本文選題：MgAPO-11晶體　切入點：碳納米管　出處：《深圳大學(xué)》2017年博士論文

【摘要】：自首次被發(fā)現(xiàn)以來,碳納米管(carbon nanotubes,CNTs)就因為其獨特的物理結(jié)構(gòu)以及所表現(xiàn)出來的各種優(yōu)異性能成為物理學(xué)、化學(xué)、材料學(xué)和生物醫(yī)學(xué)等領(lǐng)域研究的熱點材料之一。單壁碳納米管(single-walled carbon nanotubes,SWCNTs)的電子結(jié)構(gòu)與其直徑和手性密切相關(guān),能否獲得均一尺寸和性質(zhì)的單壁碳納米管是對其展開基礎(chǔ)研究和投入實際應(yīng)用的關(guān)鍵。傳統(tǒng)方法所制備的單壁碳納米往往含有雜質(zhì),而且產(chǎn)物是多種直徑碳管的混合體。能否選擇性地合成金屬型性或者半導(dǎo)體性的單壁碳納米管是目前迫切需要解決的難題。碳納米管獨特新穎的性質(zhì)主要源于其納米尺度的直徑,隨著碳納米管直徑的減小,量子效應(yīng)將更加明顯,從而表現(xiàn)出很多大直徑的碳管所不具備的奇異性能。理論計算預(yù)言,能在自由空間穩(wěn)定存在的最小碳納米管的直徑為0.4 nm。2000年,直徑僅為0.4 nm的單壁碳納米管成功被合成出來,由于直徑接近理論極限,這些碳納米管表現(xiàn)出一維超導(dǎo)特性、一維光學(xué)吸收特性和高效率光致發(fā)光、選擇性吸附、高容量儲鋰等特殊性能。這些引起了人們對超細直徑碳納米管的極大興趣,其焦點是:碳納米管究竟可以小到什么程度?這些碳納米管又具有什么樣的光學(xué)和電學(xué)性能?可能有什么用途?從2000年到現(xiàn)在,陸續(xù)有幾個研究小組觀察到了0.3 nm單壁碳納米管的存在,但皆為與其他大直徑碳管的混合,而且數(shù)量極少,難以對其進行實驗上的測試研究。有研究人員利用第一性原理計算了0.3 nm(2,2)單壁碳納米管的結(jié)構(gòu)穩(wěn)定性和電學(xué)性能,但還有許多問題需要繼續(xù)深入系統(tǒng)的研究。如何可控合成出尺寸均勻,規(guī)整排列并且手性單一的0.3 nm單壁碳納米管陣列,以便能夠操控,并進一步測試其性能,也就成為了全球科學(xué)家努力的目標。2008年,直徑為0.3 nm的(2,2)碳納米管陣列在沸石晶體孔道中被合成出來,但是沸石主體的電中性骨架導(dǎo)致所得碳納米管的密度較低,不利于后續(xù)的研究應(yīng)用。本文主要研究了沸石基高質(zhì)量(2,2)碳納米管陣列的制備,并對其進行了拉曼光譜和偏振吸收光譜表征。最后把含有(2,2)碳納米管的MgAPO-11晶體作為可飽和吸收體引入到摻銩光纖激光器中,得到了穩(wěn)定的孤子鎖模脈沖。本文的主要創(chuàng)新性研究內(nèi)容如下:1.通過同晶取代往AlPO4-11(AEL)磷酸鋁晶體骨架中引入Mg離子,在水熱條件下制備MgAPO-11晶體,并且系統(tǒng)研究了合成條件以及凝膠配比對晶體生長的影響。通過優(yōu)化各種合成參數(shù)包括晶化時間,結(jié)晶溫度,鎂鋁摩爾比,有機模板劑二丙胺(DPA)含量以及不同鎂源等,成功在無氟系統(tǒng)中合成出了高質(zhì)量、迄今為止尺寸最大的MgAPO-11晶體(25×157×254μm~3),為后續(xù)單壁碳納米管陣列的制備提供了很好的主體模板。X射線粉末衍射(XRD)表明,所合成的MgAPO-11晶體是純的AEL相。2.利用MgAPO-11晶體作為模板,通過真空高溫裂解有機碳前驅(qū)物的方法合成出了尺寸均一、排列整齊的單壁碳納米管陣列。隨后測試了所合成的單壁碳納米管的拉曼光譜,包括室溫下的拉曼光譜,偏振拉曼光譜和變溫拉曼光譜。拉曼光譜顯示所制備的單壁碳納米管的手性為(2,2)扶手椅型管,且其在沸石孔道中的填充密度比之前所報道的有很大的提高。金屬性G-峰和半導(dǎo)體性G-峰的存在說明金屬性的(2,2)納米管和半導(dǎo)體性(2,2)納米管是共存于MgAPO-11晶體孔道中的,并且半導(dǎo)體性(2,2)納米管的比例稍高。偏振拉曼光譜表明碳納米管是按照MgAPO-11晶體孔道方向排列的。隨著溫度的上升,碳納米管的各個拉曼模式的頻率會發(fā)生紅移,強度逐漸下降,線寬也隨之增大。3.測試了(2,2)碳納米管陣列的偏振吸收光譜,光譜所表現(xiàn)出來的強烈偏振相關(guān)性說明(2,2)碳納米管在MgAPO-11晶體孔道中是高度定向的,(2,2)扶手椅型管電子態(tài)密度中的范霍夫奇點在光譜中得到了清晰的體現(xiàn),從另一個方面證明了金屬性(2,2)納米管和半導(dǎo)體性(2,2)納米管共存于MgAPO-11晶體孔道中。對比介電函數(shù)的計算結(jié)果,我們把位于2.67 eV和2.40 eV處的兩個吸收峰歸因于金屬性的(2,2)碳納米管,而2.95 eV處的吸收峰則源自半導(dǎo)體性的(2,2)碳納米管。4.利用(2,2)碳納米管的可飽和吸收特性,把SWCNTs@MgAPO-11晶體作為可飽和吸收體引入到摻銩光纖激光器中,通過調(diào)節(jié)激光腔內(nèi)的偏振態(tài),得到了穩(wěn)定的孤子鎖模運轉(zhuǎn)。當泵浦功率為251 mW時,輸出孤子脈沖的中心波長位于1950 nm,光譜寬度為4.2nm。輸出脈沖寬度為972 fs,重復(fù)頻率為21.05 MHz。當泵浦功率達到420 mW時,得到的平均輸出功率為2.3 mW.
[Abstract]:Since it was found that carbon nanotubes (carbon nanotubes CNTs) because of its unique physical structure and show excellent performance as physics, chemistry, materials science and biomedical research in the field of the hot material. Single walled carbon nanotubes (single-walled carbon, nanotubes, SWCNTs) of the electronic structure and the diameter and chirality closely related to whether single-walled carbon nanotubes to obtain a uniform size and property is the fundamental research and the key into practical application. The traditional method for single wall carbon nanotube preparation often contain impurities, and the product is a mixture of various diameter carbon nanotubes. Whether single-walled carbon nanotube selective synthesis of metal or the semiconductor is a problem need to be solved urgently at present. The main source of carbon nanotube diameter properties unique to the nanometer scale, with the diameter of carbon nanometer tube The reduced quantum effect will be more obvious, which showed a lot of singular performance of large diameter carbon nanotubes are not available. The theoretical calculation predicts that the minimum carbon nanotubes are stable in the free space of 0.4 nm.2000 in diameter, diameter of only 0.4 nm single wall carbon nanotubes were successfully synthesized, as close to the diameter the theoretical limit, these carbon nanotubes exhibit one-dimensional superconducting properties, one-dimensional optical properties and photoluminescence, selective adsorption, high lithium storage capacity and other special properties. These caused the people of ultrafine diameter carbon nanotubes is of great interest, the focus is: carbon nanotubes can actually small to what extent? These carbon nanotubes and with the optical and electrical properties of what may have what use?? from 2000 to now, have been observed several research groups to 0.3 nm single wall carbon nanotubes, but are instead He large diameter carbon nanotubes are mixed, but the number is very small, it is difficult to test the experiment study on it. The researchers used the first principle calculation of 0.3 nm (2,2) structure stability and electrical properties of single-walled carbon nanotubes, but there are still many problems need to continue in-depth research. How to achieve the controlled synthesis of uniform size the regular arrangement, and a single 0.3 nm chiral single-walled carbon nanotube array, in order to be able to control, and further test its performance, has become the global efforts to the goal of scientists in.2008, diameter of 0.3 nm (2,2) carbon nanotube arrays were synthesized in the zeolite pores, but neutral zeolite skeleton body the result obtained carbon nanotube density is low, is not conducive to the following research. This paper mainly studies the high quality zeolite (2,2) carbon nanotube arrays were prepared, and has carried on the Raman spectrum and partial The vibration absorption spectra. The (2,2) MgAPO-11 crystal containing carbon nanotubes as the saturable absorber into the thulium doped fiber laser, the stable soliton mode-locked pulse. The main innovation of the research contents of this paper are as follows: 1. by isomorphous substitution to AlPO4-11 (AEL) Mg ions introduced aluminum phosphate crystal skeleton. Preparation of MgAPO-11 crystal under hydrothermal conditions, and the effects of synthesis conditions and gel ratio on crystal growth. Through the optimization of various synthesis parameters including crystallization time, crystallization temperature, the molar ratio of Mg to Al, organic template agent two amine (DPA) content and different sources of magnesium, success in the synthesis of fluorine free system high quality, by far the largest size of MgAPO-11 crystal (25 x 157 x 254 m~3), preparing for the subsequent single-walled carbon nanotube arrays were the main template.X ray powder diffraction (XRD) showed good, the MgAPO-11 crystal is the synthesis of pure phase AEL.2. as template using MgAPO-11 crystal by means of vacuum pyrolysis of organic carbon precursor was synthesized with uniform size, arrangement of single walled carbon nanotube array orderly. Raman spectra of single wall carbon nanotubes synthesized by the test then, including the room temperature Raman spectrum, Raman polarization temperature dependent Raman spectroscopy. Spectroscopy and Raman spectra show that the chiral single-walled carbon nanotubes prepared for (2,2) armchair tube, and the zeolite in the filling density than previously reported has been greatly improved. The metal of G- peak and G- peak of semiconductor is that of the metallic (2,2) nanotubes and semiconductor (2,2) nanotubes coexist in MgAPO-11 crystal pores, and semiconducting nanotubes (2,2) slightly higher proportion. Polarized Raman spectroscopy showed that carbon nanotubes are in accordance with the direction of drainage channels of MgAPO-11 crystals Column. With the increase of temperature, the frequency of Raman modes of carbon nanotubes will shift the strength gradually decreased, the linewidth increases.3. test (2,2) polarization arrays of carbon nanotubes show strong absorption spectra, polarization correlation spectra shown in (2,2) carbon nanotubes are highly oriented in the channels of MgAPO-11 crystals in (2,2) armchair tube van Hove singularities in the electronic density of states clearly reflected in the spectrum, from another aspect that metallic and semiconducting nanotubes (2,2) nanotubes (2,2) coexist in the channels of MgAPO-11 crystals. The calculation results of the dielectric function, we put in 2.67 eV and 2.40 eV of the two peaks attributed to metal (2,2) of carbon nanotubes, and the absorption peak at 2.95 eV from semiconducting carbon nanotubes (2,2) using.4. (2,2) carbon nanotube saturable absorber S WCNTs@MgAPO-11 crystal as saturable absorber into the thulium doped fiber laser, the polarization state of the laser cavity has been adjusted, the stable soliton mode-locked operation. When the pump power is 251 mW, the output wavelength of soliton pulses at 1950 nm, the spectral width is 4.2nm. output pulse width is 972 FS, repetition rate of 21.05 MHz. when the pump power reached 420 mW, average output power is 2.3 mW.

【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TB383.1;TN248

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