铟、钇氢氧化物和氧化物以及光子晶体的制备与性能研究
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摘要
纳米材料是指特征维度尺寸在纳米数量级(1~100 nm)的固体材料。由于具有量子尺寸效应,小尺寸效应以及表面效应等特殊性质,纳米材料的光学性质表现一系列不同于块体材料的新奇性质。氢氧化铟和氧化铟是重要的半导体材料,块体的氧化铟在室温下没有任何荧光性质,但当尺寸减小到纳米级时,由于晶体有氧空穴的存在,所以具有了良好的荧光性质。氢氧化钇和氧化钇由于钇离子的电子层结构,表现出光学惰性,是优异的发光基质材料。光子晶体是一种介电常数随空间周期性变化的新型光学微结构材料,可以用于控制光的传播方向。因此,对纳米材料光学性质的研究和光子晶体的研究是一个统一的课题。
本文主要研究了铟、钇氢氧化物和氧化物微纳米结构的合成以及蝴蝶翅膀的光子晶体结构,并对它们的光学性质进行了初步研究。
一、以In_2O_3粉体为原料,加入一定浓度的NaOH溶液,通过简单的水热处理,得到了去角去棱状的In(OH)_3微晶。通过高温煅烧后,得到了去角去棱状的In_2O_3微晶,且尺寸大小与前驱体相当。改变反应时间对去角去棱状In(OH)_3的形成机理进行探讨,发现这种结构的形成主要有两个步骤:首先是In_2O_3和NaOH反应生成In(OH)_3立方晶体,然后是合成的In(OH)_3和剩余的NaOH发生了两性反应,由于立方晶体的顶点和晶棱能量比相应晶面的能量要高,所以In(OH)_3立方晶体的顶点和晶棱率先和NaOH反应,在适当的反应时间下,便得到了这种特殊的去角去棱状结构。荧光光谱表明,去角去棱状In(OH)_3和In_2O_3与完整的和去角状的In(OH)_3和In_2O_3立方晶体相比,具有更优异的光致发光性质。
二、以Y(NO_3)_3?6H2O和十八胺分子(ODA)为原料,用无水乙醇作为溶剂和反应体系,经过溶剂热处理,得到了米状的Y(OH)_3粒子。通过改变反应时间,反应温度,反应体系的极性以及碱源等影响因素,对米状的Y(OH)_3粒子的形成机理进行了初步探讨。结果表明,在此实验中,无水乙醇是得到米状产物的关键因素。将米状的Y(OH)_3在500°C的空气氛围下煅烧,可以得到了立方晶型的米状Y_2O_3粒子,其形貌和大小与前驱体基本相同。
采用相同的实验步骤合成了米状的Y(OH)_3: Eu~(3+)和Y_2O_3: Eu~(3+),并利用荧光分光光度计分别对其进行了光致发光光谱分析。
三、以柑橘凤蝶翅膀为研究对象,对其光子晶体结构和光学性质进行了研究。然后以此翅膀为模板,采用溶胶-凝胶法和后续的煅烧处理,得到了TiO_2,SiO_2和Al_2O_3的翅膀结构复制体。测试结果表明,所得的氧化物复制体不但具有翅膀的微观结构,而且产生了一定的光谱带隙。漫反射光谱图显示,与原始蝴蝶翅膀的光谱图相比,无机氧化物复制体基本复制了蝴蝶翅膀的光子晶体特性,只是反射光波段的起始位置都发生了红移。
Nanomaterials have been defined as the material which possess the characteristic dimensional size at 1~100 nm. Due to their special properties, such as quantum size effects, small size effect and surface effect, nanomaterials show novel optical properties which are different from their bulk counterparts. Indium hydroxide (In(OH)_3) and indium oxide (In_2O_3) are important semiconductor materials. In_2O_3 nanostructures show excellent photoluminescence properties due to the oxygen cavity, however, the bulk In_2O_3 can not emit light at room temperature. Yttrium hydroxide (Y(OH)_3) and yttrium oxide (Y2O3) are outstanding luminescence carrier because of the electronic shell of Y~(3+). Photonic Crystals is a new sort of optical microstructure materials, in which their dielectric constants change with the periodic space. This structure can be applied in controlling the broadcasting direction of light due to their photonic forbidden band. From this point, research on the optical properties of nanomaterials and photonic crystals is a uniform subject.
In this paper, the synthesis and optical properties of indium hydroxide/oxide micro/nanostructure, yttrium hydroxide/oxide micro/nanostructure have been reported, and the photonic structures and optical properties of the butterfly wings and their corresponding inorganic replica have been also investigated.
Indium Hydroxide Truncated Polyhedral Microcrystals (IHTPM) have been synthesized by hydrothermally treating commercial In_2O_3 powders in the NaOH solution. Indium Oxide Truncated Polyhedral Microcrystals (IOTPM) have been obtained by thermal decomposition method using the IHTPM as precursor. The formation mechanism of the IHTPM has been proposed by adjusting the reaction time, which indicates the In(OH)_3 cubic crystals were formed by the reaction of In_2O_3 and NaOH initially. The reaction between In(OH)_3 cubic microcrystals and NaOH occurs subsequently. As we known, the energy of corners and edges of a cube is higher than its surfaces, so the corner and edge of In(OH)_3 cubic microcrystals will firstly react with NaOH. As a result, the truncated polyhedral structure has been formed. Photoluminescence (PL) spectra show that both the IHTPM and the IOTPM exhibit more excellent luminescence properties than the cubic microcrystals and the corner truncated microcrystals.
Ricelike Y(OH)_3 have been successfully synthesized by hydrothermally treating Y(NO3)_3 and ODA molecular as the raw materials, ethanol as the solvent and solution system. The formation mechanism of Ricelike Y(OH)_3 has been investigated by adjusting the reaction time, reaction temperature and solution system. The results show that the ethanol plays a key role to products with ricelike morphology. The ricelike morphology of Y(OH)_3 precursor was sustained after thermal decomposition to Y2O3. Y(OH)_3: Eu~(3+) and Y2O3:Eu~(3+) with ricelike morphology have also been prepared via the same experiment procedure, and their photoluminescence properties have been investigated.
The photonic crystals structure and optical property of butterfly (Papilio xuthus Linnaeus) wings have been studied. Later, the titania (TiO_2), silica (SiO_2) and alumina (Al_2O_3) replicas with photonic structures were prepared using butterfly wings as the templates by dip-coating processes and subsequent calcination in atmosphere. The results demonstrate that these inorganic replicas not only inherit the complex morphology of the biotemplate but also possess certain spectra banning band. Diffuse reflectance spectra reveal the inorganic replicas own similar optical properties with the original wing, only all of the starting points of the corresponding spectra are red-shifted compared to the original templates.
本文主要研究了铟、钇氢氧化物和氧化物微纳米结构的合成以及蝴蝶翅膀的光子晶体结构,并对它们的光学性质进行了初步研究。
一、以In_2O_3粉体为原料,加入一定浓度的NaOH溶液,通过简单的水热处理,得到了去角去棱状的In(OH)_3微晶。通过高温煅烧后,得到了去角去棱状的In_2O_3微晶,且尺寸大小与前驱体相当。改变反应时间对去角去棱状In(OH)_3的形成机理进行探讨,发现这种结构的形成主要有两个步骤:首先是In_2O_3和NaOH反应生成In(OH)_3立方晶体,然后是合成的In(OH)_3和剩余的NaOH发生了两性反应,由于立方晶体的顶点和晶棱能量比相应晶面的能量要高,所以In(OH)_3立方晶体的顶点和晶棱率先和NaOH反应,在适当的反应时间下,便得到了这种特殊的去角去棱状结构。荧光光谱表明,去角去棱状In(OH)_3和In_2O_3与完整的和去角状的In(OH)_3和In_2O_3立方晶体相比,具有更优异的光致发光性质。
二、以Y(NO_3)_3?6H2O和十八胺分子(ODA)为原料,用无水乙醇作为溶剂和反应体系,经过溶剂热处理,得到了米状的Y(OH)_3粒子。通过改变反应时间,反应温度,反应体系的极性以及碱源等影响因素,对米状的Y(OH)_3粒子的形成机理进行了初步探讨。结果表明,在此实验中,无水乙醇是得到米状产物的关键因素。将米状的Y(OH)_3在500°C的空气氛围下煅烧,可以得到了立方晶型的米状Y_2O_3粒子,其形貌和大小与前驱体基本相同。
采用相同的实验步骤合成了米状的Y(OH)_3: Eu~(3+)和Y_2O_3: Eu~(3+),并利用荧光分光光度计分别对其进行了光致发光光谱分析。
三、以柑橘凤蝶翅膀为研究对象,对其光子晶体结构和光学性质进行了研究。然后以此翅膀为模板,采用溶胶-凝胶法和后续的煅烧处理,得到了TiO_2,SiO_2和Al_2O_3的翅膀结构复制体。测试结果表明,所得的氧化物复制体不但具有翅膀的微观结构,而且产生了一定的光谱带隙。漫反射光谱图显示,与原始蝴蝶翅膀的光谱图相比,无机氧化物复制体基本复制了蝴蝶翅膀的光子晶体特性,只是反射光波段的起始位置都发生了红移。
Nanomaterials have been defined as the material which possess the characteristic dimensional size at 1~100 nm. Due to their special properties, such as quantum size effects, small size effect and surface effect, nanomaterials show novel optical properties which are different from their bulk counterparts. Indium hydroxide (In(OH)_3) and indium oxide (In_2O_3) are important semiconductor materials. In_2O_3 nanostructures show excellent photoluminescence properties due to the oxygen cavity, however, the bulk In_2O_3 can not emit light at room temperature. Yttrium hydroxide (Y(OH)_3) and yttrium oxide (Y2O3) are outstanding luminescence carrier because of the electronic shell of Y~(3+). Photonic Crystals is a new sort of optical microstructure materials, in which their dielectric constants change with the periodic space. This structure can be applied in controlling the broadcasting direction of light due to their photonic forbidden band. From this point, research on the optical properties of nanomaterials and photonic crystals is a uniform subject.
In this paper, the synthesis and optical properties of indium hydroxide/oxide micro/nanostructure, yttrium hydroxide/oxide micro/nanostructure have been reported, and the photonic structures and optical properties of the butterfly wings and their corresponding inorganic replica have been also investigated.
Indium Hydroxide Truncated Polyhedral Microcrystals (IHTPM) have been synthesized by hydrothermally treating commercial In_2O_3 powders in the NaOH solution. Indium Oxide Truncated Polyhedral Microcrystals (IOTPM) have been obtained by thermal decomposition method using the IHTPM as precursor. The formation mechanism of the IHTPM has been proposed by adjusting the reaction time, which indicates the In(OH)_3 cubic crystals were formed by the reaction of In_2O_3 and NaOH initially. The reaction between In(OH)_3 cubic microcrystals and NaOH occurs subsequently. As we known, the energy of corners and edges of a cube is higher than its surfaces, so the corner and edge of In(OH)_3 cubic microcrystals will firstly react with NaOH. As a result, the truncated polyhedral structure has been formed. Photoluminescence (PL) spectra show that both the IHTPM and the IOTPM exhibit more excellent luminescence properties than the cubic microcrystals and the corner truncated microcrystals.
Ricelike Y(OH)_3 have been successfully synthesized by hydrothermally treating Y(NO3)_3 and ODA molecular as the raw materials, ethanol as the solvent and solution system. The formation mechanism of Ricelike Y(OH)_3 has been investigated by adjusting the reaction time, reaction temperature and solution system. The results show that the ethanol plays a key role to products with ricelike morphology. The ricelike morphology of Y(OH)_3 precursor was sustained after thermal decomposition to Y2O3. Y(OH)_3: Eu~(3+) and Y2O3:Eu~(3+) with ricelike morphology have also been prepared via the same experiment procedure, and their photoluminescence properties have been investigated.
The photonic crystals structure and optical property of butterfly (Papilio xuthus Linnaeus) wings have been studied. Later, the titania (TiO_2), silica (SiO_2) and alumina (Al_2O_3) replicas with photonic structures were prepared using butterfly wings as the templates by dip-coating processes and subsequent calcination in atmosphere. The results demonstrate that these inorganic replicas not only inherit the complex morphology of the biotemplate but also possess certain spectra banning band. Diffuse reflectance spectra reveal the inorganic replicas own similar optical properties with the original wing, only all of the starting points of the corresponding spectra are red-shifted compared to the original templates.
引文
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