Optics & Laser Technology 60 (2014) 80–84

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Optics & Laser Technology

journal homepage: www.elsevier.com/locate/optlastec

Quantum optical lithography from 1 nm resolution to pattern transfer

on silicon wafer
E. Pavel a,n, S.I. Jinga b,n, B.S. Vasile b, A. Dinescu c, V. Marinescu d, R. Trusca e, N. Tosa f
a
Storex Technologies, 020892 Bucharest, Romania
b
Faculty of Applied Chemistry and Materials Science, “Politehnica” University of Bucharest, 011061 Bucharest, Romania
c
National Institute for R&D in Microtechnologies, 077190 Bucharest, Romania
d
National Institute for R&D in Electrical Engineering, 030138 Bucharest, Romania
e
METAV R&D, 020011 Bucharest, Romania
f
National Institute for R&D of Isotopic and Molecular Technologies, 400293 Cluj-Napoca, Romania

art ic l e i nf o a b s t r a c t

Article history: Many attempts have been made to break the diffraction limit, a major problem in optical lithography.
Received 29 October 2013 Here, we report and demonstrate a lithography method, quantum optical lithography, able to attain 1 nm
Received in revised form resolution by optical means using new materials (fluorescent photosensitive glass–ceramics and QMC-5
16 December 2013
resist). The performance is several times better than that described for any optical or electron beam
Accepted 20 January 2014
lithography (EBL) methods. The written patterns on resist were transferred to Si wafer. SEM measure-
ments show 5 nm line widths.
Keywords: & 2014 Elsevier Ltd. All rights reserved.
Optical nanolithography
Fluorescent photosensitive glass–ceramics
Polymer

1. Introduction
In the last 50 years, integrated circuits (ICs) have been getting
smaller, and producers have used optical lithography to make their
chips. But the light diffraction limits the size of the transistors that
optical lithography can produce. A number of works have been carried
out to achieve an improved resolution [1]. Three groups of lithography
techniques permit the access to sub-10 nm resolution domain: (i) EBL/
FIB/EBID, (ii) STM/quantum holography and (iii) quantum optical
lithography.
Electron beam lithography (EBL) is the current method for fabricat-
ing devices on nanoscale, due to its resolution and availability.
A 3–4 nm lines in poly(methymethacrylate) (PMMA) resist have been
produced by EBL [2] and smaller patterns at the 1–2 nm size scale has
been demonstrated with self‐developing metal halide resists [3].
Electron-beam-induced deposition (EBID) was used to realize the
smallest nanodots with a mean size of 0.72–1.5 nm [4,5]. Scanning
tunneling microscope (STM) [6] has provided the first images of
individual atoms on the surfaces of materials. The manipulation of the
atoms by STM has permitted the writing of patterns, such as the
initials “IBM” [7]. The single-atom limit for information storage
density was overcome [8] by using the coherence of electrons in a
two-dimensional electron gas to produce quantum holograms.
Although the resolution of scanning probe lithography methods [7,8]
n
Corresponding authors.
E-mail addresses: eugenp@rdslink.ro (E. Pavel),
sorinionjinga@yahoo.com (S.I. Jinga).
is remarkable ([7]
1.25 nm; [8]
0.31 nm), they have the inherent
problem of being limited in speed.
Direct laser writing (DLW) optical lithography uses photons
instead of electrons (EBL). Diffraction limit imposes a barrier below
210 nm [9]. Femtosecond laser direct writing of photosensitive glass
has permitted the production of 80 nm structures [10]. Quantum
optical lithography [11–14] has opened the door to decrease resolu-
tion beyond 2 nm and is suitable to continue Moore’s law [15]. When
analyzes Moore’s law, the resolution is defined in terms of half pitch.
The most advanced ICs are now written with 16 nm half pitch.
In this paper we present our results concerning the writing at 1 nm
resolution by using new materials such as fluorescent photosensitive
glass–ceramics [16] and QMC-5 resist which present quantum multi-
photon confinement effect. The experimental results obtained in
quantum optical lithography regarding the resolution improvement
were applied to the process of patterns transfer on Si wafer.
2. Experimental procedure
The writing process was carried out by a home built dynamic
tester [11], at atmospheric pressure and room temperature. The
tester consists of an optical pick-up, a stage, a motor and an
electronic system. The optical pick-up contains a 0.6 NA lens, a
detector and a CW laser diode (λ¼ 650 nm, Pmax ¼ 10 mW).
The laser beam is a Gaussian beam with 2 m focus diameter. The
computer-controlled system manages the actuators (Z and radial
movements of the optical pick-up), laser intensity, rotational speed
and processing of the detection signals. A linear speed of 9.6 m/s was

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 E. Pavel et al. / Optics & Laser Technology 60 (2014) 80–84 81

used to write all samples. We choose to work at high speed in order to

meet the industry requirements. The sample was positioned in the
stage center by an optical microscop. In order to write lines at
nanometer resolution, verical positioning is a critical issue. A first step
of the focusing procedure consists in focusing the laser beam on the
sample surface. The presence of the interface air-sample is indicated
by the detector.The second step involves the recording of 20 layers
(100 nm is the distance between two adjacent layers) above and
below the surface. The writing process was carried out on three
sample types: (1) fluorescent photosensitive-glass ceramics; (2) resist
on TEM carbon grids and (3) resist on (1 0 0)Si substrate. The
preparation of a fluorescent photosensitive glass–ceramics is described
in detail in Ref. [16]. Fabrication of the samples with substrate of TEM
carbon grids or (1 0 0)Si squares of size 10  10 mm began with spin
coating of a layer of QMC-5 resist at 3600 rpm for 60 s. Heating on a
hot plate at 70 1C for 30 min created a solid film of resist. The resist
thicknesses were 5 nm, as measured by SEM. Tight control over the
resist thickness is critical for pattern transfer on Si wafer. KOH/H2O
solution is used for preferential etching of silicon along crystal planes
[17]. The etching rate depends on the solution concentration, doping
and crystal orientation of the silicon. At room temperature 20%KOH/
H2O solution has an etching rate of 15 nm/min for (1 0 0)Si. Samples Fig. 1. TEM image of multiple 1 nm lines written in a fluorescent photosensitive
used in this study were etched in 20% KOH/H2O solution for 30 s. A glass–ceramics sample.
Bio-Rad Sputter Coater was used to cover samples by a thin layer of
gold. SEM images were acquired by three equipments: (i) Electron An issue in lithography is the pattern quality, such as line-end
beam lithography and nanoengineering workstation E_Line (RAITH roughness (LER). The precise measurement by TEM could deter-
GmbH, Germany), (ii) scanning electron microscope (FESEM-FIB) mine LER for thin lines. In Fig. 2(a) there is a clear image for a 22 nm
Auriga Zeiss and (iii) FEI Quanta Inspect F. A 300 KV high-resolution line. The line width variation is less than 2 nm, which almost meets
transmission electron microscope (HRTEM) Tecnai G2 F30 S-TWIN was critical dimension control requirements (6%) for industry.
used to analyze the written lines inside the samples. The procedure of Ref. [12] could be used to estimate the
confinement rate [D/(written line width)] realized with fluores-
cent photosensitive glass–ceramics and QMC-5 resist at 1 nm
3. Results and discussion resolution. Rayleigh scaling equation [19] gives the resolution of
the smallest printable feature:
In the first experiment, a sample of fluorescent photosensitive
D ¼ k1 λ=NA ð1Þ
glass–ceramics has been written by home built dynamic tester [11]
with a laser power of 4 mW. Transmission electron microscopy can where k1 is a process parameter, λ is the light wavelength and NA
determine the width of thin lines. Fig. 1 shows TEM image of multiple is the numerical aperture of the optical system. With the following
1 nm lines located in two bands. The group of samples consisting of parameters k1 ¼0.35, λ¼ 650 nm, NA ¼0.6 we have obtained:
TEM carbon grids covered by 5 nm thick resist is dedicated to explore D¼ 379 nm; confinement rate ¼379.
the resolution limit of quantum optical lithography. The writing In QMC-5 resist, at low laser power, the dependence of the written
process was carried with 5 laser power levels. The dependence of line width versus laser power is linear (Fig. 2). In this region, the resist
the line width versus laser power is presented in Fig. 2. A 1 nm line thickness of 5 nm is greater or equal with the line width and the writing
has been written with a laser power of 70 nW. The patern transfer proceess is mainly a 3D process. A similar linear dependence was
procedure was studied with the second group of samples formed by observed in fluorescent glass–ceramics where 3D effect is dominant
polished (1 0 0)Si squares covered by 5 nm thick resist. After writing
D ¼ k2 P ð2Þ
process with a laser power of 250 nW, the samples were coated with
2.2 nm Au particles [12] by means of a vacuum sputterer, to improve D—line width; P-laser power
electrical conductivity. In Fig. 3(a) there is presented a SEM image of There is a non-linear dependence between laser power and the
parallel lines written in resist. The thinnest line width is 7.4 nm. number of Ag atoms, N contained in recorded lines.
A new group of samples have been written with a laser power of
N ¼ k3 E 3 ð3Þ
250 nW and etched. SEM images of the etching lines on Si wafer are
presented in Fig. 3(b)–(d). A partial removal of the resist in hot E¼ Pt; P-laser power; t is the irradiation time for a sphere with
acetone (50 1C, 10 min) improves SEM contrast (Fig. 3(b)). Multiple radius R.
5–10 nm etching lines were observed. The complete resist removal The relation (3) suggests a three-photon phenomenon during
was carried out with a RIE plasma of O2 (Fig. 3(c)). There are four light absorption.
parallel etching lines with 5–10 nm width, between two 20 nm line A linear process should have the following dependence
markers. Despite significant efforts aimed at developing SEM tech-
N ¼ k4 E ð4Þ
niques to increase resolution, still there are difficulties to measure
structures below 5 nm [18]. Fig. 3(d) shows a higher resolution of
etched Si wafer covered by Au particles. Parallel etching lines with Energy consideration sustains the presence of a non-linear
the widths of 5.3 nm, 8.5 nm, 11.8 nm and 14.4 nm were marked. process with the contribution of three photons. Formation of Ag0
Improved resolution (Fig. 3(e)) was obtained by Au decoration using atoms in fluorescent photosensitive glass–ceramics is determined
plasma cleaning (treatment duration: 5 min) of the sample presented by the transfer of electrons from Ce3 þ ions [20]. These electrons
in Fig. 3(d). Thinner lines were observed. 3.39 nm and 5.74 nm could appear by illumination with 305 nm photons. The energy of
etching lines have been marked. a 305 nm photon is 6.49  10
19 J. The wavelength of the laser
82 E. Pavel et al. / Optics & Laser Technology 60 (2014) 80–84

Fig. 2. TEM images of: (a) two 20 nm modulated lines written in resist, (b) single 10 nm line, (c) single 5 nm line, (d) single 1 nm line. (e) Variation of the line width as a
function of the laser power.

diode used in writing process is 650 nm with the energy of a single An estimation based on quantum lithography theory [21] gives
photon of 3.04  10
19 J. In order to activate the electron transfer the photon number, N involved in the lithographic process of
from Ce3 þ ion to Ag þ ion, the energy balance imposes at least writing 1 nm line
three photons with the wavelength of 650 nm.
D ¼ λ=ð2 ðNAÞNÞ ð5Þ
The application of N-photon absorbing substrate in optical
lithography was proposed by Boto et al. [21]. where D ¼1 nm; λ ¼650 nm; NA ¼0.6; N ¼540
 E. Pavel et al. / Optics & Laser Technology 60 (2014) 80–84 83

Fig. 3. SEM images of a written pattern on (1 0 0)Si covered by resist: (a) multiple thin lines with 7.4 nm line width; (b) multiple etching lines with minimum width between
5 nm and 10 nm; the resist is partially removed; (c) four parallel etching lines with 5–10 nm minimum width, between two 20 nm line markers; the resist is completed
removed by plasma cleaning; (d) etching lines on a (1 0 0) Si sample covered by Au particles; 5.3 nm, 8.5 nm, 11.8 nm and 14.4 nm etching lines were marked; (e) etching
lines on a (1 0 0)Si sample covered by Au particles and treated by plasma cleaning for 5 min; 3.39 nm and 5.74 nm etching lines were marked.

4. Conclusions lithography technique for sub-5 nm regime. In our opinion quan-

In summary, we have written lines with the width of 1 nm in
two materials: (i) fluorescent photosensitive glass–ceramics and
(ii) QMC-5 resist by quantum optical lithography method.
The performance is several times better than that described for
any optical or EBL methods. Writing at 1 nm resolution in
fluorescent photosensitive glass–ceramics and resist involves only
few (5–8) individual chemical bonds (C–C: 0.120–0.154 nm;
Si–O: 0.154–0.171 nm). However, at present remains the question
about the ultimate resolution that can be achieved by quantum
optical lithography. The written patterns on resist were transferred
to Si wafer. Line widths of 5 nm were observed. The experiments
demonstrated that quantum optical lithography is a suitable
tum optical lithography involves a cooperative interaction of many
photons. A three-photon process is observed in absorption phase
and a 540 photons process is suggested by quantum lithography
theory for the writing phase.
Acknowledgments
This work was partially supported by the National Authority
for Scientific Research—Romania, Contract PN-II-PT-PCCA-2011-3,
No. 169/2012. The authors would like to thank E. Vasile and M.
Dinescu for valuable comments.
84 E. Pavel et al. / Optics & Laser Technology 60 (2014) 80–84
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