CN104561937B - 原子层沉积制备具有固体润滑作用的ws2薄膜方法 - Google Patents

原子层沉积制备具有固体润滑作用的ws2薄膜方法 Download PDF

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CN104561937B
CN104561937B CN201510005822.3A CN201510005822A CN104561937B CN 104561937 B CN104561937 B CN 104561937B CN 201510005822 A CN201510005822 A CN 201510005822A CN 104561937 B CN104561937 B CN 104561937B
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tungsten
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CN104561937A (zh
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何丹农
卢静
李争
尹桂林
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • 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]
    • 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
    • C23C16/305—Sulfides, selenides, or tellurides

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

本发明涉及一种原子层沉积制备具有固体润滑作用的WS2薄膜方法，将经严格清洗的基底放入ALD腔内，使用六羰基钨(W(CO)6)固体钨源和H2S气体硫源制备WS2薄膜。原子层沉积系统腔内沉积温度应加热到300‑400℃的沉积温度；设置钨前驱体源W(CO)6固体的加热温度为60℃，载气流量为100‑200sccm；硫前驱体源10%的H2S气体,载气流量为150‑250sccm。设置沉积过程中六羰基钨固体源的脉冲时间为0.1‑0.3秒，高纯氮气冲洗15‑25秒；H2S气体源的脉冲时间为10‑20秒，高纯氮冲洗20‑30秒。本发明涉及的制备方法，参数易控，可重复性高，适用于产业化生产环境。

Description

原子层沉积制备具有固体润滑作用的WS2薄膜方法
技术领域
本发明涉及一种固体润滑薄膜，具体涉及到一种润滑作用明显的固体WS2薄膜原子层沉积的制备方法。
背景技术
WS2（硫化钨）与多数过渡金属硫化物都因具有独特的层状晶体结构，呈现出优异性能，包括半导体、类金属和固体润滑特性，因而在太阳能电池、半导体行业特别是固体润滑领域得到高度重视。
但WS2的性能，特别是固体润滑性能主要取决于其制备方法和环境，包括离子束溅射、脉冲激光沉积、化学气相沉积等工艺在制备性能优异的WS2过程中都存在较多限制，如成本过高、不可控参数过多等，极大限制了WS2的应用。（Controlled Synthesis andTransfer of Large-Area WS2 Sheets: From Single Layer to Few Layers，ACS Nano,2013, vol. 7 (6), pp 5235–5242）
原子层沉积（ALD）技术对沉积材料可实现原子级别的精度，制备包括ZnO、Al2O3、SiO2、bZnS等材料的工艺参数已完全成熟，但制备WS2薄膜的进展有限。
发明内容
本发明针对制备高性能WS2薄膜现存的问题，提供了一种用原子层沉积制备WS2薄膜的方法。
一种原子层沉积制备具有固体润滑作用的WS2薄膜方法，其特征在于，将经严格清洗的基底放入ALD腔内，使用六羰基钨(W(CO)6)固体钨源和H2S气体硫源制备WS2薄膜。
所述腔内沉积温度控制在300-4000℃。
所述钨的前驱体源为六羰基钨固体，加热温度为60℃，载气流量控制在100-200sccm；硫的前驱体源为浓度为10%的H2S气体, 载气流量控制在150-250sccm。
所述沉积过程中六羰基钨固体源的脉冲时间为0.1-0.3秒，高纯氮气冲洗15-25秒；H2S气体源的脉冲时间为10-20秒，高纯氮冲洗20-30秒。
步骤2中金属源沉积1次和S源沉积1次构成1个WS2沉积循环，WS2薄膜的厚度可以通过沉积循环数目控制。
本发明的特点和增益效果如下：
本发明方法采用原子层沉积工艺，可以有效调整硫和钨的原子比，获得高纯度的WS2薄膜，无需专门硫化环节。且在封闭腔内进行，有利于提高金属源和气体源的利用率。可通过沉积循环次数有效控制WS2的薄膜厚度，制备的WS2薄膜力学性质优异，并能直接用于其它领域。
附图说明
图1：本发明实施案例3制备的WS2的拉曼谱图，所用的激光波长为514nm.。
图2：本发明实施案例3制备的 WS2薄膜的摩擦系数测试结果。
测试条件为：负荷50g半径4.7 mm的氮化硅球；在1Hz的频率下进行行程为1.5mm往复。
具体实施方式
本发明中所述的原子层沉积系统为芬兰的Picosun原子层沉积系统，以下为结合实施例对技术方案进行的详细说明。所有实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1：
将表面严格清洗后的Si作为基底，放入ALD沉积室内，加热至300℃，设置W(CO)6(六羰基钨)源的脉冲时间为0.3秒，冲洗时间为25秒，载气流量为100sccm；H2S气体源的脉冲时间为20秒，冲洗时间为30秒,载气流量为250sccm。本实施案例中沉积循环数目为300个。
实施例2：
将表面严格清洗后的Si作为基底，放入ALD沉积室内，加热至350℃，设置W(CO)6(六羰基钨)源的脉冲时间为0.2秒，冲洗时间为20秒，载气流量为150sccm；H2S气体源的脉冲时间为15秒，冲洗时间为25秒, 载气流量为200sccm,本实施案例中沉积循环数目为400个。
实施例3：
将表面严格清洗后的Si作为基底，放入ALD沉积室内，加热至400℃，设置W(CO)6(六羰基钨)源的脉冲时间为0.1秒，冲洗时间为15秒，载气流量为200sccm；H2S气体源的脉冲时间为10秒，冲洗时间为20秒, 载气流量为150sccm,本实施案例中沉积循环数目为500个。

Claims (1)

1.一种原子层沉积制备具有固体润滑作用的WS2薄膜方法，其特征在于，将经严格清洗的基底放入ALD腔内，使用六羰基钨(W(CO)6)固体钨源和H2S气体硫源制备WS2薄膜；
所述腔内沉积温度控制在300-400℃；
所述钨的前驱体源为六羰基钨固体，加热温度为60℃，载气流量控制在100-200sccm；硫的前驱体源为浓度为10%的H2S气体, 载气流量控制在150-250sccm；
所述沉积过程中六羰基钨固体源的脉冲时间为0.1-0.3秒，高纯氮气冲洗15-25秒；H2S气体源的脉冲时间为10-20秒，高纯氮冲洗20-30秒。
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