Establishment of the principle of the synthesis of the super-hard carbon nitride films based on the diagnosis by the threshold ionization mass spectrometry

基于阈值电离质谱诊断的超硬氮化碳薄膜合成原理的建立

• 批准号: 11650760
• 负责人: ITO Haruhiko
• 金额: $ 2.37万
• 依托单位: Nagaoka University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650760/
• 关键词: carbon nitride; ECR plasma CVD; microwave plasma CVD; cyanides; dissociative excitation; optical emission spectroscopy; threshold ionization mass spectrometry; CN radical; アモルファスCN膜; 質量分析; プラズマ診断; C原子; 炭素材料; 高分解能発光スペクトル; 高周波バイアス; プラズマCVD

The present study reports the guideline of synthesizing the mechanically-hard carbon nitride (CN_x) films with high nitrogen content based on the high-resolution emission spectroscopy and the threshold ionization mass spectrometry. The following results are obtained.1. Synthesis of CN_x films using the microwave CVD and the processing based on the high-resolution emission spectroscopyHigh-resolution emission spectrum of the CN radical was observed for the reaction of BrCN with the microwave (MW) discharge flow of Ar. It was found that the dissociative excitation reaction of BrCN proceeded competitively via [1] energy transfer from Ar(^3P_<0,2>) and [2] charge transfer from Ar^+ followed by the ion-electron recombination.2. Synthesis of CN_x films using the ECR plasma CVD and the processing based on the high-resolution emission spectroscopyAccording to the measurements of (a) the CN(B-X) emission, (b) the resonance lines of ArI and ArII, and (c) the electron probe, the CN(B) state was f … More ound to be formed from the high-energy electron-impact excitation of BrCN in the ECR plasma of the BrCN/Ar system.3. Process of formation of CN_x films based on the threshold ionization mass spectrometryMass spectra of BrCN were observed with varying the electron energy of ionization. It was confirmed that C^+ was formed by the electron impact dissociative ionization BrCN. According to this result, the difference of the nitrogen content of the films formed from the MW and ECR plasma CVD processes was explained as follows.The threshold of the production of the C atom is 11.6 eV. This value is dose to the energy, 11.5-11.9 eV, transferred to BrCN in MWCVD. Thus, the cross section of the production of the C atom from BrCN is considered to be negligibly small. The production of C^+ is energetically impossible. Hence, the precursor of the film formation is confirmed to be predominantly the CN radical, leading to the high concentration of the N atoms in the films (50%). On the other hand, the energy transferred to BrCN in ECRCVD is evaluated to be much higher than the threshold energies of production of C and C^+ from BrCN. Thus, they are produced with significant concentrations. Therefore, C and C^+ are considered to be the precursors for the film formation as well as the CN radicals. As a result, the concentration of the N atoms is suppressed in the films produced in the ECRCVD system (【less than or equal】20%). Less

本文报道了基于高分辨发射光谱和阈值电离质谱技术合成高氮含量的机械硬氮化碳（CN_x）薄膜的指导思想。得到以下结果.采用微波CVD和基于高分辨发射光谱的工艺制备CN_x薄膜观察到BrCN与Ar微波放电流反应的CN自由基的高分辨发射光谱。结果表明，BrCN的离解激发反应是通过[1] Ar（^3P_<0，2>）的能量转移和[2] Ar^+的电荷转移以及离子-电子复合竞争进行的.用ECR等离子体CVD法制备CN_x薄膜，并采用高分辨发射光谱技术进行处理。根据CN（B-X）发射光谱、Ar Ⅰ和Ar Ⅱ的共振谱线和电子探针的测量，确定了CN（B）态为F_（10）。 ...更多信息 在BrCN/Ar体系的ECR等离子体中，BrCN的高能电子碰撞激发产生了一种新的电子碰撞声.基于阈值电离质谱的CN_x薄膜形成过程观察了BrCN随电子电离能变化的质谱。证实了C^+是通过电子碰撞解离电离BrCN而形成的。根据该结果，由MW和ECR等离子体CVD工艺形成的膜的氮含量的差异被解释如下：产生C原子的阈值为11.6eV。该值是MWCVD中转移到BrCN的能量的剂量，11.5-11.9 eV。因此，从BrCN生成C原子的横截面被认为小得可以忽略。C^+的产生在能量上是不可能的。因此，膜形成的前体被证实主要是CN自由基，导致膜中的N原子的高浓度（50%）。另一方面，在ECRCVD中转移到BrCN的能量被评估为远高于从BrCN产生C和C^+的阈值能量。因此，它们以显著的浓度产生。因此，C和C^+被认为是膜形成的前体以及CN自由基。结果，在ECRCVD系统中制造的膜中，N原子的浓度被抑制（[小于或等于]20%）。少

项目成果

H. Ito, S. Kanda, K.C. Namiki, N. Ito, and H. Saitoh: "Mechanism of Formation of the CN(B^2Σ^+) State from Dissociative Excitation Reaction of BrCN with Electron Cyclotron Resonance Plasma of Ar"Japanese Journal of Applied Physics. (in press).

H. Ito、S. Kanda、K.C. Namiki、N. Ito 和 H. Saitoh：“BrCN 与 Ar 电子回旋共振等离子体的解离激发反应形成 CN(B^2Σ^+) 态的机制”应用物理学杂志（正在出版）。

H. Ito, K.C. Namiki, Y. Miyamoto, and M. Ohtaka: "Electronic Transition Moment of the A^2II_rX^2Σ^+ System of TiN"Journal of Molecular Structure. (in press).

H. Ito、K.C. Namiki、Y. Miyamoto 和 M. Ohtaka：“TiN 的 A^2II_rX^2Σ^+ 系统的电子跃迁矩”（正在出版）。

齋藤秀俊: "Hardness and Structure of a-CNx Films Synthesized by Chemical Vapor Deposition"Journal of Applied Physics. 39・7A. 4148-4152 (2000)

齐藤秀俊：“化学气相沉积合成的 a-CNx 薄膜的硬度和结构”应用物理学杂志 39・7A 4148-4152（2000）。

伊藤治彦, 伊藤典子, 高橋 勉, 高松大輔, 田中大祐, 齋藤秀俊: "Mechanism of Nitrogen Incorporation into Amorphous-CNx Films Formed by Plssma-Enhanced Chemiecal-Vapor Deposition of the Doublet and States of the CN Radical"Japanese Journal of Applied Physics. 39. 1371-1377 (2000)

Haruhiko Ito、Noriko Ito、Tsutomu Takahashi、Daisuke Takamatsu、Daisuke Tanaka、Hidetoshi Saito：“通过等离子体增强化学气相沉积双峰形成的非晶 CNx 薄膜中氮的结合机制以及 CN 自由基的状态”日本期刊应用物理学。39。1371-1377（2000）

伊藤治彦, 神田諭, 並木恵一, 伊藤典子, 齋藤秀俊: "Mechanism of Formation of the CN(B^2Σ^+) State from Dissociative Excitation Reaction of BrCN with Electron Cyclotron Resonance Plasma of Ar"Japanese Journal of Applied Physics. (印刷中).

Haruhiko Ito、Satoshi Kanda、Keiichi Namiki、Noriko Ito、Hidetoshi Saito：“BrCN 与 Ar 电子回旋共振等离子体的解离激发反应形成 CN(B^2Σ^+) 态的机制”日本应用物理学杂志。 （在新闻）。