Metal Oxide Nanoparticle Photoresists for EUV Patterning
Jing Jiang, Souvik Chakrabarty, Mufei Yu and Christopher K. Ober*
Department of Material Science and Engineering,
Cornell University, Ithaca, NY 14853
Previous studies of methacrylate based nanoparticle have demonstrated the excellent
pattern forming capability of these hybrid materials when used as photoresists under 13.5 nm
EUV exposure. HfO
2
and ZrO
2
methacrylate resists have achieved high resolution (~22 nm) at a
very high EUV sensitivity (4.2 mJ/cm
2
). Further investigations into the patterning process
suggests a ligand displacement mechanism, wherein, any combination of a metal oxide with the
correct ligand could generate patterns in the presence of the suitable photoactive compound. The
current investigation extends this study by developing new nanoparticle compositions with trans-
dimethylacrylic acid and o-toluic acid ligands. This study describes their synthesis and patterning
performance under 248 nm KrF laser (DUV) and also under 13.5 nm EUV exposures
(dimethylacrylate nanoparticles) for the new resist compositions.
Keywords: nanoparticle, EUV, photoresist, metal oxide
1. Introduction
The progression of Moore’s law demands
shrinkage in dimension of the technology nodes to
sub 25 nm features. Currently, the industry has
been relying on 193 nm immersion lithography
with double patterning to print finer features on
resist materials. Demands for further reduction in
pattern dimension would require multiple
patterning steps at the given 193 nm wavelength,
leading to a manifold increase in processing
expenditure. Recent developments in patterning
has shown that EUV radiation at 13.5 nm
wavelength holds promise in printing smaller
features in a single exposure step. A major
drawback of EUV sources is its low power output,
which would lead to a decreased throughput in
high volume manufacturing. To address this issue,
significant studies are being performed aiming at
intensifying the EUV power source. Similarly,
another approach mitigate the issue of low
throughput is to enhance sensitivity of photoresist
materials to EUV radiation while still maintaining
a high resolution and pattern LER.
An initial study on methacrylate based
nanoparticle resists have demonstrated enhanced
EUV sensitivity with high resolution patterns.
1-3
Gaining insights from prior observations
4
, the
present study describes new nanoparticle
compositions, using ligands of different
strengths
which led to resists with extremely high EUV
sensitivity. Extending the study further,
nanoparticles with o-toluic acid (strong ligand,
figure 1b) was successfully synthesized and
evaluated for patterning under 248 nm KrF laser
(DUV).
2. Materials and Methods
2.1. Materials
The respective isopropoxide of hafnium and
zirconium were obtained from Sigma Aldrich.
Dimethylacrylic acid, o-toluic acid, photoactive
compounds and reagent grade solvents were
purchased from Sigma-Aldrich and used as
received, without further purification. Silicon
wafers were purchased from WRS materials.
Nanoparticles were synthesized by sol-gel
technique as described previously. Photoresist
formulation and film formation has been reported
Figure 1. trans-dimethyl-
acrylic acid (a) and ortho-
toluic acid (b)
a
b
Journal of Photopolymer Science and Technology
Volume 27, Number 5 (2014) 663–666 © 2014SPST
Received April 2, 2014
Accepted May 15, 2014
663