Electron-Enhanced Deposition of Titanium-, Silicon- and Tungsten-Containing Films at Low Temperatures Using Volatile Precursors with Various Reactive Background Gases

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2025-06-16 DOI:10.1021/acs.chemmater.5c00264

Zachary C. Sobell, Andrew S. Cavanagh, Steven M. George

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引用次数: 0

Abstract

Electron-enhanced atomic layer deposition (EE-ALD) and electron-enhanced chemical vapor deposition (EE-CVD) can be employed for the low temperature deposition of thin films using volatile precursors with various reactive background gases (RBGs). EE-CVD expands on the previous demonstration of TiN EE-ALD using alternating Ti(N(CH₃)₂)₄ (tetrakisdimethylamino titanium (TDMAT)) and electron beam exposures with NH₃ RBG. During EE-CVD, the electron beam and the RBG are present continuously. Together with the RBG and electron beam incident on the surface, the volatile precursor is pulsed into the vacuum chamber to control the film growth. In this survey, the metal or metalloid precursors were TDMAT, Si₂H₆, and W(CO)₆. The RBGs were O₂, NH₃, CH₄, and H₂. The study focused on TiO₂ EE-ALD and SiN, SiO₂, SiC_x, SiH_x, W₂N, WO_x, and WC_x EE-CVD. Thin film growth was monitored using in situ 4-wavelength ellipsometry. To first illustrate EE-ALD, TiO₂ EE-ALD was performed at T < 80 °C using alternating TDMAT and electron beam exposures together with O₂ RBG. The growth rate for the TiO₂ EE-ALD was ∼0.7 Å/cycle. The TiO₂ EE-ALD films were nearly stoichiometric, displayed crystallinity, and were smooth as measured by atomic force microscopy (AFM). Other Ti-containing EE-ALD films were deposited using CH₄ and H₂ RBGs. Subsequently, to demonstrate EE-CVD, SiC_x EE-CVD was performed at T < 100 °C using repeating Si₂H₆ pulses with continuous electron beam and CH₄ RBG exposures. XPS revealed a 1:1 Si/C stoichiometry for a CH₄ RBG pressure of 0.45 mTorr and C-rich films for higher CH₄ RBG pressures. The SiC EE-CVD growth rate was ∼0.4 Å per Si₂H₆ pulse. The stoichiometric SiC EE-CVD films were smooth as measured by AFM. Other Si-containing EE-CVD films that were deposited included SiO₂, SiN and SiH_x. In addition, W₂N was deposited with EE-CVD at T < 120 °C using repeating W(CO)₆ pulses with continuous electron beam and NH₃ RBG exposures. The W₂N EE-CVD growth rate was ∼0.17 Å per W(CO)₆ pulse. The W₂N films had a resistivity of ∼450 μΩ cm. The W₂N EE-CVD films also displayed crystallinity and high purity. Other W-containing EE-CVD films that were deposited included WO_x and WC_x. This survey shows that the EE-ALD technique can be extended to EE-CVD with various RBGs to deposit a broad range of materials at low temperatures including oxides, nitrides and carbides.

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利用挥发性前驱体和各种反应性背景气体在低温下电子增强沉积含钛、硅和钨薄膜

电子增强原子层沉积（EE-ALD）和电子增强化学气相沉积（EE-CVD）可用于使用挥发性前驱体和各种反应性背景气体（rbg）进行薄膜的低温沉积。EE-CVD扩展了之前的TiN EE-ALD演示，使用交替的Ti(N(CH3)2)4（四甲基二甲氨基钛（TDMAT））和NH3 RBG的电子束暴露。在电子气相沉积过程中，电子束和RBG连续存在。将挥发性前驱体与入射于表面的RBG和电子束一起脉冲注入真空室，控制薄膜的生长。在本次调查中，金属或类金属前体是TDMAT， Si2H6和W(CO)6。红细胞为O2、NH3、CH4和H2。研究了TiO2 EE-ALD与SiN、SiO2、SiCx、SiHx、W2N、WOx和WCx EE-CVD的关系。采用原位四波长椭偏仪监测薄膜生长。为了首先说明EE-ALD， TiO2 EE-ALD在T <下进行；80°C，使用TDMAT和电子束交替暴露以及O2 RBG。TiO2 EE-ALD的生长速率为~ 0.7 Å/cycle。通过原子力显微镜（AFM）测量，TiO2 EE-ALD薄膜具有接近化学计量学的结晶度和光滑性。其他含ti的EE-ALD薄膜采用CH4和H2 rbg沉积。随后，为了证明EE-CVD，在T <下进行了6次EE-CVD；100°C使用重复Si2H6脉冲连续电子束和CH4 RBG曝光。XPS显示，CH4 RBG压力为0.45 mTorr时，薄膜的Si/C比例为1:1；CH4 RBG压力较高时，薄膜的C含量为富C。Si2H6脉冲的SiC EE-CVD生长速率为~ 0.4 Å。原子力显微镜（AFM）测量了化学计量SiC EE-CVD膜的光滑性。沉积的其他含硅EE-CVD薄膜包括SiO2、SiN和SiHx。此外，采用电子气相沉积法（EE-CVD）沉积了W2N；120°C使用重复W(CO)6脉冲连续电子束和NH3 RBG曝光。W2N EE-CVD生长速率为每W(CO)6脉冲0.17 Å。W2N薄膜的电阻率为~ 450 μΩ cm。W2N EE-CVD薄膜也表现出结晶度高、纯度高的特点。沉积的其他含w的EE-CVD薄膜包括WOx和WCx。这项调查表明，EE-ALD技术可以扩展到EE-CVD与各种rbg在低温下沉积广泛的材料，包括氧化物，氮化物和碳化物。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.