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

本文报道了基于高分辨发射光谱和阈值电离质谱仪合成高氮含量机械硬质氮化碳(CN_X)薄膜的指导思想。得到了以下结果1.微波CVD法制备CN_x薄膜及其高分辨发射光谱观察到了BrCN与Ar的微波放电反应产生的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&lt；0，2&gt；)的能量转移和[2]Ar^+的电荷转移以及离子-电子复合来竞争进行的。电子回旋共振等离子体化学气相沉积制备CN_x薄膜及基于高分辨发射光谱的处理根据(A)CN(B-X)发射，(B)ArI和ArI的共振线和(C)电子探针的测量，CN(B)态为f…在BrCN/Ar体系的ECR等离子体中，BrCN的高能电子碰撞激发可以形成更多的声音。基于阈值电离质谱学的CN_x膜的形成过程观察到BrCN的质谱图随电离电子能量的变化而变化。证实了C^+是由电子碰撞解离电离BrCN形成的。根据这一结果，解释了微波等离子体CVD工艺和ECR等离子体CVD工艺形成的薄膜中氮含量的差异：碳原子产生的阈值为11.6 eV。该值是MWCVD中转移到BrCN的能量的剂量，范围为11.5-11.9 eV。因此，从BrCN产生的C原子的横截面被认为是可以忽略不计的。C^+的产生在能量上是不可能的。因此，薄膜形成的先驱物主要是CN自由基，导致薄膜中N原子的浓度很高(50%)。另一方面，ECRCVD中转移到BrCN的能量远高于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^+被认为是成膜的前驱物质，也是CN自由基的前身。结果，在ECRCVD系统中产生的薄膜中N原子的浓度被抑制([小于或等于]20%)。较少

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