离子辐照光波导及二维材料的结构调控研究

发布时间：2018-01-20 10:59

本文关键词： 离子辐照光波导二维材料微结构　出处：《山东大学》2017年博士论文　论文类型：学位论文

【摘要】：作为一种重要的材料近表面改性和材料表面表征手段,离子辐照技术在金属材料、半导体工业、化学、磁性材料、医学、物理等各个领域具有广泛的应用。基于离子与固体材料之间的相互作用,离子辐照技术还可应用于半导体材料的有效掺杂和光波导结构的制备。"集成光学"(Integrated Optics)这个概念在1969年被美国贝尔实验室的S.E.Miller提出,其利用集成电路的方法,以薄膜的形式将所有的光学元件集成在同一个小体积衬底上,具有体积小、效率高、性能稳定、使用方便等优点,在光学信息存储、光纤传感技术、材料科学研究及大容量和远距离的光通讯等领域具有优秀的应用前景。光波导作为集成光学的基本元器件结构,可以同时进行光信号的传输和转换,因此集成光学元件的性能和作用受到光波导结构的直接影响。目前,离子辐照技术已经发展成为一种比较成熟的波导制备方法,通过控制辐照离子的种类、能量、剂量和温度等条件,已经在多种玻璃、半导体、聚合物和晶体等材料上制备出波导结构。在离子辐照过程中,离子本身的能量通过电子及核能量损失在与材料的相互作用过程中消耗掉,从而破坏衬底材料的结构,导致衬底材料的结构畸变及辐照区域折射率的变化,而集成光学元器件的应用价值受到材料结构和光学性质的影响,因此波导内部微结构的研究及光学性质的变化具有重要意义。与固体材料不同,纳米材料的元激发、电子态及材料内部的各种相互作用都有独特的性质,在能源、化工、国防、航天航空、医药等均具有广泛的应用。纳米材料的应用越来越广泛,使更多的研究人员将关注点聚集在纳米材料在苛刻的辐照环境中其结构和性质的变化及变化机理上。离子辐照虽会对材料的结构造成破坏,但是其可以修饰纳米材料表面,使材料的一些性能得到改善和优化。因此研究纳米材料的辐照机理及宏观性质变化,对未来更好的使用离子辐照技术进行纳米材料改性具有重要意义。本文工作主要围绕离子辐照光学晶体(MgAl_2O_4、Y2SiO_5、Pr:Y_2SiO_5)和纳米薄膜材料(ZnO薄膜、多层WS_2纳米片、多层MoSe_2纳米片)展开,主要内容包括:应用离子辐照技术在光学晶体上制备平面光波导结构;离子辐照光学晶体及纳米薄膜材料的晶格损伤和光学、力学等性能变化;应用离子辐照技术调控多层纳米片的层数、厚度及光学禁带宽度。本论文主要采用理论模拟与实验表征相结合的方法研究辐照前后光学晶体及纳米薄膜材料的结构、力学及光学性能的变化,具体有:应用SRIM软件模拟了离子辐照过程中电子及核能量损伤、离子射程分布等;应用棱镜耦合法测试离子辐照样品前后在可见光波段的暗模特性曲线;应用反射计算法(RCM)重构平面光波导结构的折射率分布;应用端面耦合法测试了平面光波导结构在可见光波段的近场光强分布,并利用背反射方法测试了平面光波导结构的传输损耗;应用有限差分光束传输方法(FD-BPM)在RCM重构的折射率基础上模拟光波导的光学传输情况;应用卢瑟福背散射/沟道技术(RBS/Channeling)测试离子辐照前后样品的损伤情况、元素分布及膜厚;应用二次离子质谱(SIMS)分析离子辐照后波导层元素的分布情况;应用X射线衍射(XRD)、拉曼散射(Raman scattering)、紫外-可见-近红外分光光度计(UV-Vis-NIR)、金相显微镜、原子力显微镜(AFM)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)测试了离子辐照前后样品的结构、表面形貌、膜厚及层数和光学等特性变化;此外,纳米压痕技术用来测试了样品在离子辐照前后力学性质变化。具体研究如下:镁铝尖晶石(MgAl_2O_4)属于立方晶系,具有耐腐蚀、耐高温、较高的硬度和抗弯强度、稳定的物理化学性能、良好的紫外光至红外光波段光学透过率等优良特性,是一种理想的功能材料,被广泛应用于短波长通信、化工、电子器件、激光器材料等领域。采用能量为6.0 MeV,剂量为1.5 × 1015 ions/cm~2的O~(3+)辐照MgAl_2O_4单晶样品制备平面光波导结构。研究结果表明离子辐照后形成了一个典型的"位垒+势阱"型光波导结构,O~(3+)辐照MgAl_2O_4单晶样品的过程中,造成了晶格损伤,产生色心,略微增大了辐照后样品的吸收率。利用不同能量(6.0 MeV、(6.0+ 6.0)MeV)及剂量(5 × 1014 ions/cm~2、1 ×1015 ions/cm~2、1.5 × 1015 ions/cm~2、(4 × 1014 + 5 × 1014)ions/cm~2)的 C~(3+)辐照MgAl204制备平面光波导结构。研究结果表明C~(3+)辐照后形成了 "位垒+势阱"型波导结构,C~(3+)辐照的样品可以很好的限制光的传输,且传输损耗小于O~(3+)辐照后的样品的传输损耗,多能量多剂量的C~(3+)辐照过程中产生的晶格损伤和色心改变了样品的晶格结构,增大了样品在可见光至近红外波段的光吸收率。硅酸钇单晶Y_2SiO_5(YSO)作为一种应用广泛的新型激光晶体材料,具有化学稳定性强,热膨胀系数低,光学性能和导热性能优良等优点,引起了诸多学者的关注。应用能量为6.0MeV、剂量为1 × 1015ion/cm~2的C~(3+)辐照Y_2SiO_5(YSO)晶体制备了平面光波导结构。研究结果表明C~(3+)辐照后形成"位垒"型光波导结构,辐照后样品XRD谱图的FWHM增大,峰位向高角度偏移(2θ值变大),晶粒尺寸变小,Raman峰强度发生变化,且辐照后样品的硬度和杨氏模量均增大,C~(3+)辐照对样品的结构造成损伤,此外,C~(3+)辐照对YSO样品在紫外光波段的吸收特性产生影响,而在可见光及近红外波段则无影响。应用不同能量和剂量的C~(3+)和O~(3+)分别辐照YSO和Pr:YSO晶体制备了多个光波导结构。测试结果表明离子辐照后的样品在TE及TM模式下分别形成了不同类型的波导结构,且C~(3+)辐照形成的波导结构在可见光波段可支持单模传输。O~(3+)辐照形成的波导结构在可见光波段可支持多模传输,O~(3+)辐照较C~(3+)辐照对样品造成的损伤较大。离子辐照后样品在紫外光波段的吸收明显增强,且吸收率随辐照剂量的增大而增加。经C~(3+)辐照后YSO样品的硬度和杨氏模量均随辐照剂量的增大而增加,而经O~(3+)辐照后Pr:YSO样品的硬度和杨氏模量均减小。非金属离子掺杂ZnO材料在可见光区域可以有效提高样品的光吸收,而N离子因其具有与O离子相似的电子结构和离子半径,低的离子能,易于处理和资源丰富等优点,常被考虑作为一种有效的掺杂离子。应用磁控溅射技术在蓝宝石(Al_2O_3)衬底上制备了 ZnO纳米薄膜,选取其中的一部分样品进行能量为90 keV,剂量为1×1015ions/cm~2的N~+辐照处理,对未辐照和辐照后的样品分别进行100至500 ℃的退火处理,研究结果表明N~+辐照和增加退火温度均可提高样品的结晶质量,离子辐照后样品的禁带宽度增大;增大退火温度,未辐照样品的透过率降低,辐照后样品的禁带宽度减小。通过离子辐照技术在合适的退火温度下可以制备高质量的ZnO纳米薄膜材料。因具有层数和面积可控、带隙可在1-2 eV范围调控等诸多优势,单原子层或者几个原子层厚度的二维过渡金属硫化物在润滑剂、催化、能源、光电器件和功能纳米复合材料等众多领域应用广泛。应用能量为600 keV和6.0 MeV,剂量为1 × 1014 ions/cm~2和1 × 1015 ions/cm~2的O离子辐照多层WS_2纳米片,研究结果表明离子辐照后多层WS_2纳米片的层数减少,厚度变薄,高能量的O~(3+)辐照破坏了多层WS_2纳米片原有的三角形结构。辐照对纳米薄膜样品产生损伤,光学禁带宽度Eg随着辐照离子能量的增大而增加,随辐照剂量的增大而减小。因此,通过调控O离子的辐照条件可以有效调控多层WS_2纳米片的层数及光学禁带宽度。应用能量为 600 keV 和 6.0 MeV,剂量为 1×1014 ions/cm~2 和 1×1015 ions/cm~2的O离子辐照多层MoSe_2纳米片,研究结果表明辐照后的样品的纳米片尺寸变大,有聚集叠加生长的趋势,其形状不再是完美的三角形结构。高能量高剂量的辐照使纳米片厚度降低,低能量高剂量的O~+辐照使样品的结晶性更好。离子辐照破坏了多层MoSe_2纳米片中层与层之间的范德华力及其电子结构,使样品的透过率增大,改变了多层MoSe_2纳米片的禁带宽度。
[Abstract]:As a kind of important material in surface modification and surface characterization of ion irradiation technology in metal materials, semiconductor industry, chemistry, medicine, magnetic materials, has been widely used in various fields such as physics. The interaction between ions and solids based on effective doped optical waveguide structure and ion irradiation technology can also be used in the semiconductor material. The preparation of "integrated optics" (Integrated Optics) this concept is the Baer laboratory S.E.Miller proposed in 1969, using the method of integrated circuit, the film will be in the form of all optical components are integrated into a small volume of substrate, has the advantages of small volume, high efficiency, stable performance. Easy to use, in the optical information storage, optical fiber sensing technology, material science research and the capacity and distance of the optical communication and other fields has a good application prospect. As optical waveguide The basic structure of integrated optical components, can also carry out optical signal transmission and conversion, so the performance and function of integrated optical components is directly influenced by optical waveguide structure. At present, ion irradiation technology has developed into a mature waveguide preparation method, through the control of the ion energy type, irradiation dose and temperature, etc. has been in a variety of conditions, semiconductor, glass, crystal and polymer materials prepared by ion irradiation in the waveguide structure. In the process of ion energy through electronic and nuclear energy loss in the interaction with the process of material consumed, the structure of substrate material damage and lead to changes in the structure, and the irradiation area of substrate refractive distortion the rate of the materials, and the application value of integrated optical components affected by the structure and optical properties of materials, so the microstructure study of waveguide and optical properties Has the important significance of qualitative change. Unlike solid materials, nano materials excited element, various internal electronic states and material interactions have unique properties in energy, chemical industry, national defense, aerospace, medicine etc. they are widely used. The application of nano materials is more and more widely, to make more researchers the focus will gather in nano materials in harsh radiation environment in the change of its structure and properties and change mechanism. Although ion irradiation will damage the structure of the material, but it can make a surface modification of nano materials, some properties of materials is improved and optimized. The change mechanism of irradiation of nano materials and so on the macroscopic properties, modification of nano materials has important significance on the use of ion irradiation technology in the future better. This paper mainly focuses on the ion irradiation optical crystals (MgAl_2O_4, Y2SiO_5, Pr: and Y_2SiO_5). M thin films (ZnO films, WS_2 multilayer nano film, multilayer nano MoSe_2), the main contents include: the application of ion irradiation technology for preparation of planar optical waveguide structures in optical crystal; lattice damage and optical ion irradiation optical crystal and nano film materials, the mechanical properties change; ion irradiation technology application layer control multilayer films, thickness and optical band gap. This thesis mainly adopts the structure of optical crystal and nano film materials before and after irradiation of theoretical simulation and experimental characterization of combining the mechanical and optical properties of the specific changes include: application of SRIM software to simulate the electronic and nuclear energy damage during ion irradiation, ion range distribution; application of prism coupling test samples before and after ion irradiation in the visible band Dark mode characteristic curve; application of reflection method (RCM) reconstruction of planar optical waveguide structures The refractive index distribution; face coupling method of planar optical waveguide structures in the near field intensity distribution in the visible band, and the transmission loss of back reflection method of planar optical waveguide structures test; application of finite difference beam propagation method (FD-BPM) in the reconstruction of the refractive index of the RCM rate based on the simulation of optical transmission optical waveguide; application of Rutherford backscattering / channeling (RBS/Channeling) damage sample test before and after ion irradiation, element distribution and film thickness; two secondary ion mass spectrometry (SIMS) distribution of ion irradiated waveguide elements; application of X ray diffraction (XRD), Raman scattering, UV (Raman scattering) visible near infrared spectrophotometer (UV-Vis-NIR), optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) structure of the sample before and after ion irradiation test, surface morphology The film thickness, and the number of layers and optical properties change; in addition, the nano indentation technique is used to test the changes in the mechanical properties of samples before and after ion irradiation. The specific studies are as follows: spinel (MgAl_2O_4) belongs to cubic crystal system, corrosion resistant, high temperature resistance, high hardness and bending strength, physical and chemical properties of stability, good UV to infrared transmittance and other excellent properties, is a kind of ideal functional material, is widely used in short wave communication, chemical, electronics, laser field materials. The energy is 6 MeV, at a dose of 1.5 * 1015 ions/cm~2 O~ (3+) irradiation of MgAl_2O_4 single crystal sample preparation of planar optical waveguide structures the results show that ion irradiation. After the formation of a typical "barrier + trap" optical waveguide structure, O~ (3+) MgAl_2O_4 single crystal samples in the irradiation process, caused the lattice damage, irradiation, slightly The sample absorption rate increased after irradiation. The use of different energy (6 MeV (6.0+ 6) MeV) and dose (5 x 1014 ions/cm~2,1 * 1015 ions/cm~2,1.5 * 1015 ions/cm~2 (4 * 1014 + 5 * 1014) ions/cm~2) C~ (3+) MgAl204 Irradiation Preparation of planar optical waveguide structures. The results show that C~ (3+) after irradiation, forming a "barrier + trap" waveguide structure, C~ (3+) transmission of irradiated samples can limit the light well, and the transmission loss is less than O~ (3+) transmission loss of irradiated samples, multi energy dose of C~ (3+) generated during irradiation the lattice damage and color center changes the lattice structure of the sample, increasing the sample absorption in the visible to infrared light. Yttrium silicate single crystal Y_2SiO_5 (YSO) model of laser crystal material as a kind of widely used, with high chemical stability, low thermal expansion coefficient, excellent optical properties and thermal conductivity Has attracted the attention of many scholars. The application of energy for 6.0MeV, at a dose of 1 * 1015ion/cm~2 C~ (3+) Y_2SiO_5 irradiation (YSO) planar optical waveguide structures by crystal. The results show that the C~ (3+) after irradiation to form a "barrier" type optical waveguide structure, XRD spectra of irradiated samples the increase of FWHM, the peak positions of high angle offset (2 theta larger), the grain size and changes in Raman peak intensity, hardness and Young's modulus of the samples increased after irradiation and C~ (3+), the damage caused by radiation on the structure of samples in C~ (3+) irradiation on YSO sample impact in the absorption of ultraviolet light, and there is no effect in the visible light and near infrared band. The application of different energy and dose of C~ (3+) and O~ (3+) were irradiated YSO and Pr:YSO crystals were prepared by a plurality of optical waveguide structures. The test results show that the ion irradiated samples in TE and TM mode respectively. The formation of different types The structure of the waveguide, and the waveguide structure C~ (3+) irradiation can be formed by.O~ support single mode transmission in visible light (3+) irradiation of waveguide structure can support multimode transmission in visible band, O~ (3+) irradiation than C~ (3+) irradiation on the damage caused by large sample ion absorption in the ultraviolet radiation. Band samples significantly enhanced after irradiation, and the absorption rate increases with the increase of irradiation dose increased. The C~ (3+) after irradiation hardness and Young's modulus of YSO samples increased with the increase of irradiation dose increased, while the O~ (3+) after irradiation hardness and Young's modulus of Pr:YSO samples decreased. Non metal ion doping the ZnO material in the visible region can effectively improve the light absorption of the samples, and N ion because of its electronic structure and ionic radius similar to O ion, low ion energy, easy to handle and the advantages of rich resources, is often considered as a kind of effective application of doped ions. Magnetron sputtering on sapphire (Al_2O_3) substrate ZnO nano film was prepared, the samples were part of the energy of 90 keV, at a dose of 1 * 1015ions/cm~2 N~+ irradiation treatment, annealing treatment on non irradiated and irradiated samples were 100 to 500 DEG C, the results of the study show that N~+ irradiation and increased the annealing temperature can improve the crystalline quality of the samples, after ion irradiation the band gaps of the samples increases; increasing the annealing temperature, the transmittance of the unirradiated sample decreased after irradiation. The band gaps of the samples decreased by ion irradiation technology can prepare high quality ZnO nano film materials in suitable annealing temperature. Because of the number of layers and area controllable, band gap in the advantages of 1-2 eV range control, a single atomic layer or two transition metal sulfides several atomic layer thickness in the lubricant, catalysis, energy, light and power devices Can be widely used in many fields of nano composite materials. The application of energy is 600 keV and 6 MeV, the dose of O ion irradiation multilayer nano WS_2 1 * 1014 * 1015 ions/cm~2 and 1 ions/cm~2, the results show that ion irradiation of multilayer WS_2 nanosheets were decreased, thickness, high energy O~ (3+) irradiation destroyed the nano WS_2 multilayer structure. The original triangle produced by irradiation damage on nanoscale thin films, optical band gap of Eg increased with the increase of irradiation of the ion energy, decreases with the increase of irradiation dose. Therefore, effective regulation of multilayer WS_2 nano sheet layers and the optical band gap through the regulation of O ion irradiation conditions. The application of energy was 600 keV and 6 MeV, the dose of O ion irradiation multilayer nano MoSe_2 1 * 1014 * 1015 ions/cm~2 and 1 ions/cm~2, the research results show that the nano size of irradiated samples Change, has gathered the superposition growth trend, its shape is no longer a perfect triangle structure. High dose irradiation of high energy nano film thickness to reduce, O~+ low energy high dose irradiation to better the crystallinity of the samples. The destruction of Vander Ed Ley ion irradiation and electronic structure of MoSe_2 nano multilayer film with middle layer between. The sample transmittance increases, the band gap change multilayer MoSe_2 nano sheet width.

【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TN25

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