氧化铝颗粒的表面改性及其在C平面(0001)蓝宝石衬底上的化学机械抛光(CMP)性质

doi:10.15541/jim20170036

摘要/Abstract

摘要：

为了提高氧化铝颗粒的CMP性能, 本工作探索了一种合适的改性方法。同时, 为了改善其化学机械性能, 通过与其表面羟基的硅烷化化学反应和与Al和仲胺的络合两种作用, 用N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷表面改性氧化铝颗粒。本工作给出了化学反应机理, 即N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷接枝到氧化铝表面。通过傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)表征了改性氧化铝颗粒的组成和结构。结果表明: N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷已被成功地接枝到氧化铝颗粒的表面, 导致改性比未改性的氧化铝颗粒具有更好的化学和机械性能。测试了未改性和改性的氧化铝颗粒在蓝宝石基底上的CMP性能。结果显示: 改性氧化铝颗粒比未改性氧化铝颗粒有更高的材料去除速率和更好的表面质量。即, 改性氧化铝颗粒在pH=10时比未改性氧化铝颗粒在pH=13.00时表现出更高的材料去除率, 这将为减少设备腐蚀提供新思路。

关键词: 改性方法, N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷, 化学机械抛光, CMP, 氧化铝抛光液

Abstract:

To improve the Chemical Mechanical Polishing (CMP) performance of alumina particles in aqueous solution, a suitable modification method was explored. Meanwhile, in order to improve their chemical mechanical performance, alumina particles were surface modified with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane through silanization chemical reaction with their surface hydroxyl groups and complexation with Al and secondary amine. This work gives a detailed and thorough chemical reaction mechanism that N-(2-aminoethyl)-3-aminopropyltrimethoxysilane grafted onto the surface of alumina. The compositions and structures of the modified alumina particles were characterized by Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results supported that the N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was perfectly grafted onto the surface of alumina particles, which led to the modified alumina particles with better surface chemical and mechanical properties than unmodified alumina particles. Then, CMP performance of the unmodified and modified alumina particles on the sapphire substrate was tested. The results showed that the modified alumina particles exhibited higher material removal rate (MRR) and better surface quality than unmodified alumina particle. The focus is that the modified alumina particles manifested higher MRR at pH 10.00 than the unmodified alumina particles at PH 13.00, which may open a way to reduce corrosion of equipment.

Key words: modification method, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, chemical mechanical polishing, Chemical Mechanical Polishing (CMP), alumina slurry

中图分类号:

TQ174

汪为磊, 刘卫丽, 白林森, 宋志棠, 霍军朝. 氧化铝颗粒的表面改性及其在C平面(0001)蓝宝石衬底上的化学机械抛光(CMP)性质[J]. 无机材料学报, 2017, 32(10): 1109-1114.

WANG Wei-Lei, LIU Wei-Li, BAI Lin-Sen, SONG Zhi-Tang, HUO Jun-Chao. Surface Modified Alumina Particles and Their Chemical Mechanical Polishing (CMP) Behavior on C-plane (0001) Sapphire Substrate[J]. Journal of Inorganic Materials, 2017, 32(10): 1109-1114.

图/表 11

Fig. 1 FTIR spectra of alumina particles before and after modification

Fig. 2 XPS survey spectra of alumina particles before and after modification

Table 1 Binding energy of abrasives containing before and after modified alumina particles

Elements in sample	Al2p	O1s
Binding energy/eV	74.03 73.08	531.06 530.87

Table 2 Cmposition of elements on the surface of alumina particles before and after modification

Atomic%	Al	O	C	N	Si
Unmodified alumina	30.67	52.44	16.89	0	0
Modified alumina	27.35	46.41	21.19	2.77	2.28

Fig. 3 XPS narrow scan spectra results of element Al2p (a), O1s (b) in modified alumina

Table 3 Binding energy of Al2p

Chemical state	Band energy/eV
(-Si(OCH₃)₂O-)_xAl_y	73.8
AlN	73.1

Table 4 Binding energy of O1s

Chemical state	Band energy/eV
(-Si(OCH₃)₂O-)_xAl_y	531.10
Al₂O₃	530.30

Fig. 4 Chemical reaction schemes for modification process

Fig. 5 COF as a function of polishing time for sapphire substrates polished by unmodified alumina particles and modified alumina particles

Table 5 Surface roughness (Rq) and material removal rate（MRR）by applying before and after modified alumina particles in different pH

pH	Type of particles	MRR (0.0001 g/30 min)	Before polishing R_q Roughness/nm	After polishing R_q Roughness/nm
10.00	Pure alumina	46	0.968	0.610
10.00	Modified alumina	127	0.610	0.329
10.00	Modified alumina	139	0.981	0.315
13.00	Pure alumina	93	0.916	0.552
13.00	Modified alumina	122	0.552	0.311

Fig. 6 (a, b, f) AFM morphologies of sapphire substrate before polishing; (c) polished by pure alumina particles at pH 10.00; (d) polished by modified alumina particle (using sapphire substrate polished by pure alumina particles (c)) at pH 10.00; (e) polished by modified alumina particle at pH 10.00; (g) polished by modified alumina particle at pH 13.00; (h) polished by pure alumina particles (using sapphire substrate polished by pure alumina particles (g)) at pH 13.00

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