基于自支撑金刚石薄膜的晶体管和紫外探测器制备与性能研究
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摘要
由于金刚石薄膜具有优异的力学、热学、光学、电学和化学稳定性,使得它成为一种理想的电子器件用宽禁带半导体材料,基于金刚石薄膜的器件尤其适用于在高温、高功率、强辐射和腐蚀性的苛刻环境下应用。CVD金刚石薄膜,尤其是具有光滑表面的CVD自支撑金刚石薄膜的制备及其器件应用已经成为国际前沿课题。本论文主要研究了高质量自支撑CVD金刚石薄膜的制备及其在晶体管和光电探测器件方面的应用。
采用热丝辅助化学气相沉积(HFCVD)法和微波等离子体化学气相沉积(MPCVD)法制备自支撑金刚石薄膜。研究了衬底预处理方法对金刚石薄膜成核的影响。利用扫描电镜(SEM)、原子力显微镜(AFM)和X射线衍射仪(XRD)对薄膜厚度、薄膜成核面的表面形貌和取向性进行了分析,结果表明HFCVD法和MPCVD法制备的自支撑金刚石薄膜的成核面均十分平整;采用HFCVD法制备薄膜的速度要快于MPCVD法。通过Raman光谱仪及半导体特性表征系统研究了表面处理及退火处理对薄膜质量及电学性能的影响。结果表明采用MPCVD法制备的薄膜质量要优于HFCVD法制备的薄膜。
对MPCVD法制备的自支撑金刚石薄膜的成核面进行氢等离子处理,研究了不同的氢等离子处理工艺以及退火工艺对薄膜表面p型导电性能的影响规律。并通过紫外拉曼光谱、傅立叶变换红外光谱及二次离子质谱等方法研究了薄膜表面导电层产生的原因及厚度。主要得到以下结果:采用氢等离子体处理金刚石薄膜的成核面可以使得薄膜表面形成一层40-50nm厚的p型导电层;这种p型导电层形成的原因可能与氢和碳悬挂键的结合有关;氢等离子体处理温度(600-750oC)以及处理时间(5-30min)的增加,可以提高薄膜表面的载流子浓度,降低电阻率;在空气中退火温度大于200oC,或真空中退火温度大于600oC时,氢从金刚石薄膜表面脱出使得薄膜逐渐丧失表面导电性;采用氧等离子体处理可以使金刚石薄膜的表面导电性能消失。
研究了金属电极与氢终端p型金刚石薄膜的接触性能,结果表明金可以与p型金刚石薄膜形成较好的欧姆接触,而铝则与p型金刚石薄膜形成了肖特基接触。研究了氢终端p型金刚石基肖特基势垒栅场效应晶体管(MESFET)的制备工艺及器件的性能,结果表明该器件具有明显的增强型晶体管的特性。
采用射频磁控溅射法在自支撑金刚石衬底上制备ZnO薄膜。研究了沉积功率、沉积气压以及同质缓冲层对ZnO薄膜性能的影响,并对ZnO/金刚石结构在光电探测器方面的应用进行了初步研究。主要得到以下结论:当溅射功率为150W、沉积气压为0.3Pa以及添加同质缓冲层时可以制备出高度c轴取向高质量的ZnO薄膜;相对于未添加缓冲层的样品,通过添加缓冲层,可以明显提高薄膜的质量,降低缺陷;添加缓冲层也有助于改善ZnO/金刚石薄膜结构紫外光探测器的光电性能和光谱响应特性。
Due to the unique mechanical, thermal, optical, electrical properties and outstanding chemical stability, diamond film is an ideal wide-band-gap semiconductor material for electron devices, especially devices operating at high temperature, high power, high radiation and corrosion environments. It has been the international interesting subjects that the fabrication of CVD diamond films, especially freestanding diamond films with smooth nucleation surface, and their applications for devices. In this thesis, the fabrication of high quality CVD diamond films and their applications in transistors and photodetectors were studied.
The freestanding diamond (FSD) films were grown by hot filament chemical vapor deposition (HFCVD) method and microwave plasma chemical vapor deposition (MPCVD) method, respectively. The influence of substrate pretreatment methods on the nucleation density of diamond films was studied. The thickness of FSD films, the structure, and morphology of the FSD nucleation surface were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). The results indicated that the nucleation sides of FSD films prepared by both methods were very smooth; The growth rate of diamond films was much higher by using HFCVD method. The effects of surface treatment and annealing process on the quality and electrical properties of FSD films were investigated by semiconductor characterization system and Raman spectroscopy. The results showed that the FSD films with better crystal quality could be obtained by MPCVD method.
The nucleation sides of FSD films prepared by MPCVD method were exposed to hydrogen plasma treatment. The effects of hydrogen plasma treatment and annealing process on the p-type behavior of FSD films were investigated. The origin of this high-conductivity layer of FSD films was also discussed by using ultraviolet (UV) Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR) and secondary ion mass spectrometry (SIMS). The main results were as follows: The nucleation side of FSD films with a p-type conductivity layer (~50nm thick) could be obtained by hydrogen plasma treatment; The origin of this conductivity layer may be related to the complexes of absorbed hydrogen atoms with carbon dangling bonds; The sheet carrier concentration of the FSD film increased and sheet resistivity decreased with the time (5-30min) and temperature (600-750oC) of plasma treatment; Surface conductivity of hydrogenated diamond surfaces disappeared gradually after annealing at temperature above 200°C in the air, or above 600°C in the vacuum; The conductive surface layer could also be removed by oxidation using oxygen plasma treatment.
The properties of metal contacts on hydrogenated p-type diamond surfaces were discussed. The results suggested that ohmic contacts could be realized between the p-type diamond and the Au electrodes. However, it’s easy to form schottky contacts between Al electrodes and the p-type diamond. Preparation technology of p-type channel metal–semiconductor field effect transistors (MESFETs) was studied. The properties of the device were analyzed by semiconductor characterization system, which showed a typical characteristic of enhancement-mode MESFET.
The ZnO films were grown on the nucleation sides of FSD substrates by radio-frequency (RF) magnetron sputtering method. The effects of sputtering power, gas pressure and homobuffer layer on the properties of the ZnO film were studied. The ZnO/diamond structure was also applied for UV photodetectors use. The main results were as follows: High quality ZnO films with highly c-axis orientation can be obtained when sputtering power was 150W, gas pressure was 0.3Pa and homobuffer layer was applied; Compared with films prepared without buffer layer, the samples with buffer layer showed a better crystalline quality; The homobuffer layer was also helpful to improve electrical properties and spectral response performance of the ZnO/diamond structure photodetectors.
采用热丝辅助化学气相沉积(HFCVD)法和微波等离子体化学气相沉积(MPCVD)法制备自支撑金刚石薄膜。研究了衬底预处理方法对金刚石薄膜成核的影响。利用扫描电镜(SEM)、原子力显微镜(AFM)和X射线衍射仪(XRD)对薄膜厚度、薄膜成核面的表面形貌和取向性进行了分析,结果表明HFCVD法和MPCVD法制备的自支撑金刚石薄膜的成核面均十分平整;采用HFCVD法制备薄膜的速度要快于MPCVD法。通过Raman光谱仪及半导体特性表征系统研究了表面处理及退火处理对薄膜质量及电学性能的影响。结果表明采用MPCVD法制备的薄膜质量要优于HFCVD法制备的薄膜。
对MPCVD法制备的自支撑金刚石薄膜的成核面进行氢等离子处理,研究了不同的氢等离子处理工艺以及退火工艺对薄膜表面p型导电性能的影响规律。并通过紫外拉曼光谱、傅立叶变换红外光谱及二次离子质谱等方法研究了薄膜表面导电层产生的原因及厚度。主要得到以下结果:采用氢等离子体处理金刚石薄膜的成核面可以使得薄膜表面形成一层40-50nm厚的p型导电层;这种p型导电层形成的原因可能与氢和碳悬挂键的结合有关;氢等离子体处理温度(600-750oC)以及处理时间(5-30min)的增加,可以提高薄膜表面的载流子浓度,降低电阻率;在空气中退火温度大于200oC,或真空中退火温度大于600oC时,氢从金刚石薄膜表面脱出使得薄膜逐渐丧失表面导电性;采用氧等离子体处理可以使金刚石薄膜的表面导电性能消失。
研究了金属电极与氢终端p型金刚石薄膜的接触性能,结果表明金可以与p型金刚石薄膜形成较好的欧姆接触,而铝则与p型金刚石薄膜形成了肖特基接触。研究了氢终端p型金刚石基肖特基势垒栅场效应晶体管(MESFET)的制备工艺及器件的性能,结果表明该器件具有明显的增强型晶体管的特性。
采用射频磁控溅射法在自支撑金刚石衬底上制备ZnO薄膜。研究了沉积功率、沉积气压以及同质缓冲层对ZnO薄膜性能的影响,并对ZnO/金刚石结构在光电探测器方面的应用进行了初步研究。主要得到以下结论:当溅射功率为150W、沉积气压为0.3Pa以及添加同质缓冲层时可以制备出高度c轴取向高质量的ZnO薄膜;相对于未添加缓冲层的样品,通过添加缓冲层,可以明显提高薄膜的质量,降低缺陷;添加缓冲层也有助于改善ZnO/金刚石薄膜结构紫外光探测器的光电性能和光谱响应特性。
Due to the unique mechanical, thermal, optical, electrical properties and outstanding chemical stability, diamond film is an ideal wide-band-gap semiconductor material for electron devices, especially devices operating at high temperature, high power, high radiation and corrosion environments. It has been the international interesting subjects that the fabrication of CVD diamond films, especially freestanding diamond films with smooth nucleation surface, and their applications for devices. In this thesis, the fabrication of high quality CVD diamond films and their applications in transistors and photodetectors were studied.
The freestanding diamond (FSD) films were grown by hot filament chemical vapor deposition (HFCVD) method and microwave plasma chemical vapor deposition (MPCVD) method, respectively. The influence of substrate pretreatment methods on the nucleation density of diamond films was studied. The thickness of FSD films, the structure, and morphology of the FSD nucleation surface were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). The results indicated that the nucleation sides of FSD films prepared by both methods were very smooth; The growth rate of diamond films was much higher by using HFCVD method. The effects of surface treatment and annealing process on the quality and electrical properties of FSD films were investigated by semiconductor characterization system and Raman spectroscopy. The results showed that the FSD films with better crystal quality could be obtained by MPCVD method.
The nucleation sides of FSD films prepared by MPCVD method were exposed to hydrogen plasma treatment. The effects of hydrogen plasma treatment and annealing process on the p-type behavior of FSD films were investigated. The origin of this high-conductivity layer of FSD films was also discussed by using ultraviolet (UV) Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR) and secondary ion mass spectrometry (SIMS). The main results were as follows: The nucleation side of FSD films with a p-type conductivity layer (~50nm thick) could be obtained by hydrogen plasma treatment; The origin of this conductivity layer may be related to the complexes of absorbed hydrogen atoms with carbon dangling bonds; The sheet carrier concentration of the FSD film increased and sheet resistivity decreased with the time (5-30min) and temperature (600-750oC) of plasma treatment; Surface conductivity of hydrogenated diamond surfaces disappeared gradually after annealing at temperature above 200°C in the air, or above 600°C in the vacuum; The conductive surface layer could also be removed by oxidation using oxygen plasma treatment.
The properties of metal contacts on hydrogenated p-type diamond surfaces were discussed. The results suggested that ohmic contacts could be realized between the p-type diamond and the Au electrodes. However, it’s easy to form schottky contacts between Al electrodes and the p-type diamond. Preparation technology of p-type channel metal–semiconductor field effect transistors (MESFETs) was studied. The properties of the device were analyzed by semiconductor characterization system, which showed a typical characteristic of enhancement-mode MESFET.
The ZnO films were grown on the nucleation sides of FSD substrates by radio-frequency (RF) magnetron sputtering method. The effects of sputtering power, gas pressure and homobuffer layer on the properties of the ZnO film were studied. The ZnO/diamond structure was also applied for UV photodetectors use. The main results were as follows: High quality ZnO films with highly c-axis orientation can be obtained when sputtering power was 150W, gas pressure was 0.3Pa and homobuffer layer was applied; Compared with films prepared without buffer layer, the samples with buffer layer showed a better crystalline quality; The homobuffer layer was also helpful to improve electrical properties and spectral response performance of the ZnO/diamond structure photodetectors.
引文
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