金属基极紫外光刻胶

由于具有光源波长短（13.5 nm）、图案化分辨率高等优点,极紫外（extreme ultraviolet, EUV）光刻技术被认为是突破5 nm甚至是3 nm半导体芯片制程节点的关键技术,与之相对应的EUV光刻胶研发广受关注。但传统的基于聚合物体系的化学放大光刻胶（chemical amplified resist, CAR）因尺寸过大、对EUV吸收低,限制了其在EUV光刻技术的应用进程。部分含有d轨道电子的金属元素具有高的EUV吸收截面,在光刻胶分子中引入这些金属元素可以有效提高对EUV的灵敏度。通过分子设计制备尺寸小、EUV吸收高的金属基光刻胶材料是解决EUV光刻胶服役性能问题的有效途径,已得到了广泛的研究。本文按金属氧簇（MOCs）、金属氧化物纳米粒子（NP）、金属-有机小分子（MORE）进行分类,对目前国内外的EUV光刻胶研究进展进行总结,并对EUV光刻胶未来所面临的机遇和挑战进行了展望。     

光刻胶树脂结构与性能技术进展

光刻工艺随集成电路的发展成为核心环节,被誉为集成电路制造这顶皇冠上最耀眼的明珠。而光刻技术离不开其辅助材料光刻胶,每一代光刻技术得到的突破都将在相应光刻胶技术上得到体现,从436 nm光刻技术到248 nm KrF光刻技术、193 nm ArF光刻技术再到EUV光刻技术等,与之相应的光刻胶也不尽相同。     

先进光刻胶材料的研究进展

本文简述了光刻技术及光刻胶的发展过程,并对应用于193纳米光刻和下一代EUV光刻的光刻胶材料的研究进展进行了综述,特别对文献中EUV光刻胶材料的研发进行了较为详细的介绍,以期对我国先进光刻胶的研发工作有所帮助.     

我国光刻胶的市场现状及发展趋势

现代微电子技术按照摩尔定律在不断发展．光刻技术也经历了从G线（436nm）,I线（365nm）,到深紫外248nm．及目前的193nm光刻的发展历程．相对应于各曝光波长的光刻胶也应运而生．光刻胶中的关键组分,如成膜树脂、感光剂、添加剂也随之发生变化．使光刻胶的综合性能能更好地满足集成工艺制程要求。目前集成电路制作中使用的主要光刻胶见表1。     

EUV光致抗蚀剂研究进展

波长13．5nm的极紫外（EUV）光刻技术可以刻画线幅〈32nm的图像,能满足信息技术对于光致抗蚀剂高分辨率的要求,即将成为下一代纳米成像技术,利用EUV成像技术,可以实现集成电路的超小型化。本文调研了近几年来EUV抗蚀剂的研究进展,指出影响抗蚀剂性能的主要因素,包括分辨率、LWR、LER、成像灵敏度、产气作用、成像侧面角度等,对近几年来有关EUV光致抗蚀剂的研究开发情况进行了归纳总结。     

用于浸没式工艺的光刻胶研究进展

浸没式光刻技术是在原干法光刻的基础上采用高折射率浸没液体取代原来空气的空间,从而提高光刻分辨率的一种先进技术.此项技术的实际应用,为当前IC产业的飞速发展起到了关键的作用.本文概述了浸没式光刻技术的发展历程和浸没式光刻胶遇到的挑战及要求;对浸没式光刻胶主体树脂、光致产酸剂及添加剂的研究进展进行了综述;最后对浸没式光刻胶的研究发展方向作了进一步的探讨及初步预测.     

产品开发

电子化学品的种类繁多,为IC产业配套的主要是光刻胶、高纯试剂、电子特种气体、封装材料等。光刻胶是光刻过程中的惟一介质,光刻技术是IC产业发展的推动力。随着目前集成电路线宽的不断缩小,与之对应的各类光刻胶的研制开发也在不断进行。我国目前除已具备普通436 nm光刻胶和紫外负型光刻胶约100吨的产能外,无锡市化工研究院已能提供少量电子束光刻胶和其他一些特种光刻胶。“十五”期间,国内科研单位在193nm光刻胶和电子束化学增幅光刻胶的研究上取得进展,两种样品的分辨率已分别达到 0．1μm和0．15μm。     

先进制程用光刻胶及TMAH显影液的改进

光刻是一种利用曝光、显影和刻蚀等工艺将光掩模上的图形转移到衬底材料上的工艺,是半导体器件制造工艺中的重要步骤.其中,在光刻胶层刻画图形时,主要涉及材料为光刻胶、显影液.在G线(436 nm)、I线(365 nm)光刻工艺中,光刻胶主要是酚醛树脂-重氮萘醌体系,显影液一般采用2.38 wt％的四甲基氢氧化铵(TMAH)水...     

彩色光刻胶用蒽醌染料的合成及稳定性研究

为实现彩色滤光片更高分辨率的发展需求，作为关键原材料的彩色光刻胶着色剂从颜料向染料体系转变是重要的趋势。然而染料分子的光热稳定性较差，亟需从分子结构方面探索提升稳定性的有效策略。以1,4,9,10-蒽四醇为原料，合成了9种1,4-二氨基取代的蓝色蒽醌染料分子，探索了不同取代基对染料分子光物理性质、溶解性以及光热稳定性的影响。结果表明，所有染料分子在590~600 nm和630~650 nm波长范围内呈现双吸收峰性质，具有高的摩尔消光系数。其中三甘醇及单甲醚取代的染料分子热分解温度为300℃，在230℃加热0.5 h后失重约2%，365 nm波长光照射8 h后色差低于1.73，表现出优异的光热稳定性。研究为进一步制备光热稳定性优异的彩色光刻胶用染料分子奠定了基础。     

高效绿色磷光铱配合物的合成与发光性能

设计、合成了一个新颖的环金属配体1-（4-甲氧基-苯甲基）-2-（4-甲氧基苯基）-苯并咪唑（MBMPB）,并以乙酰丙酮（Hacac）为辅助配体合成了高效绿色铱配合物Ir（MBMPB）2（acac）。通过1H NMR和元素分析对其进行结构表征,且详细研究了其光物理性质。结果表明,配合物在402 nm和446 nm处存在1MLCT和3MLCT的吸收带,在492 nm处有较强的绿光发射,同时具有高的光致发光效率和短的激发态寿命。     

Molecular Glass Photoresists with High Resolution,Low LER,and High Sensitivity for EUV Lithography

Novel molecular glasses (MGs) containing bisphenol A backbone (BPA‐6 and BPA‐10) are synthesized and characterized. BPA‐6 and BAP‐10 are excellent amorphous materials for extreme ultraviolet (EUV) patterning applications with good thermal stability (T_d more than 160 °C). The MGs can be used as positive‐tone photoresists combined with triphenylsulfonium perfluoro‐1‐butanesulfonate and trioctylamine dissolved in propylene glycol monomethyl ether acetate. High‐resolution feature sizes as small as 23.1 nm with extremely low line edge roughness (less than 2 nm), high sensitivity (less than 20 mJ cm^?2), and good high aspect ratio patterns are obtained by using EUV lithography.     

Design and synthesis of new photoresist materials for ArF lithography

A new class of photoresist matrix polymers based on vinyl ether–maleic anhydride (VEMA) alternating copolymers was developed for ArF single‐layer lithography. These polymers were synthesized by copolymerization of alkyl vinyl ether and maleic anhydride alternating copolymers with acrylate derivatives containing bulky alicyclic acid‐labile protecting groups. The resulting polymers showed good control of polymerization and high transmittance. Also, these resists exhibited good adhesion to the substrate, high dry‐etching resistance against CF₄ mixture gas (1.02 times the etching rate of deep UV resist), and high selectivity to silicon oxide etching. Using an ArF excimer laser exposure system with 0.6 NA, 120‐nm L/S patterns were resolved under conventional illumination. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 165–170, 2004     

Study on organosilicon positive resist. II. Organosilicon positive photoresist (OSPR–1334) and its application to bilayer resist system

A new alkali-developable organosilicon positive photoresist (OSPR–1334) and a bilayer resist process with OSPR–1334 has been developed. OSPR–1334 is composed of poly(p-hydroxybenzylsilsesquioxane) and naphthoquinone diazide. The sensitivity and the resolution are almost the same as those of conventional novolac-based resists when aqueous tetrakis (2-hydroxyethyl) ammonium hydroxide is used as a developer. Also, OSPR–1334 has excellent resistance to O₂RIE. The etching rate is 3.6 nm/min, while that of polyimide resins or hard-baked novolac-based resists is 100 nm/min. OSPR–1334 is suitable for use as the top layer of the bilayer resist system. OSPR–1334, after O₂RIE, can be eliminated by dissolving an unchanged layer followed by spinning out or filtrating a changed surface layer. Submicron patterns with a high aspect ratio can easily be obtained with this bilayer resist process.     

Ultrafast deep UV lithography using excimer lasers

Various excimer laser wavelengths have been used, both in mid- and deep-UV regions—308 nanometers (nm) from XeCl, 249 nm from KrF and 222 nm from KrCl–to delineate images in a number of resists. The quality of the images obtained with the laser exposures, the absence of speckle, and the insignificant loss of resist reciprocity make excimer laser lithography an attractive technique. The ultrafast exposures possible with this method significantly lessen the sensitivity requirements on deep UV resists, making the choice of the resist more flexible.     

Reliable processing of graphene using metal etchmasks

Graphene exhibits exciting properties which make it an appealing candidate for use in electronic devices. Reliable processes for device fabrication are crucial prerequisites for this. We developed a large area of CVD synthesis and transfer of graphene films. With patterning of these graphene layers using standard photoresist masks, we are able to produce arrays of gated graphene devices with four point contacts. The etching and lift off process poses problems because of delamination and contamination due to polymer residues when using standard resists. We introduce a metal etch mask which minimises these problems. The high quality of graphene is shown by Raman and XPS spectroscopy as well as electrical measurements. The process is of high value for applications, as it improves the processability of graphene using high-throughput lithography and etching techniques.     

Synthesis of chemically amplified photoresist polymer containing four (Meth)acrylate monomers via RAFT polymerization and its application for KrF lithography

KrF photoresist polymers (PASTMs) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Four (meth)acrylates with lithographic functionalities including styrene (St), 4-acetoxystyrene (AST), 2-methyl-2-adamantyl methacrylate (MAMA), and tert-butyl acrylate(TBA) were used as monomer components and 2-methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl]propanoic acid (MDFC) was used as RAFT agent, varying the RAFT content could modulate molecular weight. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H NMR) indicated that the synthesis was successful. Gel permeation chromatography (GPC) showed that the molecular weight decreased with the increased content of MDFC, and all the polymers possessed weight-average molecular weight below ten thousand and polydispersity less than 1.32. Thermogravimetric analysis (TGA) characterized the thermal properties, the results implied that initial thermal decomposition temperature reached 200 °C, which could satisfy the lithography process. Differential scanning calorimetry (DSC) showed that the Tg decreases with molecular weight. The RAFT polymerization kinetics plots demonstrated that the polymerization was first-order, the number-average molecular weights of the polymers with relatively low polydispersity index values increased with total monomer conversions indicating that the concentration of growing radicals was constant throughout the polymerization process. The narrow molecular weight distribution and composition uniformity of the polymers prepared by RAFT polymerization could be beneficial for lithography, after alcoholysis, lithography evaluation under KrF lithography showed that this homogeneous polymer photoresist exhibited better space and line (S/L) pattern with resolution of 0.18 μm according to the SEM image.     

Dissolution inhibition-type photoresists for deep-UV lithography

A short introduction to photolithography with an emphasis on the classification of photoresists and the basic chemistry of conventional resists is given. The chemistry of positive type photoresists used for deep-UV lithography is reviewed and new developments in this field presented. The introduction of novel sulphonium compounds (SUCCESS) to inhibit the dissolution of poly(p-hydroxystyrene), the use of non-photoactive dissolution inhibitors together with acid generators and the protection of hydroxy groups in poly(p-hydroxystyrene) to decrease its solubility present ways of obtaining resists with high sensitivity and resolution.