Non-aqueous negative-tone development of inorganic metal oxide nanoparticle photoresists for next generation lithography

Ouyang, Can; Chung, Yeon Sook; Li, Li; Neisser, Mark; Cho, Kyoungyong; Giannelis, Emmanuel P.; Ober, Christopher K.

doi:10.1117/12.2011282

Cited by 14 publications

(12 citation statements)

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“…SEM images (Figure ) showed good 1:1 line-and-space patterns with feature sizes of 16, 15, 14, and 13 nm, with doses of 45, 47, 36, and 35 mJ cm –2 , respectively. Unlike those of previously reported resists based on ZrO 2 or HfO 2 nanoparticles, ,,, the roughness was significantly improved even at higher resolution (15 nm). A possible reason for this improvement is the Zn- m TA cluster’s smaller size, its narrow size distribution, and its homogeneous films.…”

Section: Resultscontrasting

confidence: 77%

Metal–Organic Framework-Inspired Metal-Containing Clusters for High-Resolution Patterning

Sakai

Kasahara

et al. 2018

Chem. Mater.

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We report the preparation of discrete nanometer-scale zinc-based clusters and use them to form sub-15 nm structures by means of extreme ultraviolet lithography. By taking advantage of a metal-containing building unit derived by a metal–organic frameworkMOF-2, we found the 3-methyl-phenyl-modified Zn-mTA cluster that formed is well-defined with controlled size and structure and demonstrates extremely high solubility. Progress in recent years in metal–organic frameworks has created a rich variety of metal-containing structures that are useful for numerous applications. Substitution of the bridging ligands with monovalent ligands produces a discrete metal–organic cluster that strongly interacts with soft X-rays at a wavelength of 13 nm. Here we describe the design, preparation, computational modeling, and physical characterization of these new materials. Such metal-containing structures may form the basis of photoresists that enable the next generation of microelectronic devices.

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Section: Resultscontrasting

confidence: 77%

Metal–Organic Framework-Inspired Metal-Containing Clusters for High-Resolution Patterning

Sakai

Kasahara

et al. 2018

Chem. Mater.

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“…This idea was further demonstrated by the lithographic result of hafnium benzoate nanoparticles (HfBA) that bound benzoic acid with an even lower pKa of 4.2 to the metal oxide, requiring a higher dose of 17.5 mJ/cm2 ( Figure 2) for good exposure. [5]- [8] Therefore we hypothesize that, in general, the higher the pKa, the lower of sensitivity. Experimental results of the zirconium oxide nanoparticles are also consistent with this observation.…”

Section: Introductionmentioning

confidence: 98%

New developments in ligand-stabilized metal oxide nanoparticle photoresists for EUV lithography

et al. 2015

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The introduction of EUV lithography to manufacturing requires the development of both new EUV exposure tools and photoresists. The main challenges for photoresists are to achieve high resolution, and low roughness patterning at very high sensitivity given the limited intensity of current sources. A new class of photoresist formed from ligand-stabilized metal oxide nanoparticles shows extraordinary sensitivity for EUV lithography. These nanoparticles are processed in traditional organic solvents for both deposition and development as negative tone resist; positive tone images are possible if the aqueous base developer is used in addition to a post-exposure bake step. This paper presents new developments in the study of ligand-stabilized nanoparticle photoresists for EUV lithography. It is our current understanding that a key aspect of the solubility change of these photoresists during exposure involves ligand displacement by anions generated from photoactive compounds such as sulfonic acid photoacid generators. Both positive and negative tone patterning are possible and depend on thermal treatment history and choice of developer. On the basis of a non-chemically amplified ligand exchange mechanism, new resist structures were created. Both aromatic and aliphatic carboxylic acids with different functional groups have been studied in the formation of the nanoparticles and include dimethylacrylic acid, isobutyric acid, toluic acid. It has been shown that those nanoparticles with higher binding affinity ligands show better resolution and line edge roughness under EUV exposure. Some formulations demonstrate EUV sensitivity as high as 1.4 mJ/cm 2 , while other formulations demonstrate that improved LER values of 3-5nm. The overall resolution, sensitivity and roughness tradeoff has been evaluated and provides an understanding of structure -property relationships. In this paper, we also discuss major efforts on the further understanding of the patterning mechanism. By testing the dissolution rate and plotting it in Hansen interaction triangles, we can compare the differences between different formulations and choose a suitable developer for each formulation. We also used the dissolution rate study to confirm the important role of PAG and ligand exchange for pattern formation. In addition, aspects of the EHS properties of these new photoresists have been investigated and will be discussed.

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“…A systematic study with different developer solutions led to the fabrication of resist patterns down to ∼32 nm with ketone-based solvent developers. 182 The approach was further extended to resist formulations containing ZnO x , TiO x , InO x and SnO x ; with optimization of resist processing, 15-nm half pitch patterns were achieved. 183 However, the patterned features suffered from high LER along with significant residual scum artifact that could be the consequence of nanoparticle size and high concentration of photoacid generator (PAG).…”

Section: Ligand Capped Nanoparticle Resistsmentioning

confidence: 99%

Review of metal-containing resists in electron beam lithography: perspectives for extreme ultraviolet patterning

Saifullah

Tiwale

Ganesan

2022

J. Micro/Nanopattern. Mats. Metro.

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Background: Metal-containing resists entered the mainstream semiconductor industry process flow to mitigate the low absorbance of extreme ultraviolet (EUV) radiation by thin films of organic resists that lead to poor sensitivity and their inability to handle rigors of development and etching conditions.Aim: The long and rich history of using metal-containing resists in electron beam lithography can offer interesting lessons, pointers, and insights to the relatively newcomer EUV lithography, which is slightly over a decade old.Approach: Electron beam lithography has been enjoying a considerable amount of freedom in the choice of resist materials for close to 50 years; especially the use of metal-containing resists to attain not only single digit nanometer resolution, higher sensitivity, and etch resistance but also lower line-edge roughness. Here, we make a comprehensive historical review of the progress made in the patterning of metal-containing resists in electron beam lithography and derive insights that can be potentially useful in EUV patterning.Perspectives: Small molecular weight resists are proven to be crucial for achieving higher resolution with low line-edge roughness. Simplifying process flow by reducing etch-stack-layers is conceivable with metal-containing resists, along with direct-patterning of functional materials for heterogeneous integration. Efficient contact hole patterning at tighter pitches may be incumbent on progress in positive-tone resist research.

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Non-aqueous negative-tone development of inorganic metal oxide nanoparticle photoresists for next generation lithography

Cited by 14 publications

References 0 publications

Metal–Organic Framework-Inspired Metal-Containing Clusters for High-Resolution Patterning

Metal–Organic Framework-Inspired Metal-Containing Clusters for High-Resolution Patterning

New developments in ligand-stabilized metal oxide nanoparticle photoresists for EUV lithography

Review of metal-containing resists in electron beam lithography: perspectives for extreme ultraviolet patterning

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