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

本研究报告了基于高分辨率发射光谱和阈值电离质谱合成高氮含量机械硬氮化碳（CN_x）薄膜的指南。得到如下结果： 1．微波CVD合成CN_x薄膜和基于高分辨率发射光谱的处理观察了BrCN与微波(MW)放电流Ar的反应的CN自由基的高分辨率发射光谱。研究发现BrCN的解离激发反应通过[1]Ar(^3P_<0,2>)的能量转移和[2]Ar^+的电荷转移以及离子-电子复合来竞争性地进行。2．利用ECR等离子体CVD合成CN_x薄膜并基于高分辨率发射光谱进行处理根据(a) CN(B-X)发射、(b) ArI和ArII的共振线以及(c)电子探针的测量，发现CN(B)态是由高能电子碰撞激发形成的 BrCN/Ar系统ECR等离子体中BrCN的含量。3．基于阈值电离质谱法的CN_x薄膜形成过程通过改变电离电子能量观察了BrCN的质谱。证实C^+是通过电子碰撞解离电离BrCN形成的。根据这一结果，MW和ECR等离子体CVD工艺形成的薄膜的氮含量差异解释如下。C原子产生的阈值是11.6eV。该值与在 MWCVD 中转移至 BrCN 的能量 11.5-11.9 eV 相关。因此，从 BrCN 生产 C 原子的截面被认为是小到可以忽略不计。 C^+的产生在能量上是不可能的。因此，薄膜形成的前体被证实主要是CN自由基，导致薄膜中N原子的浓度很高（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，它们的生产浓度很高。因此，C和C^+以及CN自由基被认为是成膜的前体。结果，ECRCVD系统生产的薄膜中N原子的浓度被抑制（【小于或等于】20%）。较少的

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）。