丙烯酸配位有机锡光刻胶的制备及高分辨光刻研究

doi:10.11949/0438-1157.20241135

化工学报 ›› 2025, Vol. 76 ›› Issue (4): 1820-1830.DOI: 10.11949/0438-1157.20241135

• 材料化学工程与纳米技术 • 上一篇下一篇

丙烯酸配位有机锡光刻胶的制备及高分辨光刻研究

赵英东¹(), 姬沛君²(), 丛日尧¹, 付海超³, 张家龙²(), 陈鹏忠¹(), 彭孝军¹()

^1.大连理工大学智能材料化工前沿科学中心，精细化工国家重点实验室，辽宁大连 116024
^2.中石化（上海）石油化工研究院有限公司，上海 201208
^3.中节能万润股份有限公司研发中心，山东烟台 264006

收稿日期:2024-10-14 修回日期:2024-11-30 出版日期:2025-04-25 发布日期:2025-05-12
通讯作者: 张家龙,陈鹏忠,彭孝军
作者简介:赵英东(1998—)，男，博士研究生，billzyd@mail.dlut.edu.cn
姬沛君（1999—），女，工程师，jipj1995.sshy@sinopec.com
基金资助:
国家自然科学基金项目(22378052);山东省重点研发(重大科技创新工程)项目(2021CXGC010308)

Preparation and high-resolution lithography study of organic tin photoresists containing acrylates

Yingdong ZHAO¹(), Peijun JI²(), Riyao CONG¹, Haichao FU³, Jialong ZHANG²(), Pengzhong CHEN¹(), Xiaojun PENG¹()

^1.State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^2.Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China
^3.Research and Development Center of Valiant Co. , Ltd. , Yantai 264006, Shandong, China

Received:2024-10-14 Revised:2024-11-30 Online:2025-04-25 Published:2025-05-12
Contact: Jialong ZHANG, Pengzhong CHEN, Xiaojun PENG

摘要/Abstract

摘要：

集成电路产业中光刻技术的迅速发展对光刻胶的性能提出了更高的要求。有机-锡配合物在光刻分辨率和线边缘粗糙度方面表现出优异的特性，但其光刻灵敏度和薄膜稳定性相对较差。本文报道了一种新型的丙烯酸配位的三苯基锡光刻材料Sn1Ac，该材料可同时用于深紫外光刻和电子束光刻。通过与四（3-巯基丙酸）季戊四醇酯（PETMP）形成氢键，成功克服了旋涂薄膜稳定性差的缺陷，其光刻留膜率超过93%。Sn1Ac与PETMP的混合薄膜显示出卓越的负性图案化性能。在电子束光刻条件下，该混合薄膜的分辨率优于15 nm，且线边缘粗糙度低于2 nm。通过X射线光电子能谱等测试手段，提出了锡-碳酸根和硫醇-烯点击反应的协同交联曝光机理。

关键词: 光刻胶, 旋涂, 表面, 配合物, 纳米材料, 光响应材料

Abstract:

The rapid advancements in lithography within the integrated circuit industry have necessitated enhanced performance from photoresists. Organic-tin complexes show excellent properties in lithography resolution and line edge roughness, but their lithography sensitivity and film stability are relatively poor. This study presents an acrylic-coordinated triphenyl-tin carboxylate photoresist, designated as Sn1Ac, which is suitable for both deep-ultraviolet and electron-beam lithography applications. By forming hydrogen bonds with the additive tetrakis (3-mercaptopropionic acid) pentaerythritol ester, the instability of spin-coated films has been effectively eliminated, resulting in a photolithography film retention rate exceeding 93%. The hybrid films demonstrate excellent negative patterning properties. Under electron-beam lithography, these hybrid films achieve a resolution better than 15 nm and a line edge roughness of less than 2 nm. Through X-ray photoelectron spectroscopy and other testing methods, this paper proposed the synergistic cross-linking exposure mechanism of tin-carbonate and thiol-ene click reactions.

Key words: photoresist, spin-coating, surface, complexes, nanomaterials, photo-responsive materials

中图分类号:

O 644.1

赵英东, 姬沛君, 丛日尧, 付海超, 张家龙, 陈鹏忠, 彭孝军. 丙烯酸配位有机锡光刻胶的制备及高分辨光刻研究[J]. 化工学报, 2025, 76(4): 1820-1830.

Yingdong ZHAO, Peijun JI, Riyao CONG, Haichao FU, Jialong ZHANG, Pengzhong CHEN, Xiaojun PENG. Preparation and high-resolution lithography study of organic tin photoresists containing acrylates[J]. CIESC Journal, 2025, 76(4): 1820-1830.

图/表 8

图1 (a) Sn1Ac的合成路线；(b) Sn1Ac晶体在显微镜下的形貌图；(c) 沿a轴和b轴观察的晶体结构图；(d)粉末XRD谱图；(e) 红外透射光谱图；(f) 热重分析和差示扫描量热分析曲线

Fig.1 (a) The synthesis route of Sn1Ac; (b) The morphology image of Sn1Ac crystal under a microscope; (c) The crystal structure viewed along the a-axis and b-axis; (d) Powder XRD patterns; (e) IR transmission spectra; (f) Thermogravimetric analysis and differential scanning calorimetry curves

图2 (a) Sn1Ac和Sn1Ac+PETMP形貌及旋涂膜形貌；(b) 真空处理前后薄膜厚度测试；(c) Hirshfeld表面分析及(d) 二维指纹图谱；(e) 分子间氢键理论计算；(f) Sn1Ac、PETMP和Sn1Ac+PETMP红外光谱分析

Fig.2 (a) PMorphology of Sn1Ac alone and Sn1Ac+PETM and morphology of spin-coated film; (b) The film thickness tests before and after vacuum treatment; (c) Hirshfeld surface analysis diagram and (d) 2D fingerprintingspectrum; (e) Theoretical calculations of intermolecular hydrogen bonds; (f) Infrared spectral analyses of Sn1Ac, PETMP and Sn1Ac+PETMP

图3 Sn1Ac和Sn1Ac+PETMP薄膜电子束曝光后的原子力显微镜测试图及相应的对比度曲线

Fig.3 AFM images and corresponding contrast curves of Sn1Ac and Sn1Ac+PETMP films after electron beam exposure

图4 电子束线曝光后膜的扫描电镜和原子力显微镜测试图（三个数字依次代表剂量-线宽-线边缘粗糙度，单位为nC/cm-nm-nm）

Fig.4 Scanning electron microscopy and AFM test images of films after single-line electron beam exposure

图5 Sn1Ac+PETMP膜深紫外曝光10 min并显影的光学显微镜图像

Fig.5 Optical microscope images of Sn1Ac+PETMP film exposed to deep UV for 10 min followed by development

图6 Sn1Ac+PETMP和Sn1Ac膜深紫外曝光30 min和60 min并显影的光学显微镜及原子力显微镜图像（LW、Th、RMS依次代表线条图案的线宽、厚度和表面粗糙度）

Fig.6 Optical microscopy and AFM of Sn1Ac+PETMP and Sn1Ac films exposed to deep UV for 30 and 60 min followed by development (LW, Th, and RMS represent the line width, thickness, and surface roughness of the line patterns, respectively)

图7 (a) 曝光过程实时介电固化监测；(b) 曝光前后红外透射光谱；(c) 不同曝光剂量下碳、氧和硫的相对含量；(d) 不同曝光剂量下Sn 3d5/2的结合能谱图；曝光前(e)、后(f) O1s的XPS精细谱；(g) 不同曝光剂量下O的各化学态含量变化曲线；曝光前(h)、后(i) S 2p的XPS精细谱；(j) 不同曝光剂量下S的各化学态含量变化曲线

Fig.7 (a) Real-time dielectric monitoring during exposure; (b) Infrared spectra obtained before and after exposure; (c) Relative contents of carbon, oxygen, and sulfur at different exposure doses; (d) Binding energies of Sn 3d5/2 at different exposure doses; XPS spectrum of O 1s before (e) and after (f) exposure; (g) The changes in chemical state content of O at different exposure doses; XPS spectrum of S 2p before (h) and after (i) exposure; (j) The changes in chemical state content of S at different exposure doses

图8 可能的曝光反应机理

Fig.8 The possible exposure reaction mechanism

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丙烯酸配位有机锡光刻胶的制备及高分辨光刻研究

Preparation and high-resolution lithography study of organic tin photoresists containing acrylates

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