中国科学院机构知识库网格系统: 新型金属偶氮的制备及其红光超分辨记录特性的研究

中国科学院机构知识库网格

Chinese Academy of Sciences Institutional Repositories Grid

新型金属偶氮的制备及其红光超分辨记录特性的研究

文献类型：学位论文


作者	陈文忠
学位类别	博士
答辩日期	2007
授予单位	中国科学院上海光学精密机械研究所
导师	吴谊群
关键词	金属偶氮螯合物光谱性质热学性质薄膜光学性质超分辨记录性能
其他题名	Synthesis of novel metal-azo dyes and their recording properties for red-ray super resolution
中文摘要	本文综述了近年来超分辨近场功能薄膜的研究概况，在全面分析了超分辨近场功能薄膜的膜层结构、作用机理，掩膜层、记录层、保护层材料的性质、类型及其对超分辨性能的影响的基础上，开展了新型金属偶氮的分子结构设计、合成，成膜特性、热学性质、薄膜的光学性质和红光超分辨记录特性的研究，现将主要研究结果阐述如下：（1）设计并合成了27种唑类偶氮金属螯合物，包括噻唑类偶氮金属螯合物、苯并噻唑类偶氮金属螯合物、异噁唑类偶氮金属螯合物、噻二唑类偶氮金属螯合物和三唑类偶氮金属螯合物。其中25种金属偶氮螯合物尚未见文献报道。采用元素分析，1H-NMR、红外光谱以及质谱分析证明所制备的化合物组成、结构与目标化合物一致。（2）吸收光谱的研究表明，所合成的27种金属螯合物薄膜的吸收光谱的最大吸收峰波长在540-670nm范围，中心金属、偶氮配体的类型、取代基等对螯合物的吸收光谱均有一定影响，其规律如下： 1）中心金属对偶氮螯合物吸收光谱的影响：中心金属的配位对偶氮螯合物吸收光谱的最大吸收峰波长有明显的红移作用。在配体相同的情况下，不同中心金属对螯合物薄膜吸收光谱的红移程度不同。噻唑类：Cu2+>Ni2+>Co2+>Zn2+；苯并噻唑类和三唑类：Co2+>Cu2+>Ni2+>Zn2+；异噁唑：Cu2+>Ni2+、Co2+>Zn2+；噻二唑类Ni2+>Zn2+。 2）偶氮配体的类型对金属螯合物吸收光谱的影响：当中心金属相同时，不同偶氮配体对金属螯合物吸收光谱的红移作用的影响程度为：苯并噻唑类噻唑类噻二唑类三唑类和异噁唑类； 3）取代基对金属螯合物吸收光谱的红移作用：硝基取代（50-80 nm）>>乙氧基取代（15-20 nm）乙巯基取代（10-15 nm）二甲基取代（~10nm）叔丁基取代（7-8nm）单甲基取代（~6nm）。（3）热分解性质的研究表明，偶氮配体的分子结构、取代基以及参与配位的金属离子对化合物的热分解性质都有一定的影响，其规律如下： 1）偶氮配体的种类对螯合物热分解性能有较大的影响，对同一种配位的金属离子而言，当偶氮配体含有同种取代基时，其热稳定性的顺序为：噻二唑类>苯并噻唑类>噻唑类>异噁唑类。初始分解温度与偶氮染料分子的π电子的离域程度有关，π电子的离域程度越大，即分子的共轭程度越高，其热稳定性越高。噻唑类、苯并噻唑类和噻二唑类金属螯合物的初始分解温度均在250℃以上，分解温度范围一般为10-50℃，失重率在30%以上，特别是Ni-ACTDATFS失重率达到59%，分解温度范围仅为18℃，热重分解曲线非常陡峭，这对于红光超分辨记录十分有利。 2）偶氮配体取代基对螯合物的热分解性能有一定的影响。对同种配体而言，取代基对染料热分解性能的影响顺序为二甲基取代单甲基取代>无取代基>硝基取代；甲基取代乙巯基取代；甲基取代>叔丁基取代；无取代基>乙氧基取代。 3）金属离子对偶氮螯合物热分解性能的影响：金属离子对偶氮螯合物热分解性能的影响随偶氮染料配体的结构不同而不同。在本文研究的Ni2+，Co2+，Cu2+，Zn2+四种金属离子中，铜类螯合物的初始分解温度要比相同配体的其他三种金属的低，其他三种金属离子螯合物的热分解性能和染料配体结构有关。（4）对新化合物在四氟丙醇（TFP，制盘时的特定溶剂）中的溶解性研究表明，金属偶氮螯合物在四氟丙醇（TFP）中的溶解性与偶氮配体的种类和结构有密切的关系，不同偶氮配体的金属螯合物在的四氟丙醇（TFP）中的溶解性顺序为：异噁唑类噻唑类三唑类噻二唑类苯并噻唑类。取代基对偶氮金属螯合物溶解性的影响的顺序为：叔丁基>单甲基>二甲基>无取代基>>硝基取代。不同中心金属的螯合物溶解性顺序为：Cu Ni、Zn Co。采用新化合物Ni-ACTDATFS制备的旋涂膜的表面粗糙度仅为0.432nm，均匀性符合红光超分辨记录的要求。（5）使用椭圆偏振光谱法分别测定了金属螯合物Ni-ACTDATFS、Co-ACTDATFS、Ni-DTDATFS和Zn-DTDATFS旋涂膜的光学常数。Ni-ACTDATFS 和Co-ACTDATFS和折射率n分别为2.38和2.39，消光系数k分别为0.19和0.20；Ni-DTDATFS的n和k分别为2.7和0.7，而Zn-DTDATFS薄膜的n和k分别为2.6和0.4。这些金属螯合物具有较大的n值，同时k值略高于传统的DVD-R染料，这对于降低红光超分辨可录光盘的记录功率、提高记录灵敏度非常重要。（6）薄膜反射光谱的研究表明，偶氮配体对镍螯合物薄膜在650nm处的相对反射率有较大的影响，其影响程度为：噻唑类偶氮配体和噻二唑偶氮配体三唑类偶氮配体异噁唑类偶氮配体和苯并噻唑类偶氮配体。噻唑类偶氮金属螯合物和噻二唑类偶氮金属螯合物薄膜在650nm处的相对反射率（无金属反射膜时）大于24%，其中噻唑类偶氮金属螯合物Ni-TDATFS和Ni-ACTDATFS达到35%以上；是一类有希望的红光超分辨记录材料。（7）本文首次以有机材料金属偶氮作为超分辨记录层， Sb作为掩膜层，进行了红光超分辨记录性能的研究，并考察了不同记录功率下介电层厚度和掩膜层厚度对超分辨记录性能的影响，得到以下研究结果： 1）介电层的厚度对样品的超分辨效果的影响：介电层的厚度对样品的超分辨效果有较大的影响，这种影响与记录功率密切相关：当记录功率为6-9mW时，样品的超分辨效果大体上随介电层厚度的增加而减低。当记录功率为6-7mW时，介电层的厚度在20-250 nm时，均可获得10%以上的超分辨效果；特别是当介电层的厚度为20nm、记录功率为6mW时，超分辨效果可达到36%以上。当记录功率≧9mW、介电层的厚度在20-250 nm时，均不能得到有效的超分辨记录。 2）掩膜层的厚度对样品的超分辨效果的影响：掩膜层的厚度对样品的超分辨效果有重要影响，这种影响也与记录功率密切相关：不同掩膜层厚度的样品对其超分辨性能的影响趋势大体上是随着记录功率的增大而降低。记录功率在6.5--7mW时，超分辨性能随样品掩膜层厚度的增加而增强；当记录功率为6.5mW、Sb薄膜厚度为10nm时，记录点尺寸由无超分辨功能膜时的962nm降低至748nm，缩小率为22%；Sb掩膜厚度为25nm时，缩小率则增大至34%；当记录功率为7mW、Sb掩膜厚度为25nm时，有机材料金属偶氮Ni-ACTDATFS作为记录层的超分辨效果可达到37%以上。但当记录功率低于6 mW、高于7mW，Sb掩膜厚度＜25nm时，一般不能得到有效的超分辨记录。记录点AFM形貌观察表明，金属偶氮Ni-ACTDATFS的超分辨记录点形状规整，没有明显的热扩散窜扰现象，且比无机记录材料具有较高的记录灵敏度。（8）以Bi代替Sb作为掩膜层、以(ZnS)80(SiO2)20替代SiN作介电保护层、以Ni-MTDTS作为记录层，进行了红光超分辨静态记录性能探试[实验样品的膜层结构及各层的厚度为：基片/ (ZnS)80(SiO2)20(10nm) / Bi(10nm) / (ZnS)80(SiO2)20(10nm) / Ni-MTDTS（100nm）]。当记录功率为7mW，记录脉宽为200ns时，记录点尺寸减少了44.4%。更深入、系统的研究还有待于进一步进行。研究表明本文制备的金属偶氮Ni-ACTDATFS和Ni-MTDTS可以作为红光超分辨记录介质，其超分辨记录性能可以通过功能膜层和记录条件的优化而进一步提高。上述研究结果为金属偶氮类有机材料作为可录光存储介质的应用开辟了新的途径，同时对于具有我国自主知识产权的新一代红光高密度可录光盘的研制具有重要意义。
英文摘要	In this thesis, the recent research and development of super resolution near-field structure (Super-RENS) optical storage were reviewed. The structure and work mechanism of Super-RENS functional films were analyzed in detail. Based on the analysis of the properties and types of mask layer, recording layer and protective layer and their influence on properties of super resolution, we designed and synthesized a series of novel azo ligand and their metal complexes. Their solubility, thermal properties and optical properties of thin films were studied. The static recording property of red-ray super resolution was also researched. The main research results were shown: (1) Twenty-seven new metal complexes of metal-azo complexes were designed and synthesized including thiazole metal-azo complexes, benzothiazole metal-azo complexes, isoxazole metal-azo complexes, thiadiazole metal-azo complexes and triazole metal-azo complexes. Except the Ni-TDATFS and the Ni-MTDTS, other metal-azo complexes have not been reported until now. The structures of compounds were confirmed by elemental analysis, 1H-NMR, FT-IR and MS. (2) The absorption spectra of twenty-seven metal-azo complexes in films show their maximum absorption wavelengths (λmax) are located at 540-670nm. The absorption spectra of metal-azo complexes in films are mainly influenced by the central metallic ion, type and substitutes of azo ligand. 1) The influence of central metallic ion: The absorption spectra of metal-azo complexes are redshifted much, compared to the azo pigand. When the azo ligands are the same, the absorption spectra of the metal-azo complexes containing of the same azo ligand follow the sequence: Thiazolyazo: Cu2+>Ni2+>Co2+>Zn2+; Benzothiazolyazo and Triazolyazo: Co2+>Cu2+>Ni2+>Zn2+; Isoxazolyazo: Cu2+>Ni2+, Co2+>Zn2+; Thiadiazolyazo: Ni2+>Zn2+ 2 ) The influence of type of azo dye: When the central metal-ion is the same, the maximum absorptions of the metal-azo complexes containing of the different azo ligand follow the sequence: Benzothiazolyazo>Thiazolyazo> Thiadiazolyazo> Triazolyazo and Isoxazolyazo. 3) The influence of substitutes of diazonium group follow the sequence: Nitro-substitution (50-80 nm) >> Ethoxy-substitution (15-20nm)>C2H5S-substitution (10-15) nm> Double CH3-substitution (~10nm)> butyl- substitution (7-8nm)> CH3-substitution (~6nm). (3) The thermal properties of twenty-two metal-azo complexes were analysized by TGA-DSC. The results indicate that the thermal properties of metal-azo complexes are dominated by type of azo ligand, substitutes of azo ligand and central metallic ion. 1) The influence of type of azo dye: When the central metal-ion is the same, the thermal properties of the metal-azo complexes containing of the same substitutes follow the sequence: Thiadiazolyazo> Benzothiazolyazo> Thiazolyazo> Isoxazolyazo. The decomposition temperature of the metal-azo complexes is dominated by the conjugation of π-electrons. The higher is the conjugation of π-electrons and the higher is the temperature of decomposition. The initial decomposition temperature of thiazolyazo, benzothiazolyazo and thiadiazolyazo is above 250℃. The weight reductions is above 30% at a temperature region of 10-50℃. It is noteworthy that Ni-ACTDATFS showed a sharp weight reduction of 59% at a small temperature region of 18℃, which would be advantageous for the recording of red light super resolution. 2) The influence of substitutes of azo ligand: When the azo ligand is the same, the thermal properties of the metal-azo complexes containing of the different substitutes follow the sequence: Double CH3-substitution> CH3-substitution >non substitution>Nitro-substitution; CH3-substitution>C2H5S-substitution; non substitu- tion > Ethoxy-substitution. 3) The influence of central metallic ion: When the structure of azo ligand is different, the different metallic ion has a different influence on the thermal property. Thermal properties of the metal-azo complexes follow the sequence: Cu2+2.0mg/ml) in TFP and smooth films could be prepared easily by spin-coating method. The solubility of the metal-azo complexes follow the sequence: Isoxazolyazo> Thiazolyazo> Thiadiazolyazo> Benzothiazolyazo; butyl-substitution>CH3-substitution>Double CH3-substitution>non substitution> Nitro-substitution; Cu2+ Ni2+, Zn2+ Co2+. (5) The complex refractive indexes N(N=n+ik) of Ni-ACTDATFS, Co-ACTDATFS, Ni-DTDATFS and Zn-DTDATFS spin-coated thin films were determined by an scanning ellipsometer in the wavelength 400-800nm and their incidence angle were 65°, 70° and 75°. The n values of Ni-ACTDATFS and Co-ACTDATFS were 2.38 and 2.39, respectively. Their k values were 0.19 and 0.20, respectively. The n and k values of Ni-DTDATFS and Zn-DTDATFS were 2.7, 0.7 and 2.6, 0.4, respectively. The metal complexes had high n values and their k values were bigger than the recording media of DVDR, which will be helpful for the reduction of the recording power and the improvement of recording sensitivity. (6) The reflective spectra of the films are dominated by the structure of azo ligand and follow the sequence: Thiazolyazo and Thiadiazolyazo> Triazolyazo>Isoxazolyazo and Benzothiazolyazo. The reflective spectra of thiazolyazo-metal complexes and thiadiazolyazo-metal complexes had a contrast reflectility of above 24% (on K9 glass substrate). The contrast reflectility is above 35% in Ni-TDATFS and Ni-ACTDATFS film. (7) Organic material was firstly used for the recording layer of super resolution in thesis. The static recording tests were carried out for the study on super resolution performance, where Sb was used for the mask layer, SiN for the dielectric layer and Ni-ACTDATFS for recording layer. The recording properties of super resolution were studied using different thick dielectric layer and mask layer film in different recording power. 1) The influence of thickness of dielectric layer film: When the recording power (RP) is between 6mW and 9 mW, super resolution effect (SPE) will reduce with the increasing of thickness of dielectric layer film. When RP is between 6mW and 7 mW and the thickness of dielectric layer film is between 20nm and 250nm, above 10% of SPE can be obtained. When the thickness of dielectric layer film is 20nm and the RP is 6 mW, 36% of SPE can be obtained. We can’t obtain super resolution performance with ≧9mW of RP and 20-250nm of thickness of dielectric layer film. 2) The influence of thickness of Sb mask layer film: As a whole, Super resolution performance will descend with the increasing of RP. When RP is between 6.5 and 7 mW, SPE will increase with increasing of thickness of mask layer film. The recording marks descend from 962nm without mask layer to 748nm with 10nm of mask layer with 6.5mW of RP and SPE is 22%. SPE will reach 34% when the thickness of mask layer is 25nm. SPE will be further improved when RP and thickness of mask layer is 7mW and 25nm, respectively. When RP <6mW or RP>7mW and thikness of mask layer is below 25nm, no super resolution performance be observed. (8) The static recording tests were elementarily carried out when Bi was used for the mask layer, (ZnS)80(SiO2)20 for dielectric layer and Ni-MTDTS for the recording layer. SPE is 44% with 7mW of RP and 200ns of pulse width. The static recording tests should be further carried out for the study on super resolution performance in order that we can improve super resolution performance. These results demonstrate that the Ni-ACTDATFS and Ni-MTDTS are promising candidates as recording media for red-ray super resolution. The recording properties of super resolution can be further improved by adjusting the structure of super-resolution functional film and recording conditions. The above results will be helpful for the novel application of metal -azo organic materials as the recording media in recordable optical storage.
语种	中文
源URL	[http://ir.siom.ac.cn/handle/181231/15541]
专题	上海光学精密机械研究所_学位论文
推荐引用方式 GB/T 7714	陈文忠. 新型金属偶氮的制备及其红光超分辨记录特性的研究[D]. 中国科学院上海光学精密机械研究所. 2007.

入库方式： OAI收割

来源：上海光学精密机械研究所

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