Performance and mechanism of novel antimony oxo cluster photoresist

doi:10.11949/0438-1157.20231414

Abstract

Abstract:

With the increasing integration of semiconductor industry, higher requirements are put forward for lithographic materials. In recent years, metal- oxygen oxo clusters (MOCs) photoresists have been widely studied due to the small size and flexible structure design. At present, antimony-based photoresistsare limited to antimony-containing complexes. In this paper, a novel antimony-oxygen oxo cluster photoresist was developed, and the advantages of the self-assembly strategy was demonstrated by comparing the solubility difference between metal-organic assembled Sb₄O-1 and self-assembled Sb₄O-2. Atomic force microscopy (AFM) confirmed that Sb₄O-2 photoresists can form smooth films with a low roughness value (root mean square roughness<0.3 nm). Electron beam lithography (EBL) demonstrated the excellent patterning ability of Sb₄O-2 photoresist(line width<50 nm), and theoretical calculations supported a novel self-assembled Sb₄O-2 “ligand dissociation” mechanism analyzed by X-ray photoelectron spectroscopy (XPS). This work inspired the exploration of additional metal oxygen oxo cluster materials.

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

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，金属氧簇光刻胶由于尺寸小、结构设计灵活，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。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。

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

CLC Number:

O 644.1

Youming SI, Lingfeng ZHENG, Pengzhong CHEN, Jiangli FAN, Xiaojun PENG. Performance and mechanism of novel antimony oxo cluster photoresist[J]. CIESC Journal, 2024, 75(4): 1705-1717.

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, 2024, 75(4): 1705-1717.

Figures/Tables 13

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

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

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

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

Fig.5 Three-dimensional image of Sb4O-2 patterns morphology exposed with different exposure doses and developed with isopropanol

Table 1 Height of Sb4O-2 pattern under different exposure 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

Fig.6 Sb4O-2 patterns under L/3S and different exposure doses

Fig.7 Sb4O-2 patterns under L/6S and different exposure doses

Fig.8 Sb4O-2 patterns under L/4S and different exposure doses

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

占空比	曝光剂量/(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

Fig.9 Total spectrum (a), quantification of Sb4O-2 XPS results at different exposure doses (b), and inferred Sb4O-2 lithography process (c)

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

Fig.10 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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