KR100490658B1 - Method of forming insulating thin film for semiconductor device - Google Patents
Method of forming insulating thin film for semiconductor device Download PDFInfo
- Publication number
- KR100490658B1 KR100490658B1 KR10-2003-0043057A KR20030043057A KR100490658B1 KR 100490658 B1 KR100490658 B1 KR 100490658B1 KR 20030043057 A KR20030043057 A KR 20030043057A KR 100490658 B1 KR100490658 B1 KR 100490658B1
- Authority
- KR
- South Korea
- Prior art keywords
- thin film
- gas
- forming
- source
- semiconductor device
- Prior art date
Links
Classifications
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
- 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
- H01L21/02123—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 silicon
- H01L21/02142—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02145—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing aluminium, e.g. AlSiOx
-
- 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
- H01L21/02123—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 silicon
- H01L21/02142—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
-
- 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
- H01L21/02123—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 silicon
- H01L21/02142—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02153—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 silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing titanium, e.g. TiSiOx
Abstract
본 발명은 ALD에 의한 Al2O3 박막/HfO2 박막 또는 Al2O 3 박막/TiO2 박막의 다층 절연박막을 단일 챔버에서 형성할 수 있는 방법을 제공한다.The present invention provides a method for forming a multilayer insulating thin film of an Al 2 O 3 thin film / HfO 2 thin film or an Al 2 O 3 thin film / TiO 2 thin film by ALD in a single chamber.
본 발명은 원자층 증착에 의한 반도체 소자의 절연박막 형성방법으로서, 웨이퍼 상에 산화원 개스로서의 O3 개스와 Al 소스 및 NH3 개스를 사용하여 알루미나 박막을 형성하는 제 1 단계; 및 알루미나 박막 상부에 산화원 개스로서의 O3 개스와 Hf 소스를 사용하여 하프늄산화 박막을 형성하는 제 2 단계를 포함하고, 제 1 및 제 2 단계는 단일 챔버에서 수행하는 것에 의해 달성될 수 있다. 또한, 제 1 및 제 2 단계를 소정 회수만큼 반복하여 다층의 알루미나 박막/하프늄산화 박막으로 이루어진 다층 절연박막을 형성하거나, 제 1 단계를 n회 반복한 후, 제 2 단계를 m회 반복하여 n층의 Al2O3 박막/m층의 HfO2 박막으로 이루어진 다층 절연박막을 형성하는 제 3 단계를 더 포함하며, Hf는 Ti로 대체될 수 있다.The present invention provides a method for forming an insulating thin film of a semiconductor device by atomic layer deposition, comprising: a first step of forming an alumina thin film using an O 3 gas, an Al source, and an NH 3 gas as an oxide source gas on a wafer; And a second step of forming a hafnium oxide thin film using an H 3 source and an O 3 gas as an oxide gas on top of the alumina thin film, wherein the first and second steps can be accomplished by performing in a single chamber. In addition, the first and second steps may be repeated a predetermined number of times to form a multilayer insulating thin film composed of a multilayer alumina thin film / hafnium oxide thin film, or the first step is repeated n times, and then the second step is repeated m times. And a third step of forming a multilayer insulating thin film consisting of an Al 2 O 3 thin film / m layer of HfO 2 thin film, wherein Hf may be replaced with Ti.
Description
본 발명은 반도체 소자의 절연박막 형성방법에 관한 것으로, 특히 원자층증착(Atomic Layer Deposition; ALD)에 의한 반도체 소자의 다층 절연박막 형성방법에 관한 것이다.The present invention relates to a method for forming an insulating thin film of a semiconductor device, and more particularly to a method for forming a multilayer insulating thin film of a semiconductor device by atomic layer deposition (ALD).
반도체 소자의 고집적화에 따라 캐패시터 유전박막의 증착기술이 보다 우수한 스텝커버리지(step coverage) 및 막질 등의 박막특성과 우수한 쓰루풋(throughput)을 요구하게 되면서, 캐패시터 유전박막으로서 알루미나(Al2O3)박막/하프늄산화(HfO2)박막 또는 Al2O3 박막/티타늄산화(TiO2 ) 박막 등의 다층 절연박막을 ALD에 의해 형성하는 공정개발이 이루어지고 있다. 그러나, 이들 박막을 기존의 산화원인 H2O 증기(vapor)를 이용하여 형성할 경우 박막 내에 -OH 등의 불순물이 잔류하여 박막특성이 저하되는 문제가 있기 때문에, 최근에는 이를 해결하기 위해 산화원으로서 H2O 증기 대신 오존(O3) 개스를 이용하는 공정개발이 이루어지고 있다.As the high integration of semiconductor devices, the deposition technology of the capacitor dielectric thin film requires more thin film characteristics such as step coverage and film quality and excellent throughput, and thus alumina (Al 2 O 3 ) thin film as the capacitor dielectric thin film. Process development for forming a multilayer insulating thin film such as a hafnium oxide (HfO 2 ) thin film or an Al 2 O 3 thin film / titanium oxide (TiO 2 ) thin film by ALD has been made. However, when these thin films are formed by using H 2 O vapor, which is a conventional oxidation source, impurities such as -OH remain in the thin film, thereby deteriorating the thin film characteristics. As a result, a process development using ozone (O 3 ) gas instead of H 2 O steam has been made.
그러나, O3 개스를 이용하여 ALD에 의해 Al2O3 박막을 형성할 경우에는 증착온도가 400℃ 이상이 되어야만 요구되는 박막의 특성을 확보할 수 있는 반면, HfO2 박막의 경우에는 300℃ 이상의 온도에서는 ALD에 의해 박막을 형성하는 것이 불가능하다. 즉, 도 1은 TMA : Al(CH3)3 의 Al 소스와 O3를 이용하여 ALD에 의해 Al2O3 박막을 형성할 때의 온도에 따른 박막의 증착속도 변화를 나타낸 도면이고, 도 2는 TEMAH : Hf[N(C2H5CH3)]4의 Hf 소스와 O3를 사용하여 ALD에 의해 HfO2 박막을 형성할 때의 온도에 따른 증착속도 변화를 나타낸 도면으로서, Al2O3 박막의 경우에는 도 1에 나타낸 바와 같이, 200 내지 500℃의 넓은 온도영역에서 증착이 이루어지지만, 400℃ 이하(A 영역)에서는 박막 내에 탄소(C) 및 수소(H) 등의 불순물이 잔류하고 400℃ 이상(B 영역)에서는 이러한 불순물이 잔류하지 않기 때문이며, HfO2 박막의 경우에는 도 2에 나타낸 바와 같이 300℃ 이상의 온도에서는 TEMAH 소스의 열분해가 발생하여 증착이 불안정해지기 때문인데, 이는 TiO2 박막의 경우에도 동일하게 나타난다.However, in case of forming Al 2 O 3 thin film by ALD using O 3 gas, it is possible to secure the required thin film characteristics only when the deposition temperature is 400 ° C or higher, whereas HfO 2 thin film is higher than 300 ° C. At temperature, it is impossible to form a thin film by ALD. That is, FIG. 1 is a view showing a change in deposition rate of a thin film according to temperature when forming an Al 2 O 3 thin film by ALD using an Al source of TMA: Al (CH 3 ) 3 and O 3 , FIG. 2. is TEMAH: Hf [N (C 2 H 5 CH 3)] a view showing the deposition rate changing according to the temperature when using a 4 Hf source and the O 3 to form a HfO 2 thin films by ALD, Al 2 O In the case of three thin films, as shown in FIG. 1, deposition is performed in a wide temperature range of 200 to 500 ° C., but impurities such as carbon (C) and hydrogen (H) remain in the thin film at 400 ° C. or lower (area A). This is because such impurities do not remain at 400 ° C or higher (B region), and in the case of the HfO 2 thin film, thermal decomposition of the TEMAH source occurs at 300 ° C or higher as shown in FIG. The same applies to the TiO 2 thin film.
따라서, Al2O3 박막/TiO2 박막 또는 Al2O3 박막/HfO 2 박막과 같은 다층 절연박막을 형성할 경우 300℃ 이상의 온도에서는 단일 챔버에서의 증착공정이 불가능하고 2개의 챔버가 요구되기 때문에, 장비 투자 측면에서의 비용증가 뿐만 아니라 챔버간 웨이퍼 이동에 의한 인-시튜(in-situ) 환경의 단절로 인하여 다층 절연박막의 전기적 특성 및 쓰루풋 저하가 야기된다.Therefore, in the case of forming a multilayer insulating thin film such as an Al 2 O 3 thin film / TiO 2 thin film or an Al 2 O 3 thin film / HfO 2 thin film, a deposition process in a single chamber is impossible and two chambers are required at a temperature higher than 300 ° C. Therefore, not only the cost increase in terms of equipment investment but also the in-situ environment caused by wafer movement between chambers causes the electrical characteristics and throughput degradation of the multilayer insulating thin film.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위하여 제안된 것으로, ALD에 의한 Al2O3 박막/HfO2 박막 또는 Al2O3 박막/TiO2 박막의 다층 절연박막 형성시 Al2O3 박막의 증착온도를 충분히 낮춰 다층 절연박막을 단일 챔버에서 형성함으로써 제조비용을 절감시키고 다층 절연박막의 전기적 특성 및 쓰루풋을 향상시킬 수 있는 반도체 소자의 절연박막 형성방법을 제공하는데 그 목적이 있다.The present invention has been proposed to solve the problems of the prior art as described above, Al 2 O 3 Al 2 O 3 thin film / HfO 2 thin film or Al 2 O 3 thin film / TiO 2 thin film by forming a multi-layer insulating film of Al 2 O 3 It is an object of the present invention to provide a method for forming an insulating thin film of a semiconductor device capable of reducing a manufacturing cost and improving electrical characteristics and throughput of a multilayer insulating thin film by forming a multilayer insulating thin film in a single chamber by sufficiently lowering a deposition temperature of a thin film.
상기의 기술적 과제를 달성하기 위한 본 발명의 일 측면에 따르면, 상기의 본 발명의 목적은 원자층 증착에 의한 반도체 소자의 절연박막 형성방법으로서, 웨이퍼 상에 산화원 개스로서의 O3 개스와 Al 소스 및 NH3 개스를 사용하여 알루미나 박막을 형성하는 제 1 단계; 및 알루미나 박막 상부에 산화원 개스로서의 O3 개스와 Hf 소스를 사용하여 하프늄산화 박막을 형성하는 제 2 단계를 포함하고, 제 1 및 제 2 단계는 단일 챔버에서 수행하는 것에 의해 달성될 수 있다.According to an aspect of the present invention for achieving the above technical problem, an object of the present invention is to form an insulating thin film of a semiconductor device by atomic layer deposition, O 3 gas and Al source as an oxide source gas on the wafer And a first step of forming an alumina thin film using NH 3 gas; And a second step of forming a hafnium oxide thin film using an H 3 source and an O 3 gas as an oxide gas on top of the alumina thin film, wherein the first and second steps can be accomplished by performing in a single chamber.
또한, 제 1 및 제 2 단계를 소정 회수만큼 반복하여 다층의 알루미나 박막/하프늄산화 박막으로 이루어진 다층 절연박막을 형성하거나, 제 1 단계를 n회 반복한 후, 제 2 단계를 m회 반복하여 n층의 Al2O3 박막/m층의 HfO2 박막으로 이루어진 다층 절연박막을 형성하는 제 3 단계를 더 포함하며, Hf는 Ti로 대체될 수 있다.In addition, the first and second steps may be repeated a predetermined number of times to form a multilayer insulating thin film composed of a multilayer alumina thin film / hafnium oxide thin film, or the first step is repeated n times, and then the second step is repeated m times. And a third step of forming a multilayer insulating thin film consisting of an Al 2 O 3 thin film / m layer of HfO 2 thin film, wherein Hf may be replaced with Ti.
또한, 제 1 단계는 챔버 내부로 Al 소스와 NH3 개스를 공급하는 단계; 챔버를 퍼지하는 단계; 챔버 내부로 O3 개스를 공급하는 단계; 및 챔버를 퍼지하는 단계를 포함하고, 제 2 단계는 챔버 내부로 Hf 소스를 공급하는 단계; 챔버를 퍼지하는 단계; 챔버 내부로 O3 개스를 공급하는 단계; 및 챔버를 퍼지하는 단계를 포함한다.The first step also includes supplying an Al source and NH 3 gas into the chamber; Purging the chamber; Supplying O 3 gas into the chamber; And purging the chamber, wherein the second step comprises supplying an Hf source into the chamber; Purging the chamber; Supplying O 3 gas into the chamber; And purging the chamber.
여기서, Al 소스물질로서는 TMA 나 MPTMA를 사용하고, Hf 소스로서는 TEMAH : Hf[N(C2H5)CH3]4, TDMAH : Hf[N(CH3)2 ]4, TDEAH : Hf[N(C2H5)2]4, 및 Hf(OtBu) 4 : Hf[OC(CH3)3]4 중 선택되는 하나를 사용하며, Al 소스, Hf 소스 및 O 3 개스의 공급시간은 각각 0.1 내지 10 초 이내로 제어한다. 또한, NH3 개스의 유량은 10 내지 300sccm 으로 조절하고, 퍼지는 진공펌프를 사용하여 잉여 Al 소스 및 NH3 개스를 펌핑하거나 퍼지개스로서 Ar 또는 N2를 공급하여 수행하며, 퍼지시간은 0.1 내지 10초 이내로 제어한다.Here, TMA or MPTMA is used as the Al source material, TEMAH: Hf [N (C 2 H 5 ) CH 3 ] 4 , TDMAH: Hf [N (CH 3 ) 2 ] 4 , TDEAH: Hf [N (C 2 H 5 ) 2 ] 4 , and Hf (OtBu) 4 : Hf [OC (CH 3 ) 3 ] 4 is used, and the feed time of Al source, Hf source and O 3 gas is 0.1, respectively. To within 10 seconds. In addition, the flow rate of the NH 3 gas is adjusted to 10 to 300sccm, pumping the excess Al source and NH 3 gas using a purge vacuum pump or by supplying Ar or N 2 as a purge gas, the purge time is 0.1 to 10 Control within seconds
이하, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자가 본 발명을 보다 용이하게 실시할 수 있도록 하기 위하여 본 발명의 바람직한 실시예를 소개하기로 한다.Hereinafter, preferred embodiments of the present invention will be introduced in order to enable those skilled in the art to more easily carry out the present invention.
도 3은 본 발명의 실시예에 따른 ALD에 의한 반도체 소자의 다층 절연박막 형성방법을 설명하기 위한 도면으로서, 1주기(cycle) 동안의 공정순서를 나타낸다.3 is a view for explaining a method for forming a multilayer insulating thin film of a semiconductor device by ALD according to an embodiment of the present invention, and shows a process sequence for one cycle.
도 3에 나타낸 바와 같이, 먼저 챔버 내부에 웨이퍼가 삽입된 상태에서 챔버내부로 Al 소스와 NH3 개스를 공급하여 웨이퍼 표면에 Al 소스를 흡착시키는 제 1 단계를 수행한다. 여기서, 웨이퍼는 Si, SiO2 또는 GaAs 등과 같은 반도체 기판이거나, 상기 반도체 기판 상부에 폴리실리콘막, Ru막, Pt막, 또는 TiN막 등의 도전박막이 형성된 기판이며, 도전박막은 스퍼터링(sputtering), 화학기상증착 (Chemical Vapor Deposition; CVD) 또는 ALD에 의해 형성된다. 또한, Al 소스물질로서는 TMA 나 MPTMA를 사용하고, Al 소스 공급시간은 0.1 내지 10 초 이내로 제어하며, NH3 개스의 유량은 10 내지 300sccm으로 조절한다. 그 다음, 챔버 내부를 퍼지(purge)하여 잉여 Al 소스 및 NH3 개스를 제거하는 제 2 단계를 수행한다. 바람직하게, 퍼지는 진공펌프를 사용하여 잉여 Al 소스 및 NH3 개스를 펌핑(pumping) 하거나, 퍼지개스로서 Ar 또는 N2를 공급하여 펌핑효과를 증대시키는 방법으로 수행하며, 퍼지시간은 0.1 내지 10초 이내로 제어한다. 그 후, 산화원 개스로서 O3 개스를 공급하여 Al 소스분자를 산화시켜 Al2O3 박막을 형성하는 제 3 단계를 수행한다. 여기서, O3 공급시간은 0.1 내지 10초 이내로 제어한다. 그 다음, 제 2 단계에서와 동일한 방법으로 챔버를 퍼지하여 산화반응에 의해 형성된 반응부산물과 잉여 O3를 제거하는 제 4 단계를 수행한다. 즉, Al 소스 이외에 NH3 개스를 첨가하게 되면, 도 4에 나타낸 바와 같이, NH3 개스를 첨가하지 않은 경우에 비해 박막내의 탄소 불순물 농도를 충분히 낮출 수 있기 때문에, 도 4에 나타낸 바와 같이, 증착온도를 300℃ 이하로 충분히 낮출 수 있다.As shown in FIG. 3, first, an Al source and NH 3 gas are supplied into the chamber while the wafer is inserted into the chamber to adsorb the Al source onto the wafer surface. Here, the wafer is a semiconductor substrate such as Si, SiO 2 or GaAs, or a substrate having a conductive thin film such as a polysilicon film, a Ru film, a Pt film, or a TiN film formed on the semiconductor substrate, and the conductive thin film is sputtered. It is formed by chemical vapor deposition (CVD) or ALD. In addition, TMA or MPTMA is used as the Al source material, the Al source supply time is controlled within 0.1 to 10 seconds, and the flow rate of NH 3 gas is adjusted to 10 to 300 sccm. A second step is then performed to purge the interior of the chamber to remove excess Al source and NH 3 gas. Preferably, a purge is performed by using a vacuum pump to pump excess Al source and NH 3 gas or by supplying Ar or N 2 as a purge gas to increase the pumping effect, and a purge time of 0.1 to 10 seconds. Control within. Thereafter, a third step of forming an Al 2 O 3 thin film by oxidizing an Al source molecule by supplying O 3 gas as an oxidizing source gas is performed. Here, the O 3 supply time is controlled within 0.1 to 10 seconds. Then, a fourth step of purging the chamber in the same manner as in the second step to remove the reaction by-product and excess O 3 formed by the oxidation reaction is performed. That is, when NH 3 gas is added in addition to the Al source, as shown in FIG. 4, the concentration of carbon impurities in the thin film can be sufficiently lowered as compared with the case where NH 3 gas is not added. The temperature can be sufficiently lowered below 300 ° C.
그 후, 챔버 내부로 Hf 소스를 공급하여 Al2O3 박막이 형성된 웨이퍼 표면에 Hf 소스를 흡착시키는 제 5 단계를 수행한다. 바람직하게, Hf 소스로서 TEMAH : Hf[N(C2H5)CH3]4, TDMAH : Hf[N(CH3)2 ]4, TDEAH : Hf[N(C2H5)2]4, 및 Hf(OtBu) 4 : Hf[OC(CH3)3]4 중 선택되는 하나를 사용하며, Hf 소스 공급시간은 0.1 내지 10초 이내로 제어한다. 그 다음, 제 2 단계에서와 동일한 방법으로 챔버를 퍼지하여 잉여 Hf 소스를 제거하는 제 6 단계를 수행한다. 그 후, 산화원 개스로서 O3를 공급하여 Hf 소스분자를 산화시켜 Al2O3 박막 상부에 HfO2 박막을 형성하는 제 7 단계를 수행한다. 여기서, O3 공급시간은 제 3 단계에서와 마찬가지로 0.1 내지 10초 이내로 제어한다. 그 다음, 제 2 단계에서와 동일한 방법으로 챔버를 퍼지하여 산화반응에 의해 형성된 반응부산물과 잉여 O3를 제거하는 제 8 단계를 수행한 후, 제 1 내지 제 8 단계를 소정 두께가 될 때까지 소정 회수만큼 반복하여 다층의 Al2O3 박막/HfO2 박막으로 이루어진 다층 절연박막을 형성하는 제 9 단계를 수행한다.Thereafter, a fifth step of supplying the Hf source into the chamber to adsorb the Hf source on the wafer surface on which the Al 2 O 3 thin film is formed is performed. Preferably, as the Hf source, TEMAH: Hf [N (C 2 H 5 ) CH 3 ] 4 , TDMAH: Hf [N (CH 3 ) 2 ] 4 , TDEAH: Hf [N (C 2 H 5 ) 2 ] 4 , And Hf (OtBu) 4 : Hf [OC (CH 3 ) 3 ] 4 , and the Hf source supply time is controlled within 0.1 to 10 seconds. A sixth step is then performed to purge the chamber in the same manner as in the second step to remove the excess Hf source. Thereafter, a seventh step of forming HfO 2 thin film on the Al 2 O 3 thin film by oxidizing Hf source molecules by supplying O 3 as an oxidizing source gas is performed. Here, the O 3 supply time is controlled within 0.1 to 10 seconds as in the third step. Then, purging the chamber in the same manner as in the second step, after performing the eighth step of removing the reaction by-products formed by the oxidation reaction and the excess O 3 , until the first to eighth steps have a predetermined thickness. The ninth step is repeated by a predetermined number of times to form a multilayer insulating thin film composed of a multi-layered Al 2 O 3 thin film / HfO 2 thin film.
상기 실시예에 의하면, 산화원 개스로서 O3를 이용하는 ALD에 의한 Al2O3 박막/HfO2 박막의 다층 절연박막 형성시, Al 소스 이외에 NH3 개스를 첨가하여 Al 2O3 박막 내의 탄소 불순물농도를 낮춰 증착온도를 300℃ 이하로 충분히 낮춤에 따라 단일 챔버에서 Al2O3 박막/HfO2 박막의 다층 절연박막을 형성하는 것이 가능해짐으로써, 제조비용을 절감할 수 있을 뿐만 아니라 다층 절연박막의 전기적 특성 및 쓰루풋을 향상시킬 수 있게 된다.According to the above embodiment, when forming a multilayer insulating thin film of an Al 2 O 3 thin film / HfO 2 thin film by ALD using O 3 as an oxide source gas, carbon impurities in the Al 2 O 3 thin film by adding NH 3 gas in addition to the Al source By lowering the concentration to sufficiently lower the deposition temperature below 300 ° C., it becomes possible to form a multilayer insulating thin film of Al 2 O 3 thin film / HfO 2 thin film in a single chamber, thereby not only reducing manufacturing cost but also multilayer insulating thin film. It is possible to improve the electrical characteristics and throughput of the.
한편, 상기 실시예에서는 Al2O3 박막/HfO2 박막의 다층 절연박막에 대해서만 설명하였지만, 제 5 단계에서 Hf 소스 대신 Ti 소스를 공급하여 Al2O3 박막/TiO 2 박막의 다층 절연박막을 형성할 수도 있는데, 이 경우 Ti 소스로서 Ti(OiPr)4 등의 알콕사이드 계열의 소스를 사용한다.On the other hand, the multi-layer insulation film of the embodiment, the Al 2 O 3 thin film / HfO 2 thin film multi-layer insulation has been described only for the thin film, by feeding the Hf source instead of the Ti source in the fifth step Al 2 O 3 thin film / TiO 2 thin film of In this case, an alkoxide-based source such as Ti (OiPr) 4 is used as the Ti source.
또한, 상기 실시예에서와 같이 다층의 Al2O3 박막/HfO2 박막으로 이루어진 다층 절연박막을 제 1 내지 제 8 단계를 반복하여 형성하는 대신, Al2O3 박막을 형성하는 제 1 내지 제 4 단계를 원하는 두께가 될 때까지 n회 반복한 후, HfO2 박막을 형성하는 제 5 내지 제 8 단계를 소정 두께가 될 때까지 m회 반복하여 n층의 Al2O3 박막/m층의 HfO2 박막으로 이루어진 다층 절연박막을 형성할 수도 있다.Further, the first to the forming, instead of forming the multi-layer insulating film made of a multilayer of Al 2 O 3 thin film / HfO 2 thin film first to repeat the eighth step, Al 2 O 3 thin film as described in Example After repeating step 4 n times to the desired thickness, repeating steps 5 to 8 forming the HfO 2 thin film m times until a predetermined thickness is carried out to obtain n layers of Al 2 O 3 thin film / m layers. It is also possible to form a multilayer insulating thin film made of a HfO 2 thin film.
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 are possible in the art without departing from the technical spirit of the present invention. It will be clear to those of ordinary knowledge.
전술한 본 발명은 ALD에 의한 Al2O3 박막/HfO2 박막의 다층 절연박막 형성시 Al2O3 박막의 증착온도를 충분히 낮춰 다층 절연박막을 단일 챔버에서 형성할 수 있으므로, 제조비용을 절감시킬 수 있을 뿐만 아니라 다층 절연박막의 전기적 특성 및 쓰루풋을 향상시킬 수 있다.The present invention described above can sufficiently reduce the deposition temperature of the Al 2 O 3 thin film when forming a multilayer insulating thin film of Al 2 O 3 thin film / HfO 2 thin film by ALD to form a multi-layer insulating thin film in a single chamber, reducing the manufacturing cost In addition to improving the electrical properties and throughput of the multilayer insulating thin film.
도 1은 Al 소스와 O3를 이용하여 ALD에 의해 Al2O3 박막을 형성할 때의 온도에 따른 박막의 증착속도 변화를 나타낸 도면.1 is a view showing a change in deposition rate of a thin film with temperature when forming an Al 2 O 3 thin film by ALD using an Al source and O 3 .
도 2는 Hf 소스와 O3를 사용하여 ALD에 의해 HfO2 박막을 형성할 때의 온도에 따른 증착속도 변화를 나타낸 도면.2 is a graph showing deposition rate change with temperature when HfO 2 thin film is formed by ALD using Hf source and O 3 .
도 3은 본 발명의 실시예에 따른 ALD에 의한 반도체 소자의 다층 절연박막 형성방법을 설명하기 위한 도면.3 is a view for explaining a method for forming a multilayer insulating thin film of a semiconductor device by the ALD according to an embodiment of the present invention.
도 4는 NH3 첨가 여부에 따른 Al2O3 박막의 탄소 불순물 농도를 XPS(X-ray Photoemission Spectroscopy)로 분석한 결과를 나타낸 도면.Figure 4 is a view showing the results of analyzing the carbon impurity concentration of the Al 2 O 3 thin film with or without NH 3 by X-ray Photoemission Spectroscopy (XPS).
도 5는 Al 소스와 NH3 개스 및 O3를 이용하여 ALD에 의해 Al2O3 박막을 형성할 때의 온도에 따른 박막의 증착속도 변화를 나타낸 도면.5 is a view showing the deposition rate change of the thin film according to the temperature when forming the Al 2 O 3 thin film by ALD using an Al source, NH 3 gas and O 3 .
Claims (17)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0043057A KR100490658B1 (en) | 2003-06-30 | 2003-06-30 | Method of forming insulating thin film for semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0043057A KR100490658B1 (en) | 2003-06-30 | 2003-06-30 | Method of forming insulating thin film for semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20050002011A KR20050002011A (en) | 2005-01-07 |
| KR100490658B1 true KR100490658B1 (en) | 2005-05-24 |
Family
ID=37217579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-2003-0043057A KR100490658B1 (en) | 2003-06-30 | 2003-06-30 | Method of forming insulating thin film for semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100490658B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100652420B1 (en) | 2005-03-23 | 2006-12-01 | 삼성전자주식회사 | Method of manufacturing a dielectric film and method of manufacturing Metal Insulator Metal capacitor having the dielectric film and batch type atomic layer deposition apparatus for manufacturing the dielectric film |
| KR100717768B1 (en) | 2005-08-30 | 2007-05-11 | 주식회사 하이닉스반도체 | Capacitor in semiconductor device and method for forming the same, non-volatile memory device and method manufacturing the same |
| KR102382025B1 (en) | 2015-03-04 | 2022-04-04 | 삼성디스플레이 주식회사 | Display apparatus |
-
2003
- 2003-06-30 KR KR10-2003-0043057A patent/KR100490658B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050002011A (en) | 2005-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6468924B2 (en) | Methods of forming thin films by atomic layer deposition | |
| KR100819318B1 (en) | Manufacturing method of semiconductor apparatus | |
| KR100555543B1 (en) | Method for forming high dielectric layer by atomic layer deposition and method for manufacturing capacitor having the layer | |
| KR100591508B1 (en) | Atomic layer deposition of oxide film | |
| KR100716654B1 (en) | Method for manufacturing tetragonal zirconium oxide and method for manufacturing capacitor with the same | |
| KR100640654B1 (en) | Method of forming zro2 thin film using plasma enhanced atomic layer deposition and method of manufacturing capacitor of semiconductor memory device having the thin film | |
| US20060257563A1 (en) | Method of fabricating silicon-doped metal oxide layer using atomic layer deposition technique | |
| US20080085610A1 (en) | Ald of metal silicate films | |
| JP4505494B2 (en) | Semiconductor device manufacturing method and substrate processing apparatus | |
| JP2005536063A (en) | High-k metal oxide atomic layer deposition | |
| US7094712B2 (en) | High performance MIS capacitor with HfO2 dielectric | |
| KR100829608B1 (en) | Method of manufacturing a thin layer and methods of manufacturing a gate structure and a capacitor using the same | |
| KR20110006450A (en) | Method of forming dielectric thin film for semiconductor device | |
| KR100490658B1 (en) | Method of forming insulating thin film for semiconductor device | |
| KR20040059878A (en) | Method of forming insulating thin film for semiconductor device | |
| KR100770276B1 (en) | Method of forming mim capacitor in semiconductor device | |
| KR100528799B1 (en) | Method for forming a dielectric film and method for manufacturing a capacitor using the same | |
| KR100511914B1 (en) | Method for fabricating of semiconductor device using PECYCLE-CVD | |
| KR20070114519A (en) | Dielectric layer in capacitor and fabricating using the same and capacitor in semiconductor device and fabricating using the same | |
| KR100766007B1 (en) | METHOD FOR FORMING HfO2 FILM USING Hf Metal Organic Compound | |
| KR20040055458A (en) | Method of forming insulating thin film for semiconductor device | |
| KR20040059833A (en) | Hafnium oxide capacitor in semiconductor device and method for forming the same | |
| KR20050015442A (en) | Method for the Deposition of Thin Layers by Metal Organic Chemical Vapor Deposition | |
| KR20060027087A (en) | Method of forming a hafnium nitride layer on a substrate using an atomic layer deposition | |
| KR20070004193A (en) | Method of forming a layer and method of manufacturing a capacitor using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20110429 Year of fee payment: 7 |
|
| LAPS | Lapse due to unpaid annual fee |