WO2017188546A1 - Thin-film deposition method - Google Patents

Thin-film deposition method Download PDF

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WO2017188546A1
WO2017188546A1 PCT/KR2016/014887 KR2016014887W WO2017188546A1 WO 2017188546 A1 WO2017188546 A1 WO 2017188546A1 KR 2016014887 W KR2016014887 W KR 2016014887W WO 2017188546 A1 WO2017188546 A1 WO 2017188546A1
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formula
metal element
thin film
compound represented
precursor
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French (fr)
Korean (ko)
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이근수
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주식회사 유진테크 머티리얼즈
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • H—ELECTRICITY
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    • 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
    • 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
    • H01L21/02205—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 the layer being characterised by the precursor material for deposition
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67739—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations into and out of processing chamber

Definitions

  • the present invention relates to a thin film deposition method, and more particularly, to a thin film deposition method capable of effectively depositing a thin film containing a metal element by atomic layer deposition.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • An object of the present invention is to provide a thin film deposition method that can effectively deposit a thin film containing a metal element by atomic layer deposition.
  • the ligand replacement compound may substitute a ligand of a precursor including the metal element adsorbed on the substrate in the first adsorption step by a nucleophilic substitution reaction.
  • the ligand substitution compound may be a compound represented by ⁇ Formula 1>.
  • the ligand substitution compound is supplied to the reactor as a compound represented by ⁇ Formula 2>, and the compound represented by ⁇ Formula 2> is thermally decomposed into a compound represented by ⁇ Formula 1> to include the metal element
  • the ligand of the precursor can be substituted.
  • the ligand substitution compound may be a compound represented by the following ⁇ Formula 3>.
  • R is any one selected from C 1 to C 5 linear or branched alkyl group.
  • the ligand substitution compound may be a compound represented by the following ⁇ Formula 5>.
  • R a to R e are each independently selected from hydrogen (H), C 1 to C 5 , linear, branched or cyclic alkyl groups.
  • the ligand substitution compound represented by ⁇ Formula 5> may be a compound represented by the following ⁇ Formula 6>.
  • the ligand substitution compound represented by ⁇ Formula 5> may be a compound represented by the following ⁇ Formula 7>.
  • the precursor including the metal element may be any one of a precursor including titanium, a precursor including zirconium, or a precursor including hafnium.
  • the precursor including the metal element may be a compound represented by the following ⁇ Formula 8>.
  • R 1 and R 2 are each selected from C 1 to C 5 linear or branched alkyl groups.
  • the precursor including the metal element may be a compound represented by the following ⁇ Formula 9>.
  • R 3 and R 4 are each selected from a linear or branched alkyl group of C 1 to C 5 , and n is an integer of any one selected from 0, 1, and 2.
  • the precursor including the metal element may be a compound represented by the following ⁇ Formula 10>.
  • the thin film deposition method may further include an ozone supplying step of supplying a gas containing ozone to the deposition chamber after the second adsorption step.
  • the thin film deposition method may be performed in a plurality of cycles by configuring the first adsorption step, the substitution step, the second adsorption step, and the ozone supply step.
  • a compound for ligand substitution of the precursor is supplied to replace the ligand of the precursor, and then the precursor is selectively supplied onto the substrate.
  • the deposition density of can be effectively increased.
  • Thin film deposition method according to an embodiment of the present invention can be implemented without changing the design of the conventional atomic layer deposition equipment, it is possible to effectively reduce the cost according to the design cost of the atomic layer deposition equipment.
  • FIG. 1 is a view schematically showing an example in which a zirconium precursor is adsorbed on an oxide film on which a passivation film is formed.
  • FIG. 2 is a view schematically showing a flow chart of a thin film deposition method according to an embodiment of the present invention.
  • 3 to 5 are schematic views showing a thin film deposition method according to an embodiment of the present invention.
  • the present invention relates to a thin film deposition method, it will be described embodiments of the present invention using the formula and drawings attached below.
  • the embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.
  • FIG. 1 is a view schematically showing an example in which a zirconium precursor is adsorbed on an oxide film on which a passivation film is formed.
  • the passivation film P is formed on the substrate W, thereby forming an oxygen-hydrogen (O-H) bond on the surface of the oxide film.
  • O-H oxygen-hydrogen
  • ALD atomic layer deposition
  • (b) of FIG. 1 illustrates an example of a covering effect.
  • the zirconium precursor represented by the following ⁇ Formula 10> is adsorbed on the surface of the oxide film by atomic layer deposition (ALD), it is already applied to the oxide film.
  • ALD atomic layer deposition
  • the phenomenon (A) in which the zirconium precursor is not adsorbed by the adsorbed zirconium precursor to the neighboring adsorption position occurs. That is, since the zirconium precursor is not uniformly adsorbed on the oxide film, the step coverage of the deposited film is inferior.
  • a method of increasing the supply time of the zirconium precursor may be considered. However, as the process time becomes too long, the productivity may decrease. Accordingly, the present invention is to provide a thin film deposition method that can ensure the step coverage of the deposited film and at the same time ensure the deposition efficiency.
  • FIG. 2 is a view schematically showing a flow chart of a thin film deposition method according to an embodiment of the present invention.
  • the ligand replacement compound is supplied to the deposition chamber to the ligand of the precursor containing the metal element adsorbed on the substrate in the first adsorption step (S200)
  • Substituting (S300) to replace and supplying the precursor containing the metal element to the deposition chamber to selectively adsorb the precursor containing the metal element to the adsorption position on the substrate is not adsorbed in the first adsorption step (S200)
  • a second adsorption step (S400) is included.
  • the first adsorption step (S200), the substitution step (S300), the second adsorption step (S400), and the ozone supplying step (S500) include one cycle (Cycle). It can be configured and carried out, it is possible to repeatedly perform a plurality of cycles so that a thin film containing a metal element is deposited in a layer.
  • the oxide film of the present invention may be a silicon oxide film (SiO 2 ) or a titanium oxide film (TiO 2 ), but is not limited thereto, and may include all oxide films used for fabricating a semiconductor device.
  • the precursor including the metal element of the present invention may be one of a precursor including titanium (Ti), a precursor including zirconium (Zr), or a precursor including hafnium (Hf), but is not necessarily limited thereto.
  • ZAC zirconium precursor represented by the following Chemical Formula 9 is described as an example of a precursor including a metal element for convenience of description, but the precursor including the metal element of the present invention is necessarily limited thereto. It is not.
  • the precursor including the metal element of the present invention may be a compound represented by the following ⁇ Formula 8>.
  • R 1 and R 2 are each selected from C 1 to C 5 linear or branched alkyl groups.
  • the precursor including the metal element of the present invention may be a compound represented by the following ⁇ Formula 9>.
  • R 3 and R 4 are each selected from a linear or branched alkyl group of C 1 to C 5 , and n is an integer of any one selected from 0, 1, and 2.
  • the precursor including the metal element of the present invention may be a compound represented by the following ⁇ Formula 10>.
  • FIG 3 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
  • the zirconium precursor (ZAC) is supplied to adsorb the zirconium precursor (ZAC) on the substrate.
  • a cyclopentadiene (Cyclopentadiene) represented by ⁇ Formula 1> may be supplied onto a substrate as a ligand substitution compound.
  • the cyclopentadiene represented by ⁇ Formula 1> may be supplied by thermal decomposition from dicyclopentadiene (Dicyclopentadiene) represented by the following ⁇ Formula 2>, the temperature inside the reactor for pyrolysis to about 170 °C or more Can be maintained.
  • Dicyclopentadiene dicyclopentadiene
  • 3 (a) is a view showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S100) is replaced with cyclopentadiene in the substitution step (S200). That is, it can be seen that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with cyclopentadiene by a nucleophilic substitution reaction.
  • 3 (b) shows that the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is adsorbed at a position (B) where the zirconium precursor (ZAC) is not adsorbed on the oxide film in the first adsorption step (S200).
  • the ligand of the zirconium precursor (ZAC) is substituted with cyclopentadiene in the substitution step (S300), and the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is adsorbed in the first adsorption step (S200). It is not bound to the zirconium precursor (ZAC), but may be selectively adsorbed at position (B).
  • FIG. 3 (c) is a diagram schematically illustrating the formation of an oxygen-hydrogen bond by supplying a gas including ozone (O 3 ) on a substrate that has undergone the second adsorption step (S400).
  • FIG. 4 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
  • the compound represented by the following ⁇ Formula 3> as a compound for ligand replacement in the substitution step (S300) can be supplied.
  • the compound for ligand substitution represented by ⁇ Formula 3> may be a compound represented by the following ⁇ Formula 4>.
  • FIG. 4 (a) is a diagram showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S200) is replaced with the compound represented by the above ⁇ Formula 3> in the substitution step (S300). . That is, it can be confirmed that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with the compound represented by the above ⁇ Formula 3> by a nucleophilic substitution reaction.
  • FIG. 4B illustrates that the zirconium precursor ZAC supplied from the second adsorption step S400 is adsorbed at a position C in which the zirconium precursor ZAC is not adsorbed on the oxide film in the first adsorption step S200.
  • the ligand of the zirconium precursor (ZAC) in the substitution step (S300) is substituted with the compound represented by the above ⁇ Formula 3> bar
  • the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is the first adsorption step It may not be bonded to the zirconium precursor (ZAC) adsorbed in (S200), it may be selectively adsorbed in position (C).
  • Figure 4 (c) is a diagram schematically showing the formation of an oxygen-hydrogen bond by supplying a gas containing ozone (O 3 ) on the substrate passed through the second adsorption step (S400).
  • FIG. 5 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
  • the compound represented by the following ⁇ Formula 5> as a compound for ligand replacement in the substitution step (S300) can be supplied.
  • R a to R e are each independently selected from hydrogen (H), C 1 to C 5 , linear, branched or cyclic alkyl groups.
  • the ligand substitution compound represented by ⁇ Formula 5> may be a compound represented by the following ⁇ Formula 6> or ⁇ Formula 7>.
  • 5 (a) is a view showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S200) is replaced with the compound represented by the above formula (6) in the substitution step (S300). . That is, it can be confirmed that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with the compound represented by the above ⁇ Formula 6> by a nucleophilic substitution reaction.
  • FIG. 5B illustrates that the zirconium precursor ZAC supplied from the second adsorption step S400 is adsorbed at a position D in which the zirconium precursor ZAC is not adsorbed on the oxide film in the first adsorption step S200.
  • the ligand of the zirconium precursor (ZAC) in the substitution step (S300) is substituted with the compound represented by the above ⁇ Formula 6> bar
  • the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is the first adsorption step It is not bonded to the zirconium precursor (ZAC) adsorbed in (S200), it may be selectively adsorbed in the position (D).
  • FIG. 5C is a diagram schematically illustrating the formation of an oxygen-hydrogen bond by supplying a gas including ozone (O 3 ) on a substrate that has undergone the second adsorption step (S400).
  • a compound for ligand substitution of the precursor is supplied to replace the ligand of the precursor, and then the precursor is selectively supplied onto the substrate.
  • the deposition density of can be effectively increased.
  • the thin film deposition method according to an embodiment of the present invention can be implemented without changing the design of the conventional atomic layer deposition equipment, it is possible to effectively reduce the cost according to the design cost of the atomic layer deposition equipment.

Abstract

A thin-film deposition method according to an embodiment of the present invention, that deposits a thin-film including a metal element on a substrate using atomic layer deposition (ALD), comprises: a substrate supply step of supplying a substrate having an oxide film in which a passivation film is formed to a deposition chamber; a first adhesion step of supplying a precursor including a metal element to the deposition chamber so as to adhere the precursor including a metal element onto the oxide film; a substitution step of supplying a compound for ligand substitution to the deposition chamber so as to substitute a ligand of the precursor including a metal element adhered in the first adhesion step; a second adhesion step of supplying the precursor including a metal element to the deposition chamber so as to selectively adhere the precursor including a metal element onto the oxide film; and an ozone supply step of supplying gas including ozone to the deposition chamber, wherein the first adhesion step, the substitution step, the second adhesion step and the ozone supply step form a cycle, and are performed in a plurality of cycles.

Description

박막 증착 방법Thin film deposition method
본 발명은 박막 증착 방법에 관한 것이며, 상세하게는 원자층 증착에 의해 금속원소를 포함하는 박막을 효과적으로 증착할 수 있는 박막 증착 방법에 관한 것이다. The present invention relates to a thin film deposition method, and more particularly, to a thin film deposition method capable of effectively depositing a thin film containing a metal element by atomic layer deposition.
기판상에 박막을 증착하기 위한 방법으로는 물리적 기상 증착(Physical Vapor Deposition, PVD), 화학적 기상(Chemical Vapor Deposition, CVD), 원자층 증착(Atomic Layer Deposition, ALD)이 일반적으로 이용된다. 원자층 증착 방법(ALD)은 화학적 반응을 이용하여 원자를 기판위에 순차적으로 쌓아 올리는 박막 증착 기술로서, 반응물질을 시간적으로 분리하여 공급하므로 증착 정밀성을 효과적으로 확보할 수 있다.As a method for depositing a thin film on a substrate, physical vapor deposition (PVD), chemical vapor deposition (CVD), and atomic layer deposition (ALD) are generally used. Atomic layer deposition method (ALD) is a thin film deposition technique that sequentially stacks atoms on a substrate using a chemical reaction. Since the reactants are separated and supplied in time, deposition precision can be effectively secured.
본 발명의 목적은 원자층 증착에 의해 금속원소를 포함하는 박막을 효과적으로 증착할 수 있는 박막 증착 방법을 제공하는 데 있다.An object of the present invention is to provide a thin film deposition method that can effectively deposit a thin film containing a metal element by atomic layer deposition.
본 발명의 또 다른 목적들은 다음의 상세한 설명과 도면으로부터 보다 명확해질 것이다.Still other objects of the present invention will become more apparent from the following detailed description and drawings.
본 발명의 일 실시예에 의한 원자층 증착(ALD)에 의해 기판상에 금속원소를 포함하는 박막을 증착하는 박막 증착 방법은, 페시베이션막이 형성된 산화막을 구비하는 상기 기판을 증착 챔버에 공급하는 기판공급단계; 상기 증착 챔버에 금속원소를 포함하는 전구체를 공급하여 상기 산화막 상에 상기 금속원소를 포함하는 전구체를 흡착시키는 제1 흡착단계; 상기 증착 챔버에 리간드 치환용 화합물을 공급하여 상기 제1 흡착단계에서 흡착된 상기 금속원소를 포함하는 전구체의 리간드를 치환시키는 치환단계; 및 상기 증착 챔버에 상기 금속원소를 포함하는 전구체를 공급하여 상기 산화막 상에 상기 금속원소를 포함하는 전구체를 선택적으로 흡착시키는 제2 흡착단계를 포함한다.In the thin film deposition method of depositing a thin film containing a metal element on a substrate by atomic layer deposition (ALD) according to an embodiment of the present invention, a substrate for supplying the substrate having an oxide film formed with a passivation film to the deposition chamber Feeding step; A first adsorption step of supplying a precursor including a metal element to the deposition chamber to adsorb the precursor including the metal element onto the oxide film; A substitution step of supplying a compound for ligand replacement to the deposition chamber to substitute a ligand of a precursor including the metal element adsorbed in the first adsorption step; And a second adsorption step of supplying a precursor including the metal element to the deposition chamber to selectively adsorb the precursor including the metal element on the oxide film.
상기 리간드 치환용 화합물은 친핵성 치환반응에 의해 상기 제1 흡착단계에서 상기 기판상에 흡착된 상기 금속원소를 포함하는 전구체의 리간드를 치환시킬 수 있다.The ligand replacement compound may substitute a ligand of a precursor including the metal element adsorbed on the substrate in the first adsorption step by a nucleophilic substitution reaction.
상기 리간드 치환용 화합물은 하기의 <화학식 1>로 표시되는 화합물일 수 있다.The ligand substitution compound may be a compound represented by <Formula 1>.
<화학식 1><Formula 1>
Figure PCTKR2016014887-appb-I000001
Figure PCTKR2016014887-appb-I000001
상기 리간드 치환용 화합물은 하기의 <화학식 2>로 표시되는 화합물로 상기 반응기에 공급되며, 상기 <화학식 2>로 표시되는 화합물은 상기 <화학식 1>로 표시되는 화합물로 열분해되어 상기 금속원소를 포함하는 전구체의 리간드를 치환시킬 수 있다. The ligand substitution compound is supplied to the reactor as a compound represented by <Formula 2>, and the compound represented by <Formula 2> is thermally decomposed into a compound represented by <Formula 1> to include the metal element The ligand of the precursor can be substituted.
<화학식 2><Formula 2>
Figure PCTKR2016014887-appb-I000002
Figure PCTKR2016014887-appb-I000002
상기 리간드 치환용 화합물은 하기의 <화학식 3>으로 표시되는 화합물일 수 있다.The ligand substitution compound may be a compound represented by the following <Formula 3>.
<화학식 3><Formula 3>
Figure PCTKR2016014887-appb-I000003
Figure PCTKR2016014887-appb-I000003
상기 <화학식 3>에서 R은 C1 내지 C5의 선형 또는 가지형 알킬기 중에서 선택된 어느 하나이다.In <Formula 3>, R is any one selected from C 1 to C 5 linear or branched alkyl group.
상기 리간드 치환용 화합물은 하기의 <화학식 5>로 표시되는 화합물일 수 있다.The ligand substitution compound may be a compound represented by the following <Formula 5>.
<화학식 5><Formula 5>
Figure PCTKR2016014887-appb-I000004
Figure PCTKR2016014887-appb-I000004
상기 <화학식 5>에서 Ra 내지 Re는 각각 독립적으로 수소(H), C1 내지 C5의 선형, 가지형 또는 고리형 알킬기 중에서 선택된 어느 하나이다.In Formula 5, R a to R e are each independently selected from hydrogen (H), C 1 to C 5 , linear, branched or cyclic alkyl groups.
상기 <화학식 5>로 표시되는 리간드 치환용 화합물은 하기의 <화학식 6>으로 표시되는 화합물일 수 있다.The ligand substitution compound represented by <Formula 5> may be a compound represented by the following <Formula 6>.
<화학식 6><Formula 6>
Figure PCTKR2016014887-appb-I000005
Figure PCTKR2016014887-appb-I000005
상기 <화학식 5>로 표시되는 리간드 치환용 화합물은 하기의 <화학식 7>로 표시되는 화합물일 수 있다.The ligand substitution compound represented by <Formula 5> may be a compound represented by the following <Formula 7>.
<화학식 7><Formula 7>
Figure PCTKR2016014887-appb-I000006
Figure PCTKR2016014887-appb-I000006
상기 금속원소를 포함하는 전구체는 티타늄을 포함하는 전구체, 지르코늄을 포함하는 전구체 또는 하프늄을 포함하는 전구체 중의 어느 하나일 수 있다.The precursor including the metal element may be any one of a precursor including titanium, a precursor including zirconium, or a precursor including hafnium.
상기 금속원소를 포함하는 전구체는 하기의 <화학식 8>로 표시되는 화합물일 수 있다.The precursor including the metal element may be a compound represented by the following <Formula 8>.
<화학식 8><Formula 8>
Figure PCTKR2016014887-appb-I000007
Figure PCTKR2016014887-appb-I000007
상기 <화학식 8>에서 상기 R1 및 R2는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이다.In <Formula 8>, R 1 and R 2 are each selected from C 1 to C 5 linear or branched alkyl groups.
상기 금속원소를 포함하는 전구체는 하기의 <화학식 9>로 표시되는 화합물일 수 있다.The precursor including the metal element may be a compound represented by the following <Formula 9>.
<화학식 9><Formula 9>
Figure PCTKR2016014887-appb-I000008
Figure PCTKR2016014887-appb-I000008
상기 <화학식 9>에서 상기 R3 및 R4는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이며, n은 0, 1 및 2 중에서 선택된 어느 하나의 정수이다.In Formula <9>, R 3 and R 4 are each selected from a linear or branched alkyl group of C 1 to C 5 , and n is an integer of any one selected from 0, 1, and 2.
상기 금속원소를 포함하는 전구체는 하기의 <화학식 10>으로 표시되는 화합물일 수 있다.The precursor including the metal element may be a compound represented by the following <Formula 10>.
<화학식 10><Formula 10>
Figure PCTKR2016014887-appb-I000009
Figure PCTKR2016014887-appb-I000009
상기 박막 증착 방법은 상기 제2 흡착단계 이후에 오존을 포함하는 가스를 상기 증착 챔버에 공급하는 오존공급단계를 더 포함할 수 있다.The thin film deposition method may further include an ozone supplying step of supplying a gas containing ozone to the deposition chamber after the second adsorption step.
상기 박막 증착 방법은, 상기 제1 흡착단계, 상기 치환단계, 상기 제2 흡착단계 및 상기 오존공급단계를 주기로 구성하여 복수의 주기로 수행될 수 있다.The thin film deposition method may be performed in a plurality of cycles by configuring the first adsorption step, the substitution step, the second adsorption step, and the ozone supply step.
본 발명의 일 실시예에 의한 박막 증착 방법은, 기판상에 전구체를 공급한 후 전구체의 리간드 치환용 화합물을 공급하여 전구체의 리간드를 치환하고, 다시 기판상에 선택적으로 전구체를 공급하는바, 박막의 증착 밀도를 효과적으로 높일 수 있다. In the method of depositing a thin film according to an embodiment of the present invention, after supplying a precursor onto a substrate, a compound for ligand substitution of the precursor is supplied to replace the ligand of the precursor, and then the precursor is selectively supplied onto the substrate. The deposition density of can be effectively increased.
본 발명의 일 실시예에 의한 박막 증착 방법은 종래의 원자층 증착 설비의 설계 변경 없이 구현 가능한바, 원자층 증착 설비의 설계 비용에 따르는 비용을 효과적으로 저감할 수 있다.Thin film deposition method according to an embodiment of the present invention can be implemented without changing the design of the conventional atomic layer deposition equipment, it is possible to effectively reduce the cost according to the design cost of the atomic layer deposition equipment.
도 1은 페시베이션막이 형성된 산화막에 지르코늄 전구체가 흡착된 일 예를 개략적으로 나타낸 도면이다.1 is a view schematically showing an example in which a zirconium precursor is adsorbed on an oxide film on which a passivation film is formed.
도 2는 본 발명의 일 실시예에 의한 박막 증착 방법의 플로우 차트를 개략적으로 나타낸 도면이다.2 is a view schematically showing a flow chart of a thin film deposition method according to an embodiment of the present invention.
도 3 내지 도 5는 본 발명의 일 실시예에 의한 박막 증착 방법을 개략적으로 나타낸 도면이다.3 to 5 are schematic views showing a thin film deposition method according to an embodiment of the present invention.
본 발명은 박막 증착 방법에 관한 것으로, 이하에 첨부된 화학식 및 도면을 이용하여 본 발명의 실시예들을 설명하고자 한다. 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 설명하는 실시예들에 한정되는 것으로 해석되어서는 안된다.The present invention relates to a thin film deposition method, it will be described embodiments of the present invention using the formula and drawings attached below. The embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.
도 1은 페시베이션막이 형성된 산화막에 지르코늄 전구체가 흡착된 일 예를 개략적으로 나타낸 도면이다.1 is a view schematically showing an example in which a zirconium precursor is adsorbed on an oxide film on which a passivation film is formed.
도 1의 (a)에 도시된 바와 같이, 기판(W) 상에 페시베이션막(P)이 성됨으로써 산화막의 표면에는 산소-수소(O-H) 결합이 형성된다. 원자층 증착(ALD)에 의해 페시베이션막이 형성된 산화막의 표면에 전구체를 흡착시키는 경우, 산화막에 기 흡착된 전구체에 의해 이웃하는 흡착위치에 전구체가 흡착되는 것을 방해하는 가리움 효과(screening effect)가 발생한다.As shown in FIG. 1A, the passivation film P is formed on the substrate W, thereby forming an oxygen-hydrogen (O-H) bond on the surface of the oxide film. When the precursor is adsorbed on the surface of the oxide film on which the passivation film is formed by atomic layer deposition (ALD), a screening effect occurs that prevents the precursor from adsorbing to a neighboring adsorption position by the precursor adsorbed on the oxide film. do.
즉, 도 1의 (b)는 가리움 효과의 일 예를 도시한 것으로, 산화막의 표면에 하기의 <화학식 10>으로 표시되는 지르코늄 전구체를 원자층 증착(ALD)에 의해 흡착시키는 경우, 이미 산화막에 흡착된 지르코늄 전구체에 의해 이웃하는 흡착위치에 지르코늄 전구체가 흡착되지 않는 현상(A)이 발생하게 된다. 즉, 지르코늄 전구체가 산화막 상에 균일하게 흡착되지 않으므로, 증착막의 스텝커버리지(step coverage)가 열위해진다. 우수한 증착막의 스텝커버리지를 얻기 위해서 지르코늄 전구체의 공급 시간을 늘리는 방안을 고려할 수 있으나, 지나치게 공정 시간이 길어짐에 따라 생산성이 떨어지는 문제가 발생할 수 있다. 따라서, 본 발명은 증착막의 스텝커버리지를 확보함과 동시에 증착 효율을 확보할 수 있는 박막 증착 방법을 제공하고자 한다.That is, (b) of FIG. 1 illustrates an example of a covering effect. When the zirconium precursor represented by the following <Formula 10> is adsorbed on the surface of the oxide film by atomic layer deposition (ALD), it is already applied to the oxide film. The phenomenon (A) in which the zirconium precursor is not adsorbed by the adsorbed zirconium precursor to the neighboring adsorption position occurs. That is, since the zirconium precursor is not uniformly adsorbed on the oxide film, the step coverage of the deposited film is inferior. In order to obtain excellent step coverage of the deposited film, a method of increasing the supply time of the zirconium precursor may be considered. However, as the process time becomes too long, the productivity may decrease. Accordingly, the present invention is to provide a thin film deposition method that can ensure the step coverage of the deposited film and at the same time ensure the deposition efficiency.
<화학식 10><Formula 10>
Figure PCTKR2016014887-appb-I000010
Figure PCTKR2016014887-appb-I000010
도 2는 본 발명의 일 실시예에 의한 박막 증착 방법의 플로우 차트를 개략적으로 나타낸 도면이다.2 is a view schematically showing a flow chart of a thin film deposition method according to an embodiment of the present invention.
도 2에 도시된 바와 같이, 본 발명의 일 실시예에 의한 박막 증착 방법은 증착 챔버에 기판을 공급하는 기판공급단계(S100), 증착 챔버에 금속원소를 포함하는 전구체를 공급하여 기판의 산화막 상에 금속원소를 포함하는 전구체를 흡착시키는 제1 흡착단계(S200), 증착 챔버에 리간드 치환용 화합물을 공급하여 제1 흡착단계(S200)에서 기판상에 흡착된 금속원소를 포함하는 전구체의 리간드를 치환시키는 치환단계(S300) 및 증착 챔버에 금속원소를 포함하는 전구체를 다시 공급하여 제1 흡착단계(S200)에서 전구체가 흡착되지 않은 기판상의 흡착위치에 금속원소를 포함하는 전구체를 선택적으로 흡착시키는 제2 흡착단계(S400)를 포함한다. 본 발명의 일 실시예에 의한 박막 증착 방법은, 제2 흡착단계(S400) 이후에 기판상에 오존(O3)을 포함하는 가스를 공급하여 산소-수소 결합을 형성하는 오존공급단계(S500)를 더 포함할 수 있다.As shown in FIG. 2, in the thin film deposition method according to the exemplary embodiment of the present invention, a substrate supplying step of supplying a substrate to a deposition chamber (S100), and supplying a precursor including a metal element to the deposition chamber to form an oxide layer on the substrate. In the first adsorption step (S200) for adsorbing the precursor containing the metal element to the supply, the ligand replacement compound is supplied to the deposition chamber to the ligand of the precursor containing the metal element adsorbed on the substrate in the first adsorption step (S200) Substituting (S300) to replace and supplying the precursor containing the metal element to the deposition chamber to selectively adsorb the precursor containing the metal element to the adsorption position on the substrate is not adsorbed in the first adsorption step (S200) A second adsorption step (S400) is included. In the thin film deposition method according to an embodiment of the present invention, an ozone supplying step (S500) of forming an oxygen-hydrogen bond by supplying a gas containing ozone (O 3 ) on a substrate after the second adsorption step (S400). It may further include.
또한, 본 발명의 일 실시예에 의한 박막 증착 방법은 제1 흡착단계(S200), 치환단계(S300), 제2 흡착단계(S400) 및 오존공급단계(S500)가 하나의 주기(Cycle)를 구성하여 실시될 수 있으며, 복수의 주기를 반복 실시하여 금속원소를 포함하는 박막이 층을 이루어 증착되도록 할 수 있다.In addition, in the thin film deposition method according to an embodiment of the present invention, the first adsorption step (S200), the substitution step (S300), the second adsorption step (S400), and the ozone supplying step (S500) include one cycle (Cycle). It can be configured and carried out, it is possible to repeatedly perform a plurality of cycles so that a thin film containing a metal element is deposited in a layer.
본 발명의 산화막은 실리콘 산화막(SiO2) 또는 티타늄 산화막(TiO2)일 수 있으나, 반드시 이에 국한되는 것은 아니며, 반도체 소자의 제작에 이용되는 모든 산화막을 포함할 수 있다. 본 발명의 금속원소를 포함하는 전구체는 티타늄(Ti)을 포함하는 전구체, 지르코늄(Zr)을 포함하는 전구체 또는 하프늄(Hf)을 포함하는 전구체 중의 하나일 수 있으나, 반드시 이들에 국한되는 것은 아니다. 또한, 이하에서는 설명의 편의를 위해 하기의 <화학식 9>로 표시되는 지르코늄 전구체(ZAC)를 금속원소를 포함하는 전구체의 일 예로 설명하나, 본 발명의 금속원소를 포함하는 전구체가 반드시 이에 국한되는 것은 아니다.The oxide film of the present invention may be a silicon oxide film (SiO 2 ) or a titanium oxide film (TiO 2 ), but is not limited thereto, and may include all oxide films used for fabricating a semiconductor device. The precursor including the metal element of the present invention may be one of a precursor including titanium (Ti), a precursor including zirconium (Zr), or a precursor including hafnium (Hf), but is not necessarily limited thereto. In addition, hereinafter, the zirconium precursor (ZAC) represented by the following Chemical Formula 9 is described as an example of a precursor including a metal element for convenience of description, but the precursor including the metal element of the present invention is necessarily limited thereto. It is not.
본 발명의 금속원소를 포함하는 전구체는 하기의 <화학식 8>로 표시되는 화합물일 수 있다. The precursor including the metal element of the present invention may be a compound represented by the following <Formula 8>.
<화학식 8><Formula 8>
Figure PCTKR2016014887-appb-I000011
Figure PCTKR2016014887-appb-I000011
상기 <화학식 8>에서 상기 R1 및 R2는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이다.In <Formula 8>, R 1 and R 2 are each selected from C 1 to C 5 linear or branched alkyl groups.
본 발명의 금속원소를 포함하는 전구체는 하기의 <화학식 9>로 표시되는 화합물일 수 있다.The precursor including the metal element of the present invention may be a compound represented by the following <Formula 9>.
<화학식 9><Formula 9>
Figure PCTKR2016014887-appb-I000012
Figure PCTKR2016014887-appb-I000012
상기 <화학식 9>에서 상기 R3 및 R4는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이며, n은 0, 1 및 2 중에서 선택된 어느 하나의 정수이다.In Formula <9>, R 3 and R 4 are each selected from a linear or branched alkyl group of C 1 to C 5 , and n is an integer of any one selected from 0, 1, and 2.
또한, 본 발명의 금속원소를 포함하는 전구체는 하기의 <화학식 10>으로 표시되는 화합물일 수 있다.In addition, the precursor including the metal element of the present invention may be a compound represented by the following <Formula 10>.
<화학식 10><Formula 10>
Figure PCTKR2016014887-appb-I000013
Figure PCTKR2016014887-appb-I000013
도 3은 본 발명의 일 실시예에 의한 박막 증착 방법을 개략적으로 나타낸 도면이다.3 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
제1 흡착단계(S100)에서 지르코늄 전구체(ZAC)를 공급하여 기판상에 지르코늄 전구체(ZAC)를 흡착시킨다. 치환단계(S200)에서는 리간드 치환용 화합물로 하기의 <화학식 1>로 표시되는 사이클로펜타디엔(Cyclopentadiene)을 기판상으로 공급할 수 있다. In the first adsorption step (S100), the zirconium precursor (ZAC) is supplied to adsorb the zirconium precursor (ZAC) on the substrate. In the substitution step (S200), a cyclopentadiene (Cyclopentadiene) represented by <Formula 1> may be supplied onto a substrate as a ligand substitution compound.
<화학식 1><Formula 1>
Figure PCTKR2016014887-appb-I000014
Figure PCTKR2016014887-appb-I000014
상기의 <화학식 1>로 표시되는 사이클로펜타디엔은 하기의 <화학식 2>로 표시되는 다이사이클로펜타디엔(Dicyclopentadiene)으로부터 열분해되어 공급될 수 있으며, 열분해를 위해 반응기 내부의 온도는 약 170℃ 이상으로 유지될 수 있다.The cyclopentadiene represented by <Formula 1> may be supplied by thermal decomposition from dicyclopentadiene (Dicyclopentadiene) represented by the following <Formula 2>, the temperature inside the reactor for pyrolysis to about 170 ℃ or more Can be maintained.
<화학식 2><Formula 2>
Figure PCTKR2016014887-appb-I000015
Figure PCTKR2016014887-appb-I000015
도 3의 (a)는 제1 흡착단계(S100)에서 산화막 상에 흡착된 지르코늄 전구체(ZAC)의 리간드가 치환단계(S200)에서 사이클로펜타디엔으로 치환되는 것을 나타낸 도면이다. 즉, NH2로 구성되는 지르코늄 전구체(ZAC)의 리간드는 친핵성 치환반응에 의해 사이클로펜타디엔으로 치환되는 것을 확인할 수 있다.3 (a) is a view showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S100) is replaced with cyclopentadiene in the substitution step (S200). That is, it can be seen that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with cyclopentadiene by a nucleophilic substitution reaction.
도 3의 (b)는 제1 흡착단계(S200)에서 산화막 상에 지르코늄 전구체(ZAC)가 흡착되지 않은 위치(B)에 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)가 흡착된 것을 개략적으로 나타낸 도면이다. 즉, 치환단계(S300)에서 지르코늄 전구체(ZAC)의 리간드가 사이클로펜타디엔으로 치환되는바, 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)는 제1 흡착단계(S200)에서 흡착된 지르코늄 전구체(ZAC)에 결합되지 않고, 위치(B)에 선택적으로 흡착될 수 있다. 3 (b) shows that the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is adsorbed at a position (B) where the zirconium precursor (ZAC) is not adsorbed on the oxide film in the first adsorption step (S200). It is a figure which shows schematically. That is, the ligand of the zirconium precursor (ZAC) is substituted with cyclopentadiene in the substitution step (S300), and the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is adsorbed in the first adsorption step (S200). It is not bound to the zirconium precursor (ZAC), but may be selectively adsorbed at position (B).
도 3의 (c)는 제2 흡착단계(S400)를 거친 기판상에 오존(O3)을 포함하는 가스를 공급하여 산소-수소 결합을 형성한 것을 개략적으로 나타낸 도면이다. FIG. 3 (c) is a diagram schematically illustrating the formation of an oxygen-hydrogen bond by supplying a gas including ozone (O 3 ) on a substrate that has undergone the second adsorption step (S400).
도 4는 본 발명의 일 실시예에 의한 박막 증착 방법을 개략적으로 나타낸 도면이다.4 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
제1 흡착단계(S200)에서 지르코늄 전구체(ZAC)를 공급하여 기판상에 지르코늄 전구체(ZAC)를 흡착시킨 후, 치환단계(S300)에서 리간드 치환용 화합물로 하기의 <화학식 3>으로 표시되는 화합물을 공급할 수 있다. After adsorbing a zirconium precursor (ZAC) on the substrate by supplying a zirconium precursor (ZAC) in the first adsorption step (S200), the compound represented by the following <Formula 3> as a compound for ligand replacement in the substitution step (S300) Can be supplied.
<화학식 3><Formula 3>
Figure PCTKR2016014887-appb-I000016
Figure PCTKR2016014887-appb-I000016
C1 내지 C5의 선형 또는 가지형 알킬기 중에서 선택된 어느 하나이며, 상기 <화학식 3>으로 표시되는 리간드 치환용 화합물은 하기의 <화학식 4>로 표시되는 화합물일 수 있다.Any one selected from a linear or branched alkyl group of C 1 to C 5 , the compound for ligand substitution represented by <Formula 3> may be a compound represented by the following <Formula 4>.
<화학식 4><Formula 4>
Figure PCTKR2016014887-appb-I000017
Figure PCTKR2016014887-appb-I000017
도 4의 (a)는 제1 흡착단계(S200)에서 산화막 상에 흡착된 지르코늄 전구체(ZAC)의 리간드가 치환단계(S300)에서 상기 <화학식 3>으로 표시되는 화합물로 치환되는 것을 나타낸 도면이다. 즉, NH2로 구성되는 지르코늄 전구체(ZAC)의 리간드는 친핵성 치환반응에 의해 상기 <화학식 3>으로 표시되는 화합물로 치환되는 것을 확인할 수 있다.4 (a) is a diagram showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S200) is replaced with the compound represented by the above <Formula 3> in the substitution step (S300). . That is, it can be confirmed that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with the compound represented by the above <Formula 3> by a nucleophilic substitution reaction.
도 4의 (b)는 제1 흡착단계(S200)에서 산화막 상에 지르코늄 전구체(ZAC)가 흡착되지 않은 위치(C)에 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)가 흡착된 것을 개략적으로 나타낸 도면이다. 즉, 치환단계(S300)에서 지르코늄 전구체(ZAC)의 리간드가 상기 <화학식 3>으로 표시되는 화합물로 치환되는바, 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)는 제1 흡착단계(S200)에서 흡착된 지르코늄 전구체(ZAC)에 결합되지 않고, 위치(C)에 선택적으로 흡착될 수 있다. 4B illustrates that the zirconium precursor ZAC supplied from the second adsorption step S400 is adsorbed at a position C in which the zirconium precursor ZAC is not adsorbed on the oxide film in the first adsorption step S200. It is a figure which shows schematically. That is, the ligand of the zirconium precursor (ZAC) in the substitution step (S300) is substituted with the compound represented by the above <Formula 3> bar, the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is the first adsorption step It may not be bonded to the zirconium precursor (ZAC) adsorbed in (S200), it may be selectively adsorbed in position (C).
도 4의 (c)는 제2 흡착단계(S400)를 거친 기판상에 오존(O3)을 포함하는 가스를 공급하여 산소-수소 결합을 형성한 것을 개략적으로 나타낸 도면이다. Figure 4 (c) is a diagram schematically showing the formation of an oxygen-hydrogen bond by supplying a gas containing ozone (O 3 ) on the substrate passed through the second adsorption step (S400).
도 5는 본 발명의 일 실시예에 의한 박막 증착 방법을 개략적으로 나타낸 도면이다.5 is a view schematically showing a thin film deposition method according to an embodiment of the present invention.
제1 흡착단계(S200)에서 지르코늄 전구체(ZAC)를 공급하여 기판상에 지르코늄 전구체(ZAC)를 흡착시킨 후, 치환단계(S300)에서 리간드 치환용 화합물로 하기의 <화학식 5>로 표시되는 화합물을 공급할 수 있다. After adsorbing a zirconium precursor (ZAC) on a substrate by supplying a zirconium precursor (ZAC) in the first adsorption step (S200), the compound represented by the following <Formula 5> as a compound for ligand replacement in the substitution step (S300) Can be supplied.
<화학식 5><Formula 5>
Figure PCTKR2016014887-appb-I000018
Figure PCTKR2016014887-appb-I000018
상기 <화학식 5>에서 Ra 내지 Re는 각각 독립적으로 수소(H), C1 내지 C5의 선형, 가지형 또는 고리형 알킬기 중에서 선택된 어느 하나이다. 또한, 상기 <화학식 5>로 표시되는 리간드 치환용 화합물은 하기의 <화학식 6> 또는 <화학식 7>로 표시되는 화합물일 수 있다.In Formula 5, R a to R e are each independently selected from hydrogen (H), C 1 to C 5 , linear, branched or cyclic alkyl groups. In addition, the ligand substitution compound represented by <Formula 5> may be a compound represented by the following <Formula 6> or <Formula 7>.
<화학식 6><Formula 6>
Figure PCTKR2016014887-appb-I000019
Figure PCTKR2016014887-appb-I000019
<화학식 7><Formula 7>
Figure PCTKR2016014887-appb-I000020
Figure PCTKR2016014887-appb-I000020
도 5의 (a)는 제1 흡착단계(S200)에서 산화막 상에 흡착된 지르코늄 전구체(ZAC)의 리간드가 치환단계(S300)에서 상기 <화학식 6>으로 표시되는 화합물로 치환되는 것을 나타낸 도면이다. 즉, NH2로 구성되는 지르코늄 전구체(ZAC)의 리간드는 친핵성 치환반응에 의해 상기 <화학식 6>으로 표시되는 화합물로 치환되는 것을 확인할 수 있다.5 (a) is a view showing that the ligand of the zirconium precursor (ZAC) adsorbed on the oxide film in the first adsorption step (S200) is replaced with the compound represented by the above formula (6) in the substitution step (S300). . That is, it can be confirmed that the ligand of the zirconium precursor (ZAC) composed of NH 2 is substituted with the compound represented by the above <Formula 6> by a nucleophilic substitution reaction.
도 5의 (b)는 제1 흡착단계(S200)에서 산화막 상에 지르코늄 전구체(ZAC)가 흡착되지 않은 위치(D)에 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)가 흡착된 것을 개략적으로 나타낸 도면이다. 즉, 치환단계(S300)에서 지르코늄 전구체(ZAC)의 리간드가 상기 <화학식 6>으로 표시되는 화합물로 치환되는바, 제2 흡착단계(S400)에서 공급된 지르코늄 전구체(ZAC)는 제1 흡착단계(S200)에서 흡착된 지르코늄 전구체(ZAC)에 결합되지 않고, 위치(D)에 선택적으로 흡착될 수 있다. 5B illustrates that the zirconium precursor ZAC supplied from the second adsorption step S400 is adsorbed at a position D in which the zirconium precursor ZAC is not adsorbed on the oxide film in the first adsorption step S200. It is a figure which shows schematically. That is, the ligand of the zirconium precursor (ZAC) in the substitution step (S300) is substituted with the compound represented by the above <Formula 6> bar, the zirconium precursor (ZAC) supplied in the second adsorption step (S400) is the first adsorption step It is not bonded to the zirconium precursor (ZAC) adsorbed in (S200), it may be selectively adsorbed in the position (D).
도 5의 (c)는 제2 흡착단계(S400)를 거친 기판상에 오존(O3)을 포함하는 가스를 공급하여 산소-수소 결합을 형성한 것을 개략적으로 나타낸 도면이다. FIG. 5C is a diagram schematically illustrating the formation of an oxygen-hydrogen bond by supplying a gas including ozone (O 3 ) on a substrate that has undergone the second adsorption step (S400).
본 발명의 일 실시예에 의한 박막 증착 방법은, 기판상에 전구체를 공급한 후 전구체의 리간드 치환용 화합물을 공급하여 전구체의 리간드를 치환하고, 다시 기판상에 선택적으로 전구체를 공급하는바, 박막의 증착 밀도를 효과적으로 높일 수 있다. 또한, 본 발명의 일 실시예에 의한 박막 증착 방법은 종래의 원자층 증착 설비의 설계 변경 없이 구현 가능한바, 원자층 증착 설비의 설계 비용에 따르는 비용을 효과적으로 저감할 수 있다.In the method of depositing a thin film according to an embodiment of the present invention, after supplying a precursor onto a substrate, a compound for ligand substitution of the precursor is supplied to replace the ligand of the precursor, and then the precursor is selectively supplied onto the substrate. The deposition density of can be effectively increased. In addition, the thin film deposition method according to an embodiment of the present invention can be implemented without changing the design of the conventional atomic layer deposition equipment, it is possible to effectively reduce the cost according to the design cost of the atomic layer deposition equipment.
이상에서 본 발명을 실시예를 통하여 상세하게 설명하였으나, 이와 다른 형태의 실시예들도 가능하다. 그러므로, 이하에 기재된 청구항들의 기술적 사상과 범위는 실시예들에 한정되지 않는다.Although the present invention has been described in detail through the embodiments, other forms of embodiments are possible. Therefore, the spirit and scope of the claims set forth below are not limited to the embodiments.

Claims (14)

  1. 원자층 증착(ALD)에 의해 기판상에 금속원소를 포함하는 박막을 증착하는 박막 증착 방법에 있어서,A thin film deposition method for depositing a thin film containing a metal element on a substrate by atomic layer deposition (ALD),
    페시베이션막이 형성된 산화막을 구비하는 상기 기판을 증착 챔버에 공급하는 기판공급단계;A substrate supplying step of supplying the substrate having an oxide film having a passivation film formed thereon to a deposition chamber;
    상기 증착 챔버에 금속원소를 포함하는 전구체를 공급하여 상기 산화막 상에 상기 금속원소를 포함하는 전구체를 흡착시키는 제1 흡착단계;A first adsorption step of supplying a precursor including a metal element to the deposition chamber to adsorb the precursor including the metal element onto the oxide film;
    상기 증착 챔버에 리간드 치환용 화합물을 공급하여 상기 제1 흡착단계에서 흡착된 상기 금속원소를 포함하는 전구체의 리간드를 치환시키는 치환단계; 및A substitution step of supplying a compound for ligand replacement to the deposition chamber to substitute a ligand of a precursor including the metal element adsorbed in the first adsorption step; And
    상기 증착 챔버에 상기 금속원소를 포함하는 전구체를 공급하여 상기 산화막 상에 상기 금속원소를 포함하는 전구체를 선택적으로 흡착시키는 제2 흡착단계를 포함하는, 박막 증착 방법.And a second adsorption step of selectively adsorbing the precursor including the metal element on the oxide layer by supplying a precursor including the metal element to the deposition chamber.
  2. 제1항에 있어서,The method of claim 1,
    상기 리간드 치환용 화합물은 친핵성 치환반응에 의해 상기 제1 흡착단계에서 상기 기판상에 흡착된 상기 금속원소를 포함하는 전구체의 리간드를 치환시키는, 박막 증착 방법The ligand substitution compound is a thin film deposition method for replacing the ligand of the precursor containing the metal element adsorbed on the substrate in the first adsorption step by nucleophilic substitution reaction
  3. 제2항에 있어서,The method of claim 2,
    상기 리간드 치환용 화합물은 하기의 <화학식 1>로 표시되는 화합물인, 박막 증착 방법.The ligand substitution compound is a compound represented by <Formula 1>, a thin film deposition method.
    <화학식 1><Formula 1>
    Figure PCTKR2016014887-appb-I000021
    Figure PCTKR2016014887-appb-I000021
  4. 제3항에 있어서,The method of claim 3,
    상기 리간드 치환용 화합물은 하기의 <화학식 2>로 표시되는 화합물로 상기 반응기에 공급되며,The ligand substitution compound is supplied to the reactor as a compound represented by the following <Formula 2>,
    상기 <화학식 2>로 표시되는 화합물은 상기 <화학식 1>로 표시되는 화합물로 열분해되어 상기 금속원소를 포함하는 전구체의 리간드를 치환시키는, 박막 증착 방법. The compound represented by <Formula 2> is pyrolyzed into a compound represented by the <Formula 1> to replace the ligand of the precursor containing the metal element, thin film deposition method.
    <화학식 2><Formula 2>
    Figure PCTKR2016014887-appb-I000022
    Figure PCTKR2016014887-appb-I000022
  5. 제2항에 있어서,The method of claim 2,
    상기 리간드 치환용 화합물은 하기의 <화학식 3>으로 표시되는 화합물인, 박막 증착 방법.The ligand substitution compound is a compound represented by <Formula 3>, a thin film deposition method.
    <화학식 3><Formula 3>
    Figure PCTKR2016014887-appb-I000023
    Figure PCTKR2016014887-appb-I000023
    상기 <화학식 3>에서 R은 C1 내지 C5의 선형 또는 가지형 알킬기 중에서 선택된 어느 하나이다.In <Formula 3>, R is any one selected from C 1 to C 5 linear or branched alkyl group.
  6. 제2항에 있어서,The method of claim 2,
    상기 리간드 치환용 화합물은 하기의 <화학식 5>로 표시되는 화합물인, 박막 증착 방법.The ligand substitution compound is a compound represented by the following formula (5), a thin film deposition method.
    <화학식 5><Formula 5>
    Figure PCTKR2016014887-appb-I000024
    Figure PCTKR2016014887-appb-I000024
    상기 <화학식 5>에서 Ra 내지 Re는 각각 독립적으로 수소(H), C1 내지 C5의 선형, 가지형 또는 고리형 알킬기 중에서 선택된 어느 하나이다.In Formula 5, R a to R e are each independently selected from hydrogen (H), C 1 to C 5 , linear, branched or cyclic alkyl groups.
  7. 제6항에 있어서,The method of claim 6,
    상기 <화학식 5>로 표시되는 리간드 치환용 화합물은 하기의 <화학식 6>으로 표시되는 화합물인, 박막 증착 방법.The ligand substitution compound represented by <Formula 5> is a compound represented by the following <Formula 6>, a thin film deposition method.
    <화학식 6><Formula 6>
    Figure PCTKR2016014887-appb-I000025
    Figure PCTKR2016014887-appb-I000025
  8. 제6항에 있어서,The method of claim 6,
    상기 <화학식 5>로 표시되는 리간드 치환용 화합물은 하기의 <화학식 7>로 표시되는 화합물인, 박막 증착 방법.The ligand substitution compound represented by <Formula 5> is a compound represented by the following <Formula 7>, thin film deposition method.
    <화학식 7><Formula 7>
    Figure PCTKR2016014887-appb-I000026
    Figure PCTKR2016014887-appb-I000026
  9. 제1항에 있어서,The method of claim 1,
    상기 금속원소를 포함하는 전구체는 티타늄을 포함하는 전구체, 지르코늄을 포함하는 전구체 또는 하프늄을 포함하는 전구체 중의 어느 하나인, 박막 증착 방법.The precursor including the metal element is any one of a precursor containing titanium, a precursor containing zirconium or a precursor containing hafnium.
  10. 제9항에 있어서,The method of claim 9,
    상기 금속원소를 포함하는 전구체는 하기의 <화학식 8>로 표시되는 화합물인, 박막 증착 방법.The precursor containing the metal element is a compound represented by the following formula (8), a thin film deposition method.
    <화학식 8><Formula 8>
    Figure PCTKR2016014887-appb-I000027
    Figure PCTKR2016014887-appb-I000027
    상기 <화학식 8>에서 상기 R1 및 R2는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이다.In the <Formula 8> wherein R 1 and R 2 is any one selected from a linear or branched alkyl group of C 1 to C 5, respectively.
  11. 제9항에 있어서,The method of claim 9,
    상기 금속원소를 포함하는 전구체는 하기의 <화학식 9>로 표시되는 화합물인, 박막 증착 방법.The precursor including the metal element is a compound represented by the following formula (9), a thin film deposition method.
    <화학식 9><Formula 9>
    Figure PCTKR2016014887-appb-I000028
    Figure PCTKR2016014887-appb-I000028
    상기 <화학식 9>에서 상기 R3 및 R4는 각각 C1 내지 C5의 선형 또는 가지형의 알킬기 중에서 선택된 어느 하나이며, n은 0, 1 및 2 중에서 선택된 어느 하나의 정수이다.In Formula <9>, R 3 and R 4 are each selected from a linear or branched alkyl group of C 1 to C 5 , and n is an integer of any one selected from 0, 1, and 2.
  12. 제9항에 있어서,The method of claim 9,
    상기 금속원소를 포함하는 전구체는 하기의 <화학식 10>으로 표시되는 화합물인, 박막 증착 방법.The precursor including the metal element is a compound represented by the following formula (10), a thin film deposition method.
    <화학식 10><Formula 10>
    Figure PCTKR2016014887-appb-I000029
    Figure PCTKR2016014887-appb-I000029
  13. 제1항에 있어서,The method of claim 1,
    상기 박막 증착 방법은 상기 제2 흡착단계 이후에 오존을 포함하는 가스를 상기 증착 챔버에 공급하는 오존공급단계를 더 포함하는, 박막 증착 방법.The thin film deposition method further comprises an ozone supplying step of supplying a gas containing ozone to the deposition chamber after the second adsorption step.
  14. 제13항에 있어서,The method of claim 13,
    상기 박막 증착 방법은,The thin film deposition method,
    상기 제1 흡착단계, 상기 치환단계, 상기 제2 흡착단계 및 상기 오존공급단계를 주기로 구성하여 복수의 주기로 수행되는, 박막 증착 방법.And the first adsorption step, the substitution step, the second adsorption step, and the ozone supply step are performed in a plurality of cycles.
PCT/KR2016/014887 2016-04-28 2016-12-19 Thin-film deposition method WO2017188546A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112779520A (en) * 2019-11-05 2021-05-11 有进科技材料股份有限公司 Method for forming thin film using surface protective material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021137595A1 (en) * 2020-01-03 2021-07-08 주식회사 유진테크 머티리얼즈 Method for forming material film using surface protection material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100008314A (en) * 2008-07-15 2010-01-25 최정길 An automatic rivet insertion machine equipment for clamp body
KR20100072021A (en) * 2007-09-14 2010-06-29 시그마-알드리치컴퍼니 Methods of preparing thin films by atomic layer deposition using monocyclopentadienyl trialkoxy hafnium and zirconium precursors
KR20150117179A (en) * 2014-04-09 2015-10-19 주식회사 유진테크 머티리얼즈 Novel precursor compounds for forming zirconium-containing film, compositions for forming zirconium-containing film comprising the same, and method of forming zirconium-containing film using them as precursors
KR101598485B1 (en) * 2014-06-20 2016-02-29 주식회사 유진테크 머티리얼즈 Precursor compositions and Method for forming a thin film using thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100072021A (en) * 2007-09-14 2010-06-29 시그마-알드리치컴퍼니 Methods of preparing thin films by atomic layer deposition using monocyclopentadienyl trialkoxy hafnium and zirconium precursors
KR20100008314A (en) * 2008-07-15 2010-01-25 최정길 An automatic rivet insertion machine equipment for clamp body
KR20150117179A (en) * 2014-04-09 2015-10-19 주식회사 유진테크 머티리얼즈 Novel precursor compounds for forming zirconium-containing film, compositions for forming zirconium-containing film comprising the same, and method of forming zirconium-containing film using them as precursors
KR101598485B1 (en) * 2014-06-20 2016-02-29 주식회사 유진테크 머티리얼즈 Precursor compositions and Method for forming a thin film using thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PARK, TAE JOO ET AL.: "Improved Growth and Electrical Properties of Atomic- Layer-Deposited Metal-Oxide Film by Discrete Feeding Method of Metal Precursor", CHEMISTRY OF MATERIALS, vol. 23, no. 7, March 2011 (2011-03-01), pages 1654 - 1658, XP055434856 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112779520A (en) * 2019-11-05 2021-05-11 有进科技材料股份有限公司 Method for forming thin film using surface protective material
TWI752516B (en) * 2019-11-05 2022-01-11 南韓商優吉尼科技材料股份有限公司 Methods of forming a thin film using a surface protection material
US11591691B2 (en) 2019-11-05 2023-02-28 Egtm Co., Ltd. Method of forming a thin film using a surface protection material

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