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法，具有高氮含量的合成硬质碳（CN_X）膜的指南。获得以下结果1。使用微波CVD和基于CN自由基的高分辨率发射光谱发射光谱的加工和处理的处理，观察到BRCN与AR的微波（MW）放电流的反应观察到CN_X膜的合成。发现BRCN的解离反应通过[1]从AR（^3P_ <00,2>）和[2]电荷转移从AR^+进行了竞争性进行，然后是离子 - 电子重组2。使用ECR血浆CVD合成CN_X膜和基于高分辨率发射光谱验证的处理，以（a）CN（a）CN（b-x）发射的测量值，（b）ARI和ARII和ARI的共振线，以及（c）cn（c）电子探测器（b）的cn（b）f for-imper for-imper for for-imper for-imper for for f. BRCN/AR系统的ECR血浆中BRCN的兴奋3。根据电离的电子能量，观察到基于BRCN的阈值电离质谱谱系光谱的CN_X膜的形成过程。已证实C^+是由电子撞击离子电离BRCN形成的。根据此结果，由MW和ECR等离子体CVD过程形成的膜的氮含量的差异如下解释。C原子的产生阈值是11.6 eV。该值剂量为11.5-11.9 eV，在MWCVD中转移到BRCN。那就是从BRCN生产的C原子的横截面被认为忽略不计。 C^+的产生在能量上是不可能的。因此，膜形成的前体已被确认为CN自由基，导致膜中N原子的高浓度（50％）。另一方面，评估在ECRCVD中转移到BRCN的能量高于BRCN的C和C^+的生产能力。那就是它们以显着的浓度生产。因此，C和C^+被认为是膜形成以及CN自由基的前体。结果，在ECRCVD系统中产生的膜中抑制了N原子的浓度（[小于或等于] 20％）。较少的

项目成果

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）

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）。

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）。

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）。

H. Ito, K. Tanaka, A. Sato, N. Ito, and H. Saitoh: "Ion-Induced Processes in the Dissociative Excitation Reaction of BrCN to Synthesize Mechanically Hard Amorphous Carbon Nitride Films in the Microwave Plasma Chemical Vapor Deposition System"Japanese Jour

H. Ito、K. Tanaka、A. Sato、N. Ito 和 H. Saitoh：“微波等离子体化学气相沉积系统中 BrCN 解离激发反应中的离子诱导过程合成机械硬质非晶氮化碳薄膜”