KR19990074809A - Thin Film Manufacturing Method - Google Patents
Thin Film Manufacturing Method Download PDFInfo
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- KR19990074809A KR19990074809A KR1019980008641A KR19980008641A KR19990074809A KR 19990074809 A KR19990074809 A KR 19990074809A KR 1019980008641 A KR1019980008641 A KR 1019980008641A KR 19980008641 A KR19980008641 A KR 19980008641A KR 19990074809 A KR19990074809 A KR 19990074809A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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Abstract
본 발명의 박막 제조 방법은 기판이 로딩된 챔버를 소정 온도와 압력으로 유지한 후 상기 챔버에 제1 반응물을 주입하여 상기 기판 상에 화학흡착시키는 단계를 포함한다. 그리고, 상기 화학흡착된 제1 반응물이 형성된 기판을 포함하는 챔버에 불활성 가스로 1차 퍼지하여 상기 화학흡착된 제1 반응물과 상기 화학흡착된 제1 반응물 상에 물리 흡착된 제1 반응물을 남긴다. 상기 화학흡착 및 물리 흡착된 제1 반응물이 형성된 기판을 포함하는 챔버에 제2 반응물을 주입 및 반응시켜 박막을 형성한다. 상기 박막이 형성된 챔버에 불활성 가스로 2차 퍼지한다. 상기 기판 상에 제1 반응물을 화학흡착시키는 단계부터 상기 챔버에 불활성 가스를 2차 퍼지하는 단계를 순차적으로 반복 수행하여 상기 흡착된 반응물의 양을 적절히 조절함으로써 원하는 박막 두께를 얻을 수 있다. 상기 박막의 예로는 산화 알루미늄막을 들 수 있으며, 이때, 제1 반응물 및 제2 반응물은 각각 트리 메틸 알루미늄(Al(CH3)3) 및 수증기(H2O)를 이용할 수 있다. 본 발명의 박막 제조 방법에 의하면, 기판 상에 형성되는 사이클당 박막의 두께를 결정 구조상의 최밀 충진면의 주기적인 거리에 일치시킴으로써 박막의 특성을 향상시킬 수 있다.The method of manufacturing a thin film of the present invention includes maintaining a chamber loaded with a substrate at a predetermined temperature and pressure, and then injecting a first reactant into the chamber to chemisorb onto the substrate. Then, the first purge with an inert gas in the chamber including the substrate on which the chemisorbed first reactant is formed to leave the chemisorbed first reactant and the first reactant physically adsorbed on the chemisorbed first reactant. A thin film is formed by injecting and reacting a second reactant into a chamber including a substrate on which the chemisorbed and physically adsorbed first reactant is formed. Secondary purging with an inert gas in the chamber where the thin film is formed. The desired thin film thickness may be obtained by appropriately adjusting the amount of the adsorbed reactant by sequentially repeating the second purge of the inert gas into the chamber from the step of chemisorption of the first reactant on the substrate. An example of the thin film may include an aluminum oxide film, wherein the first reactant and the second reactant may use trimethyl aluminum (Al (CH 3 ) 3 ) and water vapor (H 2 O), respectively. According to the thin film manufacturing method of this invention, the characteristic of a thin film can be improved by making the thickness of the thin film per cycle formed on a board | substrate correspond to the periodic distance of the closest packing surface on a crystal structure.
Description
본 발명은 박막 제조 방법에 관한 것으로, 특히 원자막 흡착법(Atomic Layer Deposition: 이하, "ALD법"이라함)에 의한 박막 제조 방법에 관한 것이다.The present invention relates to a thin film production method, and more particularly, to a thin film production method by atomic layer adsorption (hereinafter referred to as "ALD method").
일반적으로, 박막(thin film)은 반도체 소자의 유전체(dielectrics), 액정표시소자(liquid-crystal display)의 투명한 도전체(transparant conductor) 및 전자 발광 박막 표시 소자(electroluminescent thin film display)의 보호층(protective layer) 등으로 다양하게 사용된다. 상기 박막은 흡착법(evaporation method), 화학기상흡착법(chemical vapor deposition), ALD법 등에 의하여 형성된다.In general, a thin film is a dielectric layer of a semiconductor device, a transparent conductor of a liquid-crystal display, and a protective layer of an electroluminescent thin film display. protective layer). The thin film is formed by an evaporation method, a chemical vapor deposition method, an ALD method, or the like.
이중에서, 상기 ALD법은 표면 조절 공정(surface controlled process)으로써 2차원적인 층간(layer by layer) 흡착을 이용하는 흡착법이다. 이러한 ALD법은 흡착이 항상 표면 운동 영역(surface kinetic regime)에서 이루어지므로 매우 우수한 단차 피복성(step coverage) 을 갖는다. 또한, 열분해(prolysis)가 아닌 각 반응물의 주기적 공급을 통한 화학적 치환(chemical exchange)으로 반응물(reactant)을 분해하므로 막밀도(film density)가 높고 우수한 화학양론적인(stoichoimetry) 막을 얻을 수 있다. 아울러 화학흡착(chemisorption)만을 이용하여 층간 성장(layer by layer growth)이 가능하므로 우수한 균일도와 미세한 막 두께 조절이 가능하다. 또한, 공정중 발생하는 화학적 치환에 의한 부산물은 항상 기체이므로 제거가 용이하여 챔버의 세정이 용이하고, 온도만이 공정변수이므로 공정 조절과 유지가 용이하다.In particular, the ALD method is an adsorption method using two-dimensional layer by layer adsorption as a surface controlled process. This ALD method has very good step coverage because adsorption is always performed in the surface kinetic regime. In addition, it is possible to obtain a high film density and excellent stoichoimetry membranes by decomposing the reactants through chemical exchange through periodic supply of each reactant rather than prolysis. In addition, it is possible to layer by layer growth using only chemical adsorption (chemisorption) it is possible to control the excellent uniformity and fine film thickness. In addition, by-products due to chemical substitution generated during the process is always a gas, so it is easy to remove the chamber and easy to clean the chamber, because only the temperature is a process variable, it is easy to control and maintain the process.
그러나, 종래의 ALD법은 하나의 웨이퍼 방식(single wafer type)으로 사용할 때 스루풋(throughtput)이 매우 낮으며 공정 자체가 반응물에 크게 의존하기 때문에 이미 개발되어 있는 물질 이외의 신물질 개발시 제한을 많이 받는다.However, the conventional ALD method is very limited in the development of new materials other than those already developed because the throughput is very low when using a single wafer type and the process itself is highly dependent on the reactants. .
특히, 상기 종래의 ALD법은 순수하게 화학흡착만을 이용하여 흡착하는 경우에 한 사이클(cycle, 주기)당 두께가 이론적으로 가능한 막의 두께(결정 구조상의 최밀 충진면 사이의 거리, 예컨대 산화막인 경우는 산소의 최밀 충진면와 산소의 최밀 충진면 간의 거리)에 미치지 못하여 막질의 특성이 낮아지는 문제점이 있다.In particular, in the conventional ALD method, in the case of purely adsorption using only chemical adsorption, the thickness per cycle (per cycle) is theoretically possible in the case of the distance between the closest filling surfaces of the crystal structure, for example, an oxide film. The distance between the closest packed surface of oxygen and the closest packed surface of oxygen) has a problem in that the quality of the film is lowered.
따라서, 본 발명이 이루고자 하는 기술적 과제는 한 사이클당 성장 두께를 이론적인 두께(결정 구조상의 최밀 충진면의 주기적인 거리)에 근접시킴으로써 막질의 특성을 개선할 수 있는 박막 제조 방법을 제공하는 데 있다.Accordingly, the technical problem to be achieved by the present invention is to provide a thin film manufacturing method which can improve the quality of the film by bringing the growth thickness per cycle close to the theoretical thickness (periodic distance of the closest filling surface on the crystal structure). .
도 1은 본 발명의 박막 제조 방법에 이용된 박막 제조 장치를 설명하기 위하여 도시한 개략도이고,1 is a schematic view for explaining a thin film manufacturing apparatus used in the thin film manufacturing method of the present invention,
도 2는 본 발명의 박막 제조 방법을 설명하기 위하여 도시한 흐름도이고,2 is a flowchart illustrating a thin film manufacturing method of the present invention,
도 3은 본 발명 및 종래 기술의 박막 제조 방법에 의하여 제조된 알루미늄 산화막의 사이클당 두께를 도시한 그래프이고,Figure 3 is a graph showing the thickness per cycle of the aluminum oxide film produced by the thin film production method of the present invention and the prior art,
도 4는 본 발명 및 종래 방법에 의하여 제조된 알루미늄 산화막의 사이클당 두께에 따른 굴절율을 도시한 그래프이고,4 is a graph showing the refractive index according to the thickness per cycle of the aluminum oxide film produced by the present invention and the conventional method,
도 5는 본 발명의 박막 흡착 방법에 의하여 형성된 박막의 식각속도를 설명하기 위하여 도시한 그래프이다.5 is a graph illustrating the etching rate of the thin film formed by the thin film adsorption method of the present invention.
상기 기술적 과제를 달성하기 위하여, 본 발명의 박막 제조 방법은 기판이 로딩된 챔버를 소정 온도와 압력으로 유지한 후 상기 챔버에 제1 반응물을 주입하여 상기 기판 상에 화학흡착시키는 단계를 포함한다. 그리고, 상기 화학흡착된 제1 반응물이 형성된 기판을 포함하는 챔버에 불활성 가스로 1차 퍼지하여 상기 화학흡착된 제1 반응물과 상기 화학흡착된 제1 반응물 상에 물리 흡착된 제1 반응물을 남긴다. 상기 화학흡착 및 물리 흡착된 제1 반응물이 형성된 기판을 포함하는 챔버에 제2 반응물을 주입 및 반응시켜 박막을 형성한다. 상기 박막이 형성된 챔버에 불활성 가스로 2차 퍼지한다.In order to achieve the above technical problem, the method for manufacturing a thin film of the present invention includes maintaining a chamber loaded with a substrate at a predetermined temperature and pressure, and then injecting a first reactant into the chamber to chemisorb onto the substrate. Then, the first purge with an inert gas in the chamber including the substrate on which the chemisorbed first reactant is formed to leave the chemisorbed first reactant and the first reactant physically adsorbed on the chemisorbed first reactant. A thin film is formed by injecting and reacting a second reactant into a chamber including a substrate on which the chemisorbed and physically adsorbed first reactant is formed. Secondary purging with an inert gas in the chamber where the thin film is formed.
상기 상기 기판 상에 제1 반응물을 화학흡착시키는 단계부터 상기 챔버에 불활성 가스를 2차 퍼지하는 단계를 순차적으로 반복 수행하여 원하는 박막 두께를 얻을 수 있다. 상기 박막의 에로는 산화 알루미늄막을 들 수 있으며, 이때, 제1 반응물 및 제2 반응물은 각각 트리 메틸 알루미늄(Al(CH3)3) 및 수증기(H2O)를 이용할 수 있다. 상기 제1 반응물 및 제2 반응물은 1mch∼10초 동안 공급하며, 상기 챔버의 온도는 200∼400℃로 유지하며, 상기 챔버의 압력은 1∼10,000mTorr로 유지한다. 상기 1차 퍼지 및 2차 퍼지는 0.1∼100초 동안 퍼지한다.The desired thin film thickness may be obtained by sequentially repeating the second purge of the inert gas into the chamber from the step of chemisorbing the first reactant on the substrate. An aluminum oxide film may be used as the thin film, and in this case, the first reactant and the second reactant may use trimethyl aluminum (Al (CH 3 ) 3 ) and water vapor (H 2 O), respectively. The first reactant and the second reactant are supplied for 1 mch to 10 seconds, the temperature of the chamber is maintained at 200 to 400 ° C., and the pressure of the chamber is maintained at 1 to 10,000 mTorr. The primary purge and the secondary purge are purged for 0.1-100 seconds.
본 발명의 박막 제조 방법에 의하면, 기판 상에 형성되는 사이클당 박막의 두께를 결정 구조상의 최밀 충진면의 주기적인 거리에 일치시킴으로써 박막의 특성을 향상시킬 수 있다.According to the thin film manufacturing method of this invention, the characteristic of a thin film can be improved by making the thickness of the thin film per cycle formed on a board | substrate correspond to the periodic distance of the closest packing surface on a crystal structure.
이하, 첨부 도면을 참조하여 본 발명의 실시예를 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 박막 제조 방법에 이용된 박막 제조 장치를 설명하기 위하여 도시한 개략도이고, 도 2는 본 발명의 박막 제조 방법을 설명하기 위하여 도시한 흐름도이다.1 is a schematic diagram illustrating a thin film manufacturing apparatus used in the method for manufacturing a thin film of the present invention, and FIG. 2 is a flowchart illustrating a thin film manufacturing method of the present invention.
먼저, 챔버(1)에 기판(3), 예컨대 웨이퍼를 로딩시킨 후 히터(5) 및 펌프(7)를 이용하여 챔버(1)를 200∼400℃의 온도와 1∼10,000mTorr의 압력을 유지한다 (스텝 100). 상기 200∼400℃의 온도와 1∼10,000mTorr의 압력은 후속의 박막 제조 공정에서 계속 유지되는 공정 온도와 공정압력이다. 이어서, 상기 200∼400℃의 공정 온도와 1∼10,000mTorr 공정 압력을 유지한 상태에서 챔버(1)에 밸브(9)를 선택적으로 작동시켜 제1 반응물(11), 예컨대 트리 메틸 알루미늄(Al(CH3)3)를 가스 라인(13) 및 샤워 헤드(15)를 통하여 상기 웨이퍼의 표면을 충분히 덮을 수 있는 시간, 예컨대 1m초∼10초 동안을 주입한다(스텝 200). 이때, 기판(3) 상에 원자 크기 정도로 화학흡착된 제1 반응물과 상기 화학흡착된 제1 반응물 상에 물리 흡착된 제1 반응물이 형성된다.First, the substrate 1 is loaded into the chamber 1, for example, a wafer, and then the chamber 1 is maintained at a temperature of 200 to 400 ° C. and a pressure of 1 to 10,000 mTorr using the heater 5 and the pump 7. (Step 100). The temperature of 200 to 400 ° C. and the pressure of 1 to 10,000 mTorr are the process temperature and the process pressure which are continuously maintained in the subsequent thin film manufacturing process. Subsequently, the valve 9 is selectively operated in the chamber 1 while maintaining the process temperature of 200 to 400 ° C. and the process pressure of 1 to 10,000 mTorr. CH 3 ) 3 ) is injected through the gas line 13 and the shower head 15 for a time sufficient to cover the surface of the wafer, for example, from 1 m to 10 seconds (step 200). At this time, the first reactant chemisorbed to the atomic size on the substrate 3 and the first reactant physically adsorbed on the chemisorbed first reactant are formed.
다음에, 상기 200∼400℃의 공정온도와 1∼10,000mTorr의 공정 압력을 유지한 상태에서 챔버(1)에 선택적으로 밸브(9)를 작동시켜 가스 소오스(15)를 통하여 불활성 가스, 예컨대 아르곤을 원하는 사이클당 두께를 얻을 수 있는 시간, 예컨대 0.1∼100 초동안 1차 퍼지한다(스텝 300). 여기서, 본 발명은 상기 제1 반응물의 주입시간 및 불활성 가스의 퍼지 시간을 조절하여 화학흡착(chemisoption)되어 있는 제1 반응물 뿐만 아니라 물리흡착(physisoption)되어 있는 반응물도 일정하게 기판(3) 상에 남겨 후속공정에서 이상적인 사이클(cycle)당 박막 두께를 얻을 수 있다.Next, the valve 9 is selectively operated in the chamber 1 while maintaining the process temperature of 200 to 400 ° C. and the process pressure of 1 to 10,000 mTorr. Then, an inert gas such as argon is supplied through the gas source 15. Is first purged for a time to obtain a desired thickness per cycle, for example, 0.1 to 100 seconds (step 300). Herein, the present invention controls the injection time of the first reactant and the purge time of the inert gas so that not only the first reactant that is chemisorbed but also the reactant that is physically adsorbed on the substrate 3 are constantly on the substrate 3. In the subsequent process, the ideal thin film thickness per cycle can be obtained.
다음에, 상기 200∼400℃의 공정온도와 1∼10,000mTorr의 공정 압력을 유지한 상태에서 챔버(1)에 선택적으로 밸브(9)를 작동시켜 제2 반응물(17), 예컨대 수증기를 가스 라인(13) 및 샤워 헤드(15)를 통하여 상기 화학흡착된 제1 반응물과 물리 흡착된 제1 반응물이 형성된 웨이퍼의 표면을 충분히 덮을 수 있는 시간, 예컨대 1m초∼10초동안 주입한다(스텝 400). 이때, 상기 제1 반응물과 제2 반응물은 반응하여 기판(3) 상에 박막, 예컨대 산화 알루미늄막이 형성된다.Next, the valve 9 is selectively operated in the chamber 1 while maintaining the process temperature of 200 to 400 ° C. and the process pressure of 1 to 10,000 mTorr, so that the second reactant 17, for example, steam (13) and the shower head 15 are injected for a time sufficient to cover the surface of the wafer on which the chemisorbed first reactant and the physically adsorbed first reactant are formed, for example, from 1 m to 10 seconds (step 400). . In this case, the first reactant and the second reactant react to form a thin film, such as an aluminum oxide film, on the substrate 3.
계속하여, 상기 200∼400℃의 공정온도와 1∼10,000mTorr의 공정 압력을 유지한 상태에서 챔버(1)에 밸브(9)를 선택적으로 작동시켜 가스 소오스(15)를 통하여 불활성 가스, 예컨대 아르곤 가스를 원하는 사이클당 두께를 얻을 수 있는 시간, 예컨대 0.1∼100초동안 2차 퍼지함으로써 박막을 형성하는 하나의 사이클을 완료한다. 여기서, 본 발명은 상기 제2 반응물의 주입시간 및 불활성 가스의 퍼지 시간을 조절하여 화학흡착(chemisoption)되어 있는 제2 반응물 뿐만 아니라 물리흡착(physisoption)되어 있는 제2 반응물도 일정하게 기판(3) 상에 남겨 계속되는 후속공정에서 이상적인 사이클(cycle)당 두께를 얻을 수 있다.Subsequently, the valve 9 is selectively operated in the chamber 1 while the process temperature of 200 to 400 ° C. and the process pressure of 1 to 10,000 mTorr are maintained to inert gas such as argon through the gas source 15. One cycle of forming the thin film is completed by second purging the gas for a time to achieve the desired thickness per cycle, such as 0.1 to 100 seconds. Herein, the present invention regulates the injection time of the second reactant and the purge time of the inert gas, and not only the second reactant that is chemisorbed, but also the second reactant that is physissorbed constantly. The ideal thickness per cycle can be obtained in subsequent processing which is left on the bed.
이후에, 상기한 바와 같은 원자 크기 정도의 두께의 박막을 형성하는 단계, 즉 제1 반응물 주입부터 2차 퍼지하는 단계까지를 주기적(cycle)으로 반복 수행하여 적정 두께, 예컨대 10Å 내지 1000Å 정도의 박막이 형성되었는지를 확인한다(스텝 600). 적정 두께가 되면 상기 사이클을 반복하지 않고 챔버의 공정온도와 공정압력을 상온 및 상압으로 유지함으로써 박막 제조 과정을 완료한다(스텝 700).Subsequently, the step of forming a thin film having an atomic size as described above, that is, the step of injecting the first reactant to the second purge may be repeated periodically to obtain a thin film having an appropriate thickness, for example, about 10 μs to about 1000 μs. Is formed (step 600). When the proper thickness is reached, the thin film manufacturing process is completed by maintaining the process temperature and the process pressure of the chamber at room temperature and normal pressure without repeating the cycle (step 700).
결과적으로, 본 발명의 박막 제조 방법은 챔버 온도와 압력을 공정 온도와 공정 압력으로 일정하게 유지한 상태에서 제1 반응물 주입, 1차 퍼지, 제2 반응물 주입 및 2차 퍼지를 사이클로 반복하여 수행한다. 이때, 상기 제1 반응물 및 제2 반응물의 주입 시간 및 불활성 가스의 퍼지 시간을 조절하여 한 사이클당 박막 두께를 이론적인 두께, 즉 결정 구조 상의 최밀 충진면의 주기적인 거리에 근접되게 형성할 수 있다.As a result, the thin film manufacturing method of the present invention performs the first reactant injection, the first purge, the second reactant injection and the second purge in cycles while maintaining the chamber temperature and the pressure at the process temperature and the process pressure. . At this time, the injection time of the first reactant and the second reactant and the purge time of the inert gas may be adjusted to form the thin film thickness per cycle close to the theoretical thickness, that is, the periodic distance of the closest filling surface on the crystal structure. .
여기서, 본 발명의 박막 제조 방법을 이용하여 제조된 알루미늄 산화막를 예로 들어 본 발명을 상세히 설명한다.Here, the present invention will be described in detail by taking an aluminum oxide film manufactured by using the thin film manufacturing method of the present invention as an example.
도 3은 본 발명 및 종래 기술의 박막 제조 방법에 의하여 제조된 알루미늄 산화막의 사이클당 두께를 도시한 그래프이고, 도 4는 본 발명 및 종래 방법에 의하여 제조된 알루미늄 산화막의 사이클당 두께에 따른 굴절율을 도시한 그래프이다.Figure 3 is a graph showing the thickness per cycle of the aluminum oxide film produced by the thin film production method of the present invention and the prior art, Figure 4 is a refractive index according to the thickness per cycle of the aluminum oxide film produced by the present invention and the conventional method It is a graph shown.
구체적으로, 종래의 ALD법으로 흡착된 알루미늄 산화막의 사이클당 두께는 도 3의 참조부호 "a"에 도시한 바와 같이 1.1Å이고, 이에 따른 굴절율은 도 4에 도시한 바와 같이 1.65이다. 다시 말하면, ALD법의 기본 특성인 화학흡착과 화학치환을 이용한 박막 흡착 속도가 사이클당 1.1Å 이하에서만 이루어짐을 의미한다.Specifically, the thickness per cycle of the aluminum oxide film adsorbed by the conventional ALD method is 1.1 kPa as shown by reference numeral "a" in FIG. 3, and the refractive index thereof is 1.65 as shown in FIG. In other words, the adsorption rate of the thin film using chemisorption and chemical substitution, which are the basic characteristics of the ALD method, is achieved only at 1.1 Pa or less per cycle.
이에 비하여, 본 발명의 방법에 의하여 흡착된 알루미늄 산화막의 사이클당 두께는 도 3의 참조부호 "b"에 도시한 바와 같이 1.91Å이며, 이에 따른 굴절율은 도 4에 도시한 바와 같이 1.694로 벌크형태의 알루미늄 산화막과 가까운 값을 보였다. 한편, 본 발명자는 사이클당 두께가 0.5Å인 경우 박막은 우수한 스텝 커버리지와 균일한 표면을 보이지만 박막의 굴절율은 1.62정도임을 확인하였다. 아울러, 사이클당 두께가 10Å정도로 크면 증기상에서의 반응에 의하여 박막의 표면이 매우 거칠어지며 막의 잔류 불순물이 증가한다. 결과적으로, 본 발명의 박막 제조 방법에 의하여 형성된 박막은 사이클당 두께가 일정하고 단차 피복성이 우수할 뿐만 아니라 벌크 형태의 알루미늄 산화막의 굴절률과 밀도에 가까운 물성을 가진다.In contrast, the thickness per cycle of the aluminum oxide film adsorbed by the method of the present invention is 1.91 1. as shown by reference numeral “b” of FIG. 3, and the refractive index thereof is 1.694 as shown in FIG. 4 in bulk form. The value was close to that of aluminum oxide. On the other hand, the inventors found that the thin film shows excellent step coverage and uniform surface when the thickness per cycle is 0.5 ms, but the refractive index of the thin film is about 1.62. In addition, when the thickness per cycle is large, about 10 μs, the surface of the thin film becomes very rough due to the reaction in the vapor phase and the residual impurities of the film increase. As a result, the thin film formed by the thin film manufacturing method of the present invention has a constant thickness per cycle, excellent step coverage, and physical properties close to the refractive index and density of the bulk aluminum oxide film.
도 5는 본 발명의 박막 흡착 방법에 의하여 형성된 박막의 식각속도를 설명하기 위하여 도시한 그래프이다.5 is a graph illustrating the etching rate of the thin film formed by the thin film adsorption method of the present invention.
구체적으로, 본 발명자가 실험한 결과 박막의 흡착속도가 사이클당 10Å인 경우의 식각속도는 2500Å/분 이상이었고, 사이클당 0.5Å인 경우는 1200Å/분이었다. 반면에, 본 발명에 의하여 제조된 박막의 흡착속도가 사이클당 1.91Å인 경우 500Å/분임을 확인하였다. 이는 오직 화학흡착에 의해 표면 조절된 공정이 진행되는 경우인 사이클당 0.5Å의 흡착속도를 갖는 막은 균일도와 단차 피복성이 우수하더라도 식각속도가 커서 벌크에 비하여 불량함으로 보여준다. 결국, 본 발명에 의하여 제조된 박막은 식각속도가 낮아 막질이 우수할 뿐만 아니라 90%이상의 단차피복성을 가지며, 균일도가 향상된다.Specifically, as a result of experiments by the present inventors, the etching rate when the adsorption rate of the thin film was 10 kPa / cycle was 2500 kPa / min or more, and when the kPa was 0.5 kPa / cycle, it was 1200 kPa / min. On the other hand, when the adsorption rate of the thin film prepared according to the present invention is 1.91Å per cycle, it was confirmed that it is 500Å / min. This shows that the membrane having a 0.5 kPa adsorption rate per cycle, which is a surface controlled process only by chemisorption, is poor in comparison to the bulk due to its large etching rate even though it has excellent uniformity and step coverage. As a result, the thin film prepared according to the present invention has a low etching rate and excellent film quality, and has a step coverage of more than 90% and improves uniformity.
이상, 실시예를 통하여 본 발명을 구체적으로 설명하였지만, 본 발명은 이에 한정되는 것이 아니고, 본 발명의 기술적 사상 내에서 당 분야에서 통상의 지식으로 그 변형이나 개량이 가능하다.As mentioned above, although this invention was demonstrated concretely through the Example, this invention is not limited to this, A deformation | transformation and improvement are possible with the conventional knowledge in the art within the technical idea of this invention.
상술한 바와 같이 본 발명은 순차적으로 반응물을 유입하여 박막을 제조할 때 화학흡착되어 있는 반응물 뿐만 아니라 물리흡착되어 있는 반응물도 일정하게 남김으로써 이론적으로 가능한 사이클당 막 두께를 결정구조상의 최밀충진면의 주기적인 거리에 일치시켜 막질의 특성을 향상시킬 수 있다.As described above, in the present invention, when the thin film is prepared by sequentially introducing the reactants, not only the chemically adsorbed reactants but also the physically adsorbed reactants remain constant so that the theoretically possible film thickness per cycle is determined by the closest packing surface of the crystal structure. Matching the periodic distance can improve the quality of the film.
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| US20060096531A1 (en) * | 2002-06-10 | 2006-05-11 | Tokyo Electron Limited | Processing device and processing method |
| US7262133B2 (en) | 2003-01-07 | 2007-08-28 | Applied Materials, Inc. | Enhancement of copper line reliability using thin ALD tan film to cap the copper line |
| US20040198069A1 (en) | 2003-04-04 | 2004-10-07 | Applied Materials, Inc. | Method for hafnium nitride deposition |
| KR20060079144A (en) | 2003-06-18 | 2006-07-05 | 어플라이드 머티어리얼스, 인코포레이티드 | Atomic Layer Deposition of Barrier Materials |
| CN110473769A (en) * | 2018-05-11 | 2019-11-19 | 圆益Ips股份有限公司 | Film Formation Method |
| KR102141547B1 (en) * | 2019-09-25 | 2020-09-14 | 솔브레인 주식회사 | Method for forming thin film |
-
1998
- 1998-03-14 KR KR1019980008641A patent/KR19990074809A/en not_active Withdrawn
- 1998-06-22 TW TW087109982A patent/TW384315B/en active
- 1998-06-23 JP JP10176197A patent/JPH11269652A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100417893B1 (en) * | 2001-05-31 | 2004-02-11 | 삼성전자주식회사 | Method of forming a thin film using atomic layer deposition |
| WO2006098565A1 (en) * | 2005-03-16 | 2006-09-21 | Ips Ltd. | Method of depositing thin film using ald process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11269652A (en) | 1999-10-05 |
| TW384315B (en) | 2000-03-11 |
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