沸石基单壁碳纳米管的脉冲光纤激光器研究

发布时间：2018-04-22 05:16

本文选题：水热法 + 沸石　；参考：《深圳大学》2016年博士论文

【摘要】：沸石晶体由于其规则的孔道结构特点而得到人们的广泛关注,它具有分离,离子交换,催化等重大应用,更是作为主体材料来组装先进主客体材料的关键模板。在沸石晶体的制备方面主要追求两个方面,分别是纳米尺度的沸石晶体和大尺寸沸石单晶。这其中沸石大单晶的制备是进行晶体结构分析,晶体生长机理研究和先进功能材料组装的重要前提。近年来,单壁碳纳米管已广泛作为饱和吸收体来实现光纤激光器的脉冲输出。然而受所用单壁碳纳米管的限制,光纤激光器面临运行功率较低,脉冲的运行状态单一的问题,这大大限制了光纤激光器的应用。本文主要研究了各合成参数对多种沸石晶体生长的影响,探讨出了多种沸石晶体的最优合成条件。利用所合成的ZnAPO_4-11(AEL)和Al PO4-5(AFI)沸石晶体为模板制备了高定向的单壁碳纳米管。利用高定向的单壁碳纳米管为偏振相关的饱和吸收体实现了激光脉冲状态可切换和耐高功率运行的脉冲光纤激光器。主要工作如下:1)系统研究了凝胶组份和晶化条件对ZAPSO-43(GIS)沸石晶体生长的影响。通过优化如下合成参数:晶化温度,晶化时间,硅铝摩尔比,锌铝摩尔比,氢氟酸含量和有机模板剂DPA含量,成功合成了高质量,迄今为止尺寸最大的GIS沸石晶体(250μm)。单晶X射线衍射结果表明所合成了GIS沸石晶体结构为fddd空间点阵群结构,晶格常数a=9.9985?,b=14.2565?,c=14.5726?,α=β=γ=90°,晶胞体积为V=2077.23?3。2)系统研究了多种合成参数对Al PO-LTA沸石晶体形貌与尺寸的影响,例如陈化时间,水含量,有机模板剂NPA含量和HF含量。首次以NPA为单一模板剂,在高水含量和无氢氟酸存在的条件下合成了光学透明的Al PO-LTA沸石大单晶(170μm)。单晶衍射结果显示Al PO-LTA沸石晶体的结构为Pm3m空间点阵群结构,晶格常数a=b=c=12.02?,α=β=γ=90°,晶胞体积为V=1736.65?3。3)首次在一步温度法情况下,利用NPA为模板剂成功合成了SAPO-47(CHA)沸石晶体。研究发现产物对凝胶组份和晶化条件非常敏感。通过优化硅铝摩尔比,HF以及NPA含量,在晶化温度和晶化时间分别为170°C和50 h的条件下成功合成了完美立方形貌的CHA沸石晶体(260μm×260μm)。4)系统探讨了硅铝摩尔比,HF和DPA含量对SAPO-46(AFS)沸石晶体的影响,成功合成了完美的AFS沸石大单晶(180μm×180μm)。单晶结果表明AFS晶体结构为P63cm空间点阵群结构,晶格常数a=b=13.295?,c=26.742?,α=β=90°,γ=120°,晶胞体积为V=4093.56?3。5)探索合成了ZnAPO_4-11(AEL)和Al PO4-5(AFI)这两种具有一维孔道结构的沸石大单晶,并利用AEL和AFI为模板合成了高度定向的单壁碳纳米管,其尺寸分别为0.3 nm和0.4 nm。这种高定向的单壁碳纳米管表现出光的偏振吸收特性。6)定向单壁碳纳米管的偏振吸收特性使其可用作偏振相关的饱和吸收体,将一个宿主了定向碳管的沸石晶体置于光纤激光器腔内,成功实现了在同一泵浦功率下脉冲状态可切换(调Q和锁模)的光纤激光器。具体来说,在同一泵浦功率下,利用宿主在AEL沸石晶体孔道内的高定向0.3 nm单壁碳纳米管作为饱和吸收体同时实现了在掺铒光纤激光器和掺镱光纤激光器的脉冲运行状态在锁模和调Q之间的自由切换。其中在掺铒光纤激光器上所设定的泵浦功率为310 m W,所获得锁模脉冲的输出中心波长位置为1563.5 nm,重复频率和周期分别为21.68 MHz和46.13 ns,其脉冲宽度为180 fs。通过偏振控制器改变腔光的偏振态,上述锁模脉冲运行状态便可切换为调Q脉冲运行状态,其调Q的输出中心波长位置为1563.4 nm,脉宽和重复频率分别为4.3μs和32.55 k Hz。在掺镱光纤激光器中所设定的泵浦功率为350 m W,所获得的锁模脉冲输出中心波长位置为1048.3 nm,锁模脉冲的重复频率和周期分别为25.34 MHz和39.47 ns,脉宽为463ps。同样通过偏振控制器来改变腔内光的偏振态,锁模脉冲运行状态便可切换为调Q脉冲运行状态,其调Q脉冲的输出中心波长位置为1039.5 nm,重复频率和脉宽分别为27.85k Hz和5.8μs。利用宿主在AFI沸石孔道内的高定向0.4 nm单壁碳纳米管为偏振相关饱和吸收体实现了脉冲状态可切换的掺铒光纤激光器。所设定的泵浦功率为330 m W,所获得锁模脉冲输出中心波长位置为1563.9 nm,重复频率和周期分别为23.2 MHz和43ns,脉冲宽度为560 fs。通过调制偏振控制器,上述锁模运行状态便可切换为调Q运行状态,其输出中心波长位置为1568.5 nm,重复频率和脉宽分别为24.25 k Hz和5.2μs。
[Abstract]:Zeolite crystals have been widely concerned because of their regular pore structure characteristics. It has important applications such as separation, ion exchange and catalysis. It is the key template to assemble advanced host and guest materials as the main material. In the preparation of zeolite crystals, two aspects are mainly pursued, respectively, the nanoscale zeolite crystals and the large size of the zeolite crystals. The preparation of large zeolite single crystals is an important prerequisite for crystal structure analysis, crystal growth mechanism research and advanced functional material assembly. In recent years, single wall carbon nanotubes have been widely used as saturated absorbers to realize the pulse output of fiber laser. However, the limitation of single wall carbon nanotube and optical fiber excitation The optical device is faced with the problem of low operating power and single operating state of the pulse, which greatly restricts the application of fiber laser. This paper mainly studies the effects of various synthetic parameters on the growth of a variety of zeolite crystals, and discusses the optimal synthesis conditions of a variety of zeolite crystals. Using the combined ZnAPO_4-11 (AEL) and Al PO4-5 (AFI) zeolite crystals High directional single walled carbon nanotubes were prepared for the template. High directional single wall carbon nanotubes were used as polarization dependent saturated absorbers to realize switched laser pulse state and high power pulsed fiber laser. The main work is as follows: 1) the crystal growth and crystallization conditions of ZAPSO-43 (GIS) zeolite crystal growth are studied systematically. By optimizing the following synthetic parameters: crystallization temperature, crystallization time, Si Al mole ratio, Zn Al mole ratio, hydrofluoric acid content and organic template DPA content, high quality GIS zeolite crystal (250 u m) with the largest size to date was synthesized. The crystal structure of GIS zeolite is FDDD space point synthesized by single crystal X ray diffraction. Matrix group structure, lattice constant a=9.9985? B=14.2565?, c=14.5726?, alpha = beta = gamma =90, crystal cell volume of V=2077.23? 3.2) the effects of a variety of synthetic parameters on the crystal morphology and size of Al PO-LTA zeolite are studied, such as aging time, water content, NPA content and HF content of organic template agents. For the first time NPA is a single template, in high water content and no In the presence of hydrofluoric acid, a transparent Al PO-LTA zeolite large single crystal (170 mu m) is synthesized. The single crystal diffraction results show that the structure of Al PO-LTA zeolite crystal is Pm3m space lattice group structure, lattice constant a=b=c=12.02?, alpha = beta = gamma =90 degree, and crystal cell volume V=1736.65? 3.3) for the first time in one step temperature method, using NPA as a template agent successfully combined. The SAPO-47 (CHA) zeolite crystal was found. The results showed that the product was very sensitive to the gel component and the crystallization condition. By optimizing the mole ratio of silicon and aluminum, HF and NPA content, the perfect cubic morphology of CHA zeolite crystal (260 mu m x 260 m).4 was successfully synthesized under the conditions of crystallization temperature and crystallization time of 170 degree C and 50 h respectively. The effect of the content of HF and DPA on the crystal of SAPO-46 (AFS) zeolite successfully synthesized the perfect AFS zeolite large single crystal (180 mu m x 180 m). The results of single crystal show that the crystal structure is a lattice group structure of P63cm space, the lattice constant a=b=13.295? C=26.742?, alpha = beta =90 degree, gamma ray degree, cell volume of 3.5) -5 (AFI) two kinds of zeolite large crystal with one dimensional channel structure, and using AEL and AFI as a template to synthesize highly directional single wall carbon nanotubes, with the size of 0.3 nm and 0.4 nm., the highly directional single wall carbon nanotubes show polarization absorption properties of light. The polarization absorption properties of single wall carbon nanotubes can be used as partial polarization. A resonant saturated absorber, a zeolite crystal host with a directional carbon tube is placed in a fiber laser cavity, and a fiber laser which can switch (Q and mode locking) at the same pump power is successfully realized. At the same pump power, the high fixed 0.3 nm single wall carbon of the host in the channel of the AEL zeolite crystal is used. As a saturated absorber, the nanotube realizes the free switching between the mode locking and the Q modulation in the pulse running state of the erbium doped fiber laser and ytterbium fiber laser. The pump power set on the erbium doped fiber laser is 310 m W, and the center wavelength position of the mode lock pulse is 1563.5 nm, repeated frequency and week. The period is 21.68 MHz and 46.13 ns respectively, and the pulse width is 180 fs. to change the polarization state of the cavity light through the polarization controller. The operating state of the mode lock pulse can be switched to Q pulse operation state. The output center wavelength position of Q modulation is 1563.4 nm, and the pulse width and repetition frequency are 4.3 Mu s and 32.55 K Hz. respectively in ytterbium doped fiber laser. The pump power of the set is 350 m W, and the output center wavelength of the mode locking pulse is 1048.3 nm, the repetition frequency and the period of the mode lock pulse are 25.34 MHz and 39.47 ns respectively. The pulse width is 463ps. also changes the polarization state of the cavity light through the polarization controller, and the mode locked pulse operation state can be switched to Q pulse operation state. The output center wavelength position of the Q pulse is 1039.5 nm, the repetition frequency and pulse width are 27.85k Hz and 5.8 S. respectively. The high fixed 0.4 nm single wall carbon nanotube in the AFI zeolite pass is used as polarization dependent saturated absorber to realize the pulse state switchable erbium doped fiber laser. The set pump power is 330 m W. The center wavelength position of the mode locking pulse is 1563.9 nm, the repetition frequency and the period are 23.2 MHz and 43ns respectively. The pulse width is 560 fs. through the modulation polarization controller. The mode lock operation state can be switched to Q operation state, the output center wavelength position is 1568.5 nm, the re frequency and pulse width are 24.25 K Hz and 5.2 S. respectively.

【学位授予单位】：深圳大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TN248

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