La_2Mo_3O_（12）薄膜的制备和光学性能的研究
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摘要
稀土钼酸镧有多种结构,但研究比较多的为La2Mo2O9、La2Mo8O33、La2Mo3O12三种相。La2Mo2O9在580℃附近从低温α相向高温β相转变,转变后氧离子的传导性可提高两个数量级。La2Mo8O33是一种非同寻常的、缺陷有序排列的白钨矿结构,其阳离子缺乏及额外氧原子同时存在,与白钨矿结构PbWO4发冷光的特点类似,是探测器闪烁晶体的潜在材料。白钨矿结构超细La2Mo3O12微粒,可提高常用烃类发生选择氧化反应时作为催化剂的催化性能；掺杂后其吸收峰变宽,阈值低,增益大,效率高,是很好的激光晶体材料。
不仅如此,La2Mo3O12是稀土钼酸盐中完全不吸水,且呈现正膨胀特性的物质,与Y2Mo3O12的膨胀系数和晶格常数相匹配,二者合成后可制成零膨胀材料,用于高能激光器,航空航天飞行器中。
文献表明,La2Mo3O12高温下是四面体结构,且结构中存在大量的氧空位,其三价阳离子有非同寻常的传导性,可应用于多种领域,但La2Mo3O12在室温下的结构和薄膜制备及光学性能研究未见报道。
研究La2Mo3O12薄膜及光学性能,对于拓展其在探测器、光致发光等方面的应用具有实际价值。本文采用固相反应法自制靶材、磁控溅射法制La2Mo3O12薄膜,使用SEM、XRD、UV-vis分光光度计、椭圆偏振仪等对制备的样品进行了表征,研究了制备工艺、退火温度对其结构和微观形貌的影响,研究了薄膜的光吸收性能和光学常数。主要结论如下：
1.采用改进的固相反应法自制靶材。其最佳工艺参数为800℃、2h烧结成粉体,18MPa下冷等静压成原始胚体,空气氛围下950℃、4h二次烧结成靶材。颜色是浅黄色,表面平整、致密,收缩率为9%。
2.采用射频磁控溅射法,用自制靶材,制备出符合化学计量比的La2Mo3O12薄膜。本实验最佳工艺参数为：溅射功率180W,溅射电压800V,溅射电流200mA,背景真空1.3Pa,衬底温度180℃-240℃,工件转速是60rpm。
3.适当的退火温度能改善La2Mo3O12薄膜的表面形貌、晶体结构和晶粒分布。(1)未退火的La2Mo3O12薄膜,晶粒大小不一,呈细条形,表面凸凹不平,退火后薄膜表面变得比较平整,致密,样品结晶成树叶形状,晶粒大小变得比较均匀,为细小的枝晶结构,出现比较明显的晶界。(2)未退火的La2Mo3O12薄膜呈现典型的非晶状态,退火后结晶明显,实验发现,薄膜易结晶成四面体结构,700℃-750℃是比较理想的退火温度。
4.La2Mo3O12薄膜的结构和光学性能
用射频磁控溅射法制备了四面体结构的薄膜,随沉积温度的提高,在近紫外区透过率没有明显变化,光吸收性能非常好,其光学常数满足正常的色散关系。La2MoO12薄膜是直接带隙半导体,电子发生了间接跃迁,计算出薄膜的光学带隙大约是3.52eV折射率在1.8到2.15之间,为该材料在光学方面的应用,特别是在制作紫外光电探测器方面提够了理论依据。
The rare lanthanum molybdate has many kinds of structure, but more research for La2Mo2O9,La2Mo8O33,La2Mo3O12 of three phases. The La2Mo2O9 shows a phase transtion from the low temperatureα-phase to the high temperatureβ-phase,and the oxygen-ion conductivity ofβ-phase is almost 2 order of magnitude higher than theα-phase.La2Mo8O33 is an unusual ordered defect Sheltie with cation vacancies and an extra oxygen atom, with the Sheltie struture similar PbWO4 luminescent characteristics,It is a potential material of a scintillator in detector.Scheelite structure of ultrafine La2Mo3O12 particles can increase the occurrence of selective oxidation of hydrocarbons common reaction as the catalytic performance,After the doping,its absorption peak broaden,the threshold value is low,increases in a big way, the efficiency is high,It is the very good laser crystal material.
Not only that, La2Mo3O12 is the only rare earth molybdate completely non-absorbent, and the positive thermal expansion characteristics of material being presented, matches with the Y2Mo3O12 expansion coefficient and lattice constant. After the two synthesis, they may make zero expanding material,used in the high-energy laser, aerospace vehicle.
The literature indicated that under the high temperature, La2Mo3O12 is the tetrahedron structure, and has the massive oxygen vacancies, which are unusual trivalent cation conductivity, It can be used in a variety of areas. But at room temperature La2Mo3O12 structure and Films and Optical Properties has not been reported.
Studies the La2Mo3O12 thin film and the optical property that have the actual value, regarding develops it in aspect for detector, photoluminescence applications. In this paper, targets was made by solid state reaction method,La2Mo3O12 thin films were prepared by RF magnetron sputtering method, and were charactered by scanning electron microscope (SEM), X-ray diffraction (XRD), UV-vis spectroscopy and spectroscopic ellipsometer. The preparation technics as well as the impact of annealing temperature on microstructure and optical properties of La2Mo3O12 thin films were studied. The main conclusions are the following:
1. Target was made by improved solid state reaction method. The optimum process parameter is that powers was sintered for 2h at 800℃, pressed the original embryo under 18MPa by cold isostatic pressure, second sintered into targets for 4h at 950℃under air atmosphere. The color of target is light yellow, The surface is smooth and compact shrinkage was 9%.
2. Nearly stoichiometric La2Mo3O12 films were prepared by RF magnetron sputtering, using home-made target. In this study, the optimum parameters are sputtering power of 180W, sputtering voltage of 800V and sputtering current of 200mA, the background vacuum 1.3Pa, substrate temperature of 180℃-240℃, the workpiece rotation speed of 60rpm
3. Appropriate annealing temperature can improve the La2Mo3O12 film surface morphology, crystal structure and grain distribution.
(1).The grains of no annealing La2Mo3O12 films were small bar, the surface is rugged, after the annealing,the surface of thin films become quite smooth, compact, the sample crystallizes the leaf shape, the grain size becomes quite even, the shape shows the tiny arborescent crystal structure, grain boundaries appear obvious.
(2). La2Mo3O12 films before annealing exhibited a typical amorphous state, The crystallinity of La2Mo3O12 films are improved obviously after annealing. The experiment discovered that the films crystallize into a tetrahedral structure easily, 700℃—750℃is the quite ideal annealing temperature.
4. The structure and optical properties of La2Mo3O12 films
Tetrahedral structure of La2Mo3O12 thin films were prepared by RF magnetron sputtering. With the deposition temperature increased, The transmittance did not have obvious change and the optical absorption is very good in near ultraviolet area. Its optical constant satisfied the normal dispersion relation. The La2Mo3O12 thin film was the direct band gap semiconductor, the electron has had the indirect transition. The calculation shows that the thin film optics band gap probably is 3.52eV, the refractive index is between 1.8 and 2.15, the value provided enough theory in optical, especially in the production aspects of ultraviolet detector
不仅如此,La2Mo3O12是稀土钼酸盐中完全不吸水,且呈现正膨胀特性的物质,与Y2Mo3O12的膨胀系数和晶格常数相匹配,二者合成后可制成零膨胀材料,用于高能激光器,航空航天飞行器中。
文献表明,La2Mo3O12高温下是四面体结构,且结构中存在大量的氧空位,其三价阳离子有非同寻常的传导性,可应用于多种领域,但La2Mo3O12在室温下的结构和薄膜制备及光学性能研究未见报道。
研究La2Mo3O12薄膜及光学性能,对于拓展其在探测器、光致发光等方面的应用具有实际价值。本文采用固相反应法自制靶材、磁控溅射法制La2Mo3O12薄膜,使用SEM、XRD、UV-vis分光光度计、椭圆偏振仪等对制备的样品进行了表征,研究了制备工艺、退火温度对其结构和微观形貌的影响,研究了薄膜的光吸收性能和光学常数。主要结论如下：
1.采用改进的固相反应法自制靶材。其最佳工艺参数为800℃、2h烧结成粉体,18MPa下冷等静压成原始胚体,空气氛围下950℃、4h二次烧结成靶材。颜色是浅黄色,表面平整、致密,收缩率为9%。
2.采用射频磁控溅射法,用自制靶材,制备出符合化学计量比的La2Mo3O12薄膜。本实验最佳工艺参数为：溅射功率180W,溅射电压800V,溅射电流200mA,背景真空1.3Pa,衬底温度180℃-240℃,工件转速是60rpm。
3.适当的退火温度能改善La2Mo3O12薄膜的表面形貌、晶体结构和晶粒分布。(1)未退火的La2Mo3O12薄膜,晶粒大小不一,呈细条形,表面凸凹不平,退火后薄膜表面变得比较平整,致密,样品结晶成树叶形状,晶粒大小变得比较均匀,为细小的枝晶结构,出现比较明显的晶界。(2)未退火的La2Mo3O12薄膜呈现典型的非晶状态,退火后结晶明显,实验发现,薄膜易结晶成四面体结构,700℃-750℃是比较理想的退火温度。
4.La2Mo3O12薄膜的结构和光学性能
用射频磁控溅射法制备了四面体结构的薄膜,随沉积温度的提高,在近紫外区透过率没有明显变化,光吸收性能非常好,其光学常数满足正常的色散关系。La2MoO12薄膜是直接带隙半导体,电子发生了间接跃迁,计算出薄膜的光学带隙大约是3.52eV折射率在1.8到2.15之间,为该材料在光学方面的应用,特别是在制作紫外光电探测器方面提够了理论依据。
The rare lanthanum molybdate has many kinds of structure, but more research for La2Mo2O9,La2Mo8O33,La2Mo3O12 of three phases. The La2Mo2O9 shows a phase transtion from the low temperatureα-phase to the high temperatureβ-phase,and the oxygen-ion conductivity ofβ-phase is almost 2 order of magnitude higher than theα-phase.La2Mo8O33 is an unusual ordered defect Sheltie with cation vacancies and an extra oxygen atom, with the Sheltie struture similar PbWO4 luminescent characteristics,It is a potential material of a scintillator in detector.Scheelite structure of ultrafine La2Mo3O12 particles can increase the occurrence of selective oxidation of hydrocarbons common reaction as the catalytic performance,After the doping,its absorption peak broaden,the threshold value is low,increases in a big way, the efficiency is high,It is the very good laser crystal material.
Not only that, La2Mo3O12 is the only rare earth molybdate completely non-absorbent, and the positive thermal expansion characteristics of material being presented, matches with the Y2Mo3O12 expansion coefficient and lattice constant. After the two synthesis, they may make zero expanding material,used in the high-energy laser, aerospace vehicle.
The literature indicated that under the high temperature, La2Mo3O12 is the tetrahedron structure, and has the massive oxygen vacancies, which are unusual trivalent cation conductivity, It can be used in a variety of areas. But at room temperature La2Mo3O12 structure and Films and Optical Properties has not been reported.
Studies the La2Mo3O12 thin film and the optical property that have the actual value, regarding develops it in aspect for detector, photoluminescence applications. In this paper, targets was made by solid state reaction method,La2Mo3O12 thin films were prepared by RF magnetron sputtering method, and were charactered by scanning electron microscope (SEM), X-ray diffraction (XRD), UV-vis spectroscopy and spectroscopic ellipsometer. The preparation technics as well as the impact of annealing temperature on microstructure and optical properties of La2Mo3O12 thin films were studied. The main conclusions are the following:
1. Target was made by improved solid state reaction method. The optimum process parameter is that powers was sintered for 2h at 800℃, pressed the original embryo under 18MPa by cold isostatic pressure, second sintered into targets for 4h at 950℃under air atmosphere. The color of target is light yellow, The surface is smooth and compact shrinkage was 9%.
2. Nearly stoichiometric La2Mo3O12 films were prepared by RF magnetron sputtering, using home-made target. In this study, the optimum parameters are sputtering power of 180W, sputtering voltage of 800V and sputtering current of 200mA, the background vacuum 1.3Pa, substrate temperature of 180℃-240℃, the workpiece rotation speed of 60rpm
3. Appropriate annealing temperature can improve the La2Mo3O12 film surface morphology, crystal structure and grain distribution.
(1).The grains of no annealing La2Mo3O12 films were small bar, the surface is rugged, after the annealing,the surface of thin films become quite smooth, compact, the sample crystallizes the leaf shape, the grain size becomes quite even, the shape shows the tiny arborescent crystal structure, grain boundaries appear obvious.
(2). La2Mo3O12 films before annealing exhibited a typical amorphous state, The crystallinity of La2Mo3O12 films are improved obviously after annealing. The experiment discovered that the films crystallize into a tetrahedral structure easily, 700℃—750℃is the quite ideal annealing temperature.
4. The structure and optical properties of La2Mo3O12 films
Tetrahedral structure of La2Mo3O12 thin films were prepared by RF magnetron sputtering. With the deposition temperature increased, The transmittance did not have obvious change and the optical absorption is very good in near ultraviolet area. Its optical constant satisfied the normal dispersion relation. The La2Mo3O12 thin film was the direct band gap semiconductor, the electron has had the indirect transition. The calculation shows that the thin film optics band gap probably is 3.52eV, the refractive index is between 1.8 and 2.15, the value provided enough theory in optical, especially in the production aspects of ultraviolet detector
引文
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