【作者】 杨旭；

【导师】 周大雨；

【作者基本信息】 大连理工大学 ， 材料工程（专业学位）， 2019， 硕士

【摘要】 进入21世纪以来,随着人们在生物科学与能源科学领域的不断探索,已取得了一些技术上的突破,如在生物测序领域已成功的制备出了纳米孔生物芯片;而储能方面,人们也提出了微型超级电容器等新型储能设备的概念。但仍有大量问题亟待解决,其中,寻找高比电容、长循环寿命,好的兼容性且易制备的电极材料一直是人们研究的重点。已有相关专利和文献指出,磁控溅射TiN薄膜满足上述要求,有望作为上述器件中的工作电极使用。本论文采用射频与直流磁控溅射两种方式来进行TiN薄膜的制备。选取无导电性的K9玻璃为基底,且无集流体。在射频溅射部分,主要研究溅射功率及HF酸对基底的腐蚀这两个实验变量对TiN薄膜微观与电化学性能的影响。在直流溅射部分,则主要研究工作气压及HF酸对基底的腐蚀两个变量。另外,在这一部分还会进行循环实验以及相关的原理分析。在测试部分,分为微观测试与方阻、电化学测试。其中,微观分析有XRD、XPS和AFM,主要研究TiN薄膜的择优取向、元素成分及表面粗糙度。方阻测试主要用来计算薄膜的电阻率。电化学测试包含循环伏安法(CV)、恒流充放电法(GCD)及交流阻抗法(EIS),主要计算TiN薄膜的比电容值以及进行相应的电路拟合。实验结果表明,射频磁控溅射制备的TiN薄膜,其含有三个择优取向,且薄膜表面O含量较少,表面粗糙度小。方阻测试显示,薄膜的导电性较好。但其比电容值非常小,比电容值最大的仅为溅射功率200 w下,溅射时间为1 h,HF酸腐蚀基底时间为10 min,CV测试扫描速率为5 mV/s的0.5 mF/cm~2。对于直流试样,随着工作气压的增加,薄膜的择优取向发生改变,内部O含量逐渐上升,且薄膜的表面粗糙度越来越大,试样的电阻率逐渐增加,比电容值也在增加,但是相应的倍率性能较差。循环测试显示,直流TiN薄膜的循环性能较好,在电流为0.2 mA的条件下进行循环充放电270圈后,比电容值的保持率为94%左右。对所得数据进行分析,发现直流溅射试样高比电容值的原因是Ti-O-N结构与电解液中K~+进行化学吸脱附的结果。对直流试样来说,HF酸腐蚀基底对比电容的影响较小。更多还原

【Abstract】 Since the beginning of 21st century,with the continuous efforts human made in the fields of biological science and energy science,there has been many breakthroughs.For sequencing technology,the biochips have been manufactured.For energy storage,micro supercapacitors have been discussed.However,there are still a lot of problems to be solved.To find electrode materials with high specific capacitance,long cycle life and good compatibility is one of the most important problems among them.Some patents and researches have pointed out that sputtered TiN films have potential to be the working electrodes in the above device.In this paper,the preparation of TiN films will be carried out by RF and DC magnetron sputtering.K9 glass is chosen to be substrate and there is no current collector between substrate and TiN thin film.During RF sputtering,sputtering power and corrosion of HF acid on the substrate are main points to be discussed.In this part,the microscopic and electrochemical properties of TiN films are investigated.During DC sputtering,two variables which contained working pressure and corrosion of the substrate by HF acid are mainly studied.Microscopic test,square resistance and electrochemical test are taken to the samples.Among them,microscopic analysis includes XRD,XPS and AFM,which mainly studies the preferred orientation,elemental composition and surface roughness of TiN films.The square resistance test is mainly used to calculate the resistivity of the film.Electrochemical tests include cyclic voltammetry(CV),constant current charge and discharge(GCD)and alternating current impedance spectroscopy(EIS),which are mainly used to analyze the specific capacitance of TiN films.The experimental results show that the TiN film prepared by RF magnetron sputtering contains three preferred orientations.The O content of the film surface is low and the roughness of surface is small.The square resistance test showed that the conductivity of the film is good.However,the specific capacitance is very low.The maximum specific capacitance is only 0.5 mF/cm~2.For the DC samples,as the working pressure increases,the preferred orientation of the film changes,the internal O content gradually increases,and the surface roughness of the film becomes larger.Square resistance test shows the resistivity of the samples gradually increases.The specific capacitance value tested by electrochemical test also increases while the rate performance becomes poor.Cyclic test shows that the cycle life of DC TiN film is better.After 270 cycles of cyclic charge and discharge under the condition of current at 0.2 mA,the specific capacitance is maintained at about 94%.Analysis of the obtained data reveales that the reason for the high specific capacitance value of the DC sputtering sample is the result of chemical adsorption and desorption between Ti-O-N structure and K~+in the electrolyte.For DC samples,the corrosion of substrate has small effects on specific capacitance.更多还原