WO2018139746A1 - Method for preparing high-quality quadruple-patterning material through alloying of hetero elements - Google Patents

Method for preparing high-quality quadruple-patterning material through alloying of hetero elements Download PDF

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WO2018139746A1
WO2018139746A1 PCT/KR2017/013109 KR2017013109W WO2018139746A1 WO 2018139746 A1 WO2018139746 A1 WO 2018139746A1 KR 2017013109 W KR2017013109 W KR 2017013109W WO 2018139746 A1 WO2018139746 A1 WO 2018139746A1
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ald
patterned material
hetero
high quality
preparation
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이한보람
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인천대학교 산학협력단
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Definitions

  • the present invention relates to a method for producing a high quality quadruple patterning material through heterogeneous alloying, and more specifically, yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) using a supercycle atomic layer deposition method (Supercycle ALD).
  • the present invention relates to a method of providing a high quality quadruple patterning material by solving a problem of increasing surface roughness by a subsequent heat treatment process of an existing titanium oxide (TiO 2 ) thin film by doping into an alloy.
  • Multiple patterning refers to a technique developed for photolithography to increase feature density. For example, in double patterning, the lithography process is increased so that the expected number of features is doubled. Specifically, two exposures and two etching processes are performed.
  • multi-patterning including an exposure process is used to fabricate a highly integrated semiconductor device.
  • the conventional double patterning has reached a limit in implementing fine patterns.
  • TiO 2 has a higher film density than SiO 2 and is being studied as a potential quadruple patterning material.
  • TiO 2 has a big problem that the surface roughness of the thin film increases due to crystallization in a subsequent heat treatment process after the thin film is formed.
  • the present invention is to solve the problems of the prior art as described above, the conventional titanium oxide (TiO 2 ) to solve the problem of increasing the surface roughness of the thin film by a subsequent heat treatment process to provide a high quality quadruple patterning material. It is a technical task to provide a new way of doing this.
  • the present invention provides a method for producing a multi-patterning (particularly for quadruple patterning) material using a supercycle ALD, Atomic layer deposition (ALD) on a substrate ) Repeating the deposition of the titanium oxide (TiO 2 ) thin film 1 to 1000 times, and depositing the yttrium oxide (Y 2 O 3 ) thin film using atomic layer deposition (ALD). Repeating 1 to 1000 times as one supercycle, and doping the yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) to perform one or more cycles one or more times to form an alloyed thin film.
  • ALD Atomic layer deposition
  • the present invention forms a alloyed thin film by doping yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) using supercycle atomic layer deposition (Supercycle ALD), thereby following the conventional titanium oxide (TiO 2 ) thin film. It is possible to provide a high quality quadruple patterning material in which the problem of increasing the surface roughness by the heat treatment process is solved.
  • the present invention overcomes the limitations of the existing exposure process to enable the micropattern implementation of the semiconductor device to enable the production of super-integrated semiconductor devices.
  • the present invention has a wide applicability over all semiconductor fields, and has an advantage that it can be widely applied to an environment requiring a fine pattern such as not only a semiconductor device but also a memory field.
  • 1 is a view schematically showing a process of quadruple patterning.
  • FIG. 2 is a view schematically illustrating a process element of a method of manufacturing a material for multipatterning using a supercycle ALD according to the present invention.
  • Figure 3 shows the surface roughness changes before and after the subsequent heat treatment of the pure titanium oxide (TiO 2 ) thin film formed by atomic layer deposition and the yttrium-doped titanium oxide (TiO 2 ) thin film according to the present invention. AFM image.
  • Atomic layer deposition on the substrate by using a (Atomic layer deposition ALD) titanium oxide (TiO 2) repeated 1 to 1,000 times the step of depositing a thin film, and also the atomic layer deposition method; using (Atomic layer deposition ALD) yttrium Repeating the deposition of the oxide (Y 2 O 3 ) thin film 1 to 1000 times as one supercycle,
  • yttrium oxide Y 2 O 3
  • TiO 2 titanium oxide
  • the one supercycle is composed of one yttrium oxide (Y 2 O 3 ) ALD process and sixteen titanium oxide (TiO 2 ) ALD processes, that is, yttrium oxide (Y 2 O 3 ) ALD process and that the titanium oxide (TiO 2) ALD process performed at a ratio of 1:16 being preferred.
  • the time for performing one yttrium oxide (Y 2 O 3 ) ALD process is not particularly limited.
  • the second to 17th ALD processes are performed. Either (eg, the last ALD process) may be carried out in a yttrium oxide (Y 2 O 3 ) ALD process.
  • any substrate capable of maintaining its unique characteristics while being resistant to adverse effects such as morphology change by the atomic layer deposition process may be used.
  • a silicon (Si) substrate for example, a silicon (Si) substrate, a silica (SiO 2 ) substrate, a platinum (Pt) substrate, or the like may be used depending on the application, and a silicon (Si) substrate is suitable for a semiconductor device.
  • Si silicon
  • SiO 2 silica
  • Pt platinum
  • Y 2 O 3 which is a material doped with titanium oxide (TiO 2 )
  • TiO 2 titanium oxide
  • the thermal stability, heat resistance and durability are excellent in themselves.
  • the yttrium oxide (Y 2 O 3) ALD as the yttrium precursor of step is that which can be applied to the ALD method, for example, an organic metal, depending on the type of the ligand, (Ligand) coupled to yttrium metal atom (Metal organic), metal halides (Metal halide) and the like, preferably bis-isopropylcyclopentadienyl-di-isopropylacetamidinate-yttrium (Yerba: Y (iPrCp) 2 (N-iPr-amd)) is used. do.
  • an organic metal depending on the type of the ligand, (Ligand) coupled to yttrium metal atom (Metal organic), metal halides (Metal halide) and the like, preferably bis-isopropylcyclopentadienyl-di-isopropylacetamidinate-yttrium (Yerba: Y (iPrC
  • the yttrium oxide (Y 2 O 3) ALD unit of the process can be ongoing with the purging during the yttrium precursor adsorption for 8 seconds, 10 seconds, the reaction gas inlet for three seconds, and 10 second purge for the net
  • the execution time of each step constituting the unit process can be appropriately adjusted as necessary.
  • the titanium precursor of the titanium oxide (TiO 2 ) ALD process may be applied to the ALD method, for example, depending on the type of functional group bonded to the titanium metal atom (metal organic, metal halide) And the like, and preferably titanium tetraisopropoxide (TTIP: Ti (OC 3 H 7 ) 4 ) is used.
  • TTIP titanium tetraisopropoxide
  • the unit process of the titanium oxide (TiO 2 ) ALD may be performed in the order of titanium precursor adsorption for 2 seconds, purging for 5 seconds, injection of reaction gas for 3 seconds, and purging for 5 seconds,
  • the execution time of each step constituting the unit process can be appropriately adjusted as necessary.
  • Reaction gases for reaction with the metal precursor adsorbed in the yttrium oxide (Y 2 O 3 ) ALD process and titanium oxide (TiO 2 ) ALD process are ozone (O 3 ), oxygen (O 2 ), oxygen (O 2 ) Plasma or water vapor (H 2 O) or the like can be used, preferably ozone (O 3 ) is used.
  • Supercycle atomic layer deposition method can be carried out by maintaining the temperature of the substrate at 200 °C ⁇ 400 °C, for example, yttrium oxide (Y 2 O 3 ) ALD process and the conditions of 200 °C Titanium oxide (TiO 2 ) ALD process may be performed respectively.
  • Y 2 O 3 yttrium oxide
  • TiO 2 Titanium oxide
  • one supercycle may be performed 1 to 1000 times to obtain a multi-patterned material thin film having a desired thickness.
  • the number of supercycle runs is performed so that the thickness of the alloying thin film to be finally formed is about 15 to 18 nm. Adjust it.
  • the yttrium oxide (Y 2 O 3 ) ALD process and titanium oxide (TiO 2 ) ALD process constituting the supercycle ALD process of the present invention respectively,
  • the native oxide formed on the substrate is removed, and then heated to a predetermined temperature (for example, 200 °C),
  • a purging gas eg, inert gas
  • Step may be performed by repeating sequentially.
  • the multi-patterned material thin film prepared in accordance with the present invention is subjected to a subsequent heat treatment process, the inventors of the present invention when the subsequent heat treatment for 1 hour at 400 °C, the surface roughness of the multi-patterned material thin film does not increase, but rather reduced It was confirmed specifically through the experiment.
  • yttrium oxide (Y 2 O 3 ) and titanium oxide (TiO 2 ) were deposited at 200 ° C. using an ALD process cycle of 1:16 as one supercycle.
  • Titanium oxide (TiO 2 ) ALD process was performed as follows:
  • the native oxide film of the silicon substrate Si (100) p-type was removed, and then heated to 200 ° C.
  • TTIP a titanium (Ti) precursor vaporized over the heated substrate
  • the carrier gas (Ar) was administered with the carrier gas for 2 seconds.
  • the flow rate of the carrier gas was maintained at 50 sccm.
  • the excess precursor except for the titanium precursor physically or chemically adsorbed on the silicon substrate was removed by supplying argon purging gas at a flow rate of 50 sccm for 5 seconds.
  • ozone (O 3 ) was administered on the substrate to which the titanium precursor was adsorbed for 3 seconds to oxidize the adsorbed titanium precursor to grow a titanium oxide (TiO 2 ) thin film.
  • This process was defined as one cycle and repeated 16 times to form a thin film.
  • Yttrium oxide (Y 2 O 3 ) ALD process was performed as follows:
  • Yerba a yttrium (Y) precursor vaporized onto a silicon substrate heated to 200 ° C.
  • the carrier gas Ar
  • the flow rate of the carrier gas was maintained at 50 sccm.
  • the excess precursor except for the yttrium precursor physically or chemically adsorbed on the silicon substrate was removed by supplying argon purging gas at a flow rate of 50 sccm for 10 seconds.
  • ozone (O 3 ) was administered on the substrate to which the yttrium precursor was adsorbed for 3 seconds to oxidize the adsorbed yttrium precursor to grow a yttrium oxide (Y 2 O 3 ) thin film.
  • This process was defined as one cycle and carried out once to form a thin film.
  • one supercycle process including one yttrium oxide (Y 2 O 3 ) ALD unit process and sixteen titanium oxide (TiO 2 ) ALD unit processes was repeated to finally form a thin film having a thickness of 15 to 18 nm. .
  • the formed thin film was subsequently heat treated at 400 ° C. for 1 hour using a furnace.
  • the surface roughness (R q ) of the titanium oxide (TiO 2 ) thin film and the yttrium-doped titanium oxide (TiO 2 ) thin film formed by atomic layer deposition was compared by AFM measurement.
  • the surface roughness increased from 1.98 kPa to 2.95 kPa after the heat treatment.
  • the surface roughness decreased by 20.3% from 1.92 ⁇ to 1.53 ⁇ after heat treatment.
  • the present invention enables the production of super-integrated semiconductor devices by overcoming the limitations of the existing exposure process to enable the micro-patterns of semiconductor devices, and has wide applicability in all semiconductor fields. If the environment requires a fine pattern, it can be applied widely.

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Abstract

The present invention relates to a method for preparing a high-quality quadruple-patterning material through the alloying of hetero elements and, more specifically, to a method capable of providing a high-quality quadruple-patterning material by resolving the problem of an increase in surface roughness, caused by a subsequent heat treatment process of a conventional titanium oxide (TiO2) thin film, by using supercycle atomic layer deposition (ALD) so as to dope yttrium oxide (Y2O3) in titanium oxide (TiO2) and alloy the same.

Description

이종원소 합금화를 통한 고품질 사중패터닝 물질의 제조방법Manufacturing method of high quality quadruple patterning material through heterogeneous alloying
본 발명은 이종원소 합금화를 통한 고품질 사중패터닝 물질의 제조방법에 관한 것으로, 더욱 상세하게는 슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용하여 이트륨산화물(Y2O3)을 타이타늄산화물(TiO2)에 도핑시켜 합금화함으로써, 기존 타이타늄산화물(TiO2) 박막의 후속 열처리 공정에 의한 표면거칠기 증가 문제를 해결하여 고품질의 사중패터닝용 물질을 제공할 수 있도록 한 방법에 관한 것이다.The present invention relates to a method for producing a high quality quadruple patterning material through heterogeneous alloying, and more specifically, yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) using a supercycle atomic layer deposition method (Supercycle ALD). The present invention relates to a method of providing a high quality quadruple patterning material by solving a problem of increasing surface roughness by a subsequent heat treatment process of an existing titanium oxide (TiO 2 ) thin film by doping into an alloy.
다중패터닝(Multiple patterning)은 피처 밀도(Feature density)를 증가시키기 위한 포토리소그래피를 위해 개발된 기술을 지칭한다. 예를 들어 이중패터닝에서는 피처의 예상 개수가 2배로 생성되도록 리소그래피 공정이 늘어나는바, 구체적으로 2회의 노광 및 2회의 식각 공정이 수행되게 된다.Multiple patterning refers to a technique developed for photolithography to increase feature density. For example, in double patterning, the lithography process is increased so that the expected number of features is doubled. Specifically, two exposures and two etching processes are performed.
즉, 집적도가 높은 반도체 소자를 제작하기 위해 노광 공정을 포함한 다중패터닝을 사용하고 있는데, 종래와 같은 이중패터닝은 미세패턴을 구현하는데 있어 한계에 도달하였다.That is, multi-patterning including an exposure process is used to fabricate a highly integrated semiconductor device. However, the conventional double patterning has reached a limit in implementing fine patterns.
이를 해결하기 위해, 도 1과 같은 사중패터닝(Quadruple patterning) 방법이 제시되었으며, 이러한 사중패터닝을 위한 박막 물질로는 SiO2가 일반적으로 사용되고 있다.In order to solve this problem, a quadruple patterning method as illustrated in FIG. 1 has been proposed, and SiO 2 is generally used as a thin film material for such quadruple patterning.
그러나, 사중패터닝 물질로서 SiO2는 현재 반도체 분야 등에서 요구되는 고도의 니즈를 충족시키기에 다소 부족함이 있어, 더 높은 박막 밀도와 식각 선택비를 구현할 수 있는 새로운 물질의 개발이 요구되게 되었다.However, as a quad patterned SiO 2 material was present so there is somewhat insufficient to meet the needs of high level is required in the semiconductor field, the further development of new materials that can be implemented with high density and a thin film etch selectivity requirements.
새로운 물질 후보들 중에서 TiO2는 SiO2보다 박막 밀도가 높아, 유력한 사중패터닝 물질로 연구되고 있다.Among the new material candidates, TiO 2 has a higher film density than SiO 2 and is being studied as a potential quadruple patterning material.
그러나, 이러한 TiO2는 박막 형성 후 후속 열처리 공정에서 결정화로 인해 박막의 표면거칠기가 열처리 전보다 증가하는 큰 문제점을 지니고 있다.However, such TiO 2 has a big problem that the surface roughness of the thin film increases due to crystallization in a subsequent heat treatment process after the thin film is formed.
본 발명은 상기와 같은 종래기술의 문제점을 해결하고자 한 것으로, 기존의 타이타늄산화물(TiO2)이 후속 열처리 공정에 의해 박막의 표면거칠기가 증가하는 문제를 해결하여 고품질의 사중패터닝용 물질을 제공할 수 있는 새로운 방법을 제공함을 기술적 과제로 한다.The present invention is to solve the problems of the prior art as described above, the conventional titanium oxide (TiO 2 ) to solve the problem of increasing the surface roughness of the thin film by a subsequent heat treatment process to provide a high quality quadruple patterning material. It is a technical task to provide a new way of doing this.
상기한 기술적 과제를 달성하고자, 본 발명은 슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용한 다중패터닝용(특히, 사중패터닝용) 물질의 제조방법으로서, 기판 상에 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 타이타늄산화물(TiO2) 박막을 증착하는 단계를 1~1000회 반복하고, 또한 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 이트륨산화물(Y2O3) 박막을 증착하는 단계를 1~1000회 반복하는 것을 1 슈퍼사이클로 하며, 상기 1 슈퍼사이클을 1회 이상 수행하여 이트륨산화물(Y2O3)을 타이타늄산화물(TiO2)에 도핑시켜 합금화된 박막을 형성하는 것을 특징으로 하는, 이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법을 제공한다.In order to achieve the above technical problem, the present invention provides a method for producing a multi-patterning (particularly for quadruple patterning) material using a supercycle ALD, Atomic layer deposition (ALD) on a substrate ) Repeating the deposition of the titanium oxide (TiO 2 ) thin film 1 to 1000 times, and depositing the yttrium oxide (Y 2 O 3 ) thin film using atomic layer deposition (ALD). Repeating 1 to 1000 times as one supercycle, and doping the yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) to perform one or more cycles one or more times to form an alloyed thin film. To provide a method for producing a high quality multi-patterned material through hetero-element alloying.
본 발명은 슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용하여 이트륨산화물(Y2O3)을 타이타늄산화물(TiO2)에 도핑시켜 합금화된 박막을 형성함으로써, 기존 타이타늄산화물(TiO2) 박막의 후속 열처리 공정에 의한 표면거칠기 증가 문제가 해소된 고품질의 사중패터닝용 물질을 제공할 수 있다.The present invention forms a alloyed thin film by doping yttrium oxide (Y 2 O 3 ) to titanium oxide (TiO 2 ) using supercycle atomic layer deposition (Supercycle ALD), thereby following the conventional titanium oxide (TiO 2 ) thin film. It is possible to provide a high quality quadruple patterning material in which the problem of increasing the surface roughness by the heat treatment process is solved.
이러한 본 발명은 기존 노광 공정의 한계를 극복하여 반도체 소자의 미세패턴 구현을 가능하게 하여 초집적 반도체 소자의 생산을 가능하게 한다.The present invention overcomes the limitations of the existing exposure process to enable the micropattern implementation of the semiconductor device to enable the production of super-integrated semiconductor devices.
나아가, 본 발명은 모든 반도체 분야에 걸쳐 넓은 활용성을 가지고 있으며, 반도체 소자뿐만 아니라 메모리 분야 등 미세패턴이 필요한 환경에 광범위하게 적용할 수 있는 장점이 있다.Furthermore, the present invention has a wide applicability over all semiconductor fields, and has an advantage that it can be widely applied to an environment requiring a fine pattern such as not only a semiconductor device but also a memory field.
도 1은 사중패터닝의 공정 과정을 개략적으로 보여주는 도면이다.1 is a view schematically showing a process of quadruple patterning.
도 2는 본 발명에 따른 슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용한 다중패터닝용 물질의 제조방법에 관한 공정 요소를 개략적으로 보여주는 도면이다.FIG. 2 is a view schematically illustrating a process element of a method of manufacturing a material for multipatterning using a supercycle ALD according to the present invention.
도 3은 원자층 증착법으로 형성시킨 순수한 타이타늄산화물(TiO2) 박막과 본 발명에 따라 이트륨(Y)이 도핑된 타이타늄산화물(TiO2) 박막의 후속 열처리 전/후, 각각의 표면거칠기 변화를 보여주는 AFM 이미지이다.Figure 3 shows the surface roughness changes before and after the subsequent heat treatment of the pure titanium oxide (TiO 2 ) thin film formed by atomic layer deposition and the yttrium-doped titanium oxide (TiO 2 ) thin film according to the present invention. AFM image.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법은,Method for producing a high quality multi-patterned material through heterogeneous alloying according to the present invention,
슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용한 다중패터닝용(특히, 사중패터닝용) 물질의 제조방법으로서,As a method of manufacturing a material for multi-patterning (particularly for quadruple patterning) using a supercycle ALD,
기판 상에 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 타이타늄산화물(TiO2) 박막을 증착하는 단계를 1~1000회 반복하고, 또한 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 이트륨산화물(Y2O3) 박막을 증착하는 단계를 1~1000회 반복하는 것을 1 슈퍼사이클로 하며,Atomic layer deposition on the substrate, by using a (Atomic layer deposition ALD) titanium oxide (TiO 2) repeated 1 to 1,000 times the step of depositing a thin film, and also the atomic layer deposition method; using (Atomic layer deposition ALD) yttrium Repeating the deposition of the oxide (Y 2 O 3 ) thin film 1 to 1000 times as one supercycle,
상기 1 슈퍼사이클을 1회 이상 수행하여 이트륨산화물(Y2O3)을 타이타늄산화물(TiO2)에 도핑시켜 합금화된 박막을 형성하는 것을 특징으로 한다.By performing one supercycle at least once, yttrium oxide (Y 2 O 3 ) is doped with titanium oxide (TiO 2 ) to form an alloyed thin film.
본 발명에 있어서, 상기 1 슈퍼사이클은 1회의 이트륨산화물(Y2O3) ALD 공정 및 16회의 타이타늄산화물(TiO2) ALD 공정으로 구성되는 것, 즉 이트륨산화물(Y2O3) ALD 공정 및 타이타늄산화물(TiO2) ALD 공정이 1:16의 비율로 실행되는 것이 바람직하다. 이때 1회의 이트륨산화물(Y2O3) ALD 공정을 실행하는 시기는 특별히 제한되지 않으며, 예를 들어 타이타늄산화물(TiO2) ALD 공정을 최초 실행한 뒤, 제2회째 내지 제17회째 ALD 공정 중 어느 하나(예컨대, 마지막 ALD 공정)를 이트륨산화물(Y2O3) ALD 공정으로 실시할 수 있다.In the present invention, the one supercycle is composed of one yttrium oxide (Y 2 O 3 ) ALD process and sixteen titanium oxide (TiO 2 ) ALD processes, that is, yttrium oxide (Y 2 O 3 ) ALD process and that the titanium oxide (TiO 2) ALD process performed at a ratio of 1:16 being preferred. At this time, the time for performing one yttrium oxide (Y 2 O 3 ) ALD process is not particularly limited. For example, after performing the first titanium oxide (TiO 2 ) ALD process, the second to 17th ALD processes are performed. Either (eg, the last ALD process) may be carried out in a yttrium oxide (Y 2 O 3 ) ALD process.
다중패터닝용 물질 박막이 형성되는 상기 기판으로는 원자층 증착 공정에 의한 모폴로지 변화 등 불리한 영향을 받지 않는 내성을 지니면서 그 고유의 특성을 유지할 수 있는 임의의 기판을 사용할 수 있다.As the substrate on which the multi-pattern material thin film is formed, any substrate capable of maintaining its unique characteristics while being resistant to adverse effects such as morphology change by the atomic layer deposition process may be used.
예를 들어, 용도에 따라 실리콘(Si) 기판, 실리카(SiO2) 기판 또는 백금(Pt) 기판 등을 사용할 수 있으며, 반도체 소자용으로는 실리콘(Si) 기판을 사용하는 것이 적합하다.For example, a silicon (Si) substrate, a silica (SiO 2 ) substrate, a platinum (Pt) substrate, or the like may be used depending on the application, and a silicon (Si) substrate is suitable for a semiconductor device.
타이타늄산화물(TiO2)에 도핑되는 물질인 상기 이트륨산화물(Y2O3)은 희토류 산화물의 일종으로서, 타이타늄산화물(TiO2)과 합금을 형성하여 후속 열처리 공정에 의한 타이타늄산화물(TiO2) 박막의 품질 저하(표면거칠기 증가) 문제를 해결함과 동시에, 그 자체로도 열적 안정성, 내열성 및 내구성이 우수한 장점이 있다.The yttrium oxide (Y 2 O 3 ), which is a material doped with titanium oxide (TiO 2 ), is a rare earth oxide, and forms an alloy with titanium oxide (TiO 2 ) to form a titanium oxide (TiO 2 ) thin film by a subsequent heat treatment process. In addition to solving the problem of quality deterioration (surface roughness), the thermal stability, heat resistance and durability are excellent in themselves.
상기 이트륨산화물(Y2O3) ALD 공정의 이트륨 전구체로는 ALD법에 적용될 수 있는 것, 예를 들어 이트륨 금속 원자에 결합된 리간드(Ligand)의 종류에 따라 유기 금속(Metal organic), 할로겐화 금속(Metal halide) 등을 사용할 수 있으며, 바람직하게는 비스-이소프로필사이클로펜타디에닐-디-이소프로필아세트아미디네이트-이트륨(Yerba: Y(iPrCp)2(N-iPr-amd))을 사용한다.The yttrium oxide (Y 2 O 3) ALD as the yttrium precursor of step is that which can be applied to the ALD method, for example, an organic metal, depending on the type of the ligand, (Ligand) coupled to yttrium metal atom (Metal organic), metal halides (Metal halide) and the like, preferably bis-isopropylcyclopentadienyl-di-isopropylacetamidinate-yttrium (Yerba: Y (iPrCp) 2 (N-iPr-amd)) is used. do.
또한, 상기 이트륨산화물(Y2O3) ALD의 단위 공정은 8초 동안의 이트륨 전구체 흡착, 10초 동안의 퍼징, 3초 동안의 반응가스 주입, 및 10초 동안의 퍼징 순으로 진행되는 것일 수 있으나, 단위 공정을 구성하는 각 단계의 실행시간은 필요에 따라 적절히 조절할 수 있다.Further, the yttrium oxide (Y 2 O 3) ALD unit of the process can be ongoing with the purging during the yttrium precursor adsorption for 8 seconds, 10 seconds, the reaction gas inlet for three seconds, and 10 second purge for the net However, the execution time of each step constituting the unit process can be appropriately adjusted as necessary.
상기 타이타늄산화물(TiO2) ALD 공정의 타이타늄 전구체로는 ALD법에 적용될 수 있는 것, 예를 들어 타이타늄 금속 원자에 결합된 기능기의 종류에 따라 유기 금속(Metal organic), 할로겐화 금속(Metal halide) 등을 사용할 수 있으며, 바람직하게는 타이타늄테트라이소프로폭사이드(TTIP: Ti(OC3H7)4)를 사용한다.The titanium precursor of the titanium oxide (TiO 2 ) ALD process may be applied to the ALD method, for example, depending on the type of functional group bonded to the titanium metal atom (metal organic, metal halide) And the like, and preferably titanium tetraisopropoxide (TTIP: Ti (OC 3 H 7 ) 4 ) is used.
또한, 상기 타이타늄산화물(TiO2) ALD의 단위 공정은 2초 동안의 타이타늄 전구체 흡착, 5초 동안의 퍼징, 3초 동안의 반응가스 주입, 및 5초 동안의 퍼징 순으로 진행되는 것일 수 있으나, 단위 공정을 구성하는 각 단계의 실행시간은 필요에 따라 적절히 조절할 수 있다.In addition, the unit process of the titanium oxide (TiO 2 ) ALD may be performed in the order of titanium precursor adsorption for 2 seconds, purging for 5 seconds, injection of reaction gas for 3 seconds, and purging for 5 seconds, The execution time of each step constituting the unit process can be appropriately adjusted as necessary.
상기 이트륨산화물(Y2O3) ALD 공정 및 타이타늄산화물(TiO2) ALD 공정에서 흡착된 금속 전구체와의 반응을 위한 반응가스로는 오존(O3), 산소(O2), 산소(O2) 플라즈마 또는 수증기(H2O) 등을 사용할 수 있으며, 바람직하게는 오존(O3)을 사용한다.Reaction gases for reaction with the metal precursor adsorbed in the yttrium oxide (Y 2 O 3 ) ALD process and titanium oxide (TiO 2 ) ALD process are ozone (O 3 ), oxygen (O 2 ), oxygen (O 2 ) Plasma or water vapor (H 2 O) or the like can be used, preferably ozone (O 3 ) is used.
본 발명에 따른 슈퍼사이클 원자층 증착법(Supercycle ALD)은 기판의 온도를 200℃~400℃로 유지하여 수행할 수 있으며, 예를 들어 200℃의 조건에서 이트륨산화물(Y2O3) ALD 공정 및 타이타늄산화물(TiO2) ALD 공정을 각각 수행할 수 있다.Supercycle atomic layer deposition method (Supercycle ALD) according to the present invention can be carried out by maintaining the temperature of the substrate at 200 ℃ ~ 400 ℃, for example, yttrium oxide (Y 2 O 3 ) ALD process and the conditions of 200 ℃ Titanium oxide (TiO 2 ) ALD process may be performed respectively.
본 발명에서는, 상기 1 슈퍼사이클을 1~1000회 수행하여 원하는 두께의 다중패터닝 물질 박막을 얻을 수 있으며, 바람직하게는 최종 형성되는 합금화 박막의 두께가 15~18 nm 정도가 되도록 슈퍼사이클 실행 횟수를 조절하도록 한다.In the present invention, one supercycle may be performed 1 to 1000 times to obtain a multi-patterned material thin film having a desired thickness. Preferably, the number of supercycle runs is performed so that the thickness of the alloying thin film to be finally formed is about 15 to 18 nm. Adjust it.
일 구체예에서, 본 발명의 슈퍼사이클 원자층 증착법(Supercycle ALD)을 구성하는 이트륨산화물(Y2O3) ALD 공정 및 타이타늄산화물(TiO2) ALD 공정 각각은,In one embodiment, the yttrium oxide (Y 2 O 3 ) ALD process and titanium oxide (TiO 2 ) ALD process constituting the supercycle ALD process of the present invention, respectively,
a) 사이클을 수행하기 전에, 기판으로서 실리콘(Si) 기판을 준비한 후, 기판 상에 형성된 자연 산화막(Native oxide)을 제거한 다음, 소정 온도(예컨대, 200℃)로 가열하고,a) prior to performing the cycle, after preparing a silicon (Si) substrate as a substrate, the native oxide formed on the substrate is removed, and then heated to a predetermined temperature (for example, 200 ℃),
b) 가열된 기판 위로 기화된 금속 전구체를 공급(투여)하여 흡착시키고, 퍼징가스(예컨대, 비활성 기체)를 통해 흡착되지 않은 전구체를 제거하는 단계; 및b) supplying (dosing) the vaporized metal precursor over the heated substrate to adsorb and removing unadsorbed precursor through a purging gas (eg, inert gas); And
c) 금속 전구체가 흡착된 기판 위에 오존(O3)을 접촉(투여) 및 금속 전구체와 반응시켜 금속산화물 박막을 형성하고, 퍼징가스를 통해 오존(O3)을 비롯한 잉여의 화학물질을 제거하는 단계;를 순차적으로 반복하여 수행되는 것일 수 있다.c) contacting (administering) and reacting ozone (O 3 ) with the metal precursor on the substrate to which the metal precursor is adsorbed to form a metal oxide thin film, and removing excess chemicals including ozone (O 3 ) through a purging gas. Step; may be performed by repeating sequentially.
본 발명에 따라 제조된 다중패터닝 물질 박막은 후속 열처리 공정을 거치기 되는데, 본 발명자들은 400℃에서 1시간 동안의 후속 열처리를 수행한 경우, 다중패터닝 물질 박막의 표면거칠기가 증가하지 않고, 오히려 감소하게 됨을 실험을 통해 구체적으로 확인하였다.The multi-patterned material thin film prepared in accordance with the present invention is subjected to a subsequent heat treatment process, the inventors of the present invention when the subsequent heat treatment for 1 hour at 400 ℃, the surface roughness of the multi-patterned material thin film does not increase, but rather reduced It was confirmed specifically through the experiment.
이하, 실시예 및 실험예를 통해 본 발명을 보다 구체적으로 설명한다. 그러나 이들 예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들 예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.
실시예: 고품질 사중패터닝 물질의 제조EXAMPLES Preparation of High Quality Quadruple Patterning Materials
고품질 사중패터닝 물질 제조를 위해, 실리콘 기판 위에서 슈퍼사이클 원자층 증착법을 수행하였다.For the production of high quality quadruple patterning materials, supercycle atomic layer deposition was performed on silicon substrates.
도 2와 같이 이트륨산화물(Y2O3)과 타이타늄산화물(TiO2)을 1:16의 ALD 공정사이클을 1 슈퍼사이클로 하여 200℃에서 증착을 진행하였다.As shown in FIG. 2, yttrium oxide (Y 2 O 3 ) and titanium oxide (TiO 2 ) were deposited at 200 ° C. using an ALD process cycle of 1:16 as one supercycle.
타이타늄산화물(TiO2) ALD 공정은 다음과 같이 수행하였다:Titanium oxide (TiO 2 ) ALD process was performed as follows:
먼저, 실리콘 기판(Si(100) p-type)의 자연 산화막을 제거한 후, 200℃로 가열하였다.First, the native oxide film of the silicon substrate (Si (100) p-type) was removed, and then heated to 200 ° C.
이어서, 가열된 기판 위로 기화된 타이타늄(Ti) 전구체인 TTIP를 캐리어 가스(Ar)와 함께 2초 동안 투여하였다. 이때 캐리어 가스의 유량은 50sccm으로 유지하였다.Subsequently, TTIP, a titanium (Ti) precursor vaporized over the heated substrate, was administered with the carrier gas (Ar) for 2 seconds. At this time, the flow rate of the carrier gas was maintained at 50 sccm.
이어서, 실리콘 기판 위에 물리적 또는 화학적으로 흡착된 타이타늄 전구체를 제외한 잉여 전구체를 아르곤 퍼징가스(Purging gas)를 50sccm의 유량으로 5초 동안 공급하여 제거하였다.Subsequently, the excess precursor except for the titanium precursor physically or chemically adsorbed on the silicon substrate was removed by supplying argon purging gas at a flow rate of 50 sccm for 5 seconds.
이어서, 타이타늄 전구체가 흡착된 기판 위에 오존(O3)을 3초 동안 투여하여 흡착된 타이타늄 전구체를 산화시켜 타이타늄산화물(TiO2) 박막을 성장시켰다.Subsequently, ozone (O 3 ) was administered on the substrate to which the titanium precursor was adsorbed for 3 seconds to oxidize the adsorbed titanium precursor to grow a titanium oxide (TiO 2 ) thin film.
마지막으로, 반응에 참여하지 않고 남은 화학물질을 아르곤 퍼징가스를 50sccm의 유량으로 5초 동안 공급하여 제거하였다.Finally, the chemicals remaining without participating in the reaction were removed by argon purging gas for 5 seconds at a flow rate of 50 sccm.
이러한 공정을 1 사이클로 정하고 16회 반복하여 박막을 형성시켰다.This process was defined as one cycle and repeated 16 times to form a thin film.
이트륨산화물(Y2O3) ALD 공정은 다음과 같이 수행하였다:Yttrium oxide (Y 2 O 3 ) ALD process was performed as follows:
200℃로 가열된 실리콘 기판 위로 기화된 이트륨(Y) 전구체인 Yerba를 캐리어 가스(Ar)와 함께 8초 동안 투여하였다. 이때 캐리어 가스의 유량은 50sccm으로 유지하였다.Yerba, a yttrium (Y) precursor vaporized onto a silicon substrate heated to 200 ° C., was administered for 8 seconds along with the carrier gas (Ar). At this time, the flow rate of the carrier gas was maintained at 50 sccm.
이어서, 실리콘 기판 위에 물리적 또는 화학적으로 흡착된 이트륨 전구체를 제외한 잉여 전구체를 아르곤 퍼징가스(Purging gas)를 50sccm의 유량으로 10초 동안 공급하여 제거하였다.Subsequently, the excess precursor except for the yttrium precursor physically or chemically adsorbed on the silicon substrate was removed by supplying argon purging gas at a flow rate of 50 sccm for 10 seconds.
이어서, 이트륨 전구체가 흡착된 기판 위에 오존(O3)을 3초 동안 투여하여 흡착된 이트륨 전구체를 산화시켜 이트륨산화물(Y2O3) 박막을 성장시켰다.Subsequently, ozone (O 3 ) was administered on the substrate to which the yttrium precursor was adsorbed for 3 seconds to oxidize the adsorbed yttrium precursor to grow a yttrium oxide (Y 2 O 3 ) thin film.
마지막으로, 반응에 참여하지 않고 남은 화학물질을 아르곤 퍼징가스를 50sccm의 유량으로 10초 동안 공급하여 제거하였다.Finally, the chemicals remaining without participating in the reaction were removed by supplying argon purging gas for 10 seconds at a flow rate of 50 sccm.
이러한 공정을 1 사이클로 정하고 1회 실시하여 박막을 형성시켰다.This process was defined as one cycle and carried out once to form a thin film.
상기와 같이 1회의 이트륨산화물(Y2O3) ALD 단위 공정 및 16회의 타이타늄산화물(TiO2) ALD 단위 공정으로 이루어진 1 슈퍼사이클 공정을 반복수행하여 두께 15~18 nm의 박막을 최종적으로 형성하였다.As described above, one supercycle process including one yttrium oxide (Y 2 O 3 ) ALD unit process and sixteen titanium oxide (TiO 2 ) ALD unit processes was repeated to finally form a thin film having a thickness of 15 to 18 nm. .
이어서, 형성된 박막을 퍼니스를 이용하여 질소분위기 하에서 400℃로 1시간 동안 후속 열처리하였다.Subsequently, the formed thin film was subsequently heat treated at 400 ° C. for 1 hour using a furnace.
실험예: 열처리 전/후 표면거칠기 측정Experimental Example: Measurement of Surface Roughness Before and After Heat Treatment
원자층 증착법으로 형성시킨 타이타늄산화물(TiO2) 박막과 이트륨이 도핑된 타이타늄산화물(TiO2) 박막의 표면거칠기(Rq)를 AFM 측정을 통해 비교하였다.The surface roughness (R q ) of the titanium oxide (TiO 2 ) thin film and the yttrium-doped titanium oxide (TiO 2 ) thin film formed by atomic layer deposition was compared by AFM measurement.
도 3과 같이, 순수한 타이타늄산화물(TiO2) 박막의 경우, 열처리 후에 표면거칠기가 1.98Å에서 2.95Å으로 증가하였다.As shown in FIG. 3, in the case of pure titanium oxide (TiO 2 ) thin film, the surface roughness increased from 1.98 kPa to 2.95 kPa after the heat treatment.
반면, 이트륨이 도핑된 타이타늄산화물(TiO2) 박막의 경우, 열처리 후에 표면거칠기가 1.92Å에서 1.53Å으로 20.3%나 감소하였다.On the other hand, in the case of the yttrium-doped titanium oxide (TiO 2 ) thin film, the surface roughness decreased by 20.3% from 1.92 Å to 1.53 Å after heat treatment.
본 발명은 기존 노광 공정의 한계를 극복하여 반도체 소자의 미세패턴 구현을 가능하게 하여 초집적 반도체 소자의 생산을 가능하게 하고, 모든 반도체 분야에 넓은 활용성을 가지고 있으며, 반도체 소자뿐만 아니라 메모리 분야 등 미세패턴이 필요한 환경이라면 폭 넓게 적용이 가능한 기술이다.The present invention enables the production of super-integrated semiconductor devices by overcoming the limitations of the existing exposure process to enable the micro-patterns of semiconductor devices, and has wide applicability in all semiconductor fields. If the environment requires a fine pattern, it can be applied widely.

Claims (14)

  1. 슈퍼사이클 원자층 증착법(Supercycle ALD)을 이용한 다중패터닝용 물질의 제조방법으로서,As a method of manufacturing a material for multi-patterning using Supercycle ALD,
    기판 상에 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 타이타늄산화물(TiO2) 박막을 증착하는 단계를 1~1000회 반복하고, 또한 원자층 증착법(Atomic layer deposition; ALD)을 이용하여 이트륨산화물(Y2O3) 박막을 증착하는 단계를 1~1000회 반복하는 것을 1 슈퍼사이클로 하며,Atomic layer deposition on the substrate, by using a (Atomic layer deposition ALD) titanium oxide (TiO 2) repeated 1 to 1,000 times the step of depositing a thin film, and also the atomic layer deposition method; using (Atomic layer deposition ALD) yttrium Repeating the deposition of the oxide (Y 2 O 3 ) thin film 1 to 1000 times as one supercycle,
    상기 1 슈퍼사이클을 1회 이상 수행하여 이트륨산화물(Y2O3)을 타이타늄산화물(TiO2)에 도핑시켜 합금화된 박막을 형성하는 것을 특징으로 하는,Characterized in that the alloy is formed by doping the yttrium oxide (Y 2 O 3 ) to the titanium oxide (TiO 2 ) by performing one or more supercycles one or more times,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  2. 제1항에 있어서,The method of claim 1,
    제조된 다중패터닝 물질은 사중패터닝(Quadruple patterning)에 사용되는 것을 특징으로 하는,The prepared multipatterning material is characterized in that it is used for quadruple patterning,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  3. 제2항에 있어서,The method of claim 2,
    상기 1 슈퍼사이클은 1회의 이트륨산화물(Y2O3) ALD 공정 및 16회의 타이타늄산화물(TiO2) ALD 공정으로 구성되는 것을 특징으로 하는,The one supercycle is composed of one yttrium oxide (Y 2 O 3 ) ALD process and 16 titanium oxide (TiO 2 ) ALD process,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  4. 제1항에 있어서,The method of claim 1,
    상기 기판으로는 실리콘(Si) 기판을 사용하는 것을 특징으로 하는,As the substrate, characterized in that using a silicon (Si) substrate,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  5. 제3항에 있어서,The method of claim 3,
    상기 이트륨산화물(Y2O3) ALD 공정의 전구체로는 비스-이소프로필사이클로펜타디에닐-디-이소프로필아세트아미디네이트-이트륨(Yerba: Y(iPrCp)2(N-iPr-amd))을 사용하는 것을 특징으로 하는,As a precursor of the yttrium oxide (Y 2 O 3 ) ALD process, bis-isopropylcyclopentadienyl-di-isopropylacetamidinate-yttrium (Yerba: Y (iPrCp) 2 (N-iPr-amd)) Characterized in that using,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  6. 제3항에 있어서,The method of claim 3,
    상기 이트륨산화물(Y2O3) ALD의 단위 공정은 8초 동안의 이트륨 전구체 흡착, 10초 동안의 퍼징, 3초 동안의 반응가스 주입, 및 10초 동안의 퍼징 순으로 진행되는 것을 특징으로 하는,The unit process of the yttrium oxide (Y 2 O 3 ) ALD is carried out in the order of yttrium precursor adsorption for 8 seconds, purging for 10 seconds, injection of reaction gas for 3 seconds, and purging for 10 seconds. ,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  7. 제3항에 있어서,The method of claim 3,
    상기 타이타늄산화물(TiO2) ALD 공정의 전구체로는 타이타늄테트라이소프로폭사이드(TTIP: Ti(OC3H7)4)를 사용하는 것을 특징으로 하는,As a precursor of the titanium oxide (TiO 2 ) ALD process, titanium tetraisopropoxide (TTIP: Ti (OC 3 H 7 ) 4 ) is used.
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  8. 제3항에 있어서,The method of claim 3,
    상기 타이타늄산화물(TiO2) ALD의 단위 공정은 2초 동안의 타이타늄 전구체 흡착, 5초 동안의 퍼징, 3초 동안의 반응가스 주입, 및 5초 동안의 퍼징 순으로 진행되는 것을 특징으로 하는,The unit process of the titanium oxide (TiO 2 ) ALD is characterized in that the titanium precursor adsorbed for 2 seconds, purging for 5 seconds, reaction gas injection for 3 seconds, and purging for 5 seconds,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  9. 제3항에 있어서,The method of claim 3,
    상기 이트륨산화물(Y2O3) ALD 공정 및 타이타늄산화물(TiO2) ALD 공정의 반응가스로는 오존(O3)을 사용하는 것을 특징으로 하는,Characterized in that the reaction gas of the yttrium oxide (Y 2 O 3 ) ALD process and titanium oxide (TiO 2 ) ALD process using ozone (O 3 ),
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  10. 제1항에 있어서,The method of claim 1,
    상기 슈퍼사이클 원자층 증착법(Supercycle ALD)은 200℃에서 수행되는 것을 특징으로 하는,The supercycle atomic layer deposition method (Supercycle ALD) is characterized in that carried out at 200 ℃,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  11. 제1항에 있어서,The method of claim 1,
    상기 1 슈퍼사이클을 1~1000회 수행하여 원하는 두께의 다중패터닝 물질 박막을 얻는 것을 특징으로 하는,Characterized in that to perform the 1 supercycle 1 to 1000 times to obtain a multi-patterned material thin film of a desired thickness,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  12. 제11항에 있어서,The method of claim 11,
    제조된 다중패터닝 물질 박막의 두께는 15~18 nm인 것을 특징으로 하는,The thickness of the prepared multi-patterned material thin film, characterized in that 15 to 18 nm,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  13. 제1항에 있어서,The method of claim 1,
    제조된 다중패터닝 물질 박막에 대해 400℃에서 1시간 동안 후속 열처리를 수행하는 것을 특징으로 하는,It characterized in that the subsequent heat treatment for 1 hour at 400 ℃ for the prepared multi-patterned material thin film,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
  14. 제13항에 있어서,The method of claim 13,
    상기 후속 열처리 후 다중패터닝 물질 박막의 표면거칠기가 1.92Å에서 1.53Å으로 감소하는 것을 특징으로 하는,After the subsequent heat treatment, the surface roughness of the multi-patterned material thin film is characterized in that from 1.92 Å to 1.53 Å,
    이종원소 합금화를 통한 고품질 다중패터닝 물질의 제조방법.Process for the preparation of high quality multi-patterned material through hetero-element alloying.
PCT/KR2017/013109 2017-01-25 2017-11-17 Method for preparing high-quality quadruple-patterning material through alloying of hetero elements WO2018139746A1 (en)

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