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Nanomaterials in optics, electronics and energy applications

Chun-Wei Chen Department of Materials Science and Engineering , National Taiwan University 2012/11/01

Outline
Part I: Optics and electronics of lowdimensioal nanomaterials Part II: CNTs and graphene

Part III: Nanomatreials in Energy gy

Size of Nano??
Organic molecule <1nm DNA 1-100 nm

Bacteria 1 m

m 10-5 10-4 10-3 10-2

10-10

10-9

10-8

10-7

10-6

SOI transistor width 0.12m

Transistors
QDs(CdSe) 5nm Memory 1012 bits/cm2 (1Tbit/cm2) Circuit design Copper wiring width 200 nm (Now ~ 20nm)

IBM PowerPC 750TM Microprocessor 7.56mm8.799mm 6.35106

Definition of Nanomaterial
Original quantum size effect where the electronic properties of solids are
altered with great reductions in particle size

New
On 18 October 2011, the European Commission adopted the following definition of a nanomaterial:[2] A natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm 100 nm. I

Quantum confinement effect


L U MO

E 1
H O MO

= 2 2 1 1 1 .8 e 2 + E ( R ) = Eg + R m m 2R2 h e

me and mh : effective masses e : bulk optical dielectric coefficient

Size-dependent optical properties of CdSe QDs


Band gaps change with their average sizes

Ab bsorbance (a.u.)

4 2 nm 4.2 Pho otoluminescen nce (a.u u.)

3.8 nm 3.0 nm

2 5 nm 2.5
300

Wavelength (nm)

500

700

900

Chen, et. al. Langmuir 15, 6845 (1999)

Lotus Effect
Lotus

Nano array on glass substrate

Self-cleaning

Park, K. C. et. al., ACS Nano 2012, in ASAP.

http://www.youtube.com/watch?v=zjsWFvUkh7M

Photocatylysts using Nanomaterials


Bulk TiO2 V.S. TiO2 nanorods/nanoparticles
http://www.hiwtc.com/products/tio2-ultra-fineand-high-purity-333573-22847.htm

http://www.35664.net/new/public/tag.php?name= %E4%B8%93%E9%A2%98&page=14

Journal of American Chemical Society, 133,11614,


(2011)

Photocatalytic y effect
Harmless
http://proj3.moeaidb.gov.tw/nanomark/License /2/#d

TiO2

Radical

Photoniccrystals

1-D

2-D

3-D

periodic in one direction

periodic in two directions

periodic in three directions

periodicelectromagnetic p g media

From

How to make Nanomaterials ??


Topdown p (Physical ( y a method): ): lithography g ap y Advantage: Easily controlled Disadvantage: Expensive

http://www.beilsteinjournals.org/bjnano/single/articleFull Text.htm?publicId=2190-4286-2-50 p

http://spie.org/x32391.xml

Bottom up (Chemical Method)


Au

Ge

Au

NiPt Nanoparticles

All Rights Reserved, Copyright The Japan Society of Mechanical Engineers

Ahrenstorf, K. et. al., Adv. Funct. Mater. 2008, 18, 38503856

Atomic Foundry
Different shapes of CdSe

Different shapes of Ag NPs

Min, Y. et. al., Nature Materials 7, 527 - 538 (2008)

Tao. A. R. et. al., small 2008, 4, No. 3, 310 325

How to observe Nanomaterials??


JEOL JEM-1400 Transmission electron microscopy(TEM)

Lin, , H. M. et. al., , Nano Lett., , Vol. 3, , No. 4, , 2003

Kinder, E. et. al., J. Am. Chem. Soc. 2011, 133, 2048820499

3DSTEMTomographyimagesofP3HT/TiO2 hybrids
TiO2 nanorod (NR) 4nmx20nm TiO2 nanoparticle (NP) 5nmx5nm

STEMHAADFelectrontomography (2resolution)

Phaseseparateddomain

Welldispersed

3DSTEMTomographyimagesofP3HT/TiO2 hybrids
TiO2 nanorod (NR) 4nmx20nm TiO2 nanoparticle (NP) 5nmx5nm

Welldispersed

Phaseseparateddomain

Journal of American Chemical Society, 133,11614, (2011)

3DSTEMTomographyimagesofP3HT/TiO2 hybrids
TiO2 nanorod (NR) 4nmx20nm TiO2 nanoparticle (NP) 5nmx5nm

Phaseseparateddomain

Welldispersed

3Dscanningtransmissionelectronmicroscopy(STEM) Electron lectrontomographyofP3HT/TiO2 hybrids


TiO2 nanorod (NR) 4nmx20nm TiO2 nanoparticle (NP) 5nmx5nm

STEMHAADFelectrontomography

Phaseseparateddomain

Moredispersed

Scanning electron microscopy(STM)

(Quantumtunnelingeffct )

http://www.personal.psu.edu/ewh10/ResearchBackground.ht m

Silicon atoms on a surface


http://www.exo.net/~pauld/workshops/Atoms.html

AtomicForceMicroscopy(AFM)
AtomicForceMicroscopy(AFM) singlewallcarbonnanotube

Grapheneoxide)

O ti land Optical delectronic l t i applications li ti of f nanomaterials

0D: nanoparticles

1D: nanowires

2D: nanosheets

Bulk crystal

Quantum wire (nanowires, nanorods) Quantum well

Quantum dot (nanocrystals) 0 d

Densityof states

St tates

3d

2d

1d

Energy gy

Threedimensionalsystem(bulk)

V=0 Freeelectronmodelin3D

D( E ) E

Twodimensionalsystem

V=infiniteatzdirection

D( E ) const
1Dconfinement,2Dfreeelectron

1Dsystem(Quantumwire)

D( E ) 1 / E

2Dconfined,1Dfreeelectron

0Dsystem y (Quantumdot)

Discreteenergylevel

3Dconfined

Opticalabsorptionandexcitonsin semiconductorquantumwell

Superlattice

= 2n2 = = E g + 2 2 2 d
(Noexitoniceffect)

Bulk

Quantum well

RoomTexcitoneffectisobserved. StrongCoulombinteractionastheeh distancedecreases.

Bindingenergyincreasesfrom4 meV(bulk)to10meV(QW)

Size-dependent optical properties of CdSe QDs


Band gaps change with their average sizes

Ab bsorbance (a.u.)

4 2 nm 4.2 Pho otoluminescen nce (a.u u.)

3.8 nm 3.0 nm

2 5 nm 2.5
300

Wavelength (nm)

500

700

900

Chen, et. al. Langmuir 15, 6845 (1999)

Surface plasmonic effect


Gold nanoparticcels

Nano Size Nano-Size

Nano-Size

50 nm

Silvernanoparticles

Different Geometries (Gold nanorods)

Surface plasma enhanced Raman (SERS)

Dr. W.L.Wang, IAMS, Academic Sinica

Adv.Mater,2006,18,491

Gas sensor
For detecting Combustible, Combustible flammable and toxic gases, and oxygen depletion.

Portablegasdetector

Classification of g gas sensor


z Thermal gas sensor: flammable gas, gas CH4, Cl2, H2, CO z Field effect transistor gas sensor

Schematicofcatalyticsensor

SchematicofMOSFETsensor

Nanomaterials on gas sensor application


Fabricated by carbon nanotube

Currentvoltagecurvesforelectrical breakdownforNH3,CO2,N2,O2,He, A and Ar dair i


A.Modi,N.Koratkar,E.Lass,B.Wei,andP.M.Ajayan,Miniaturizedgasionizationsensorsusingcarbonnanotubes, Nature,vol.424,no.6945,pp.171174,2003.

Nanomaterials on gas sensor application


Fabricated by Graphene

Concentration,n,ofchemically inducedchargecarriersinsingle layergrapheneexposedtodifferent concentrations,C,ofNO2.

Changesinresistivity,,atzeroB causedbygraphene graphenes s exposureto variousgasesdilutedin concentrationto1p.p.m.

grapheneisanexceptionallylownoisematerialelectronicallyfor chemicaldetectors. F. SCHEDIN, et. al., nature materials 2006, 6, 652

Nanomaterials on gas sensor application


Fabricated by Silicon nanowire

Densearraysofsiliconnanowires overlarge areascreatedbynanoimprint lithography

VariationinISD vs VG foraSiNW array exposedtoammoniaNH3vapor.


Talin,A.A.,Appl.Phys.Lett.2006,89,153102

theshiftedthresholdvoltageofthefieldeffecttransistor asignatureofchargetransferbetweentheanalytes andthenanowires.

Nanomaterials on gas sensor application


Fabricated by WO3 nanowire

IVcurvesofgassensorsbasedon Sensingresponsecurves theWO3 nanowire arraybeing ofthesensor. exposedtoairdilutedNO2 with differentconcentrations.

highly sensitive to NO2 (50 ppb)


Cao,B.et.al.,J.Mater.Chem.,2009,19,23232327

Quantum dot barcodes for multiplexed immunosensing in a microfluidic device with external optical detection.
QDs with their corresponding surface conjugated antigens and fluorescence spectra

Fluorescent image of quantum dots on chip

Microfluidic chip

Klostranec,J.M.et.al.,NanoLett., 2007, 7 (9),pp 28122818

Using reduced graphene oxide FET as detecting hormonal catecholamine molecules and their dynamic secretion from living cells
the setup of front-gate Graphene FET for sensing g application pp Optical image of PC12 cells grown conuently on poly-L-lysine coated rGO PET device

Real-time l i response of f rGO/PET GO/ FET to the h vesicular i l secretion i of f catecholamines h l i f from PC12 cells stimulated by high K+ solution.

Q.Y.He,et.al.,ACSNano,Vol.4,32013208(2010)