물이 형성된 결과물을 질소함유기체 분위기에서 열처리하여 수행하거나, 상기 금속산화물을 질소함유 플라즈마 분위기에 노출시켜 플라즈마 처리하여 수행하거나, 또는 상기 금속산화물에 질소성분을 이온주입하여 수행할 수 있다. 본 발명에 의하면, 금속산화막을 형성한 후에 질화처리 및 재산화 공정을 거침으로써 고온후속열처리 공정에 의한 유효두께 및 누설전류의 증가를 현저히 감소시킬 수 있다.The present invention includes the steps of forming a metal oxide on a silicon substrate, a nitriding treatment step containing a nitrogen component in the metal oxide, and a reoxidation step of oxidizing the metal oxide containing the nitrogen component. do. Here, the metal oxide may be ZrO 2 or HfO 2 , La 2 O 3 , Al 2 O 3 or Ta 2 O 5 , and ZrSi x O y , HfSi x O y , LaSi x O y , AlSi x O y or TaSi x O y may be used. The nitriding treatment may be performed by heat-treating the resultant product on which the metal oxide is formed in a nitrogen-containing atmosphere, or performing plasma treatment by exposing the metal oxide to a plasma atmosphere containing nitrogen, or ionizing a nitrogen component to the metal oxide. Can be done by injection. According to the present invention, an increase in the effective thickness and leakage current by the high temperature subsequent heat treatment process can be significantly reduced by performing the nitriding treatment and reoxidation process after forming the metal oxide film.

Description

반도체장치의 게이트절연막 제조방법 {Method of fabricating gate dielectric for use in semiconductor device}Method for fabricating a gate insulating film of a semiconductor device {Method of fabricating gate dielectric for use in semiconductor device}

본 발명은 반도체장치의 게이트절연막 제조방법에 관한 것으로서, 특히 질화처리를 이용하여 고유전율을 갖는 게이트 절연막을 제조하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a gate insulating film of a semiconductor device, and more particularly, to a method of manufacturing a gate insulating film having a high dielectric constant using a nitriding process.

차세대 고유전 게이트 절연막으로 많이 연구되고 있는 고유전박막인 ZrO2박막은 다양한 공정 최적화를 통하여 우수한 전기적 특성을 얻을 수 있음이 보고되고 있다. 그러나, 대부분의 다른 금속산화물과 마찬가지로 ZrO2박막을 MOSFET의 게이트절연막으로 응용할 경우에 필수적으로 거치는 고온열처리 과정에서, 결정화에 기인한 누설전류의 증가와, 실리콘 기판과 ZrO2박막과의 계면에 형성되는 실리케이트(silicate) 또는 실리콘산화물(silicon oxide)과 같은 계면층의 성장에 기인한 유효두께의 급격한 증가가 문제시 되고 있다.It is reported that ZrO 2 thin film, which is a high dielectric thin film that is being studied as a next-generation high-k gate insulating film, can obtain excellent electrical characteristics through various process optimizations. However, like most other metal oxides, the ZrO 2 thin film is formed at the interface between the silicon substrate and the ZrO 2 thin film in an increase in leakage current due to crystallization during the high temperature heat treatment process, which is essential for application of a gate insulating film of a MOSFET. The rapid increase in effective thickness due to the growth of interfacial layers such as silicates or silicon oxides has become a problem.

따라서, 본 발명이 이루고자 하는 기술적 과제는, ZrO2막 등과 같은 금속산화막을 일단 형성하고 질화 및 재산화공정을 거침으로써, 고온공정에서도 유효두께 및 누설전류의 증가가 억제되는 반도체장치의 게이트절연막 제조방법을 제공하는 데 있다.Accordingly, the technical problem to be achieved by the present invention is to manufacture a gate insulating film of a semiconductor device in which an increase in effective thickness and leakage current is suppressed even in a high temperature process by forming a metal oxide film such as a ZrO 2 film and performing a nitriding and reoxidation process. To provide a way.

도 1은 후속열처리 시에 ZrOxNy막과 ZrO2막에 대한 유효두께의 증가를 비교하여 나타낸 그래프;1 is a graph showing an increase in the effective thickness for ZrO x N y film and ZrO 2 film during the subsequent heat treatment;

도 2는 후속열처리 시에 ZrOxNy막과 ZrO2막에 대한 누설전류의 증가를 비교하여 나타낸 그래프;2 is a graph showing an increase in leakage current for ZrO x N y films and ZrO 2 films during subsequent heat treatment;

도 3a 및 도 3b는 ZrO2막과 ZrOxNy막을 800℃에서 5분동안 각각 열처리한 경우의 전자현미경 단면사진들이다.3A and 3B are electron microscope cross-sectional photographs when the ZrO 2 film and the ZrO x N y film were heat-treated at 800 ° C. for 5 minutes, respectively.

상기 기술적 과제를 달성하기 위한 본 발명에 따른 반도체장치의 게이트절연막 제조방법은, 실리콘 기판 상에 금속산화물을 형성하는 단계와, 상기 금속산화물에 질소성분을 함유시키는 질화처리 단계와, 상기 질소성분이 함유된 금속산화물을 산화시키는 재산화 단계를 포함하는 것을 특징으로 한다.According to another aspect of the present invention, there is provided a method of manufacturing a gate insulating film of a semiconductor device, the method including forming a metal oxide on a silicon substrate, a nitriding step of containing a nitrogen component in the metal oxide, and And a reoxidation step of oxidizing the contained metal oxide.

여기서, 상기 금속산화물로는 ZrO2을 사용하거나 HfO2, La2O3, Al2O3또는Ta2O5을 사용할 수 있으며, ZrSixOy, HfSixOy, LaSixOy, AlSixOy또는 TaSixOy을 사용할 수도 있다.Here, ZrO 2 may be used as the metal oxide, or HfO 2 , La 2 O 3 , Al 2 O 3, or Ta 2 O 5 may be used, and ZrSi x O y , HfSi x O y , LaSi x O y , AlSi x O y or TaSi x O y may be used.

그리고, 상기 질화처리 단계는 상기 금속산화물이 형성된 결과물을 질소함유기체 분위기에서 열처리하여 수행하거나, 상기 금속산화물을 질소함유 플라즈마 분위기에 노출시켜 플라즈마 처리하여 수행하거나, 또는 상기 금속산화물에 질소성분을 이온주입하여 수행할 수 있다.The nitriding treatment may be performed by heat-treating the resultant product on which the metal oxide is formed in a nitrogen-containing atmosphere, or performing plasma treatment by exposing the metal oxide to a nitrogen-containing plasma atmosphere, or ionizing a nitrogen component to the metal oxide. Can be done by injection.

이 때, 상기 질소함유기체로는 N2O, NO 또는 NH3기체를 사용할 수가 있으며, 상기 열처리는 300~1000℃의 온도범위에서 10초 내지 1시간 동안 수행하는 것이 바람직하다. 상기 질소함유 플라즈마로는 N2또는 NH3플라즈마를 사용할 수 있다.At this time, N 2 O, NO or NH 3 gas may be used as the nitrogen-containing gas, the heat treatment is preferably performed for 10 seconds to 1 hour in the temperature range of 300 ~ 1000 ℃. N 2 or NH 3 plasma may be used as the nitrogen-containing plasma.

한편, 상기 재산화 단계는 O2, O3또는 H2O(g) 분위기에서 열처리함으로써 수행할 수 있으며, 이 때의 열처리는 300~1000℃의 온도범위, 10초 내지 1시간 동안 행하는 것이 바람직하다.On the other hand, the reoxidation step may be carried out by heat treatment in O 2 , O 3 or H 2 O (g) atmosphere, the heat treatment at this time is preferably carried out for a temperature range of 300 ~ 1000 ℃, 10 seconds to 1 hour. Do.

이하에서, 본 발명의 바람직한 실시예들을 첨부한 도면들을 참조하여 상세히 설명한다.Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail.

[실시예 1]Example 1

먼저, 실리콘 기판 상에 ZrO2막을 증착한다. 다음에, NH3기체 분위기에서 700℃에서 60초간 열처리를 하여 ZrO2막 내에 질소성분을 함유시킨다. 그리고, 425℃에서 상기 질소성분이 함유된 ZrO2막을 습식산화법으로 다시 산화하여 ZrOxNy막을 형성한다.First, a ZrO 2 film is deposited on a silicon substrate. Next, heat treatment is performed at 700 ° C. for 60 seconds in an NH 3 gas atmosphere to contain a nitrogen component in the ZrO 2 film. At 425 ° C., the ZrO 2 film containing the nitrogen component is oxidized again by a wet oxidation method to form a ZrO x N y film.

[실시예 2]Example 2

먼저, 실리콘 기판 상에 ZrO2막을 증착한다. 다음에, ZrO2막을 NH3또는 N2플라즈마 분위기에 노출시켜 ZrO2막을 플라즈마 처리함으로써 ZrO2막 내에 질소성분을 함유시킨다. 그리고, 상기 질소성분이 함유된 ZrO2막을 산소함유 플라즈마에 노출시켜 재산화시킴으로써 ZrOxNy막을 형성한다.First, a ZrO 2 film is deposited on a silicon substrate. Next, the ZrO 2 film is exposed to NH 3 or N 2 plasma atmosphere, and the ZrO 2 film is plasma treated to contain a nitrogen component in the ZrO 2 film. The ZrO 2 film containing the nitrogen component is exposed to an oxygen-containing plasma and reoxidized to form a ZrO x N y film.

[실시예3]Example 3

먼저, 실리콘 기판 상에 ZrO2막을 증착한다. 다음에, 질소 이온주입 및 열처리를 수행하여 ZrO2막 내에 질소성분을 함유시킨다. 그리고, 질소성분이 함유된 ZrO2막을 425℃에서 습식산화법으로 다시 산화하여 ZrOxNy막을 형성한다.First, a ZrO 2 film is deposited on a silicon substrate. Next, nitrogen ion implantation and heat treatment are performed to contain the nitrogen component in the ZrO 2 film. The ZrO 2 film containing the nitrogen component is oxidized again by wet oxidation at 425 ° C. to form a ZrO x N y film.

[비교예 1]Comparative Example 1

도 1은 후속열처리 시에 실시예 1에서 형성된 ZrOxNy막과 종래의 ZrO2막에 대한 유효두께의 증가를 비교하여 나타낸 그래프이다. 도 1을 참고하면, ZrO2막의 경우에 비해 ZrOxNy막의 경우가 유효두께의 증가가 현저히 작음을 알 수 있다.1 is a graph showing an increase in the effective thickness of the ZrO x N y film formed in Example 1 and the conventional ZrO 2 film during the subsequent heat treatment. Referring to FIG. 1, it can be seen that the increase in the effective thickness of the ZrO x N y film is significantly smaller than that of the ZrO 2 film.

[비교예 2]Comparative Example 2

도 2는 후속열처리 시에 실시예 1에서 형성된 ZrOxNy막과 종래의 ZrO2막에 대한 누설전류의 증가를 비교하여 나타낸 그래프이다. 누설전류는 1.5V를 인가하여 측정하였다. 도 2를 참조하면, 700℃이상에서는 ZrO2의 누설전류가 큰 폭으로 감소하기는 하지만 전체적으로 ZrO2막의 경우가 ZrOxNy막의 경우보다 큰 누설전류를 갖는다는 것을 알 수 있다. 특히, 700℃ 이하에서는 ZrO2막보다는 ZrOxNy막의 경우가 누설전류가 훨씬 작다는 것을 알 수 있다.FIG. 2 is a graph showing an increase in leakage current for the ZrO x N y film formed in Example 1 and the conventional ZrO 2 film during the subsequent heat treatment. Leakage current was measured by applying 1.5V. It may be seen that the reference to Figure 2 when, in the more than 700 ℃ to reduce the width, the leakage current of the ZrO 2 is larger, but a whole if the ZrO 2 film has a larger leakage current than that ZrO x N y film. In particular, it can be seen that the leakage current is much smaller in the case of the ZrO x N y film than the ZrO 2 film below 700 ° C.

ZrOxNy막은 후속열처리 이후에도 여전히 비정질 구조를 유지하지만, ZrO2막은 후속열처리에 의해 결정화되어 다결정 구조를 갖게 된다. 이렇게 다결정 구조를 갖기 때문에 같은 유효두께에 대해 ZrOxNy의 경우보다 ZrO2의 경우가 더 큰 누설전류를 갖게 되는 것이다.The ZrO x N y film still maintains the amorphous structure after the subsequent heat treatment, but the ZrO 2 film is crystallized by the subsequent heat treatment to have a polycrystalline structure. Because of this polycrystalline structure, ZrO 2 has a larger leakage current for the same effective thickness than that of ZrO x N y .

[비교예 3]Comparative Example 3

도 3a 및 도 3b는 스퍼터링방법으로 형성된 ZrO2막과 실시예 1에서 형성된 ZrOxNy막을 800℃에서 5분동안 각각 열처리한 경우의 전자현미경 단면사진들이다. 도면을 참조하면, 모두가 계면층들이 형성되기는 하였지만 도 3a의 경우가 물리적인 두께가 더 큼을 알 수 있다.3A and 3B are electron microscope cross-sectional photographs when the ZrO 2 film formed by the sputtering method and the ZrO x N y film formed in Example 1 were heat treated at 800 ° C. for 5 minutes, respectively. Referring to the drawings, although all of the interfacial layers are formed, it can be seen that the physical thickness of FIG. 3A is larger.

ZrOxNy막을 형성하는 방법만을 구체적으로 예로 들어 설명하였지만, 일반적인 금속산화물막의 경우에도 본 발명을 적용할 수 있으며, 본 발명에 따른 반도체장치의 게이트절연막 제조방법에 의하면, 금속산화막을 형성한 후에 질화처리 및 재산화 공정을 거침으로써 고온후속열처리 공정에 의한 유효두께 및 누설전류의 증가를 현저히 감소시킬 수 있다.Although only a method of forming a ZrO x N y film has been specifically described as an example, the present invention can be applied to a general metal oxide film, and according to the method for manufacturing a gate insulating film of a semiconductor device according to the present invention, after forming a metal oxide film By going through the nitriding and reoxidation process, the increase in the effective thickness and leakage current by the high temperature subsequent heat treatment process can be significantly reduced.

본 발명은 상기 실시예들에만 한정되지 않으며, 본 발명의 기술적 사상 내에서 당 분야에서 통상의 지식을 가진 자에 의해 많은 변형이 가능함은 명백하다.The present invention is not limited to the above embodiments, and it is apparent that many modifications are possible by those skilled in the art within the technical spirit of the present invention.

Claims (14)

실리콘 기판 상에 금속산화물을 형성하는 단계와,Forming a metal oxide on the silicon substrate, 상기 금속산화물에 질소성분을 함유시키는 질화처리 단계와,A nitriding step of containing a nitrogen component in the metal oxide; 상기 질소성분이 함유된 금속산화물을 산화시키는 재산화 단계를 포함하는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.And a reoxidation step of oxidizing the nitrogen oxide-containing metal oxide. 제1항에 있어서, 상기 금속산화물이 ZrO2인 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the metal oxide is ZrO 2 . 제1항에 있어서, 상기 금속산화물이 HfO2, La2O3, Al2O3및 Ta2O5으로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the metal oxide is any one selected from the group consisting of HfO 2 , La 2 O 3 , Al 2 O 3, and Ta 2 O 5 . 제1항에 있어서, 상기 금속산화물이 ZrSixOy, HfSixOy, LaSixOy, AlSixOy및 TaSixOy로 이루어진 군 중에서 선택된 어느 하나인 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the gate of the semiconductor device is characterized in that the metal oxide ZrSi x O y, HfSi x O y, LaSi x O y, AlSi x O y and TaSi is any one selected from the group consisting of x O y Method of manufacturing insulating film. 제1항에 있어서, 상기 질화처리 단계가 상기 금속산화물이 형성된 결과물을질소함유기체 분위기에서 열처리함으로써 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of manufacturing a gate insulating film of a semiconductor device according to claim 1, wherein said nitriding step is performed by heat-treating the product in which said metal oxide is formed in a nitrogen-containing gas atmosphere. 제5항에 있어서, 상기 질소함유기체가 N2O, NO 또는 NH3기체 인 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 5, wherein the nitrogen-containing gas is N 2 O, NO, or NH 3 gas. 제5항에 있어서, 상기 열처리가 300~1000℃의 온도범위에서 행해지는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of manufacturing a gate insulating film of a semiconductor device according to claim 5, wherein said heat treatment is performed at a temperature range of 300 to 1000 캜. 제7항에 있어서, 상기 열처리가 10초 내지 1시간 동안 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 7, wherein the heat treatment is performed for 10 seconds to 1 hour. 제1항에 있어서, 상기 질화처리 단계가 상기 금속산화물을 질소함유 플라즈마 분위기에 노출시켜 플라즈마 처리함으로써 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the nitriding step is performed by exposing the metal oxide to a nitrogen-containing plasma atmosphere to perform plasma treatment. 제9항에 있어서, 상기 질소함유 플라즈마가 N2또는 NH3플라즈마인 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.10. The method of claim 9, wherein the nitrogen-containing plasma is N 2 or NH 3 plasma. 제1항에 있어서, 상기 질화 처리단계가 상기 금속산화물에 질소성분을 이온주입함으로써 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the nitriding treatment step is performed by ion implanting a nitrogen component into the metal oxide. 제1항에 있어서, 상기 재산화 단계가 O2, O3또는 H2O(g) 분위기에서 열처리함으로써 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of manufacturing a gate insulating film of a semiconductor device according to claim 1, wherein said reoxidation step is performed by heat treatment in an O 2 , O 3 or H 2 O (g) atmosphere. 제1항에 있어서, 상기 재산화 단계가 300~1000℃의 온도범위에서 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.The method of claim 1, wherein the reoxidation is performed at a temperature in a range of 300 ° C. to 1000 ° C. 7. 제13항에 있어서, 상기 재산화 단계가 10초 내지 1시간 동안 수행되는 것을 특징으로 하는 반도체장치의 게이트절연막 제조방법.15. The method of claim 13, wherein the reoxidation is performed for 10 seconds to 1 hour.
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