KR100321702B1 - Method for forming tantalum oxide and method for fabricating capacitor by the same - Google Patents
Method for forming tantalum oxide and method for fabricating capacitor by the same Download PDFInfo
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- KR100321702B1 KR100321702B1 KR1019980057289A KR19980057289A KR100321702B1 KR 100321702 B1 KR100321702 B1 KR 100321702B1 KR 1019980057289 A KR1019980057289 A KR 1019980057289A KR 19980057289 A KR19980057289 A KR 19980057289A KR 100321702 B1 KR100321702 B1 KR 100321702B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02183—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing tantalum, e.g. Ta2O5
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
Abstract
본 발명은 탄탈륨 산화막 형성 후 실시되는 열처리 조건을 개선하여 탄탈륨 산화막의 누설전류를 향상시킬 수 있는 탄탈륨 산화막 형성 방법 및 그를 이용한 탄탈륨 산화막 캐패시터 제조 방법에 관한 것으로, 본 발명은 탄탈륨 산화막 내의 탄소 제거 및 산소 결핍을 억제하기 위해 고온의 O2또는 N2O 가스 분위기에서 관상열처리(Furnace Anneal)하여 탄탈륨산화막 내의 탄소를 제거하고, 저온에서 O2또는 N2O 가스 플라즈마 처리를 실시하여 탄탈륨 산화막 내에 산소를 보충하여 누설전류를 감소시키는데 그 특징이 있다.The present invention relates to a method for forming a tantalum oxide film capable of improving the leakage current of the tantalum oxide film by improving the heat treatment conditions performed after the formation of the tantalum oxide film, and a method of manufacturing a tantalum oxide film capacitor using the same. In order to suppress the deficiency, the carbon in the tantalum oxide film is removed by heating annealing in a high temperature O 2 or N 2 O gas atmosphere, and the oxygen is absorbed into the tantalum oxide film by performing O 2 or N 2 O gas plasma treatment at a low temperature. It is supplemented to reduce leakage current.
Description
본 발명은 반도체 소자 제조 방법에 관한 것으로, 특히 고집적 반도체 메모리 소자에 이용되는 고유전 특성을 지닌 탄탈륨 산화막(Ta2O5) 형성 방법 및 그를 이용한 탄탈륨 산화막 캐패시터 제조 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a method of forming a tantalum oxide film (Ta 2 O 5 ) having high dielectric properties used in a highly integrated semiconductor memory device, and a method of manufacturing a tantalum oxide film capacitor using the same.
종래의 탄탈륨 산화막 캐패시터 제조 방법에서는 하부전극 상에 탄탈륨 산화막(Ta2O5)을 증착한 후, 후속 열처리로 305 ℃ 내지 400 ℃ 저온에서 O2또는 N2O 가스로 플라즈마 처리하여 1차적으로 탄탈륨 산화막내의 탄소 제거 및 산소 결핍을 감소시키고, 700 ℃ 내지 800 ℃ 고온의 O2또는 N2O 분위기에서 관상 열처리(Furnace Anneal)하여 Ta2O5막을 결정화하는 과정에서 2차적으로 탄탈륨 산화막 내의 탄소 제거 및 산소 결핍을 감소시킨 다음, 상부전극을 형성한다.In the conventional tantalum oxide capacitor manufacturing method, a tantalum oxide film (Ta 2 O 5 ) is deposited on a lower electrode, and then tantalum is primarily treated by plasma treatment with O 2 or N 2 O gas at a low temperature of 305 ° C. to 400 ° C. by a subsequent heat treatment. Carbon removal in the oxide film is reduced and oxygen deficiency is reduced, and in the process of crystallizing the Ta 2 O 5 film in a tubular heat treatment (Furnace Anneal) in a high temperature O 2 or N 2 O atmosphere of 700 ℃ to 800 ℃ secondary carbon removal in the tantalum oxide film And reduce oxygen deficiency, and then form an upper electrode.
도1a 내지 도1d는 시험용 웨이퍼 상에 탄탈륨 산화막을 증착한 후, TDS(Thermal Desorption Spectrum)를 분석한 결과를 보이는 그래프이다.1A to 1D are graphs showing the results of analyzing a thermal deposition spectrum (TDS) after depositing a tantalum oxide film on a test wafer.
도1b의 결과로부터 산소는 450 ℃ 부분에서 많이 떨어져 나오고, 도1c 및 도1d의 결과로부터 C2H2및 C2H4분자는 400℃ 이상의 온도에서 떨어져 나옴을 알 수 있다. 이는 탄탈륨 산화막을 저온에서 O2또는 N2O 가스 플라즈마 처리하는 경우에는 박막내의 탄소를 제거하는 효과보다는 산소를 채워주는 효과가 더 뛰어나고,700℃ 내지 800℃의 고온에서 O2또는 N2O 가스 분위기로 관상열처리(Furnace Anneal)하는 경우는 산소 보충 효과보다는 탄소 제거 효과가 더 크다는 것을 예상할 수 있다.It can be seen from the results of FIG. 1B that oxygen is separated much at the portion of 450 ° C., and from the results of FIGS. 1C and 1D, C 2 H 2 and C 2 H 4 molecules are separated at a temperature of 400 ° C. or higher. When the tantalum oxide film is subjected to O 2 or N 2 O gas plasma treatment at a low temperature, it is more effective to fill oxygen than to remove carbon in the thin film, and O 2 or N 2 O gas at a high temperature of 700 ° C. to 800 ° C. Furnace Anneal can be expected to have a greater carbon removal effect than oxygen replenishment.
그러나, 전술한 바와 같은 종래의 탄탈륨 산화막 형성 공정에서는 저온 플라즈마 처리를 실시한 후, 고온에서 관상열처리를 실시함에 따라 탄소 제거 효과 및 산소 보충 정도가 낮아 탄탈륨 산화막의 누설전류 특성을 효과적으로 향상시킬 수 없다.However, in the conventional tantalum oxide film forming process as described above, after performing the low temperature plasma treatment and performing the tubular heat treatment at a high temperature, the carbon removal effect and the oxygen replenishment degree are low, so that the leakage current characteristics of the tantalum oxide film cannot be effectively improved.
상기와 같은 문제점을 해결하기 위하여 안출된 본 발명은 탄탈륨 산화막 형성 후 실시되는 열처리 조건을 개선하여 탄탈륨 산화막의 누설전류를 향상시킬 수 있는 탄탈륨 산화막 형성 방법 및 그를 이용한 탄탈륨 산화막 캐패시터 제조 방법을 제공하는데 그 목적이 있다.The present invention devised to solve the above problems provides a method of forming a tantalum oxide film and a method of manufacturing a tantalum oxide capacitor using the same, which can improve the leakage current of the tantalum oxide film by improving the heat treatment conditions performed after the formation of the tantalum oxide film. There is a purpose.
도1a 내지 도1d는 종래 기술에 따라 형성된 탄탈륨산화막 TDS 특성을 보이는 그래프,1a to 1d is a graph showing the tantalum oxide film TDS characteristics formed according to the prior art,
도2a 내지 도2c는 본 발명의 일실시예에 따른 탄탈륨 산화막 캐패시터 제조 공정 단면도,2A to 2C are cross-sectional views of a tantalum oxide capacitor manufacturing process according to an embodiment of the present invention;
도3은 N2O 또는 O2가스 분위기에서 관상로 열처리시 탄소, 수분 제거 및 산소 결함 억제를 보이는 모식도.Figure 3 is a schematic diagram showing the removal of carbon, water and suppression of oxygen defects during annealing a tubular furnace in an N 2 O or O 2 gas atmosphere.
* 도면의 주요 부분에 대한 도면 부호의 설명* Explanation of reference numerals for the main parts of the drawings
10: 반도체 기판 11: 폴리실리콘막10: semiconductor substrate 11: polysilicon film
12: 질화층 13: 탄탈륨 산화막12: nitride layer 13: tantalum oxide film
14: TiN막14: TiN film
상기와 같은 목적을 달성하기 위한 본 발명은 기판 상에 탄탈륨 산화막을 형성하는 제1 단계; 상기 탄탈륨 산화막을 700 ℃ 내지 800 ℃ 온도의 관상로(furnace)에서 산소 가스를 이용하여 열처리하는 제2 단계; 및 상기 탄탈륨 산화막을 300 ℃ 내지 400℃ 온도에서 산소 가스를 이용하여 플라즈마 처리하는제3 단계를 포함하는 탄탈륨 산화막 형성 방법을 제공한다.The present invention for achieving the above object is a first step of forming a tantalum oxide film on the substrate; A second step of heat treating the tantalum oxide film using oxygen gas in a furnace at a temperature of 700 ° C. to 800 ° C .; And a third step of plasma treating the tantalum oxide film using oxygen gas at a temperature of 300 ° C. to 400 ° C.
또한, 상기 목적을 달성하기 위한 본 발명은 캐패시터의 하부전극을 형성하는 제1 단계; 상기 하부전극 상에 탄탈륨 산화막(Ta2O5)을 형성하는 제2 단계; 상기 탄탈륨 산화막을 700 ℃ 내지 800 ℃ 온도의 관상로(furnace)에서 산소 가스를 이용하여 열처리하는 제3 단계; 상기 탄탈륨 산화막을 300 ℃ 내지 400℃ 온도에서 산소 가스를 이용하여 플라즈마 처리하는 제4 단계; 및 상기 탄탈륨 산화막 상에 상부전극을 형성하는 제5 단계를 포함하는 캐패시터 제조 방법을 제공한다.In addition, the present invention for achieving the above object is a first step of forming a lower electrode of the capacitor; A second step of forming a tantalum oxide film Ta 2 O 5 on the lower electrode; A third step of heat treating the tantalum oxide film using oxygen gas in a furnace at a temperature of 700 ° C. to 800 ° C .; A fourth step of plasma treating the tantalum oxide film using oxygen gas at a temperature of 300 ° C. to 400 ° C .; And a fifth step of forming an upper electrode on the tantalum oxide film.
본 발명은 탄탈륨 산화막 내의 탄소 제거 및 산소 결핍을 억제하기 위해 고온의 O2또는 N2O 가스 분위기에서 관상열처리(Furnace Anneal)하여 탄탈륨산화막 내의 탄소를 제거하고, 저온에서 O2또는 N2O 가스 플라즈마 처리를 실시하여 탄탈륨 산화막 내에 산소를 보충하여 누설전류를 감소시키는데 그 특징이 있다.The present invention removes the carbon in the tantalum oxide film by heating an annealing in a high temperature O 2 or N 2 O gas atmosphere to suppress the carbon removal and oxygen deficiency in the tantalum oxide film, O 2 or N 2 O gas at low temperature Plasma treatment is performed to replenish oxygen in the tantalum oxide film to reduce leakage current.
도2a 내지 도2c를 참조하여 본 발명의 일실시예에 따른 탄탈륨산화막 제조 방법을 설명한다.A tantalum oxide film production method according to an embodiment of the present invention will be described with reference to FIGS. 2A to 2C.
먼저, 반도체 기판(10) 상에 폴리실리콘막(11)으로 캐패시터의 하부전극을 형성하고, 폴리실리콘막(11) 표면의 자연산화막(도시하지 않음)을 HF 또는 완충산화식각제(Buffered Oxide Etchant)로 식각하여 제거한다. 이어서, 폴리실리콘막(11) 표면을 700 ℃ 내지 950 ℃ 온도 및 1 slm 내지 10 slm의 질소분위기에서 30초 내지 100 초간 질화시켜 질화층(12)을 형성한다.First, a lower electrode of the capacitor is formed on the semiconductor substrate 10 using the polysilicon film 11, and a natural oxide film (not shown) on the surface of the polysilicon film 11 is HF or a buffered oxide etchant. Etch with) to remove. Subsequently, the surface of the polysilicon film 11 is nitrided at a temperature of 700 ° C. to 950 ° C. and a nitrogen atmosphere of 1 slm to 10 slm for 30 seconds to 100 seconds to form the nitride layer 12.
이와 같이 캐패시터의 하부전극을 이루는 폴리실리콘막 표면을 질화시키는 이유는, Ta2O5막 증착 공정 및 증착 후 열처리 공정의 산소 분위기에서 폴리실리콘막 표면이 산화되어 캐패시터의 유효산화막 두께가 증가되는 것을 방지하기 위함이다.The reason for nitriding the surface of the polysilicon film constituting the lower electrode of the capacitor is that the surface of the polysilicon film is oxidized in the oxygen atmosphere of the Ta 2 O 5 film deposition process and the post-deposition heat treatment process to increase the effective oxide film thickness of the capacitor. This is to prevent.
다음으로, 저압화학기상증착(LPCVD, low pressure chemical vapor deposition) 방법으로 탄탈륨 산화막을 형성하기 위하여, 0.001 cc 내지 2 cc의 탄탈륨 에칠레이트(Ta(OC2H5)5)를 170 ℃ 내지 190 ℃의 온도로 유지되는 기화기에서 기상상태로 만들고, 반응 가스로 10 sccm 내지 1000 sccm의 O2를 주입하고, 반응로 내의 입력을 0.1 torr 내지 10 torr로 유지하고, 350 ℃ 내지 450 ℃ 온도로 가열된 반도체 기판(10) 상에 도2b에 도시한 바와 같이 탄탈륨 산화막(13)을 증착한다.Next, in order to form a tantalum oxide film by low pressure chemical vapor deposition (LPCVD), 0.001 cc to 2 cc of tantalum acrylate (Ta (OC 2 H 5 ) 5 ) is 170 to 190 ° C. The vaporizer was kept in a vaporizer maintained at a temperature of 10 sccm to 1000 sccm of O 2 was injected into the reaction gas, and the input in the reactor was maintained at 0.1 torr to 10 torr, and heated to a temperature of 350 to 450 ℃. A tantalum oxide film 13 is deposited on the semiconductor substrate 10 as shown in Fig. 2B.
다음으로, 700 ℃ 내지 800 ℃ 온도의 N2O 또는 O2가스 분위기에서 10 분 내지 40 분 동안 관상로 열처리(Furnace Anneal)한다. 이때, N2O 또는 O2가스의 양은 5 slm 내지 10 slm이 되도록 한다.Next, the furnace is heat treated (Furnace Anneal) for 10 to 40 minutes in N 2 O or O 2 gas atmosphere at 700 ℃ to 800 ℃ temperature. At this time, the amount of N 2 O or O 2 gas to be 5 slm to 10 slm.
도3은 N2O 또는 O2가스 분위기에서 관상로 열처리시 탄소 및 수분이 제거되고, 산소 결함이 억제되는 것을 보이는 모식도이다.3 is a schematic diagram showing that carbon and water are removed and oxygen defects are suppressed when the tubular heat treatment is performed in an N 2 O or O 2 gas atmosphere.
도 3에 도시된 것처럼, 700 ℃ 내지 800 ℃ 온도의 관상로 열처리후, 탄탈륨산화막(13)내 탄소, 수분 등을 제거하여 탄탈륨 산화막(13)을 결정화시킨다.As shown in FIG. 3, after the heat treatment of the tubular furnace at a temperature of 700 ° C. to 800 ° C., the carbon and water in the tantalum oxide film 13 are removed to crystallize the tantalum oxide film 13.
이어서, 300 ℃ 내지 400℃ 온도 및 0.1 torr 내지 1 torr 압력 조건에서 100 W 내지 300 W의 RF 전력을 인가하여 N2O 또는 O2가스에 플라즈마를 여기시켜 5분 내지 10 분 동안 탄탈륨 산화막(13)을 처리한다.Subsequently, an RF power of 100 W to 300 W is applied at 300 ° C. to 400 ° C. and 0.1 to 1 torr pressure to excite the plasma to the N 2 O or O 2 gas to provide a tantalum oxide film 13 for 5 to 10 minutes. ).
이와 같이, 탄탈륨산화막(13)을 결정화시킨후, 300 ℃ 내지 400℃ 온도에서 플라즈마처리하므로써 탄탈륨산화막(13)내 산소를 충분히 보충시켜준다.As described above, after the tantalum oxide film 13 is crystallized, plasma treatment is performed at 300 ° C to 400 ° C to sufficiently replenish oxygen in the tantalum oxide film 13.
상술한 바와 같이, 종래 저온 플라즈마처리에 의해 산소를 보충한 후, 고온 열처리를 통해 탄소를 제거하여 탄탈륨산화막을 결정화시키고 있으나, 고온열처리를 통해 탄탈륨산화막을 먼저 결정화시킨 후, 플라즈마처리에 의해 산소를 보충해주면 탄탈륨산화막의 누설전류를 더욱 감소시킬 수 있다.As described above, after replenishing oxygen by a low temperature plasma treatment, carbon is removed through a high temperature heat treatment to crystallize the tantalum oxide film, but after the first crystallization of the tantalum oxide film through a high temperature heat treatment, oxygen is removed by plasma treatment. By supplementing, leakage current of tantalum oxide film can be further reduced.
다음으로, 도2c에 도시한 바와 같이 탄탈륨산화막(13) 상에 상부전극을 이루는 TiN막(14)을 형성한다. 이때, TiN막은 500 ℃ 내지 700 ℃ 온도 및 0.1 torr 내지 2 torr 압력 조건에서 100 Å 내지 500 Å 두께로 형성한다.Next, as shown in FIG. 2C, a TiN film 14 forming an upper electrode is formed on the tantalum oxide film 13. At this time, the TiN film is formed to a thickness of 100 kPa to 500 kPa at a temperature of 500 ° C to 700 ° C and a pressure of 0.1 torr to 2 torr.
전술한 캐패시터는 실린더, 핀, 반구형 실리콘 등의 복잡한 구조로 형성될 수 있다.The above-described capacitor may be formed into a complicated structure such as a cylinder, a pin, hemispherical silicon, or the like.
이상에서 설명한 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다는 것이 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어 명백할 것이다.The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes can be made in the art without departing from the technical spirit of the present invention. It will be apparent to those of ordinary knowledge.
상기와 같이 이루어지는 본 발명은 탄탈륨 산화막 내의 탄소 제거 및 산소 결핍을 억제하기 위해 고온에서 O2또는 N2O 관상로 열처리를 먼저 실시하여 탄탈륨 산화막 내의 탄소를 제거하고, 저온에서 O2또는 N2O 가스를 이용하여 플라즈마 처리하여 탄탈륨 산화막 내에 산소를 효과적으로 보충시킴으로써 탄탈륨 산화막의 누설전류 특성을 보다 개선시킬 수 있다.The present invention made as described above is subjected to an O 2 or N 2 O tubular heat treatment first at a high temperature to suppress carbon removal and oxygen deficiency in the tantalum oxide film to remove the carbon in the tantalum oxide film, O 2 or N 2 O at low temperature Plasma treatment using a gas effectively supplements oxygen in the tantalum oxide film, thereby further improving leakage current characteristics of the tantalum oxide film.
Claims (8)
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| KR100761406B1 (en) * | 2001-06-30 | 2007-09-27 | 주식회사 하이닉스반도체 | Method for fabricating capacitor with tantalum oxide |
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| JPH05110024A (en) * | 1991-10-18 | 1993-04-30 | Sharp Corp | Semiconductor device and manufacture thereof |
| JPH0714986A (en) * | 1993-06-22 | 1995-01-17 | Toshiba Corp | Method and apparatus for manufacturing semiconductor device |
| JPH10200074A (en) * | 1996-04-10 | 1998-07-31 | United Microelectron Corp | Formation of low pressure chemical vapor deposited tantalum oxide film with few leakage current |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05110024A (en) * | 1991-10-18 | 1993-04-30 | Sharp Corp | Semiconductor device and manufacture thereof |
| JPH0714986A (en) * | 1993-06-22 | 1995-01-17 | Toshiba Corp | Method and apparatus for manufacturing semiconductor device |
| JPH10200074A (en) * | 1996-04-10 | 1998-07-31 | United Microelectron Corp | Formation of low pressure chemical vapor deposited tantalum oxide film with few leakage current |
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