3.3.

X- ray lithography

This lithography processes involve the category of nanolithographic

techniques, through which transistors with smaller features can be patterned.
It uses X-rays to transfer a geometric pattern from a mask to a light-sensitive
chemical photoresist, or simply "resist," on the substrate. A series of chemical
treatments then engraves the produced pattern into the material underneath
the photoresist.

X-ray lithography can be extended to an optical resolution of 15 nm by

using the short wavelengths of 1 nm for the illumination. This is implemented
by the proximity printing approach. The technique is developed to the extent
of batch processing. The extension of the method relies on Near Field X-rays
in Fresnel diffraction: a clear mask feature is "demagnified" by proximity to a
wafer that is set near to a "Critical Condition". This Condition determines the
mask-to-wafer Gap and depends on both the size of the clear mask feature
and on the wavelength. The method is simple because it requires no lenses.
This technique originated as a candidate for next-generation lithography for
the semiconductor industry, with batches of microprocessors successfully
produced. Having short wavelengths (below 1 nm), X-rays overcome the
diffraction limits of optical lithography, allowing smaller feature sizes. If the
X-ray source isn't collimated, as with a synchrotron radiation, elementary
collimating mirrors or diffractive lenses are used in the place of the refractive
lenses used in optics. Fig. 7 illustrate the process of X-ray lithography.

Figure 7.
(a) Schematic process of X-ray lithography. (b) structure produced with X-ray lithography
(Courtesy Source : SAL, Inc.). (Scale bar is not mentioned)

The X-rays illuminate a mask placed in proximity of a resist-coated wafer.

The X-rays are broadband, typically from a compactsynchrotron radiation
source, allowing rapid exposure. Deep X-ray lithography (DXRL) uses yet
shorter wavelengths on the order of 0.1 nm and modified procedures such as
the LIGA process, to fabricate deep and even three-dimensional structures.
X-rays are usually generate secondary electrons as in the cases of extreme
ultraviolet lithography and electron beam lithography. While the fine pattern
definition is due principally to secondaries from Auger electrons with a short
path length, the primary electrons will sensitize the resist over a larger region
than the X-ray exposure.
3.3.1. Advantages of X-ray lithography

There are several advantages in X-ray lithography.

1. Resolves diffraction issues

2. Shorter wavelengths ( 0.1 - 10 nm) can be used
3. Smaller features can be patterned
3.3.2. Disadvantages of X-ray Lithography

The following are the disadvantages of X-ray Lithography

1. Usage of X-ray masks

2. Deformation during the process
3. Vibrations during the process
4. Time consuming process
3.5. Alternate nanolithographic techniques

3.5.1. Micro-contact printing (soft lithography)

This is known as soft lithography that usually uses the relief patterns on a
PDMS (poly-dimethylsiloxane) stamp in order to form patterns of self-
assembled monolayers (SAMs) of ink on the surface of a substrate through
conformal contact. This technique has wide range of application in cell
biology, microelectronics, surface chemistry, micromachining, Patterning
cells, patterning DNA and Patterning protein.

Figure 9 represents the process of Micro-contact printing. This process

involves the application of ink to stamp, application of stamp to surface,
removal of stamp and residues rinsed off

Figure 9.

Schematic of the Micro-contact printing process (Courtesy: IBM Zurich)

Advantages of Micro-contact printing:

1. Very simple and easy pattern procedures to create micro-scale features

2. This can be done in a traditional laboratory environment. No need clean
room facility
3. Using single master, multiple stamps can be made
4. Reliability of individual stamps which can be used for many times.
5. It is a cheaper method.

Limitation in Micro-contact Printing:

1. Diffusion of ink from PDMS stamp to surface during pattering

 2. Shrinking of stamp is one of main problem in which stamp can
eventually shrink in size resulting difference in desired dimensions of
the substrate patterning
3. Contamination of substrate
4. Stamp deformation
3.5.2. Nano-imprint lithography

Nanoimprint lithography (NIL) is an emerging process that can produce sub-

10nm features. It is a simple process that uses a mould to emboss the resist
with the required pattern. After embossing the resist, compressed resist
material is removed using anisotropic etching and the substrate exposed. It
can produce features at extremely small resolutions that cover a large area
with a high throughput and relatively low cost, which is main advantage of
this technique. It can be adapted to transfer all components needed to create a
thin film transistor on a plastic substrate. It involves pressing and heating a
thin film between a patterned template and a substrate. Upon heating, the
patterned film adheres only to the substrate [ref Fig. 10]. This has high
throughput and is relatively inexpensive compared to developing extreme
deep UV lithography for commercial viability. It is also flexible enough to be
used at chip level with several layers or at the wafer level when single layer is
required. It can give resolutions lower than 10nm with high throughput at low
cost. One of the current barriers to production at these resolutions is the
development of mould. It can be used for fabricating nanoscale photo-
detectors, silicon quantum-dot, quantum wire and ring transistors (Chou, S.Y.
1996)
Figure 10.

Schematic diagram of the steps involved in the nanoimprint lithographic

process [Courtesy: Source: AZoNano]

Applications of Nanoimprint lithography

1. It can be used to make optical, photonic, electrical and biological

devices.
2. Advances in mould manufacturing will have wide application of NIL in
smaller devices.
3.5.3. Scanning Probe Lithography (SPL)

SPL is an emerging area of research in which the scanning tunneling

microscope (STM) or the atomic force microscope (AFM) is used to pattern
nanometer-scale features. The patterning methods include mechanical
pattering such as scratching or nano-indentation, or local heating with sharp
tip (Dagata, 1995). When a voltage bias is applied between a sharp probe tip
and a sample, an intense electric field is generated in the vicinity of the tip
(Ref. Fig. 11).
Figure 11.

Schematic diagram of the Scanning probe lithography. Electrical bias

between a conducting tip and a substrate induces a highly localized enhanced
oxidation [Courtesy Source: Dagata et al, Science, Vol.270, pp.1625-1626,
1995]

Advantages:

1. This process can make nanopatterns without optical apparatus.

2. It can control deposited material by hydrophobicity of the surface.
3. This process can make arbitrary patterns by controlling the trajectory of
AFM tip.
4. This process involves small scan area, Low throughout.
5. By using this technique, it is possible to make nanowire, SET, etc.. By
using an organic solvent, the organic material can be deposited on the
surface.
SPL method is a recognized as a lithographic tool in the deep sub-micron
regime, as it is compatible with standard semiconductor processing. There are
four main factors which dictate the viability of SPL as a known patterning
method for the semiconductor industry. They are

1. Throughput (wafers/hour)
2. Resolution
3. Alignment accuracy
4. Reliability

Scanning probe lithography involves a set of lithographic techniques, in

which a microscopic or nanoscopic stylus is moved mechanically across a
surface to form a pattern. In this method, another technique describes a SPL
technique which is known as Dip Pen Nanolithography.

Dip Pen Nanolithography - in this process, the patterning is done by directly

transferring chemical species to the surface. We can call this process as
constructive process.
3.5.3.1. Dip Pen Nanolithography (DPN)

Dip Pen Nanolithography (DPN) is known as a soft-lithography technique

that uses an AFM scanning probe tip to draw nanostructures. In this process,
a probe tip is coated with liquid ink, which then flows onto the surface to
make patterns wherever the tip makes contact. This kind of directwrite
technique provides high-resolution patterning capabilities for a number of
molecular and biomolecular “inks” on a variety of substrates. Substrates are
the base material that the images are printed on. Some of the applications of
the DPN technique include sol gel templates that are used to prepare
nanotubes and nanowires, and protein nanoarrays to detect the amount of
proteins in biological samples such as blood. (Ref. Fig. 12).

This process was first developed by Professor Chad Mirkin at Northwestern

University Nanotechnology Institute for depositing thin organic films in
patterns with feature sizes of around 10 nm ( about 20 times better than the
best optical lithography) (Mirkin, 1999).

In DPN technology, the ink on a sharp object is transported to a paper

substrate via capillary forces. The capillary transport of molecules from the
AFM tip to the solid substrate is used in DPN to directly “write” pattern
consisting of a relatively small collection of molecules in nanometer
dimesions. An AFM tip is used to write alkanethiols with 30-nm line width
resolution on a gold thin film in a manner analogous to that of a dip pen.
Molecules are delivered from the AFM tip to a solid substrate of interest via
capillary transport, making DPN a potentially useful tool for creating and
functionalizing nanoscale devices (Mirkin, 1999).

Several factors decide the resolution of DPN:

1. The grain size of the substrate affects DPN resolution much as the
texture of paper controls the resolution of conventional writing.
2. The tip-substrate contact time and thus the scan speed influence DPN
resolution.
3. Chemisorption and self-assembly of the molecules can be used to limit
the diffusion of the molecules after deposition.
4. Relative humidity seems to affect the resolution of the lithographic
process by controlling the rate of ODT transport from the tip to the
substrate. The size of the water meniscus that bridges the tip and
substrate depends on relative humidity. For example, the 30-nm wide
line required 5 min to generate in a 34% relative humidity environment,
whereas the 100-nm line required 1.5 min to generate in a 42% relative
humidity environment.
Figure 12.

Schematic representation of DPN. A water meniscus forms between the AFM

tip coated with ODT and the Au substrate. The size of the meniscus, which is
controlled by relative humidity, affects the ODT transport rate, the effective
tip-substrate contact area and DPN resolution. [Courtesy: C.A. Mirkin, et al,
Science 283, 661, 1999]
3.5.3.2. DPN application on semiconductor surfaces

Dip-Pen Nanolithography can not only apply to gold surface using alkyl or
aryl thiols as inks, but also to semiconductor surfaces, such as silicon and
gallium arsenide. Hexamethyldisilazane (HMDS) is used as the ink to pattern
and modify (polarity) the surface of semiconductors. Lateral force
microscopy (LFM) can be used to differentiate between oxidized
semiconductor surfaces and patterned areas with the deposited monolayers of
HMDS. The choice of the silazane ink is a critical component of the process
since the traditional adsorbates such as trichlorosilanes are incompatible with
the water meniscus and polymerize during ink deposition. This work provides
insight into additional factors, such as temperature and adsorbate reactivity,
that control the rate of the DPN process and paves the way for researchers to
interface organic and biological structures generated via DPN with
electronically important semiconductor substrates (Ivanisevic, 2001).
3.5.3.3. DPN application on magnetic materials: Approach to high density recording and storage

Over the past decade, there has been considerable interest in methods for
synthesizing and patterning nanoscale magnetic materials. These
nanomaterials show novel size-dependent properties, are potentially useful
for high-density recording. Two of the main challenges in this field are: (a)
site-and shape-specific patterning of hard magnetic nanostructure on the sub-
100 nm scale; (b) ability to reliably and reproducibly read/write such minute
features. The conventional top-down approach in recording media is plagued
by the difficulties of etching and patterning novel hard magnetic systems,
especially as the individual recording elements approach the super
paramagnetic limit at room temperature operations. DPN can be used as a
direct-write method for fabricating "hard" magnetic barium hexaferrite,
BaFe12O19 (BaFe), nanostructures. This method utilizes a conventional atomic
force microscope tip, coated with the BaFe precursor solution, to generate
patterns that can be post-treated at elevated temperature to generate magnetic
features consisting of barium ferrite in its hexagonal magnetoplumbite (M-
type) structure. Features ranging from several hundred nm down to below
100 nm can be generated. (Fu, 2003).