Preparation, microstructure and properties of LaCePr polishing slurry for optical glass CMP
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摘要: 以包头混合型稀土矿经浓硫酸强化焙烧、水浸、中和除杂、P507萃取转型分级的产物为原料配制LaCePr氯化液,以碳酸氢铵和氨水的混合液为沉淀剂,氢氟酸为氟化剂,聚丙烯酸钠、六偏磷酸钠、氢氧化钠等为添加助剂,通过并流沉淀、氟化、高温焙烧、引入助剂、调浆湿法球磨等工序成功制备LaCePr稀土CMP抛光液。借助扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-Ray衍射仪(XRD)、平面精密研磨抛光机及光学3D表面轮廓仪对制备的抛光液性能进行表征。结果表明:La、Pr和F元素均以溶质原子固溶的方式进入CeO2晶格中,LaCePr抛光液风干后样品中的立方萤石结构CeO2、四方结构LaOF、面心立方Pr6O11起协同CMP作用。累积抛光H-K9L光学玻璃片120 min后,其最大抛蚀速率可达219.7 nm/min,表面粗糙度Sa由抛光前的1.123 nm降至抛光后的0.668 nm。相同条件下用于对比测试的LaCe抛光液的最大抛蚀速率仅为199.9 nm/min,且抛光后的表面粗糙度Sa降至0.659 nm。因此,制备的LaCePr CMP抛光液综合性能较优。Abstract: Objectives: In recent years, cerium-based rare earth polishing liquids have been widely used in the field of chemical mechanical polishing (CMP) of glass and other materials due to their excellent selectivity and good polishing efficiency, but their polishing performance needs to be further improved. Using Baotou mixed rare earth ore as the raw material and other additives as auxiliary materials, the LaCePr rare earth CMP polishing solution with good comprehensive performance was prepared through a complex process. The microstructure, the element distribution, and phases were studied, and specific polishing experiments were conducted to evaluate its polishing performance. Methods: The LaCePr chlorination solution was prepared using the product of Baotou mixed rare earth ore, which underwent concentrated sulfuric acid enhanced roasting, water leaching, neutralization and impurity removal, P507 extraction transformation and grading. The mixture of ammonium bicarbonate and ammonia water was used as a precipitant, hydrofluoric acid was used as a fluorinating agent, and sodium polyacrylate, sodium hexametaphosphate, sodium hydroxide and other additives were added. The LaCePr rare earth CMP polishing solution samples were prepared through processes such as co-flow precipitation, fluorination, high-temperature roasting, introduction of additives, slurry mixing, and wet ball milling. Subsequently, the macroscopic structure of the prepared polishing solution was observed, and the elemental distribution in the sample was measured using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The solid polishing powder sample of the LaCePr rare earth polishing solution after air drying was analyzed using X-ray diffraction (XRD). The CMP polishing performances of the prepared LaCePr rare earth polishing solution were tested, and the polishing effect of the workpiece was evaluated using the planar precision polishing machine and the optical 3D surface profilometer. Results: (1) The morphology of the solid polishing powder after air-drying of the polishing liquid consists of irregular polygonal spherical grains tightly aggregated, which mainly shows that the fine particles are agglomerated together. In addition, there are no coarse particles in the whole cluster, indicating that the introduction of F and doping of Pr have a positive effect on the lattice distortion of CeO2. (2) The microstructure and the element distribution diagram of the solid polishing powder show that the solid solution second-phase particles appear around the grain boundaries of individual particles, indicating that the doped La and Pr elements mainly enter the CeO2 lattice in a solid-solution manner. The La, Ce, Pr and O elements are uniformly distributed, confirming that the introduction of the F element can play a role in grain refinement. (3) In addition to the characteristic peaks of the CeO2 phase, the diffraction peaks of LaOF, Pr6O11, LaF3, PrOF and other phases are also observed in the rare earth polishing solution sample, indicating that the doped La, Pr and F elements enter the CeO2 lattice in the form of a solid solution of solute atoms. The face-centered cubic Pr6O11 structure is the same as that of CeO2, so it can exert a synergistic polishing effect together with CeO2. (4) The initial polishing ability of the LaCe rare earth polishing solution is 182.6 nm/min. After polishing for 40, 60, 80 and 120 minutes, the polishing abilities of the LaCe polishing solution are 199.3, 199.9, 193.8 and 158.2 nm/min, respectively. The initial polishing ability of the newly prepared LaCePr rare earth polishing solution is 203.4 nm/min. After polishing for 40, 60, 80, and 120 minutes, the polishing abilities of the LaCePr polishing solution are 219.7, 214.7, 206.3 and 189.8 nm/min, respectively. (5) The surface roughness Sa of the glass after five CMP cycles with the LaCe polishing solution is 0.659 nm, while the surface roughness Sa of the glass after five CMP cycles with the LaCePr polishing solution is 0.668 nm. Conclusions: By using LaCePr rare earth chloride solution, the LaCePr rare earth polishing solution can be successfully prepared through processes such as precipitation, fluorination, high-temperature calcination, additive blending, and wet ball milling. The entire process of the preparing polishing solution has achieved zero wastewater discharge, which is a green polishing solution preparation process. After air drying, the LaCePr rare earth polishing solution, the medium particles in the sample are well-formed and evenly distributed. The doped La, Pr and F elements all enter the CeO2 lattice through solute atom solid solution. The cubic fluorite structure of CeO2, the tetragonal structure of LaOF, and the face-centered cubic structure of Pr6O11 in the LaCePr rare earth polishing solution exhibit a synergistic polishing effect. After 120 minutes of cumulative polishing of H-K9L optical glass, the maximum polishing rate of the LaCe polishing solution is 199.9 nm/min, while the maximum polishing rate of the LaCePr polishing solution can reach 219.7 nm/min. The polishing quality of H-K9L glass is basically the same after polishing with the two kinds of polishing solutions, and the surface roughness Sa decreases from the initial 1.123 nm to 0.659 nm and 0.668 nm, respectively. Therefore, the comprehensive properties of the prepared LaCePr CMP polishing liquid are better.
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表 1 LaCePr氯化液化学成分
Table 1. Chemical compositions of LaCePr chlorination solution
元素 质量分数 ω / % La 33.46 Ce 65.97 Pr 0.50 其他 <0.10 -
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