新型锑氧簇光刻胶的性能与机理研究

doi:10.11949/0438-1157.20231414

摘要/Abstract

摘要：

随着半导体行业集成度越来越高，对光刻材料提出了更高的要求。近年来，由于小尺寸、结构设计灵活，金属氧簇光刻胶得到了广泛的研究。目前锑基金属光刻胶仅局限于含锑配合物。本文开发出新型锑氧簇光刻胶，通过对比金属有机组装Sb₄O-1与自组装Sb₄O-2的溶解度差异说明自组装策略优势。原子力显微镜证实Sb₄O-2光刻胶可形成光滑薄膜，并获得低粗糙度值（均方根粗糙度< 0.3 nm）。电子束光刻（EBL）证明Sb₄O-2光刻胶优异的图案化能力（线宽< 50 nm），理论计算支持X射线光电子能谱（XPS）分析的新型自组装Sb₄O-2“配体解离”机制。这启发了对更多金属氧簇材料的探索。

关键词: 锑氧簇, 自组装, 光刻胶, 理论计算, 电子束光刻, 成像, 溶解性, 纳米材料

Key words: antimony oxo cluster, self-assembly, photoresist, theoretical calculations, electron beam lithography, imaging, solubility, nanomaterials

中图分类号:

O644.1

司友明, 郑凌峰, 陈鹏忠, 樊江莉, 彭孝军. 新型锑氧簇光刻胶的性能与机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20231414.

Youming SI, lingfeng Zheng, Pengzhong CHEN, Jiangli FAN, Xiaojun PENG. The performance and mechanism of the novel antimony oxo cluster photoresist[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231414.

图/表 11

图1 自组装锑氧簇Sb4O-2光刻示意图

Fig.1 Schematic diagram of self-assembled antimony-oxo cluster Sb4O-2 lithography

图2 金属有机组装锑氧簇Sb4O-1(a)与自组装锑氧簇Sb4O-2(b)的合成路线以及Sb4O-1(c)与Sb4O-2(d)的单晶结构

Fig.2 Synthesis routes of (a) metal-organic assembled antimony-oxo cluster Sb4O-1 and self-assembled antimony-oxo cluster Sb4O-2, and single crystal structure of (c) Sb4O-1 and (d) Sb4O-2

图3 Sb4O-2的Hirshfeld表面分析(a)以及Sb4O-2分子间不同相互作用力的分解指纹图谱(b)

Fig.3 Hirshfeld surface analysis of Sb4O-2(a) and decomposition fingerprint of different intermolecular interactions in Sb4O-2 molecules(b)

图4 使用氯仿、二氯乙烷以及PGMEA制备Sb4O-2薄膜的形貌以及粗糙度注:(a) 氯仿 (b) 二氯乙烷 (c)PGMEA

Fig.4 Morphology and roughness of Sb4O-2 thin films prepared using chloroform dichloroethane and PGMEA

图5 使用(a) 400 μC/cm2 (b) 500 μC/cm2 (c) 600 μC/cm2 (d) 700 μC/cm2 (e) 800 μC/cm2 以及 (f) 900 μC/cm2剂量曝光并使用异丙醇显影的SbO4-2三维图案形貌

Fig.5 Three dimensional image of SbO4-2 patterns morphology exposed with (a) 400 μC/cm2 (b) 500 μC/cm2 (c) 600 μC/cm2 (d) 700 μC/cm2 (e) 800 μC/cm2 and (f) 900 μC/cm2 dose and developed with isopropanol

表1 不同曝光剂量及不同占空比条件下Sb4O-2图案高度

Table 1 Height of Sb4O-2 pattern under different doses and L/S

占空比	曝光剂量/(μC/cm²)	图案高度/nm
L/3S	400	15.5
	500	22.8
	600	27.5
	700	24.5
	800	37.4
	900	39.7
L/4S	400	26.9
	500	32.8
	600	40.6
	700	40.9
	800	47.6
	900	49.5
L/6S	400	25.2
	500	30.2
	600	30.8
	700	35.7
	800	45.5
	900	47.6

图6 使用(a) 400 μC/cm2 (b) 500 μC/cm2 (c) 600 μC/cm2 (d) 700 μC/cm2 (e) 800 μC/cm2 以及 (f) 900 μC/cm2剂量曝光的SbO4-2 L/3S图案；使用(g) 400 μC/cm2 (h) 500 μC/cm2 (i) 600 μC/cm2 (j) 700 μC/cm2 (k) 800 μC/cm2 以及 (l) 900 μC/cm2剂量曝光的SbO4-2 L/6S图案；使用(m) 400 μC/cm2 (n) 500 μC/cm2 (o) 600 μC/cm2 (p) 700 μC/cm2 (q) 800 μC/cm2 以及 (r) 900 μC/cm2剂量曝光的SbO4-2 L/4S图案

Fig.6 SbO4-2 L/3S patterns exposed with (a) 400 μC/cm2 (b) 500 μC/cm2 (c) 600 μC/cm2 (d) 700 μC/cm2 (e) 800 μC/cm2 and (f) 900 μC/cm2 dose；SbO4-2 L/6S patterns exposed with (g) 400 μC/cm2 (h) 500 μC/cm2 (i) 600 μC/cm2 (j) 700 μC/cm2 (k) 800 μC/cm2 and (l) 900 μC/cm2 dose；SbO4-2 L/4S patterns exposed with (m) 400 μC/cm2 (n) 500 μC/cm2 (o) 600 μC/cm2 (p) 700 μC/cm2 (q) 800 μC/cm2 and (r) 900 μC/cm2 dose

表2 不同占空比条件下Sb4O-2图案的LW及LER及Z值

Table 2 LW， LER， and Z values of Sb4O-2 pattern under different L/S conditions

L/S	Dose/(μC/cm²)	LW/nm	LER/nm	Z/μC nm³
L/3S	400	43.0
	500	46.5	16.3	1.34×10^-4
	600	44.5	9.9	5.18×10^-5
	700	52.3	10.6	1.13×10^-4
	800	59.7	7.4	9.32×10^-5
	900	64.8	8.9	1.94×10^-4
L/4S	400	128.5	12.3	1.28×10^-3
	500	122.6	9.9	9.03×10^-4
	600	139.3	9.9	1.59×10^-3
	700	146.8	8.3	1.53×10^-3
	800	156.8	5.6	9.67×10^-4
	900	167.0	9.2	3.55×10^-3
L/6S	400	73.0
	500	101.2
	600	51.9	7.1	4.23×10^-5
	700	59.2	9.1	1.20×10^-4
	800	63.5	5.6	6.42×10^-5
	900	72.4	6.2	1.31×10^-4

图7 不同曝光剂量的Sb4O-2 XPS总谱(a)与量化结果(b)以及推测的Sb4O-2光刻过程(c)

Fig.7 Total spectrum(a) and quantification of Sb4O-2XPS results at different exposure doses(b) and inferred Sb4O-2 lithography process(c)

表3 Sb4O-2光刻胶在不同的曝光剂量下原子浓度

Table 3 Atomic concentration of Sb4O-2 photoresist at different exposure doses

曝光剂量/(μC/cm²)	C原子浓度/%	O原子浓度/%	Sb原子浓度/%
0	68.9	27.6	3.45
200	61.5	34	4.5
600	59.37	35.95	4.69
800	50.44	43.34	6.22
1000	50.27	43.42	6.31

图8 Sb4O-2曝光前(a)和曝光后(b) 的部分原子电荷和曝光前(c)和曝光后(d)的表面电势分布

Fig.8 Sb4O-2 partial atomic charge before (a) and after (b) exposure and surface potential distribution before (c) and after (d) exposure

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