Establishment of coating technology of superhard carbon nitrides films based on the measurement of the surface reaction probabilities.

采用射频偏压和化学气相沉积相结合的方法，在Ar的微波放电下，利用BrCN的分解反应，制备了机械硬质非晶氮化碳(α-CNx)薄膜。为了获得机械硬度，进行了以下两个实验：(1)在基片段内循环冷却水施加射频偏置电压的情况下抑制基片温升的沉积；在-V&lt；Rf&gt；=30V的条件下，当基片冷却时，薄膜的最大硬度为17.5 Gpa，约为未冷却时的2倍。从薄膜的红外光谱中观察到了三维的C-N网络结构。这一结果表明，衬底冷却有效地维持了薄膜中的sp3杂化键合，从而抑制了薄膜的内应力松弛。[2]第二个实验是在-V_&lt；rf&gt；=40-100V范围内的射频偏置电压的加压操作。通过这个操作，在这个高V_&lt；rf&gt；区域内可以形成薄膜，尽管当连续施加该电压时由于严重的溅射而没有形成薄膜。作为显微硬度测量的结果，在t_&lt；on&gt；/t_&lt；off&gt；[大于或等于]7/3的情况下，超过通过施加连续RF偏置获得的最大硬度17.5 Gpa。在T=1000 S条件下形成的薄膜的硬度高于在T=100 S条件下形成的薄膜的硬度，在T=1000 S，-V_&lt；Rf&gt；=100V，t_&lt；on&gt；/t_&lt；off&gt；=8/2的条件下，薄膜的最大硬度达到46.1 GPa.当t_&lt；on&gt；/t_&lt；off&gt；=9/1时，薄膜没有沉积.因此，开/关的最佳状态介于8/2和9/1之间

Mechanically hard amorphous carbon nitride (α-CN_x) films were prepared by applying a combination of the RF bias voltage to the substrate and the chemical vapor deposition process using the decomposition reaction of BrCN with the microwave discharge flow of Ar. In order to obtain the mechanical hardness, following two experiments were made.[1]The first was the deposition with suppressing temperature rise of the substrate during the application of the RF bias voltage by circulating cooling water inside the substrate stage. When the substrate was cooled, the maximum hardness of the film was 17.5 GPa under the condition of -V_<RF>=30 V, being 【approximately equal】2 times higher than that prepared without cooling. From the IR spectra of the films, three-dimensional C-N network structure was observed. This result suggested that the substrate cooling is effective for maintaining the sp^3-hybridized bonding in the films and, consequently, for suppressing the relaxation of the internal stress of the film.[2]The second experiment was the pursed operation of the RF bias voltage in the range of -V_<RF>=40-100 V. Film formation became possible in this high -V_<RF> region by this operation, although films were not formed due to severe sputtering when this voltage was applied continuously. As a result of measurement of the microhardness, it was in the case that t_<on>/t_<off>【greater than or equal】7/3 to exceed maximum hardness, 17.5 GPa, obtained by applying continuous RF bias. Hardness of the films formed under the condition of T=1000 s was higher than that formed under T=100 s. The maximum hardness of the film was 46.1 GPa, being obtained under the condition of T=1000 s, -V_<RF>=100 V, and t_<on>/t_<off>=8/2. Under the condition of t_<on>/t_<off>=9/1, the films were not deposited. Therefore, the optimum condition of t_<on>/t_<off> lies between 8/2 and 9/1