محاضره نانو -دكتور عمر نور

Nanotechnology and it’s Application

Omer Salih Mohamed Nour(O. Nur)

Physical Electronics and Nanotechnology, Department of Science and Technology, Campus Norrköping, Linköping

University, Sweden

Linköping University


24h credit hours course

Orgnaization of the lecture(s)

1. Introduction

2. Nano-biophotonics and bioelectronics

3. Nano-photonics

4. Nano-mechanics

5. Experimental tutorial

6. Literature is provided

7. Exam !


What is nanotechnology?

Background

Classification of growth methods

Chemical growth methods

Hydrothermal chemical growth

Why Metal oxides nanostructures?

Examples of growth and devices

Motivation of the course

Background


Chemical growth methods


Why Metal oxides nanostructures?


Outline of the lecture

Nanotechnology

Materials and devices at the nano-scale (DOT). (a nanometer is one billionth of one meter) hold vast promise for innovation in virtually every industry and public endeavor including health, electronics, transportation,………., and has been heralded as

"the next industrial revolution ".

1. What is nanotechnology?

Definition of NanotechnologyThe essence of nanotechnology is the ability to work at the molecular

level atom by atom, to create large structures with fundamentally new molecular organization. [...] [but see later changes].


Nanotechnology Market: (2008)

(1) Nano-materials: 120 Billion US$/year*

*

(2) Nanoelectronics: around hundra Billion US$/year

2.General applications

Identify new business and collaborative opportunities with the new series of The Institute of Nanotechnology(IoN) reports, allowing your company to access the latest R&D and

commercial applications in nanotechnology. These reports cover the following areas:

1. Nanotechnologies for Car Interiors- Functionalised materials for interiors, in order to increase the

occupants' overall perceived comfort- Materials (plastics, textiles, leathers) and coatings having the

function of thermal insulation- Functionality on clothes(sensorized, anti-bacterial, isothermal)

- Stain repellents: hydrophilic and hydrophobic - Nanofibres

- Scratch-resistant surfaces - Electronic noses and tongues

- Surface modification with protective anti-fouling coatingsPrice: £300

2. Nanotechnologies for the Oil and Energy Industry- Nanofluids for improved heat transfer - Emission controls- Selective gas adsorption/conversion/separation- Cost effective and robust nanocoatings to prevent fouling and corrosion- Down hole refinery- Nanoreactor cages for highly selective reactions- Selective separation using

3. Nanotechnologies for Composites, Surface Coatings and Sensors- Cutting tools and enhanced metals - Nanocomposite containers for long term storage of chemicals - Self-healing composites- Fatigue resistant materials - Smart surfaces/Coatings- Chemically/electrically tuned carbon nanotube composites as effective self cleaning materials and molecular sensors- Ultra-Sensitive Chemical Sensor Coatings - Dendrimer/nanoparticle assemblies as chemical toxin deactivation coatings- Wear and Corrosion Resistant Coatings - Carbon nanotube and fibre based composites-Tunable, adaptive, self-healing and stress-smar sensing systems - Super Strong Functional Composite Coatings and Textiles Based on Carbon Nanotubes - Sensory/responsive textiles - Cut resistant materials- BioSensors - Sensor Probes- Carbon Nanotube Sensors - Nanotube Sensor Networks - Smart dust - Boron isotopes based semiconductors as sensitive elements- Nanoporous Materials for multifunctional sensors and devices - RFID Hydrogen Sensors

4. Nanotechnologies for Novel Optical Effects- Materials Delivering Novel Optical Effects On Surfaces as polymer films, zeolites, paper, textile- Materials that modify the basic optical properties of surfaces- Materials that impart luminescence- Materials exhibiting structural colour effects- Photochromic and Thermochromic Films- Development of Photochromic Films using nanomaterials- Development of Thermochromic Films using nanomaterials

5. Nanotechnologies for Perfume Encapsulation6. New processes and applications in nanochemistry- Commercialization of nanochemicals - Nanooxides of precious, ferromagnetic, rare metals (Ti, Zr etc.) - Nanopolymers and membranes - Nanomaterials (cement, fertilizers) - Nanopowders in chemical applications - Nanogreen chemistry - Nano energy applications - Environmental applications of nanotechnology

A Brief History of the Transistor1947

First bipolar transistor1958

First IC 1966First CMOS transistor

1961First planar IC

Shockley, Brattain and BardeenNobel Prize in Physics (1956)

J. KirbyNobel Prize in Physics (2000) G. Moore

Moore’s Law (1965)

(Attala & Khan)

Histroical backgroundBackground

Electronic Devices: The IC developement

2003

1971 20011989

2300134 000

410M42M

1991

1.2M

tran

sist

or /c

hip

10 µm 1 µm 0.1 µm 1 nmtransistor sizeHuman hair Red blood cell Bacteria Virus

Histroical backgroundBackground

When Nanotechnology startedBackground

When Nanotechnology startedFeynman said in his after dinner talk:

‘I would like to describe a field, in which little has been done, but in which an enormous amount can be done in principle.

What I want to talk about is the problem of manipulating and controlling things on a small scale.

Why cannot we write the entire 24 volumes of the Encyclopedia Brittanica on the head of a pin?

Background

In 1959 a ’’computer’’ would fill a large room.

The road already traveled: Nanoscale miniaturizationFeynman proposed shrinking computing devices toward their physical

limits where “wires should be 10 or 100 atoms in diameter”. Samsung this month announced large-scale production of devices

built with 30 nanometer technology, which is to say,

with wires at Feynman’s 100-atom scale.

Background

When Nanotechnology started1947

First bipolar transistor1958

First IC 1966First CMOS transistor

1961First planar IC

Shockley, Brattain and BardeenNobel Prize in Physics (1956)

J. KirbyNobel Prize in Physics (2000) G. Moore

Moore’s Law (1965)

(Attala & Khan)

Technology at hand at that time was not enabling us to satisfy the dream of Feynman

Background

To utlize what ’Nanotechnology’ offers is acheived by first have control over the material that enables the technology. This means to have control of a nano-material.

Different approaches to Nanotechnology

Background

To obtain nano-materials there are two main approaches:

Top-down approach.

Bottom-up approach.


Top–down and bottom–up are two approaches for the manufacture of products.

Background


Bottom–up approaches seek to have smaller (usually molecular) components built up into more complex assemblies.

Bottom-up approach

Background

Different approaches to NanotechnologyBottom-up approach

Cholera bacteria!

Background


Background


Bottom-up approach

Background


Biologists and chemists have ever been working with Nano-technology.

Background

What happens when objects are shirnks

to small sizes?The answer is simple: the physical

observation changes completely.

Why?Becuase the dominating forces do not

scale with the same way.

Effects at small sizes

General rule:When objects shrinks down

isomorphically, then the forces are scaled for those with

lower power of the linear dimensions in a way to keep them

dominating.


This menas the physical observation simply changes. It is no longer governed by the classical picture.


Nano-structures and sensitivityAs objects are scaled down the ratio of the surface to volume increases sharply. This render surface effects more pronounced.

Isolated small size electrode will possesses high sensitivity due to non-linearity effects.

It was demonstrated that an isolated nano-wire can very effeciently feels the presence of a single ion in the vicinity !


Non-linearity effects. What is it?Answer: compatibility!

You can NOT push an elephant to a room through a small door.

Effects at small sizesNano-structures and sensitivity


Small concentration elements must be available with a large volume if we have to

detect them. This volume is sometimes not available.

Fortunately sensor sensitivity scale with size.

Why ’small’ tools?

where C is the concentration, N is Avogadro’s number, Ø is the sensor efficiency (0-1).

Classically a sample volume V needed to detect an element is given by:


The growth of materials is classified according to the growth temperature into:

High temperature (few 100s degrees C).Low temperature (less than 100 degrees C).

Difficulties: cleanness, special substrate, etc..

High temperature (few 100s degrees C)

High temperature (few 100s degrees C)Vapour-Liquid-Solid growth method (VLS)

Quartz tube furnace:

Substrate

ArHolder Substrate

ZnO+C powder Au Nanoparticles on Si, SiO2 and Al2O3

Ar

Substrate

R. S. Wagner and W. C. Ellis, APL, Vol. 4, No. 5, p. 89 (1964).


Variety of nanostructures on Si and other semiconducting substrates.

VLS: Temperature effect

920 oC870 oC


Low temperature (less than 100 degrees C)

Low temperature means a temperature less than 100 degrees C.

(+) This low temperature allows the use of ’soft’ substrates.

Can be scaled-up.


Suitable for growth on sub-micrometer glass tips for use in medical sensors an devices.

Chemical engineering

Common approaches:(1) Hydrothermal chemical growth(2) Chemical path deposition (CBD)(3) Electrochemical deposition (4) Sol Gel...(5)................


Chemical engineering of inorganic materials Synthesis of nano-sized inorganic materials require receipes at low temperature to control a short range reaction. In addition a rational design and tunning of the chemcial process parameters is required.

This is a suitable approach to research in Sudan Becuase you do not need sophisticated instruments



Disadvantageoues:To conrol precis engineering has to be aopted. Otherwise, different nano-structures will be obtained.


An equimolar (0.1 M) aqueous solution (MilliQ, 18.2 MOhm)of zinc nitrate, and methenamine, C6H12N4, is placed in a regular laboratory oven and heated at 95 °C for 1-10 h, depending on the required micro-rod length. Subsequently, the thin films are thoroughly washed with water to remove any residual salt or amino complex and allowed to dry in air at room temperature.

Low temperature (less than 100 degrees C)From microrods to nanorods


AFM image of the seed layer (ZnO nanoparticles)


Effect of the pH from 1.8 up to 11.2.


Effect of the pre-curser concentration from 25 mM up to 300 mM.


Effect of the temperature from 40 degrees C up to 110 degrees C.


Plot of the aspect ratio of ZnO NRs versus growth temperature (T) under the conditions of C = 100 mM, t = 5 hrs, and inherent pH.

Why Metal Oxides Nanostructures?It is worldwide recognized that the superior properties of nanomaterials will promise a revolutionary new approach with a major impact in various innovative applications. These property improvements or even new properties derive from structural features such as particle size or layer thickness on a scale 1-100 nm, much smaller than that found in conventional materials. The screening and synthesis of new nanostructured metal oxides is a major research topic world wide.

Why Metal Oxides Nanostructures?

Easy to grow, enviromental friendly, and of interest to many applications.

We will deal with two imporant metal oxides Zinc Oxide (ZnO) and Cupper Oxide (CuO).

Suitable for Technical and Medical applictions.


The book series are suitably divided into five volumes with topics ranging from growth to properties to applications of metal oxide nanostructures. Due to the valuable properties and applications of ZnO nanostructures, the fifth volume of the book series is devoted only on ZnO nanostructures and their nanodevice applications.

Crystal structure of ZnO 60% ionicity and possess polar and non-polar surfaces

Metal Oxides Nanostructures

Nevertheless, due to the polar surfaces other complicated structures like rings, helexis ec.. can also be gorwn by varying the growth constitutents.


Metal Oxides NanostructuresZnO optical properties

Of interst for PDT

Metal Oxides NanostructuresThis implies that ZnO can be of potential for white light emission

Different emission colors from ZnO deep defect centers Klingshirn C, 2007 Phys. Stat. Solidi b 244, 3027-3073).

UV peak

(White light)


ZnO is widely used as an additive into numerous materials and products including plastics, ceramics, glass, cement, rubber (e.g. car tyres), lubricants, paints, ointments, adhesives, sealants, pigments, foods (source of Zn nutrient), batteries,

first aid tapes, etc.

No harm to human body.

Zinc oxide eugenolfor tooth filling (ZNE)

ZnO is a bio-safe and biocompatible material.

Metal Oxides Nanostructures ZnO properties

Biosafety and biocompatibility


Table 1. Mechanical energy from typical body motions and the expected electrical energy can be generated.

Activity Mechanical Electrical Electrical energy per movement

Blood flow 0.93W 0.16W 0.16JExhalation 1.00W 0.17W 1.02JBreath 0.83W 0.14W 0.84JUpper limbs 3.00W 0.51W 2.25JFingers type 6.9-19mW 1.2-3.2mW 226-406μJWalk 67.00W 11.39W 18.9J

How much energy does each of us have?

In addition ZnO possesses piezoelectric properties.Potential for self powered devices. Ambient mechanical energy is the most abundant source ofenergy.

www.nanoscience.gatech.edu/zlwang

0 10 20 30 40 50 60 70 80

-20

0

20

Vo

lta

ge

(m

V)

Time (Second)

Electricity generation by finger movement

Nano Letters, 9 (2009) 1201

Metal Oxides NanostructuresIn addition ZnO possesses piezoelectric properties.

Potential for self powered devices.


Changes in environment

Energy harvester

Energy storage

Sensors

Data processor

& controller

Data transmitter & receiver

Energy in environment

NanogeneratorCapacitor

Sensor &Transmitter

Self-powering wire-less nanosensor system


CuO properties

CuO is narrow bandgap (1.2 eV) p-type semicondcutor.

Has good electrochemcial and catalytic properties.

Less dissolvation in bio-fluids comapred to other oxide semiconductors.

CuO nanostructures can be grown by low cost chemical approaches on any susbtrate.

It is a promising material for sensing, solar cells, ..etc.

Examples of growth and devicesHigh quality nanorods grown at 50 degess C


What happens when we lower the growth temperature?

Hybrid LEDs on plastic - Spectrum analysis



Hybrid LEDs on plastic

Examples of growth and devicesPrinted electronics


ZnO nanorods grown paper at 50 oC


Hybrid LEDs on disposable paper

Examples of growth and devicesPencil drawn electronic devices

Printed electronics


Collect the nano-crystals and make an ink

Printed electronics


Printed electronics


ZnO printed electronics


Will be high-lighted in Nature Photonics

(CH2)6N4 + 6H2O ↔ 6HCHO + 4NH3

NH3 + H2O ↔ NH4+ + OH-

Cu2+ + 2 OH− ↔ Cu(OH)2

dehydrationCu(OH)2 ↔ CuO (s)+ H2O

CuO NanostructuresCuO Nanostructures


Growth of CuO microstrucutres

The 3D CuO microflowers (MFs) were synthesized by simple low temperature chemical growth method.

The Au coated glass was used as a substrate. a 5 mM copper nitrate trihydrate (Cu(NO3)2. 3H2O) and hexamethylenetetramine (HMT)

were mixed in de-ionized (DI) water, the substrate was placed in the solution and the reaction vessel was loaded in a laboratory oven held at 90 oC for

5 hrs to form the 3D CuO MFs.



CuO ostrucutres own with varying the pH from 6.5 (inherent) and up to 11.

6/7/

2012


(CH2)6N4 + 6H2O ↔ 6HCHO + 4NH3

NH3 + H2O ↔ NH4+ + OH-

Cu2+ + 2 OH− ↔ Cu(OH)2

dehydrationCu(OH)2 ↔ CuO (s)+ H2O





(a)

.

(b)

tt[100]

[100]

[001]

[001]

(101)_



020

200

(a)

(b)

5 nm

3 nm

50 nm

Low temperature growth at 60 oC of CuO/ZnO nanocorals. Selective growth of CuO NS on ZnO NR. Heterojunction p-n diode with good electrical characteristics. Promising humidity sensing capablities and high responsivity

factor. Fast response/recovery time.


A. Zainelabdin et al. J. Mater. Chem., 2012, 22, 11583


CuO/ZnO composite NSCuO/ZnO composite NS


a) b)

c)

d)



CuO/ZnO composite NSCuO/ZnO composite NS




Bioelectornics for medical analysis and drug delivery

A deep knowledge of the understanding of the chemsitry

physics of the complicated multipule path way processes

inside cells is a dream for scientists. What makes it

difficult to observe these processes is the fact that, these

processes are sometimes temporary.

Examples of growth and devicesBioelectornics for medical analysis and drug delivery

Advantageous and disadvantageous of the ion sensitive electrode

Advantges (+)(1) Direct measurement of the activity.

(2) Speed. (3) Continous measurmeents of different ions simultaneously.(4) Possibility to dectect from selective parts inside the cell. (5) Simple device set-up.(6) In vivo measurements.

Disadvantges (-)(1) Need for roboust preparation.(2) Demanding maniplulative skills. (3) Specifity difficulty.(4) Out-put signal interface.(5) Individual cell measurmenets (6) Uncertinity of the effect of penetration on cell activity.(7) Difficult to estimate the ion in and out fluxes using intracellular SIE.


Small concentration elements must be available with a large volume if we have to

detect it. This volume is sometimes not available.

Fortunately sensor sensitivity scale with size.

where C is the concentration, N is Avogadro’s number, Ø is the sensor efficiency (0-1).

Classically a sample volume V needed to detect an element is givne by:


Nano-structures and sensitivityAs objects are scaled down the ratio of the surface to volume increases sharply. This render surface effects more pronounced.

Isolated small size electrode will possesses high sensitivity due to non-linearity effects.

Small nano-strucutres are natural ideal elements for signal transduction due to compatibility with the chemcial ions or biological analyte in question.


Low temperature growth with self organized growth property and can be obtained on soft substrates

Scanning electron micrograph of (A) silver coated capillary tip, and (B) ZnO nanorods on the capillary tip and inset shows hexagonal ZnO nanorods.


Working electrode

Intracellular potentiometric sensors



Nano-systems: experimentalIntracellular selective ion detection

Calcium ion detection: measurements set-up


Calcium ion detection: results validation


Bioelectornics for medical analysis and drug delivery

Biological analytesGlucose detection: effect of insulin

0 25 50 75 100 125 150 175 200 225 250 275 3000.00

0.05

0.10

0.15

0.20With insulinWith out insulin

EM

F [m

V]

Time (s)


Localized photodynamic therapy of breast cancer cells


Using the developed technique cancer cell necrosis (premature cell death) was achieved locally in 10 minutes, compared to 120 minutes needed for conventional PDT.

Time for a Break

Thank you for your attention

Omer Nur, [email protected]

Physical ElectronicsDepartment of Science and Technology(ITN), Campus Norrköping, Linköping University,Norrköping, Sweden

محاضره نانو -دكتور عمر نور

Documents

nanotechnology materials

essence of nanotechnology

definition of nanotechnology

nanotechnology market

examples of growth

surface coatings

new molecular organization

nanoscale dot