Sei sulla pagina 1di 62

Dip-Pen Nanowriting (DPN)

Pankaj Bhooshan Agarwal


Sensors & Nanotechnology Group
CEERI, Pilani
Pankaj B. Agarwal

Outlines
Introduction to Nanotechnology
Comparison of Different Nanolithography Techniques
Atomic Force Microscopy (AFM)
Scanning Probe Lithography (SPL) Techniques
Dip-Pen Nanolithography (DPN)
Fundamental Kinds of DPN
Process Steps to Work on DPN system
Effect of Different Process Parameters on DPN
Advance Features of DPN
Applications of DPN
Conclusions

Pankaj B. Agarwal

Introduction to Nanotechnology
Nanoscale Devices:

Introduction: Length Scale

Electronic devices that are designed with


lateral features of 100 nm or less.
Nanoelectronics includes nanoscale
circuits and devices including ultra-scaled
FETs, SETs, RTDs, spin devices,
molecular electronic devices, and carbon
nanotube based FETs etc.

Basically Nanotechnology is multi-disciplinary.

Pankaj B. Agarwal

Moores Law
The number of transistors per square inch on integrated circuits had doubled
every year. Moore predicted that this trend would continue for the foreseeable
future.
In subsequent years, the pace slowed down a bit, but data density has doubled
approximately every 18 months, and this is the current definition of Moore's Law.

There are three key factors limiting


continued scaling in CMOS:
1. Minimum dimensions that can
be fabricated
2. Diminishing returns in switching
performance
3. Off-state leakage

Pankaj B. Agarwal

Limitations of Optical Lithography


Minimum feature size = k/NA
Where
k = proportionality factor
(typically 0.5 for diffraction limited systems)
= wavelength
NA = numerical aperture = sin
(2 = acceptance angle of lens at point of focus)
measure of light gathering power of lens
However, depth of focus = /(NA)2
(important because wafers are not flat)
Increasing NA is not the answer.
Reduce to reduce feature size.
Pankaj B. Agarwal

Comparison of Different Nanolithography Techniques


Serial/
Parallel

Material
Flexibility

Resolution

Accuracy

Speed

Equipment
Cost

Photolithography

Parallel

No

100 nm

High

Very Fast

$10M++

E-Beam
Lithography

Serial

No

15 nm

High

Slow

$1M-$20M

Micro-contact
Printing

Parallel

Yes*

150 nm

Low

Fast

$600k

Nanoimprint
Lithography

Parallel

No

20 nm

Low

Fast

$700k

DPN

Serial/
Parallel

YES

15 nm

High

High With
Parallel
Pens

$300k

* Single material at a time

Pankaj B. Agarwal

Atomic Force Microscopy (AFM)


AFM is based on the
measurement of the
different forces (like
attraction, repulsion,
Vander Walls) between a
sharp tip & sample
surface. The nature of the
force depends upon the
distance between the tip
and sample surface.

AFM is capable of investigating surfaces of both


conductor & insulator.
Courtesy: G. Binnig, C. F. Quate and Ch. Gerber, PRL 56, 930 (1986)

Pankaj B. Agarwal

AFM: Schematic Principle

Schematic View of AFM System


Pankaj B. Agarwal

Scanning Probe Lithography (SPL) Techniques


In Scanning Probe Lithography (SPL) technique, the
AFM/STM tip is used to change the surface
chemistry of nano-dimensional area selectively.
Types of SPL with different writing mechanisms:
Bias-induced Nanolithography,
Dip-Pen Nanolithography (DPN),
Catalytic-probe Lithography, and
Nanografting

Pankaj B. Agarwal

Various Scanning Probe Lithography (SPL) methods for SAMs

In bias-induced nanolithography, patterns


are traced with a metal-coated tip at
elevated bias onto a conductive or
semiconductive substrate.

In catalytic-probe lithography, a catalytic


reaction occurs where a coated tip
touches the surface to chemically change
the head groups of SAMs.

In DPN, patterns are written with a tip


coated with ink by liquid transfer through
a capillary meniscus onto bare surfaces
to form SAMs.

For
nano-grafting,
SAM
molecules
assemble on a gold surface from solution
onto areas shaved by force with a
scanning atomic force microscope tip.

Pankaj B. Agarwal

Dip-Pen Nanolithography (DPN)


DPN was introduced by Mirkin Group to the research community for
fabricating the nanostructures in year 1999. In this technique, ink on a
sharp object is transported to a paper substrate via capillary forces.
Quill Pen

DPN

Schematic representation of DPN. A water meniscus forms


between the AFM tip coated with ODT and the Au substrate.
Pankaj B. Agarwal

Basic Concept of DPN


In particular, n-alkanethiol molecules (and their derivatives) are suspended in
droplets at the end of an AFM tip as a molecular ink. By rastering the probe tip
close to a gold (or other metal) surface, the alkanethiol molecules are
transported to the surface via capillary action through a water meniscus that
naturally occurs between the tip and sample in ambient conditions. An array of
molecules are deposited that is a direct function of the rastering pattern of the
AFM tip.

Image shows a moving AFM head depositing "ink" molecules on the


substrate through the water meniscus.
Pankaj B. Agarwal

Self-Assembled Monolayers (SAMs)


When molecule-substrate interactions is the spontaneous self organization of
atoms and molecules on surfaces into well-ordered arrays, called as SelfAssembled Monolayer.
A thiol is a sulphur-containing organic
compound with the general formula RSH
where R is arbitrary. An example is ethyl
mercaptan,C2H5SH.
CH3(CH2)H3(CH2)nSH, Where n=1, 3, 5, 7,
9, 11, 15, 17, 21; can form closely packed
stable SAMs on gold.
It is believed that the terminal H atom is
removed and S forms a covalent bond with
the gold surface.
Alkanethiol SAM on Gold Substrate

Pankaj B. Agarwal

Self-Assembled Monolayers (SAMs)


Why alkyl chains are
tilted during assembling?
There is strong Vander
Walls interaction between
the alkyl chains that
causes the axis of the
alkyl chains to tilt by 300
from the surface normal.
Self-Assembled Monolayer of Alkanethiol on Gold

Pankaj B. Agarwal

Two Fundamental Kinds of DPN Methods

Direct Write:
Write the molecule of
interest directly onto the
surface as the ink.

Templating:
Write out an ink pattern in order to create,
or attach something else.
Pankaj B. Agarwal

DPN Templates: Molecular Glue

Charge-based Recognition

Specific Binding of Ligands

Pankaj B. Agarwal

Process Steps to Work on DPN System

Prepare Environmental Conditions

Design Pattern in InkCAD

Inking (Check whether ink is


diffusing on the Substrate)

Ink Calibration

Writing Designed Pattern &


Imaging

Pankaj B. Agarwal

Process Steps to Work on DPN System


Prepare Environmental Conditions

Pankaj B. Agarwal

Prepare Environmental Conditions

Humidity Range:
Minimum: 5% Rh,
Maximum: 75% Rh (below dew point)
Temperature Range:
Minimum: 2C less than RT
Maximum: up to 10C greater than RT

Pankaj B. Agarwal

Process Steps to Work on DPN System


Prepare Environmental Conditions

Design Pattern in InkCAD

Pankaj B. Agarwal

InkCAD Window

Pankaj B. Agarwal

InkCAD Window

Pankaj B. Agarwal

Process Steps to Work on DPN System


Prepare Environmental Conditions

Design Pattern in InkCAD

Inking (Check whether ink is


diffusing on the Substrate)

Pankaj B. Agarwal

Coating of Tips & Inking Testing

Pankaj B. Agarwal

Process Steps to Work on DPN System


Prepare Environmental Conditions

Design Pattern in InkCAD

Inking (Check whether ink is


diffusing on the Substrate)

Ink Calibration

Pankaj B. Agarwal

Ink Calibration (MHA on Gold Substrate)

Line Width: 60 nm

Calculated Line Diffusion Coefficient: 0.018 m2/sec


Pankaj B. Agarwal

Process Steps to Work on DPN System


Prepare Environmental Conditions

Design Pattern in InkCAD

Inking (Check whether ink is


diffusing on the Substrate)

Ink Calibration

Writing Designed Pattern &


Imaging

Pankaj B. Agarwal

Writing Designed Pattern

Pankaj B. Agarwal

Effect of Different Parameters on DPN Process


There are various parameters, which controls the writing phenomena or
we can say which decides the dot size / line width are as follows:
Substrate-Ink Combination
Substrate Roughness
Dwell Time/Speed
Humidity
Temperature
Tip Radius

Pankaj B. Agarwal

Substrate-Ink Combination
Different ink-substrate combinations given in the following table are
reported by various research groups.
Ink

Substrate

Notes

Alkylthiols (e.g. ODT


and MHA)

Au

30 nm resolution with sharp tips on single crystal surfaces,


<50 nm on polycrystalline surfaces

Ferrocenylthiols

Au

redox active nanostructures

Silazanes

SiOx, GaAs

patterning on oxides

Proteins

Au, SiOx

Both direct write and indirect assembly

Conjugated polymers

SiOx

polymer deposition verified spectroscopically and electrochemically

DNA

Au, SiOx

sensitive to humidity and tip

Fluorescent dyes

SiOx

luminescent patterns

Sols

SiOx

Solid-state features

Metal salts

Si, Ge

electrochemical and electroless deposition

Colloidal particles

SiOx

Viscous solution patterned from tip

Alkynes

Si

C-Si bond formation

Alkoxysilanes

SiOx

humidity control important

ROMP materials

SiOx

combinatorial polymer brush arrays

Pankaj B. Agarwal

MHA (C16H32O2S)

Hydrogen
Carbon
Sulphur
Oxygen

Pankaj B. Agarwal

ODT (C18H38S)
Hydrogen
Carbon
Sulphur

Pankaj B. Agarwal

Substrate Roughness

LFM images of MHA lines written on: (a) mica-peeled gold, yielding 14nm
minimum line width (b) evaporated gold, yielding 26nm minimum line width and
(c) sputtered gold, yielding 69nm minimum line width.

Courtesy: J. haaheim et. al., Ultramicroscopy 103, 117 (2005)

Pankaj B. Agarwal

Dwell Time/Speed

(a) Shows LFM images of ODT islands deposited on a gold surface by an


ODT-coated AFM tip for sequentially longer tip-surface contact and (b) The
measured island radii as a function of contact time. The solid line is a fit to
the radial diffusion model described in the text. The dashed line is a fit to
an alternate model requiring t1/2 dependence.

Pankaj B. Agarwal

Humidity Effects

Normalized radii (with respect to maximum radius) of MHA islands as a


function of deposition time and relative humidity.

Note: ODT shows a little dependency of the writing speed on the


ambient humidity.

Solubility of ink in water decides the ink diffusion process.


Pankaj B. Agarwal

Temperature Effects

The temperature dependencies of the growth rate of (A) ODT and (B) MHA
SAMs constructed from LFM images of dots, which were generated at nine
different temperatures in the 22-33C temperature range (Dwell Times: 2, 4,
and 8 Seconds)

The total number of solvated molecules taking part in the transport


process increases with increasing temperature because the ink
dissolution/ desorption process, which involves breaking and making
of van der Waals interactions, is facilitated.
Pankaj B. Agarwal

Tip-Radius
Tips with larger radii will lead to larger minimum line widths. For a
blunter tip, the minimum tipmeniscussubstrate interaction area is
larger, and thus it follows that minimum line widths will be higher.

LFM images of MHA lines written on peeled gold with: (a) sharpened
tip, yielding 14nm minimum line width, (b) unsharpened tip, yielding
34nm minimum line width, and (c) super-unsharpened tip, yielding
57nm minimum line width
Courtesy: J. haaheim et. al., Ultramicroscopy 103, 117 (2005)

Pankaj B. Agarwal

Advance Features of DPN System

Multiple Pens
Bias Option (Nano-Oxidation)
Universal Inkwells
2D-Nano Print Array

Pankaj B. Agarwal

Types of Pens
Pens
Passive
Single Pens

Active

Multiple Pens (Parallel Pens)

Pankaj B. Agarwal

Passive Pens

Pankaj B. Agarwal

Active Pens
Those are similar the multiple pen array only difference is that even
you can select/actuate particular pen at a time.

HOW ?

Pankaj B. Agarwal

Nano-Oxidation:
Basic Concept:
In this process the bias is applied
between tip and substrate. The
water molecules (within the
meniscus) between tip and
surface are ionized and reacts
with surface to make its oxide
form.
Applications:
Useful to oxidize the metallic and
semiconductor surface at nanolevel.
In above experiment the 11 mm silicon oxide line is fabricated on silicon surface by
applying a sequence of 23X104 pulses of 20 V for 1 ms. The achieved oxide line width is ~
13 nm.
Courtesy: M. Calleja et. al., APL 76, 3427 (2000)
Pankaj B. Agarwal

Nano-Oxidation process carried out


at Silicon Substrate (CEERI Sample)
In Nscriptor DPN System there
is bias control option, in which
upto 200 volts can be applied
between tip and substrate.

Control bias: 5 volts

Measured Line Width ~ 100 nm


* Biasing control is for passive pens only.
Pankaj B. Agarwal

Universal
Inkwells

Pankaj B. Agarwal

2D Nano-Print array

Pankaj B. Agarwal

Use of 2D Nano-Print array


Writing of complex patterns.
Replicate these and flexibly pattern a
variety of nanoscale materials over
cm2 areas.
Templating techniques have been
demonstrated with proteins, viruses,
and carbon nanotubes.
Direct-writing has been demonstrated
with MHA, ODT, and phospholipids.

Pankaj B. Agarwal

Applications for DPN

Biomolecular Micro- and Nanoarrays


Controlling Biorecognition Processes from
the Molecular to Cellular Level
DPN Templates
DPN Patterned Etch Resist

Pankaj B. Agarwal

Major Applications of DPN


Nano-electronic
Devices
Fabrication

Fabrication of
NIL Master Stamp

HIV detection

Applications
Cancer Diagnosis

DNA Writing

Fabrication of
Tunnel Junction
Pankaj B. Agarwal

MHA/ODT as Etch Resist for Nano-patterning:

1. Write regions of
octadecanethiol (ODT)
on Au thin film.

Si (100)

2. Selectively etch Au using


wet chemical etchant
(ferri/ferrocyanide 8-10 min).

3. Remove Ti and SiO2, etch


Si, and passivate Si
surface.

10 nm Au
5 nm Ti
Native SiO2

Si (100)

Si(111)

Si(100)

Weinberger et al Adv. Mater. 12, 1600 (2000).


Pankaj B. Agarwal

Fabrication of Single Electron Devices:


Gold Substrate

Electrode Structure formation

MHA

MHA

10-40 nm

Silicon Nanoparticle synthesis

Pankaj B. Agarwal

Fabrication of NIL Master Stamp

Si (100)

10 nm Au
5 nm Ti
Native SiO2

Si(111)

Si (100)

Si(100)

Si

NIL Master Stamp

Si(111)

Si(100)
Pankaj B. Agarwal

Line Test Pattern


(NIL Master Stamp were Fabricated using DPN)

Pankaj B. Agarwal

Cancer Diagnosis
The tumor markers are used for detection and diagnosis of
cancer.
What are the Tumor Markers ?
Found in the blood, other body fluids, or tissues
High level of tumor marker may mean that a certain type of
cancer is in the body.
Examples of tumor markers include
CA 125 (ovarian cancer),
CA 15-3 (breast cancer),
CEA (ovarian, lung, breast, pancreas, and gastrointestinal
tract cancers), and
PSA (prostate cancer).

Pankaj B. Agarwal

Cancer Diagnosis

SAM Layer Patterning

Tumor markers interacts with


monoclonal antibodies

Immobilization of monoclonal
antibodies

Surface Profile Detection


Pankaj B. Agarwal

Direct-Write DNA Patterns on Gold Substrate


Unmodified silicon nitride cantilevers often yield DNA patterns
with feature sizes and shapes that are not easily controlled.
Then how direct writing is possible?
Improved control over DNA patterning can be
achieved through surface modification of a
silicon nitride AFM cantilever with 39-aminopropyl-trimethoxysilane, which promotes

reliable adhesion of the DNA ink to the tip


surface.
DNA ink:
Hexanethiol-modified oligonucleotides
AFM image of hexanethiol-modified
polycrystalline gold.
Courtesy: L. M. Demers et. al., Science 296, 1836 (2002)

oligonucleotides

patterned

on

Pankaj B. Agarwal

HIV Detection
HIV is an increasingly serious disease that requires
more research and better diagnostic solutions.

How DPN is useful for HIV detection ?


DPN process is used to produce spotted
nanoarrays of protein antibodies that can be
treated with patient samples and then detect for
the presence of HIV.

Pankaj B. Agarwal

Schematic representation of the Nano-Immunoassay Formation

Courtesy: Nanoink Inc.

Pankaj B. Agarwal

Why DPN generated template is better option in


comparison to other available techniques?

We can detect at much lower


concentrations of HIV relative to current
screens (Enzyme-linked immunosorbent
i.e., ELISA).
We detect HIV in patient plasma with a
much lower number of viral copy counts
than PCR (Polymerase chain reaction.)

Pankaj B. Agarwal

Conclusions
DPN has many advantages over other nanolitholgraphy techniques
e.g.
High resolution (minimum line width reported: 14 nm)
Material flexibility
Fast writing process with parallel pens
Low Cost Process
Extensive chemistry is involved in DPN: So there is a lot of scope for
chemistry researchers.
Both direct writing and templating are possible.
In the era of inter-disciplinary, it makes bridge among different areas
of science like chemistry, biology, physics, material science.
DPN has enormous applications, which are not limited to only single
area but in various fields e.g. electronics, nanobiotechnology, biosensors
etc.
Pankaj B. Agarwal

Nscriptor DPN System in CEERI:

Pankaj B. Agarwal

Pankaj B. Agarwal

Pankaj B. Agarwal

Potrebbero piacerti anche