Size of Things

Millimeters Ball of a ball point pen Thickness of paper Human hair Talcum Powder Fiberglass fibers Carbon fiber Human red blood cell E-coli bacterium Size of a modern transistor Size of Smallpox virus 0.5 0.1 0.02 - 0.2

(orange = man-made things)

Microns Nanometers

100 20 200 40 10 5 46 1 0.25 0.2 0.3

250 200 300

Electron wavelength: ~10 nm or less Diameter of Carbon Nanotube Diameter of DNA spiral Diameter of C60 Buckyball Diameter of Benzene ring Size of one Atom 3 2 0.7 0.28 ~0.1

Below that line = Nanoscience!

Its NOT just about the metric units we prefer to use when measuring things
Things above that line are still often measured using nanometers

It IS about the SCIENCE (QM) => Electrons are mushy clouds of size ~ De Broglie
Above that line, clouds seem small: Electrons ~ hard B-B like dots

Below that line, mushy cloudiness of electrons becomes very important

Controls electrical, optical, mechanical and other properties Controls bonding and nanostructure

The Science Changes! Microscience Nanoscience

Size of Things
Millimeters Ball of a ball point pen Thickness of paper Human hair Talcum Powder Fiberglass fibers Carbon fiber Human red blood cell E-coli bacterium Visible Light Wavelength: Size of a modern transistor Size of Smallpox virus 0.5 0.1 0.02 - 0.2

(orange = man-made things)

Microns Nanometers

100 20 200 40 10 5 46 1 0.40 0.75 microns 0.25 0.2 0.3

1000 400 750 nm 250 200 300

Electron wavelength: Upper upper limit ~ 10 nm Diameter of Carbon Nanotube Diameter of DNA spiral Diameter of C60 Buckyball Diameter of Benzene ring Size of one Atom

3 2 0.7 0.28 ~0.1

Can also turn our knowledge around to get SUPER HYDROPHOBIC SURFACES
What would be required: 1) To make surfaces unattractive to water, use materials w/ NON-polarized surfaces 2) To minimize chance of Van der Waals bonding, also make them very rough

Or as shown in this computer animation of The Lotus Effect

(add credits)

Supporting webpage with full Lotus Effect movie: Lecture 11 - Supporting Materials - LotusEffect (Source: William Thielcke, Hamburg Germany)

OK it is fun to watch, but is it useful?

If dirty water flows quickly off surfaces, it will not dry there (leaving dirt behind) Further, as shown in animation, droplets can pick up and carry away earlier dirt: Thats why it is called The Lotus Effect Its a way plants keep leaf surfaces clean!

Dirt

Dirt

APPLICATIONS: Self-cleaning windows, paints, photovoltaic solar energy panels . . .

Is Nanotechnology really new?

During the middle ages, the Muslims who fought crusaders with swords of Damascus steel had a hightech edge - carbon nanotubes and nanowires in their sabres. Damascus sabres were forged from Indian steel called wootz. It is likely that the sophisticated process of forging and annealing the steel formed the nanotubes TEM image of and the nanowires, and cementite nanowires could explain the amazing mechanical properties of Nature, vol. 444, p 286 the swords
5 nm

Damascus Steel

Damascus blade showing the Damascene surface pattern containing a combined Mohammed ladder and rose pattern

http://www.tms.org/pubs/journals/JOM/9809/Verhoeven-9809.ht Cementite bands

Nanotechnology describes the creation and development of materials with structural features in between those of atoms, molecules and bulk materials, with at least one dimension in the nanometer range (nm).

Cluster (50 units)

Colloids (1 1000 nm)

Nanoparticles (1 100 nm)

Nanocrystals (1 10 nm)

Organic

Inorganic

Nanoelectronics and Related

Sensors, Affinity probes and Markers

Bio

Structural Applications

Nanomaterials

Applications
(a) Desired Properties (b) Nanodevise concept and system architectures (c) A new class of high performance materials (d) To molecular electronics, biology and biomedical

Top-Down: Fabrication of device processing on the nanoscale.

structures via monolithic

Bottom-Up: Fabrication of device structures via systematic assembly of atoms, molecules or other basic units of matter.

TACN(1,4,7-triazacyclononane), cyclen (1,4,7,10-tetraazacyclododecane), cyclam (1,4,8,11-tetraazacyclotetradecane).

(a) Delivery of payload to cell through monolayer-membrane interactions (b) ) Structure of particles and guest compounds: Bodipy, TAF, and LAP, the number of encapsulated guests per particle

Fictionalization of NPs with different groups

Radius of particle or cluster 105 nm

104 nm
Fluorescence at different wavelengths from a single UV light due to quantum confinement in semiconductor quantum dots

bulk

103 nm 102 nm 10 nm 1 nm nanoparticles quantum dots molecules

Solutions containing different sized CdSe quantum dots. The size of the particles ranges from ca. 2 nm on the left to 6 nm on the right

1A

 In nanomaterials strong chemical bonding is present, delocalization of valence electrons can be extensive. The extent of delocalization can vary with the size of the system.

Structure also changes with size.

The unusual physical and chemical properties, depending on size - Optical properties - Bandgap - Melting point - Specific heat - Surface reactivity

Electronic properties

Physical properties

Chemical properties

Quantum size effect Single Electron tunnelling Macroscopic Quantum tunnelling

microstructure, melting point, hardness ductile ceramics

structure , catalysis, reactivity

Gold building blocks from the atomic to the mesoscopic and their changing colors.

Atoms: 1A Colourless

Gold cluster: <1 nm, orange

Gold nanoparticles: 3-30 nm, red gold particles

Crimson to blue

Bulk gold film

What happens to the electrons in a small particle

Continuous to discrete energy levels

(electron wavefunctions confined)

Melting point of gold nanoparticles (2 nm) decreased by 1000o Bulk 1340K, nano (2nm) 340K
Buffat et. al. Phys. Rev. A (1976) 13, 2287

Evolution of the disordered state as size decreases

Ferroelectricity
No. of particles on surface increases

Surface Properties dominate

Incomplete compensation of surface charge as size decreases (single domains will exist) F.E. P. E. Disordered moments Paramagnetic/ paraelectric

Ordered moments
Ferromagnetic/ Ferroelectric

 In a classical sense, color is caused by the partial absorption of light by electrons in matter, resulting in the visibility of the complementary part of the light On a smooth metal surface, light is totally reflected by the high density of electrons no color, just a mirror-like appearance. Small particles absorb, leading to some color. This is a size dependent property.

Different sizes of NPs

Color of the different sizes of NPs

This is greatly influence on the optical and electronic properties of the materials.

UV-vis (left) and PL (right) spectra of CdTe QDs capped with thiolglycolic acid (TGA) in aqueous solution. The spectra were from aliquots taken from 1 to 42 h of refluxing. The exitonic peak position and emission spectra allow for the monitoring of particle growth. The image in the middle shows the different colors of the CdTe QDs with different average sizes, increasing in size from left to right or blue to red

UV-visible absorption spectra of nine hollow gold nanosphere (HGN or HAuNS) samples with varying diameters and wall thicknesses. (b) Photograph showing the different colors of HGN solutions in different vials. The vial on the far left contains solid gold nanoparticles, the rest are HNGs with varying diameters and wall thicknesses

CdTe@Thioglycolic acid

CdTe@L-cysteine

CdTe@3-mercaptopropionic acid

Absorption and Emission spectra of CdTe quantum dots capped with different thiol carboxylic acids. QD (CYS): L-cysteine; QD (MPA): 3-mercaptopropionic acid and QD (TGA): thioglycolic acid capped CdTe QDs. Inset shows molecular structures of carboxylic thiolligands used in capping CdTe quantum dots.

Emission spectra of CdSe/ZnS QDs (water-soluble QDs excited at 350 nm) (Reprinted with permission from Macmillan Publishers Ltd., Nature Biotechnology [7], Copyright 2002); (b) Illustration of size-tunable QDs and creation of the exciton (electron-hole pair) upon photoexcitation followed by radiative recombination (fluorescence emission) or relaxation through trap states.

ZrO2 and ZrO2@SiO2

2
(a) ZrO2 NPs 3795

1.5
Absorbance Absorbance
1530 1612

(b) ZrO2@SiO2 NRs

3590

0.5

1636 1400 Lewis acid

0 400

960 Zr-O-Si bond

3461

900

1400

1900

2400

2900

3400

3900

Wavenumber (cm-1) Wavenumber

(cm-1)

CdSe@MUA
1.1 1 0.9 0.8

CdSe S

COOH

Absorbance

0.7 0.6 0.5 0.4 0.3 0.2 0.1 400

1195 1649 1410

2850 1718

2918

2548 was disappeared

3450
1400 2400 3400

Wavenumber (cm-1)

Characteristic band of Fe3O4 appears at 576 cm-1

Fe3O4@C microspheres show bands at 1700 and 1625 cm-1 associated with the C=O vibration and C=C vibration, indicating the carbonization of glucose during hydrothermal reaction characteristic bands at 634 cm-1 of zirconia

FI-TR spectra of (a) as-synthesized Fe3O4 microspheres, (b) Fe3O4@C microspheres, and (c) Fe3O4@ZrO2 core-shell microspheres.

SEM operation: Air pumped out (vacuum) e- gun emits beam of high energy electrons e- beam focused via lenses Scanning coils move beam across sample Secondary electrons are knocked off surface Detector counts electrons Image given by # eResolution ~5 nm SE low energy BSE high energy

Courtesy of F. Ernst

ZnS@MPA

ZnS@citrate

ZnS@cystamine

b)

ZnS@MES

Barred ZnS

ZnS:Mn2+@cysteine

ZrO2@SiO2

ZnS:Mn2+@cysteine

CdSe@MUA

Ag2Se@ODT

Ag2Se@MUA

CdS@MBA

34

ZnS:Mn nanoparticles/PVP composite nanofibers

The SEM images of (a) unannealed fibers and (b) annealed fibers

Transmission Electron Microscopy

TEM operation: Air pumped out (vacuum) e- gun emits beam of high energy e e- beam focused via lenses Beam strikes sample and some e- are transmitted Transmitted e- are focused, amplified Image contrast enhanced by blocking out highangle diffracted e Image passed through lenses and enlarged When image hits phosphor screen, light is generated Resolution ~<1 nm

sample

lens

Courtesy of F. Ernst

Bare Ag2Se

Ag2Se@MUA

Ag2Se@ODT

Left: TEM micrograph of ZnS/Mn nanoparticles. Inset: representative high-resolution electron micrograph of one ZnS/Mn nanoparticle (aspect ratio 1.1). Right: typical number-weighted particle size distribution gn(d) of ZnS/Mn particles obtained by counting 540 nanoparticles from transmission electron micrographs.

The TEM images of: (a) cysteine-capped ZnS NPs (b) cysteine-capped ZnS NPs and ctDNA.

TEM images of (a) Fe3O4 microspheres, (b) Fe3O4@C microspheres, (c) Fe3O4@ZrO2 core-shell microspheres. (d) The EDX spectrum data of the obtained Fe3O4@ZrO2 core-shell microspheres. Journal of Proteome Research Vol. 6, No. 11, 2007

SEM image of ZrO2

SEM image of ZrO2- SiO2

TEM image of ZrO2

TEM image of ZrO2- SiO2

Analytical and Bioanalytical Chemistry, 2009, In press

Powder X-Ray Diffraction ( ~ 60 Lakhs) (Bruker D8 Advance Diffractometer)

Phase Identification (From the standard pattern given in the JCPDS file). Quantitative Phase analysis using XRD From intensities (preferably area under the peak) of non overlapping peaks of the various components Different crystalline form (polymorphic form) e.g. Different phases of TiO2 : Anatase, Brukite and Rutile. Determination of Accurate unit cell parameters. (Using software like CELL, Powdercell, Treor, GSAS)

Solid solution analysis from lattice parameters (Vegards Law)

Particle size measurement. t = 0.9 / Bcos

Crystal Structure determination.

C d

B
n = 2dsin (Braggs equation)

(100)

(110)
2000

Lin (Counts)

500 400

1000

Lin (Counts)

Scherrers formula
31 33

300

2-Theta - Scale

(111)

(200)

200 100 0
11 20 30 40

t (grain size) = 0.9 / B cos where, B2 = BM2- BS2 = Wavelength of X-ray = Bragg angle
70

(210)

(211)

50

60

2-Theta - Scale

Powder X-ray diffraction pattern of NaTaO3 prepared by reverse micelle route at 600oC and inset show the X-ray line broadening of (110) reflection.

(220)

Atomic Force Microscope

(Digital Instruments, Nanoscope III-A electron microscope)

Study of magnetic domains Surface roughness 3 dimensional surface morphology From section analysis the dimension of the particles can be studied.

the optical lever

AFM

AFM Tip

The atomic force microscope measures topography with a force probe

STM

Metals insulators

Tunnelling current
Metals a cantilever touching a sample

AFM Images of Iron succinate showing formation of spherical aggregates

AFM images of Fe2O3, obtained from heating of Iron succinate

Surface topography and HRTEM of 3 wt % n-composite of SrTiO3

a c

STM images of : (a) Si surface , Red represents the atoms and green the chemical bonds (b) crystal of TiSi2 growing on a Si ( c) Nanoparticles of gold by templating

Dynamic Light Scattering (15 to 30 Lakhs)

Nano ZS90 (Malvern Instruments, UK)

Characterization of particles or molecules can be done in liquid medium (In both aqueous and non-aqueous medium)

Size distribution Zeta potential Monodispersity of the samples Molecular weight

Protein melting point

PH and concentration can also be measured

50
Intensity (%)

30 10 0 1 10 100 Size (d. nm) 1000 10000

Dynamic Light Scattering Studies of microemulsion containing Zn acetate

Intensity (%)

30 20 10 0 1 10 100 Size (d. nm) 1000 10000

Dynamic Light Scattering Studies of microemulsion containing ZnO nanoparticle

Surface modification of NPs

1 2 3

With ZnS-3-MPA NPs

(a)

With CHCA
1 2 3 4

(b)

SALDI-TOF mass spectra of ubiquitin-like proteins in oyster mushroom by ZnS-3-MPA NPs as matrix and affinity probes (a). SA as matrix (b). Peaks 1, 2, 3, and 4 at 8063, 8384, 8593 and 10666 m/z are attributed respectively to the ubiquitin-like protein (8.0 kDa), ubiquitin-like protein (8.3 kDa), ubiquitin (8.5 kDa) and ubiquitin-like protein (10.5 kDa), respectively.
Anal. Chem., 80, 2008, 9681 - 9688.

LDI-TOF mass spectra of the peptide ACTH (18-39) (RPVKVYPNGAEDESAEAFPLEF, [M + H]+ ) 2465.20 Da) acquired by using 4-ATP-capped AuNPs (dark blue) and citratecapped AuNPs (light blue).

Nano Lett., Vol. 7, No. 10, 2007, 3023 3025.

Fe3O4 SALDI mass spectra of a cytochrome C (1.2 pmol) and b myoglobin (890 fmol) Fe3O4 SALDI mass spectra obtained after using silanized magnetic iron oxide particles to selectively concentrate target species from insulin solutions (10 nM, 50 L) at a pH 5 and b pH 8

52

Sensitivity and multicolor capability of QD imaging in live animals. (a, b) Sensitivity and spectral comparison between QDtagged and GFP transfected cancer cells (a), and simultaneous in vivo imaging of multicolor QD-encoded microbeads (b). The right-hand images in (a) show QD-tagged cancer cells (orange, upper) and GFPlabeled cells (green, lower). Approximately 1,000 of the QDlabeled cells were injected on the right flank of a mouse, while the same number of GFP-labeled cells were injected on the left flank (circle) of the same animal. Similarly, the right-hand images in (b) show QD-encoded microbeads (0.5 m diameter) emitting green, yellow or red light. Approximately 12 million beads in each color were injected subcutaneously at three adjacent locations on a host animal. In both (a) and (b), cell and animal imaging data were acquired with tungsten or mercury lamp excitation, a filter set designed for GFP fluorescence and true color digital cameras. Transfected cancer cell lines for high level expression of GFP were developed by using retroviral vectors, but the exact copy numbers of GFP per cell have not been determined quantitatively.
53

Scheme for the acid-base reaction between TNT and cysteamine and the evolution of UV-vis spectra with addition of 50 mg of cysteamine into 20 mL of 1 mM TNT solution. Color inset shows the corresponding colors of the solutions before and after adding cysteamine (solvent: ethanol/acetonitrile, 8:2).

54

Schematic illustrations for (A) the amine-capped ZnSMn2+ nanocrystal sensors for TNT detection and (B) the quenching mechanism of fluorescence by the charge transfer from nanocrystals to TNT analytes.

55

In the absence of Zn(II), the photogenerated hole on the QD will transfer to an energy level on the ligand and become trapped, preventing recombination. This causes charge separation and switches off the emission of QDs. After zinc complexation, the energy level is no longer available and the emission is switched on.
56

57

(A) Absorption ratio (A620nm/520 nm) of MPA/AMP-capped AuNPs in the presence of different concentrations of metal ions. (B) (B) Visible spectra and photographed images of a solution of MPA/AMPcapped AuNPs upon the addition of (a) 16 kinds of metal ions and (b) 16 kinds of metal ions and Hg2+.

58