CN112779520B - 利用表面保护物质的薄膜形成方法 - Google Patents

利用表面保护物质的薄膜形成方法 Download PDF

Info

Publication number
CN112779520B
CN112779520B CN202011203995.3A CN202011203995A CN112779520B CN 112779520 B CN112779520 B CN 112779520B CN 202011203995 A CN202011203995 A CN 202011203995A CN 112779520 B CN112779520 B CN 112779520B
Authority
CN
China
Prior art keywords
substance
chemical formula
thin film
surface protective
metal precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011203995.3A
Other languages
English (en)
Other versions
CN112779520A (zh
Inventor
李根守
金才玟
金荷娜
崔雄辰
郑恩爱
李东炫
李明洙
文志原
张东学
鲁贤植
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SK Hynix Inc
EGTM Co Ltd
Original Assignee
SK Hynix Inc
EGTM Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SK Hynix Inc, EGTM Co Ltd filed Critical SK Hynix Inc
Publication of CN112779520A publication Critical patent/CN112779520A/zh
Application granted granted Critical
Publication of CN112779520B publication Critical patent/CN112779520B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45561—Gas plumbing upstream of the reaction chamber
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)

Abstract

本发明涉及薄膜形成方法，更详细地涉及利用表面保护物质的薄膜形成方法。根据本发明的一实施例，利用表面保护物质的薄膜形成方法包括：金属前驱体供给步骤，向放置基板的腔体内部供给金属前驱体，将金属前驱体吸附于所述基板；净化所述腔体内部的步骤；及薄膜形成步骤，向所述腔体内部供给反应物质，与被吸附的所述金属前驱体反应并形成薄膜。该方法在所述薄膜形成步骤之前，还包括：供给所述表面保护物质而吸附于所述基板的表面保护物质供给步骤；以及净化所述腔体内部的步骤。

Description

利用表面保护物质的薄膜形成方法
技术领域
本发明涉及薄膜形成方法，更详细地涉及利用表面保护物质的薄膜形成方法。
背景技术
在半导体工艺领域，蒸镀工序是在基板上蒸镀物质的重要的工序，随着电子设备的外形持续缩小且器件的密集度增加，沟槽的纵横比日益增加。因此，台阶覆盖良好的工序受到瞩目，尤其原子层蒸镀(ALD)非常受关注。
原子层沉积(ALD)工序期间，依次向装载基板的工序腔供给反应气体，第一反应气体供给到工序腔并吸附于基板的表面。第二反应气体供给到工序腔，与通过第一种反应气体吸附的物质反应而形成蒸镀物质。
在先技术文献
专利文献
专利文献0001：韩国公开发明专利公报2007-0015958号(2007.02.06.)
发明内容
所要解决的课题
本发明的目的在于，提供一种可形成台阶覆盖良好的薄膜的方法。
本发明的其它目的在于，提供一种可以大幅改善可进行原子层沉积工序的温度范围的薄膜形成方法。
本发明的其它目的将通过下面的详细说明会变得更加清楚。
课题解决方案
根据本发明的一实施例，利用表面保护物质的薄膜形成方法，其特征在于，包括：金属前驱体供给步骤，向放置基板的腔体内部供给金属前驱体，将所述金属前驱体吸附于基板；净化所述腔体内部的步骤；及薄膜形成步骤，向所述腔体内部供给反应物质，与被吸附的所述金属前驱体反应并形成薄膜；该方法在所述薄膜形成步骤之前还包括：供给所述表面保护物质而吸附于所述基板的表面保护物质供给步骤；以及净化所述腔体内部的步骤。
所述表面保护物质可以用下述<化学式1>表示。
<化学式1>
Figure BDA0002756414800000021
所述<化学式1>中，n＝1、2，X＝CH2、0、S、NH，R＝从碳原子数为1至5的烷基中选择。
所述表面保护物质可以用下述<化学式2>表示。
<化学式2>
Figure BDA0002756414800000022
所述<化学式2>中，n＝1、2，X＝CH2、0、S、NH，R＝从碳原子数为1至5的烷基中选择。
所述表面保护物质可以用下述<化学式3>表示。
<化学式3>
Figure BDA0002756414800000031
所述表面保护物质可以用下述<化学式4>表示。
<化学式4>
Figure BDA0002756414800000032
所述反应物质可以是O3、O2、H2O中的某一个。
所述金属前驱体可以是包括以下金属中一个以上的化合物：包括Al的三价金属，包括Zr及Hf的四价金属，包括Nb及Ta的五价金属。
发明效果
根据本发明的一实施例，可以形成台阶覆盖良好的薄膜。表面保护物质在工序进行过程中具有与金属前驱体类似的作用，在高纵横比(例如，40：1以上)的沟槽结构中，在上部(或入口侧)以高密度吸附，在下部(或内部侧)以低密度吸附，在后续工序中妨碍金属前驱体被吸附。因此，可以在沟槽内均匀地吸附金属前驱体。
另外，表面保护物质缓和随温度上升的GPC增加幅度，由此可以增大可进行原子层沉积工序的温度范围(ALD Window：原子层沉积窗口)。
附图说明
图1是简要地表示根据本发明的实施例的薄膜形成方法的流程图。
图2是简要地表示根据本发明的实施例的供给周期的图表。
图3是根据本发明的比较例的按工序温度表示铪氧化膜的GPC的图表。
图4是表示根据本发明的实施例1的表面保护物质的DSC的图表。
图5是根据本发明的比较例及实施例1的按工序温度表示铪氧化膜的GPC的图表。
图6是表示根据本发明的实施例2的表面保护物质的DSC的图表。
图7是根据本发明的比较例及实施例1、2的按工序温度表示铪氧化膜的GPC的图表。
图8是表示本发明的比较例及实施例1、2中随温度增加的GPC增加率的表。
具体实施方式
下面，参考附图1至8更详细地说明本发明的优选实施例。本发明的实施例可以变形为各种形态，本发明的范围不应解释为限定于下面说明的实施例。本实施例是为了向当前发明所属的技术领域中的普通技术人员更详细地说明本发明而提供的。因此，为了强调更清楚的说明，附图中出现的各要素的形状可能夸张显示。
现有的前驱体单独工序，由于在高纵横比(例如40：1)以上的沟槽结构中，上部(或入口侧)的薄膜增厚、且下部(或内部侧)的薄膜变薄等薄膜不均匀情形，存在台阶覆盖不良的问题。
但是，下面说明的表面保护物质具有与金属前驱体相同的作用，在沟槽的上部以比下部高的密度吸附的状态下，妨碍后续工序的金属前驱体被吸附，由此能在沟槽内形成均匀厚度的薄膜。
图1是简要地表示根据本发明的实施例的薄膜形成方法的流程图，图2是简要地表示根据本发明的实施例的供给周期的图表。基板装载到工序腔的内部，调节下面的原子层沉积工序条件。原子层沉积工序条件可以包括基板或工序腔的温度、腔体压力、气体流动率，温度为200至600℃。
基板曝露于供给到腔体内部的表面保护物质，表面保护物质吸附于基板的表面。在工序进行过程中，表面保护物质具有与金属前驱体类似的作用，在高纵横比(例如，40：1以上)的沟槽结构中，在上部(或入口侧)以高密度被吸附，在下部(或内部侧)以低密度被吸附，在后续工序中妨碍金属前驱体被吸附。
表面保护物质可以用下述<化学式1>表示。
<化学式1>
Figure BDA0002756414800000051
所述<化学式1>中，n＝1、2，
X＝CH2、0、S、NH，
R＝从碳原子数为1至5的烷基中选择。
另外，所述表面保护物质可用下述<化学式2>表示。
<化学式2>
Figure BDA0002756414800000052
所述<化学式2>中，n＝1、2，
X＝CH2、0、S、NH，
R＝从碳原子数为1至5的烷基中选择。
另外，更具体地，<化学式1>可以用下述<化学式3>表示。
<化学式3>
Figure BDA0002756414800000061
另外，更具体地，<化学式2>可以用下述<化学式4>表示。
<化学式4>
Figure BDA0002756414800000062
然后，在腔内部供给净化气体(例如，诸如Ar的惰性气体)，去除或净化未吸附表面保护物质或副产物。
然后，基板曝露于供给到腔体内部的金属前驱体，在基板的表面吸附金属前驱体。金属前驱体可以含有诸如Al的三族元素、诸如Zr及Hf的四族元素、诸如Nb及Ta的五族元素。
若举例说明，在沟槽的上部比下部更致密地吸附前面说明的表面保护物质，金属前驱体不能吸附到吸附有表面保护物质的位置。即，过去，金属前驱体在沟槽的上部比下部更致密地吸附而表现出高密度，但是如本实施例，表面保护物质在沟槽的上部致密地吸附而妨碍金属前驱体的吸附，因此金属前驱体不会过度吸附于沟槽的上部，而在沟槽的上部/下部均匀地吸附，可以改善后述的薄膜的台阶覆盖。
接着，在腔体内部供给净化气体(例如，诸如Ar的惰性气体)，去除或净化未吸附金属前驱体或副产物。
然后，基板曝露于供给到腔体内部的反应物质，在基板的表面形成薄膜。反应物质与金属前驱体层反应而形成薄膜，反应物质可以是O3、O2、H2O气体，通过反应物质，可以形成金属氧化膜。这时，反应物质氧化吸附的保护物质，从基板的表面分离去除。
然后，向腔体内部供给净化气体(例如，诸如Ar的惰性气体)，去除或净化未吸附表面保护物质/未反应物质或副产物。
另外，前面说明了表面保护物质在金属前驱体之前供给，但是不同于此，表面保护物质可以在金属前驱体之后供给，或者是在金属前驱体之前及之后全部供给。
——比较例
不使用前面说明的表面保护物质，在硅基板上形成了铪氧化膜。通过原子层沉积工序形成了铪氧化膜，原子层沉积工序温度为300至360℃，反应物质使用了O3气体。
通过原子层沉积工序的铪氧化膜形成过程如下。将下面的过程作为一周期进行。
1)将Ar作为载体气体，在常温下向反应腔供给铪前驱体，在基板吸附铪前驱体。
2)向反应腔内供给Ar气，去除未吸附铪前驱体或副产物。
3)将O3气体供给到反应腔，形成单层。
4)向反应腔内供给Ar气，去除未反应物质或副产物。
图3是根据本发明的比较例的按工序温度表示铪氧化膜的GPC(周期生长率(Gouwth Per Cycle))的图表。如图3所示，到基板的温度320℃为止显示原子层沉积，但是在320～340℃区间GPC增加2.6％，在320℃以上随着基板温度上升显示GPC增加。
——实施例1
使用MTHF(2-Methyl tetrahydrofuran：2-甲基四氢呋喃)作为表面保护物质在硅基板上形成了铪氧化物膜。通过原子层沉积工序形成铪氧化膜，原子层沉积工序温度使用了300至360℃，反应物质使用了O3气体。
基于原子层沉积工序的铪氧化膜形成过程如下。将下列过程作为一周期进行(参考图1及图2)。
1)在反应腔内供给表面保护物质(MTHF)吸附于基板。
2)向反应腔内供给Ar气体，去除未吸附表面保护物质或副产物。
3)将Ar作为载体气体，在常温下将铪前驱体供给到反应腔，在基板吸附铪前驱体。
4)向反应腔内供给Ar气体，去除未吸附铪前驱体或副产物。
5)向反应腔供给O3气体，形成单层。
6)向反应腔内供给Ar气体，去除未反应物质或副产物。
图4是根据本发明的实施例1的表面保护物质的DSC(差示扫描热量分析)的图表。到400℃为止未检测出表面保护物质的分解峰值(上方向)，因此可知即使在高温下使用也不被分解而具有表面保护效果。
图5是根据本发明的比较例及实施例1的按工序温度表示铪氧化膜的GPC的图表。观察320℃～340℃区间，比较例的情况下，GPC增加2.6％，而使用MTHF作为表面保护物质的实施例1的情况下，GPC增加为1.2％，GPC增加幅度减小，到340℃为止显示出原子层沉积窗口变宽的效果。
——实施例2
除了将表面保护物质从MTHF变更为CPME(Cyclopentyl methyl ether：环戊基甲醚)，以与实施例1相同的方法形成了铪氧化膜。
图6是表示根据本发明的实施例2的表面保护物质的DSC(示差扫描热量分析)的图表。到400℃为止未检测出表面保护物质的分解峰值(上方向)，因此可知即使在高温下使用也不被分解而具有表面保护效果。
图7是根据本发明的比较例及实施例1、2的按工序温度表示铪氧化膜的GPC的图表，图8是表示本发明的比较例及实施例1、2中随温度增加的GPC增加率的表。观察320℃～340℃区间，比较例的情况下GPC增加2.6％，而使用MTHF作为表面保护物质的实施例1的情况下，GPC增加1.2％，GPC增加幅度减小，到340℃为止显示出原子层沉积窗口变宽的效果，使用CPME作为表面保护物质的实施例2的情况下，GPC增加0.48％，GPC增加幅度减小，到340℃为止显示出原子层沉积窗口变宽的效果。
作为结论，表面保护物质缓和随温度上升的GPC增加幅度，由此可以增大可进行原子层沉积工序的温度范围。另外，表面保护物质在工序进行中通过与金属前驱体类似的作用，在高纵横比(例如，40：1以上)的沟槽结构中，在上部(或入口侧)以高密度吸附，在下部(或内部侧)以低密度吸附，在后续工序中妨碍金属前驱体被吸附。因此，金属前驱体可以在沟槽内均匀地被吸附。
具体地，若比较基于本发明的比较例及实施例1、2的铪氧化膜的台阶覆盖则如下。可以确认：实施例1、2的情况下，与比较例相比，大幅改善了台阶覆盖。
台阶覆盖(300℃工序)
比较例 84.7
实施例1 89.8
实施例2 88.2
以上通过实施例详细地说明了本发明，但是与此不同形态的实施例也是可以的。因此，下面记载的权利要求的技术思想和范围不限于实施例。

Claims (6)

1.一种利用表面保护物质的薄膜形成方法，其特征在于，包括：
金属前驱体供给步骤，向放置基板的腔体内部供给金属前驱体；
净化所述腔体内部的步骤；及
薄膜形成步骤，向所述腔体内部供给反应物质，与被吸附的所述金属前驱体反应并形成薄膜；
该方法在所述薄膜形成步骤之前还包括：
供给所述表面保护物质的表面保护物质供给步骤；以及
净化所述腔体内部的步骤，
所述表面保护物质用下述<化学式1>或<化学式2>表示：
<化学式1>
Figure FDA0004049181510000011
<化学式2>
Figure FDA0004049181510000012
所述<化学式1>或<化学式2>中，n＝1、2，
X＝CH2、0、S、NH，
R从碳原子数为1至5的烷基中选择。
2.如权利要求1所述的利用表面保护物质的薄膜形成方法，其特征在于，所述表面保护物质是2-甲基四氢呋喃或环戊基甲醚。
3.如权利要求1所述的利用表面保护物质的薄膜形成方法，其特征在于，所述表面保护物质用下述<化学式3>表示：
<化学式3>
Figure FDA0004049181510000021
4.如权利要求1所述的利用表面保护物质的薄膜形成方法，其特征在于，所述表面保护物质用下述<化学式4>表示：
<化学式4>
Figure FDA0004049181510000022
5.如权利要求1所述的利用表面保护物质的薄膜形成方法，其特征在于，所述反应物质为O3、O2、H2O中的某一个。
6.如权利要求1所述的利用表面保护物质的薄膜形成方法，其特征在于，
所述金属前驱体为包括以下金属中一个以上的化合物：包括Al的三价金属，包括Zr及Hf的四价金属，包括Nb及Ta的五价金属。
CN202011203995.3A 2019-11-05 2020-11-02 利用表面保护物质的薄膜形成方法 Active CN112779520B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190140104A KR102095710B1 (ko) 2019-11-05 2019-11-05 표면 보호 물질을 이용한 박막 형성 방법
KR10-2019-0140104 2019-11-05

Publications (2)

Publication Number Publication Date
CN112779520A CN112779520A (zh) 2021-05-11
CN112779520B true CN112779520B (zh) 2023-05-12

Family

ID=70276266

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011203995.3A Active CN112779520B (zh) 2019-11-05 2020-11-02 利用表面保护物质的薄膜形成方法

Country Status (5)

Country Link
US (1) US11591691B2 (zh)
JP (1) JP7036353B2 (zh)
KR (1) KR102095710B1 (zh)
CN (1) CN112779520B (zh)
TW (1) TWI752516B (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102333599B1 (ko) * 2019-11-15 2021-11-30 주식회사 이지티엠 표면 보호 물질을 이용한 박막 형성 방법
KR102224067B1 (ko) 2020-01-09 2021-03-08 주식회사 이지티엠 표면 보호 물질을 이용한 박막 형성 방법
CN112038214A (zh) * 2020-06-19 2020-12-04 中国科学院微电子研究所 一种氧化锆膜及其沉积方法、应用
KR102635125B1 (ko) * 2020-09-01 2024-02-13 에스케이하이닉스 주식회사 증착 억제제 및 이를 이용한 유전막 형성 방법
KR102199999B1 (ko) * 2020-10-08 2021-01-08 주식회사 유진테크 머티리얼즈 표면 보호 물질을 이용한 박막 형성 방법
KR102504146B1 (ko) * 2020-11-23 2023-02-27 주식회사 이지티엠 선택성 부여제를 이용한 영역 선택적 박막 형성 방법
KR102366555B1 (ko) * 2021-01-05 2022-02-23 주식회사 이지티엠 핵성장 지연을 이용한 영역 선택적 박막 형성 방법
KR102614175B1 (ko) * 2021-03-02 2023-12-15 주식회사 이지티엠 선택성 부여제를 이용한 영역 선택적 박막 형성 방법
EP4253595A1 (en) * 2022-02-10 2023-10-04 Soulbrain Co., Ltd. Oxide film reaction surface control agent, method for forming oxide film by using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2023167483A1 (ko) * 2022-03-04 2023-09-07 솔브레인 주식회사 박막 개질 조성물, 이를 이용한 박막 형성 방법, 이로부터 제조된 반도체 기판 및 반도체 소자

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100343144B1 (ko) * 1999-10-06 2002-07-05 윤종용 원자층 증착법을 이용한 박막 형성 방법
US6759325B2 (en) * 2000-05-15 2004-07-06 Asm Microchemistry Oy Sealing porous structures
US7229405B2 (en) 2002-11-15 2007-06-12 Paracor Medical, Inc. Cardiac harness delivery device and method of use
US20100047988A1 (en) * 2008-08-19 2010-02-25 Youn-Joung Cho Methods of forming a layer, methods of forming a gate structure and methods of forming a capacitor
US8871617B2 (en) * 2011-04-22 2014-10-28 Asm Ip Holding B.V. Deposition and reduction of mixed metal oxide thin films
US8592005B2 (en) * 2011-04-26 2013-11-26 Asm Japan K.K. Atomic layer deposition for controlling vertical film growth
CN103103494B (zh) * 2013-01-29 2014-12-24 南京丰强纳米科技有限公司 利用原子层沉积技术在sers基底上制备氧化物表面的方法
KR101521800B1 (ko) * 2013-05-03 2015-05-20 한국화학연구원 황화 니켈 박막의 제조 방법
KR102358566B1 (ko) * 2015-08-04 2022-02-04 삼성전자주식회사 물질막 형성 방법
US10580650B2 (en) * 2016-04-12 2020-03-03 Tokyo Electron Limited Method for bottom-up formation of a film in a recessed feature
WO2017188546A1 (ko) * 2016-04-28 2017-11-02 주식회사 유진테크 머티리얼즈 박막 증착 방법
JP6573575B2 (ja) * 2016-05-02 2019-09-11 東京エレクトロン株式会社 凹部の埋め込み方法
US10468264B2 (en) 2016-07-04 2019-11-05 Samsung Electronics Co., Ltd. Method of fabricating semiconductor device
KR20180063754A (ko) * 2016-12-02 2018-06-12 삼성전자주식회사 주석 화합물, 그의 합성 방법, ald용 주석 전구체 화합물 및 함주석 물질막의 형성 방법
TWI769291B (zh) * 2017-08-11 2022-07-01 日商東京威力科創股份有限公司 使用鹵素去活化之選擇性膜沉積
WO2019088722A1 (ko) * 2017-11-01 2019-05-09 (주)디엔에프 루테늄함유 박막의 제조방법 및 이로부터 제조된 루테늄함유 박막

Also Published As

Publication number Publication date
JP2021077860A (ja) 2021-05-20
US11591691B2 (en) 2023-02-28
TWI752516B (zh) 2022-01-11
US20210130954A1 (en) 2021-05-06
JP7036353B2 (ja) 2022-03-15
KR102095710B1 (ko) 2020-04-01
CN112779520A (zh) 2021-05-11
TW202118890A (zh) 2021-05-16

Similar Documents

Publication Publication Date Title
CN112779520B (zh) 利用表面保护物质的薄膜形成方法
US9837281B2 (en) Cyclic doped aluminum nitride deposition
US9816180B2 (en) Selective deposition
US8329569B2 (en) Deposition of ruthenium or ruthenium dioxide
US9382270B2 (en) Substituted silacyclopropane precursors and their use for the deposition of silicon-containing films
CN114729450A (zh) 利用表面保护物质的薄膜形成方法
US11555044B2 (en) Thin-film forming raw material for use in atomic layer deposition method, thin-film forming raw material, method for producing thin-film, and compound
US20200263297A1 (en) Deposition of oxides and nitrides
TWI805171B (zh) 選擇性形成薄膜的方法
WO2017203775A1 (ja) 薄膜形成用原料及び薄膜の製造方法
KR20150078776A (ko) 코발트 함유 박막의 제조방법 및 이에 따라 제조된 코발트 함유 박막
CN116113724A (zh) 用选择剂形成区域选择性薄膜的方法
WO2018088078A1 (ja) 化合物、薄膜形成用原料、原子層堆積法用の薄膜形成用原料及び薄膜の製造方法
WO2019097768A1 (ja) ルテニウム化合物、薄膜形成用原料及び薄膜の製造方法
KR102224067B1 (ko) 표면 보호 물질을 이용한 박막 형성 방법
US20240060177A1 (en) Indium compound, thin-film forming raw material, thin film, and method of producing same
US11999756B2 (en) Method for producing organometallic compound and thin film fabricated using organometallic compound obtained thereby
WO2021200218A1 (ja) 原子層堆積法用薄膜形成用原料及び薄膜の製造方法
KR20210087808A (ko) 표면 보호 물질을 이용한 물질막 형성 방법
CN118064870A (zh) 利用化学净化物质的薄膜形成方法
JP2022090148A (ja) 原子層エッチング法用エッチング材料
KR20160062675A (ko) 신규 니켈-비스베타케토이미네이트 전구체 및 이를 이용한 니켈 함유 필름 증착방법

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 304, 3-507, Xinyuan Road, Lingtong District, Shuiyuan City, Gyeonggi do, Korea

Applicant after: EGTM Co.,Ltd.

Applicant after: Sk Hynix Inc.

Address before: 304, 3-507, Xinyuan Road, Lingtong District, Shuiyuan City, Gyeonggi do, Korea

Applicant before: EUGENETECH MATERIALS Co.,Ltd.

Applicant before: Sk Hynix Inc.

GR01 Patent grant
GR01 Patent grant