WO2018139746A1 - Procédé de préparation d'un matériau de formation de motif quadruple de haute qualité par alliage d'hétéroéléments - Google Patents

Procédé de préparation d'un matériau de formation de motif quadruple de haute qualité par alliage d'hétéroéléments 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
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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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  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'un matériau de formation de motif quadruple de haute qualité par l'alliage d'hétéroéléments et, plus spécifiquement, un procédé capable de produire un matériau de formation de motif quadruple de haute qualité en résolvant le problème d'une augmentation de la rugosité de surface, provoquée par un processus de traitement thermique ultérieur d'un film mince d'oxyde de titane (TiO2) classique, en utilisant un dépôt de couche atomique (ALD) à supercycle de manière à doper de l'oxyde d'yttrium (Y2O3) dans l'oxyde de titane (TiO2) et allier celui-ci.
PCT/KR2017/013109 2017-01-25 2017-11-17 Procédé de préparation d'un matériau de formation de motif quadruple de haute qualité par alliage d'hétéroéléments WO2018139746A1 (fr)

Applications Claiming Priority (2)

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KR1020170011978A KR101900181B1 (ko) 2017-01-25 2017-01-25 이종원소 합금화를 통한 고품질 사중패터닝 물질의 제조방법
KR10-2017-0011978 2017-01-25

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WO2018139746A1 true WO2018139746A1 (fr) 2018-08-02

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KR102666160B1 (ko) * 2022-09-16 2024-05-13 에스케이트리켐 주식회사 이트륨 또는 스칸듐 함유 박막 형성용 전구체, 이를 이용한 이트륨 또는 스칸듐 함유 박막 형성 방법 및 상기 이트륨 또는 스칸듐 함유 박막을 포함하는 반도체 소자.

Citations (5)

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US20030040196A1 (en) * 2001-08-27 2003-02-27 Lim Jung Wook Method of forming insulation layer in semiconductor devices for controlling the composition and the doping concentration
US20110203085A1 (en) * 2009-06-30 2011-08-25 Intermolecular, Inc. Titanium-based high-k dielectric films
KR20120012319A (ko) * 2010-07-30 2012-02-09 영남대학교 산학협력단 원자층 증착법에 의한 박막 형성 방법, 이를 포함하는 반도체 소자의 배선 및 그 제조 방법
KR20120075397A (ko) * 2010-12-28 2012-07-06 에이에스엠 저펜 가부시기가이샤 템플레이트 위에 금속 산화물 하드마스크를 형성시키는 방법
KR20150053253A (ko) * 2013-11-07 2015-05-15 노벨러스 시스템즈, 인코포레이티드 진보된 패터닝을 위한 소프트 랜딩 나노적층물들

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013089727A1 (fr) 2011-12-15 2013-06-20 Intel Corporation Procédés pour le traçage de motifs doubles, tripes et quadruples à exposition simple autoaligné

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030040196A1 (en) * 2001-08-27 2003-02-27 Lim Jung Wook Method of forming insulation layer in semiconductor devices for controlling the composition and the doping concentration
US20110203085A1 (en) * 2009-06-30 2011-08-25 Intermolecular, Inc. Titanium-based high-k dielectric films
KR20120012319A (ko) * 2010-07-30 2012-02-09 영남대학교 산학협력단 원자층 증착법에 의한 박막 형성 방법, 이를 포함하는 반도체 소자의 배선 및 그 제조 방법
KR20120075397A (ko) * 2010-12-28 2012-07-06 에이에스엠 저펜 가부시기가이샤 템플레이트 위에 금속 산화물 하드마스크를 형성시키는 방법
KR20150053253A (ko) * 2013-11-07 2015-05-15 노벨러스 시스템즈, 인코포레이티드 진보된 패터닝을 위한 소프트 랜딩 나노적층물들

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KR20180087665A (ko) 2018-08-02

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