Preparation and Polishing Performance of Double-shell P(MMA-MPS)/SiO2/CeO2 Core-shell Composite Abrasive

JIA Huiling; LYU Jiayi; WU Jinxiu; LI Sen; WANG Shaofeng

doi:10.16490/j.cnki.issn.1001-3660.2025.24.015

PDF(17110 KB)

Surface Technology ›› 2025, Vol. 54 ›› Issue (24) : 184-194. DOI: 10.16490/j.cnki.issn.1001-3660.2025.24.015

Precision and Ultra-precision Machining

Preparation and Polishing Performance of Double-shell P(MMA-MPS)/SiO₂/CeO₂ Core-shell Composite Abrasive

JIA Huiling^1a,2,*, LYU Jiayi^1a, WU Jinxiu^1b,2, LI Sen^1a, WANG Shaofeng^1a

Author information +

History +

Abstract

To address the issue of low material removal efficiency observed in traditional polymethyl methacrylate (PMMA)/cerium oxide (CeO₂) composite abrasives during chemical and mechanical polishing (CMP), a novel P(MMA-MPS)/ SiO₂/CeO₂ double-shell composite abrasive system was designed. Through a hierarchical structural design, this system achieved synergistic optimization of the mechanical properties and surface activity of the abrasive, providing a new material solution for the high-performance polishing process.
In terms of material preparation, a stepwise synthesis strategy was employed: Firstly, monodisperse P(MMA-MPS) core microspheres were prepared via soap-free emulsion polymerization under reflux conditions. By systematically adjusting key parameters such as reaction temperature, MPS dosage, and monomer concentration, the morphology and size of the microspheres were successfully controlled. Characterization results confirmed the successful grafting of MPS onto the PMMA chains, as evidenced by the presence of the Si—O—Si crosslinked network and the C==C bonds from the methacryloxy groups. When the MPS dosage was 2 mL, spherical microspheres with a uniform diameter of approximately 300 nm and narrow size distribution were obtained.
Subsequently, with the synthesized P(MMA-MPS) microspheres as cores, a SiO₂ inner shell layer was constructed via the sol-gel method. Under alkaline conditions and with a tetraethyl orthosilicate (TEOS) dosage of 5 mL, monodisperse P(MMA-MPS)/SiO₂composite microspheres with a uniform, dense, strawberry-like morphology were successfully prepared. This intermediate layer not only enhanced the overall structural rigidity but also provided active sites on its surface via silanol groups for the subsequent anchoring of CeO₂.
Finally, an in-situ chemical precipitation method under alkaline conditions was used to uniformly deposit a shell of CeO₂ nanoparticles onto the surface of the SiO₂ interlayer, resulting in the formation of core-double-shell structured P(MMA-MPS)/ SiO₂/CeO₂ composite abrasives. The thickness of the active polishing layer (CeO₂) was precisely controlled by varying the concentration of cerium nitrate. X-ray diffraction (XRD) analysis confirmed that the CeO₂ exhibited a typical cubic fluorite structure. X-ray photoelectron spectroscopy (XPS) analysis further revealed the formation of Si—O—Si chemical bonds between the silanol groups of MPS and the SiO₂ layer, ensuring the stability of the interlayer bonding. Particularly noteworthy was that the Ce³⁺ percentage in the double-shell structure reached 25.6%, indicating an abundance of oxygen vacancy defects on the material surface, which provided ample active centers for surface reactions during the subsequent synergistic polishing process.
To evaluate the practical polishing performance, CMP experiments were conducted on potassium dihydrogen phosphate (KDP) crystals. The results demonstrated that after polishing with the P(MMA-MPS)/SiO₂/CeO₂ composite abrasive, the workpiece surface roughness (RMS) decreased to 0.51 nm and the material removal rate (MRR) reached 302.26 nm/min. Two-dimensional atomic force microscopy (AFM) topography analysis revealed that compared with traditional PMMA/CeO₂ abrasives (which yielded RMS=1.03 nm and MRR=268.8 nm/min), the double-shell abrasive not only achieved a higher polishing rate but also produced a KDP crystal surface with superior quality. This performance enhancement was primarily attributed to the synergistic effect of the double-shell structure: the rigid SiO₂ intermediate layer provided necessary mechanical support, while the CeO₂ outer shell rich in oxygen vacancies enhanced the surface chemical reactivity, thereby achieving highly efficient synergy between chemical action and mechanical removal.

Key words

double shell / core-shell structure / P(MMA-MPS)/SiO₂/CeO₂ abrasive / preparation / polishing performance

Cite this article

EndNote

Ris (Procite)

Bibtex

Download Citations

JIA Huiling, LYU Jiayi, WU Jinxiu, LI Sen, WANG Shaofeng. Preparation and Polishing Performance of Double-shell P(MMA-MPS)/SiO₂/CeO₂ Core-shell Composite Abrasive[J]. Surface Technology. 2025, 54(24): 184-194

References

[1] ZHANG Z F, LIU W L, ZHU J K, et al.Synthesis, Characterization of Ceria-Coated Silica Particles and Their Chemical Mechanical Polishing Performance on Glass Substrate[J]. Applied Surface Science, 2010, 257(5): 1750-1755.
[2] WANG L, REN G Y, XIE W X, et al.Controllable Synthesis of Core-Shell SiO₂@CeO₂ Abrasives for Chemical Mechanical Polishing on SiO₂ Film[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 682: 132901.
[3] 陈国美, 周凌, 倪自丰, 等. pH值对CeO₂/SiO₂纳米复合磨粒分散性的影响[J]. 金刚石与磨料磨具工程, 2020, 40(5): 45-50.
CHEN G M, ZHOU L, NI Z F, et al.Effect of pH Value on Dispersity of CeO₂/SiO₂ Composite Nanoparticles[J]. Diamond & Abrasives Engineering, 2020, 40(5): 45-50.
[4] ZHAO X B, LONG R W, CHEN Y, et al.Synthesis, Characterization of CeO₂@SiO₂ Nanoparticles and Their Oxide CMP Behavior[J]. Microelectronic Engineering, 2010, 87(9): 1716-1720.
[5] 陈杨, 穆为彬, 陈志刚. 草莓状PS/SiO₂复合磨料的可控合成及其抛光性能[J]. 中国有色金属学报, 2013, 23(10): 2962-2969.
CHEN Y, MU W B, CHEN Z G.Controlled Synthesis of Strawberry-Like PS/SiO₂ Composite Abrasives and Their Polishing Behavior[J]. The Chinese Journal of Nonferrous Metals, 2013, 23(10): 2962-2969.
[6] 陈杨, 李志娜, 宋志棠, 等. 内核尺寸对核/壳结构PS/SiO₂复合磨料抛光特性的影响[J]. 功能材料, 2014, 45(19): 19121-19127.
CHEN Y, LI Z N, SONG Z T, et al.Effect of the Core Size of the Core /Shell Structured PS /SiO₂ Composite Abrasives on Oxide-CMP Behavior[J]. Journal of Functional Materials, 2014, 45(19): 19121-19127.
[7] 陈杨, 左长智, 陈爱莲, 等. 核/壳结构PS/_MSiO₂复合颗粒的制备和压缩弹性模量[J]. 材料研究学报, 2018, 32(2): 90-96.
CHEN Y, ZUO C Z, CHEN A L, et al.Synthesis, Characterization and Compressive Elastic Modulus of Core/Shell Structured PS/_MSiO₂ Composite Particles[J]. Chinese Journal of Materials Research, 2018, 32(2): 90-96.
[8] 陈杨, 陆锦霞, 陈志刚. 核壳结构PS/CeO₂复合微球的制备及其在化学机械抛光中的应用[J]. 无机化学学报, 2011, 27(1): 66-72.
CHEN Y, LU J X, CHEN Z G.Preparation of Composite Polystyrene-Core CeO₂-Shell Microspheres and Their Application in the Oxide Chemical Mechanical Polishing[J]. Chinese Journal of Inorganic Chemistry, 2011, 27(1): 66-72.
[9] 陈爱莲, 李泽锋, 陈杨. 氧化硅内核结构对核/壳包覆型SiO₂/CeO₂复合颗粒抛光性能的影响[J]. 材料研究学报, 2017, 31(6): 429-436.
CHEN A L, LI Z F, CHEN Y.Influence of Silica-Core Structure on Polishing Characteristics of Core/Shell Structured Composite Particles of SiO₂/CeO₂[J]. Chinese Journal of Materials Research, 2017, 31(6): 429-436.
[10] CHEN Y,LU J X,CHENZ G.Preparation, Characterization and Oxide CMP Performance of Composite Polystyrene- core Ceria-shell Abrasives[J]. Microelectronic Engineering, 2011, 88(2): 200-205.
[11] CHEN Y, LI Z N, MIAO N M.Polymethylmethacrylate (PMMA)/CeO₂ hybrid particles for Enhanced Chemical Mechanical Polishing Performance[J]. Tribology International, 2015, 82, 211-217.
[12] MENG F N, ZHANG Z Y, GAO P L, et al.Design of Composite Abrasives and Substrate Materials for Chemical Mechanical Polishing Applications. Applied Nanoscience, 2020, 10(5): 1379-1393.
[13] WATANABE M, TAMAI T.Sol-Gel Reaction in Acrylic Polymer Emulsions: The Effect of Particle Surface Charge[J]. Langmuir,2007, 23(6): 3062-3066.
[14] HU W D, NIE Y G, WANG Y, et al.Synthesis of Inorganic/organic Raspberry-like Composite Particles for Superhydrophobic and Superlipophilic Coatings[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 660: 130843.
[15] MARÍA A R A, AIDE M T H, MIGUEL A D C, et al. Thermal, Mechanical and UV-Shielding Properties of Poly(Methyl Methacrylate)/Cerium Dioxide Hybrid Systems Obtained by Melt Compounding[J]. Polymers, 2015, 7(9): 1638-1659.
[16] WANG D, WANG Y J, LIU N, et al.Preparation and Electromagnetic-Wave-Absorption Properties of N, O-Doped PMMA&DVB&AN Carbon Microspheres with Porous Hollow Structures[J]. Chemical Engineering Journal, 2023, 456: 140987.
[17] CAI G P, LU H D, ZHOU Y, et al.Fire Retardancy of Emulsion Polymerized Poly(methyl methacrylate)/Cerium(Ⅳ) Dioxide and Polystyrene/Cerium(Ⅳ) Dioxide Nanocomposites[J]. Thermochimica Acta, 2012, 549: 124-131.
[18] 汪继承, 雷中秋, 王振, 等. 硅烷偶联剂MPS对SiO₂-聚丙烯酸酯复合微球接枝交联结构及剪切取向能力的影响[J]. 复合材料学报, 2020, 37(5): 1096-1105.
WANG J C, LEI Z Q, WANG Z, et al.Effect of Silane Coupling Agent MPS on Crosslinking Structure and Shear Orientation Ability of SiO₂-Polyacrylate Composite Particles[J]. Acta Materiae Compositae Sinica, 2020, 37(5): 1096-1105.
[19] 陈杨. 核壳结构SiO₂/CeO₂、PS/CeO₂复合微球的可控合成及其CMP性能研究[D]. 镇江: 江苏大学, 2012.
CHEN Y.Controlled synthesis of SiO₂/CeO₂, PS/CeO₂ Composite Microspheres with Core/shell Structure and Their Chemical Mechanical Polishing Performances[D]. Zhenjiang: Jiangsu University, 2012.
[20] NI X S, LIN Z Y, QIN M Y, et al.Bioactivity and Mechanical Property of PMMA Bone Cement: Effect of Silanized Mesoporous Borosilicate Bioglass Microspheres[J]. Journal of Inorganic Materials, 2023, 38(8): 971.
[21] SHI N, CHEN Y L, YIN L, et al.Monodispersion of SiO₂/ CeO₂ Binary Nano-Abrasives with Adjustable Size in Chemical Mechanical Polishing Performance of Copper[J]. ECS Journal of Solid State Science and Technology, 2023, 12(7): 074001.
[22] 江学良, 王维, 官健, 等. PMMA模板制备CeO₂空心微球及低频阻尼性能[J]. 稀有金属材料与工程, 2015, 44(5): 1249-1253.
JIANG X L, WANG W, GUAN J, et al.Preparation of CeO₂ Hollow Nanospheres by PMMA Template and Their Low Frequency Damping Capacity[J]. Rare Metal Materials and Engineering, 2015, 44(5): 1249-1253.
[23] TIWARI S, Defect Mediated Changes in Structural, Optical and Photoluminescence Properties of Ni Substituted CeO₂[J]. ArXiv E-prints, 2018(7): 02417.
[24] SEO J.A Review on Chemical and Mechanical Phenomena at the Wafer Interface during Chemical Mechanical Planarization[J]. Journal of Materials Research, 2021, 36(1): 235-257.
[25] LI H X, JIANG J, XU X W, et al.High-Efficient Incorporation of Silica into Shell Component via Pickering Emulsion Polymerization for Fabrication of Organic-Inorganic Hybrid Latex Films[J]. Materials Today Communications, 2025, 42: 111541.

Funding

The Natural Science Foundation of China (52465053, 51965053); The Natural Science Foundation of Inner Mongolia (2022MS05038); Basic Research Fund for Universities Directly Affiliated the Autonomous Region (2024XKJX007)