Hwan-Sung Cheon

Copper(II)-catalyzed hydroxylation of aryl halides using glycolic acid as a ligand.

Copper(II)-catalyzed hydroxylation of aryl halides has been developed to afford functionalized phenols. The protocol utilizes the reagent combination of Cu(OH)2, glycolic acid, and NaOH in aqueous DMSO, all of which are cheap, readily available, and easily removable after the reaction. A broad range of aryl iodides and activated aryl bromides were transformed into the corresponding phenols in excellent yields. Moreover, it has been shown that C-O(alkyl)-coupled product, instead of phenol, can be predominantly formed under similar reaction conditions.

Novel spin-on organic hardmask with high plasma etch resistance

In recent years for memory devices under 70nm using ArF lithography, spin-on organic hardmask has become an attractive alternative process to amorphous carbon layer hardmark (ACL) in mass production due to ACL hardmasks limited capacity, high cost-of-ownership, and low process efficiency in spite of its excellent etch performance. However, insufficient plasma etch resistance of spin-on hardmask makes the etch process an issue resulting in inadequate vertical profiles, large CD bias, and narrow etch process window compared to ACL hardmask. In order to be able to apply these spin on hardmasks to varies layers including critical layers, the aforementioned problems need to be resolved and verified using several evaluation methods including etch pattern evaluation. In this paper, we report the synthesis of novel organic spin-on hardmasks (C-SOH) that incorporate various fused aromatic moieties into polymer chain and the evaluation of etch performance using dry etch tools. Organic spin-on hardmasks with 79-90 wt% carbon contents were synthesized in-house. Oxygen and fluorine based plasma etch processes were used to evaluate the etch resistance of the C-SOH. The results show our 3rd generation C-SOH has etch profiles comparable to that of ACL in a 1:1 dense pattern.

Spin-on organic hardmask materials in 70nm devices

In ArF lithography for < 90nm L/S, amorphous carbon layer (ACL) deposition becomes inevitable process because thin ArF resist itself can not provide suitable etch selectivity to sub-layers. One of the problems of ACL hardmask is surface particles which are more problematic in mass production. Limited capacity, high cost-of-ownership, and low process efficiency also make ACL hardmask a dilemma which can not be ignored by device makers. One of the answers to these problems is using a spin-on organic hardmask material instead of ACL hardmask. Therefore, several processes including bi-layer resist process (BLR), tri-layer resist process (TLR), and multi-layer resist process (MLR) have been investigated. In this paper, we have described spin-on organic hardmask materials applicable to 70nm memory devices. Applications to tri-layer resist process (TLR) were investigated in terms of photo property, etch property and process compatibility. Based on the test results described in this paper, our spin-on hardmask materials are expected to be used in mass production.

Organic underlayer materials with exceptionally high thermal stability

Multilayer hardmask (MLHM) schemes have been implemented as an indispensable process for ArF lithography which continues to demand thinner photoresist films. There are many variations of MLHM and semiconductor manufacturers choose to adopt their own designs, depending on their specific needs and technical advances. The quad-layer stack consisting of photoresist, organic ARC, CVD Si hardmask, and spin-on carbon underlayer is one of them. Despite the need for wafer transporting between the spin track and CVD equipment, this scheme is attractive because it can avoid laborious elaboration of sophisticated etching chemistries for spin-on Si-ARC and carbon underlayer. One of the issues arising from the mixed film forming process is the thermal stability of carbon underlayer at high temperatures during the CVD process of the Si hardmask. Organic underlayer which shows high thermal stability is crucial for this mixed hardmask process. These types of thermally stable organic film can also be used for other applications such as the spacer patterning technique for pitch size shrinkage. In this paper, we discuss the development of organic resins with high thermal stability, their physical properties, and their lithographic behaviors in the MLHM schemes.

Development of Spin-on Carbon Hardmasks with Comparable Etch Resistance to Amorphous Carbon Layer (ACL)

In recent microlithography of semiconductor fabrication, spin-on hardmask (SOH) process continue to gain popularity as it replaces the traditional SiON/ACL hardmask scheme which suffers from high CoO, low productivity, particle contamination, and layer alignment issues. In the SOH process, organic polymer with high carbon content is spin-cast to form a carbon hardmask film. In the previous papers, we reported the development of organic SOH materials and their application in sub-70 nm lithography. In this paper, we describe the synthesis of organic polymers with very high carbon contents (>92 wt.%) and the evaluation of the spin-coated films for the hardmask application. The high carbon content of the polymer ensures improved etch resistance which amounts to >90% of ACLs resistance. However, as the carbon content of the polymers increases, the solubility in common organic solvents becomes lower. Here we report the strategies to improve the solubility of the high carbon content resins and optimization of the film properties for the SOH application.