Quantum Dots 100 Gbit/s

Solitons
Solitons

Optical switch
Waveguides

Quantum dots
Erbium

Optical fibers Ultrafast

Nonlinear
Carlos Lenz Cesar
New Material
lenz@ifi.unicamp.br
C.L.Cesar
UNICAMP
 Carlota Perez: Technological Revolutions and Financial Capital

Financial crisis

Periphery deployment
No funds for other techwave up to this point

5 Revolutions - ~ 60 years total cycle

1. Industrial Rev. – England – 1771
2. Steam and rail-road – England – 1829
3. Steel and eletricity – England+USA+Germany – 1875
4. Oil, cars and mass production – USA – 1908
5. Information and comunications – USA – 1971
Bell Labs na Revolução da Informação
 Amplification, amplification, amplification!
Beginning 20th century - Telephone calls < 30 km .
1913 - De Forest sell triode vacuum tube patent to AT&T
San Francisco 1915 World Fair 1st Transcontinental Call

Alexander Bell

Thomas Atson Theodor Vail

Repercussions: AT&T became a monopoly

1925: Bell Labs became a company Bell labs hired PhDs:
AT&T and Western Electric only costumers Millikan main provider
13 Nobel laureates
 1947 marvelous year
Solid State: Transistor - Bardeen + Brattain + Shockley

Information Theory – Claude Shannon

Shockley - Stanford
Silicon Valley

Traitorous 8
Fairchild – 1957
 Importance of Bell Labs – 1983 AT&T breakup

Vacuum tubes 13 Nobel laureates

Photovoltaics Clinton Davisson – 1937
Transistor Bardeen + Brattain + Shockley – 1956
Satellites communicatios Phil Anderson – 1977
Cell phone Penzias + Wilson - 1978
Laser – semiconductors Steven Chu – 1997
Optical fibers Stormer + Laughlin + Tsuj - 1998
Ultrafast lasers Boyle + Smith – 2009
Non linear optics

Information theory
C
UNIX
 The beggining: 1971 first INTEL chip
1946 – ENIAC
1951 – Texas Instruments
1958 – Noyce & Kilby (Nobel 2000) 1st integrated circuit
1968 - INTEL – 1968 Robert Noyce e Gordon Moore

Gordon Moore Robert Noyce

 Hardware

IBM 486 – 1993

IBM 386 – 1991

IBM XT – 1983

IBM AT 286 1984

IBM PC 1981
Apple 1977

Microsoft 1975
INTEL 1971
 Software

2004 – Firefox

2004 – Facebook
1998 – Google
1995 Amazon
1994 – Netscape
1993 – Mosaic
1975 – Microsoft
 Optical Network

1994 – calls by OF > electronic calls

1988 – 1st TAT EDFA

1987 – Optical Amplifier

1975 OF communication

1970 Optical Fiber

Amplification, amplification, amplification!
Optical Erbium Doped Fiber Amplifier
 Bell Labs and Brazil
IFGW Founders

José Ellis Ripper Filho Sérgio Porto Rogério Cerqueira Leite

 Photonics for communications: ultrafast lasers,
Semicondutors, Non linear optics, Optical fibers,
Optical amplifiers

Brito Cruz: 1986-1987

Charles Shank:
diretor
Hugo Fragnito: 1987-1989

Carlos Lenz: 1988 – 1990

Quantum Dots in UNICAMP
Started with CdTe 1990
PbTe 1995
Colloidal 1999
Laser Ablation 2001
Teses sobre Quantum Dots disponíveis no site do IFGW
Orientação: Lenz

Doutorado
Carlos Roberto M. de Oliveira 1995
Gastón E. Tudury 2001
André A. de Thomaz 2013
Diogo B. Almeida 2014
Mestrado
Cristiane O. Faria 2000
Antônio Á. R. Neves 2002
Wendel L. Moreira 2005
Gilberto Júnior Jacob 2005
Diogo B. Almeida 2008

Outras teses Dr. recomendadas:

Eugenio Rodrigues Gonzales 2004
Lázaro A. Padilha Jr. 2006
 Quantum Dots: size controlled color!
Quantum confinement

Energy
Quantum dot diameter

Smaller cord -> higher frequency -> higher E -> smaller l

Quantum Dot: quantum confinement and size

Espectro de Absorção
Absorption spectra

Absorção

400 800 1200 1600 2000

Wavelength (nm)
Comprimento de onda (nm)
 Right wavelength: optical properties tuning

1989 1995
End of controversy quantum confinement vs stechoimetric variation
CdTe Coloidal Quantum Dots Produced at UNICAMP
 Applications and
Technological Importance
 Switching:
Ultrafast Optical Devices
 Optical Communication - On the edge

750 nm

Typical optical fiber attenuation

Bandwidth for 1 dB/km losses
Dl = 750 nm  DnDt = 0.44

Total Capacity of only one fiber

1014 = 100 Tbit/s
 Optical Device Material Requirements
Devices always based on Dn or D
Dilemma
Dn or D vs Response time
High Optical Nonlinearity Ultrafast Response time < 3 ps
resonant: resonant:
non resonant: non resonante:

Wavelength: 1.5 or 1.3 m

Compatible with Optical fibers

Quantum dots (QD’s): dilemma solution
Quantum Dots
D~4nm abs

abs

D~20nm
 High nonlinearity & ultrafast response time:
CdTe quantum dot
Transient Transmission

Dt = 0.5 ps

1 Tbit/s optical device?

Dt = 1.0 ps

Dt = 2.5 ps

-1000 0 1000 2000 3000 4000 5000

Delay (fs)
Padilha et al, Appl. Phys. Lett. 86 (16), 161111 (2005)
Aplicações dos PQs

Óptica não-linear:
Incandescente LED LED + PQs

•Chaveamento óptico
•Sistemas de 2 níveis (computadores quânticos)

Fótons Portadores
•Células fotovoltaicas (energia solar)

Portadores Fótons
•LEDs
•Displays

Fótons Fótons
•Marcadores Fluorescentes (aplicações biológicas)
•Iluminação
Aplicações PQs

Óptica não-linear:
•Chaveamento óptico
•Sistemas de 2 níveis (computadores quânticos)
Processos que precisam de alta
eficiência de fluorescência
Fótons Portadores
•Células fotovoltaicas (energia solar)

Portadores Fótons
•LEDs
•Displays

Fótons Fótons
•Marcadores Fluorescentes (aplicações biológicas)
•Iluminação
Precisamos da passivação para aumentar a eficiência dos pontos
quânticos

Capa de outro
material

+
No photobleaching!

X. Wu et al,
Nature Biotech.
21, 41 - 46 (2003).
One laser to excite all colors
Physics of the Quantum Dots

Particle in a box
 Quantum Confinement: Simple Model
Free electron function Free electron energy
c c
Bulk: Ywave = eik•R • uBloch  E = E + h2 k2 /(2m* )
g

Quantum dot: Ywave = x(R) • uBloch  E = Eg + Econf

cc cc
Envelope function Confinement energy

Infinite spherical well

spherical Bessel function Boundary condition
c c
x(R) = jn(kR) • Yn m( q, f)  jn(ka) = 0  Econf = h2 kroot 2 /(2m* )

 h2 2  
 
  U esf  Fn, l, m (r )  En, l Fn, l, m (r )
 2m 
Spherical Bessel Functions Roots

0.8 j0

0.4 1D 2S
j l (x)

j1 2P
j2
j3

0.0
1S

1P 1F
-0.4
0 2 4 6 8 10
X
 2
Regras de seleção: 1-fóton F  Y in ez   Y fin

Função de onda: Y n  xnun

Transição intersubbanda

Y in ez   Y fin  un un x n ez   x n 
 x n x n  u n ez   u n 
Transição interbanda
 Transição Intersubbanda
Y in ez   Y fin  un un x n ez   x n
2

1
0

0
1

Transição só é possível se níveis excitados

estiverem populados
 Transição Interbanda

Y in ez   Y fin  x n x n un ez   un
Dn  0
2

1
0

0
1

2
 Regras de seleção: 2-fótons
2
xval uval e   xbub xbub e   xcond ucond
F
b DEb
0

 xval e  xb xb e  xcon uval ub ub ucond  0

b
0

 xval xb xb xcond uval e   ub ub e   ucond  0

b
2
xval e   xb xb xcond uval ub ub e   ucond
 
b DEb
F
xval xb xb e   xcond uval e   ub ub ucond

b DEb
 Absorção de 2-fótons
2
2 xval e   xb xb xcond xval xb xb e   xcond
F  uval e   ucond  
b DEb b DEb

Dn  1
2

1
0

0
1

2
 Fit a cryostat at the System and gain a
Spectral platform with spatial resolution
Cooled sample
Microscope body He line
Spectrometer

FLIM

Ti:Saphire
Vacuum
Pump
405 nm

Translation stage Adapted plate

 Main Issues

High NA but long working distance: we used NA=0.6 with WD = 3mm

Small cryostat to fit under a Zeiss LSM 780 upright

 Small copper piece to bring the sample closer to optical window

Light collection must be done in backscatered geometry.

Sample deposited on a mirror to enhance light collection efficiency.

Colloidal QDs film with ureia small crystals

Mirrored microscope coverslip

Spatial/optical resolution

Pump: Ti:Saphire laser

0.7
PL SHG
0.6

Intensity (a.u.)
0.5

0.4

0.3

0.2

0.1

0
2.1 2.3 2.5 2.7 2.9 3.1 3.3
Energy (eV)

Green: QDs fluorescence

Purple: urea SHG
 CdTe quantum dot 1 and 2 photons PLE at 40 K

3500 Dn  0 Dn  1
3000 2 2
1 fóton
Intensidade (u.a.)

2500 2 fótons 1 1
2000 0 0
1500

1000

500 0 0
0 1 1
2.3 2.5 2.7 2.9 3.1 3.3
Energia (eV)
2 2
Stress Induced Phase Transition

PbTe CdTe
Colloidal vs Doped Glass QDs
Confinement Models
 Optical Transition Selection Rules 1D
1P
2 2
1S
f   fin   p  ini Ffin Fini   nn  ll  mm
m0 
1S
1P
1D
Absorption spectrum
PLE Transitions assignement

hodd1 - eeven1
40 1Sso-1Se
1Pe
Absorption coefficient (cm-1)

?? 1Se
30 1Phh-1Pe

hodd2 - eeven1
heven1 - eodd1

heven1 - eodd1
1Slh-1Se

soodd1 - eeven1
20 1Shh-1Se

10 1Shh
1Phh
1Slh
1Phh-1Se??
1Plh
0
450 550 650 750
2.0 2.4 2.8 3.2
Wavelength (nm)
Energy (eV)
  
Quantum Confinement: Full kP Hamiltonian Model
two subspaces:


r = space inside a cell (Bloch); R = space between cells (envelope)
  2
( Pr  PR ) dot lattice Spin-orbit
2 m0 potential potential interaction

2    2      
Pr  2 Pr  PR  PR Vper  Pr  S
H= ( ) + Vspheric + Vperiodi + ( )
2 m0 m0 c
comutes  with:xxx comutes  with:xxx
   
L r  L R Lr  S
Conclusions:
    
[F ,H] = 0 where F  L R  L r  S  F = good quantum number


   
More*: H(  r )  H( r )  Y (  r )   Y ( r )  parity well defined
* Germanium model
 Band Structure K·P
J , LR
Parity = LR + Lr LR = 0 LR = 1 LR = 2 LR = 3
1 3 1
J= 1 1 3 5 F1  ,0  ,1  ,1
2 1 2 2 2 2 2 C 2 V 2 SO
2
Conduction Band
3 5 7
(Lr = 0) 2 2 2
1 3 1
J= 1 1 3 5
F1  ,1  ,2  ,0
2 1 2 2 2 2 2 C 2 V 2 SO
2
Split off band 3 5 7
(Lr = 1) 2 2 2
1 3 3 1
J= 3 1 3 F3  ,2  ,1  ,3  ,1
2 2 2 2 2 C 2 V 2 V 2 SO
1
Valence Band 2 3 5
3 2 2
(Lr = 1) 2 3
2 5 7 1 3 3 1
5 2 2 F3  ,1  ,0  ,2  ,2
2 2 2 C 2 V 2 V 2 SO
7 9
2 2
 Optical transitions in the full
model 

E  p = odd operator so:
only even to odd or odd to even transitions are allowed
PLE Transitions assignement
Simple Model Full Model

hodd1 - eeven1
1Pe
F = 1/2 odd1

1Se
F = 1/2 even1

hodd2 - eeven1
heven1 - eodd1

heven1 - eodd1

soodd1 - eeven1
1Shh
1Phh F = 3/2 odd1
F = 3/2 even1
1Slh F = 3/2 odd2
F = 3/2 even2

1Plh
2.0 2.4 2.8 3.2
Energy (eV)
 PbTe Quantum Dots Physics

p = piso + l(p true-piso)

l=0
Oscillator strength (a. u.)

l = 0.2
Anisotropy

l = 0.4

l=1

0.75 1.00 1.25 1.50 1.75

Energy ( eV )
 Pump&Probe: Coherent Phonons
60
E. R. Thoen et al; “Coherent Acoustic Phonons
in PbTe Quantum Dots”, Appl. Phys. Lett. 73, 50

2149 (1998)

-6
40

DT/T ·10
43
30
Detector 42

20 41

40
10
2 4 6 8

0
-2 0 2 4 6 8 10 12
Delay (ps)

Breathing
Modes
 Coherent Phonons frequency
2Vsound
Simple Model: 
R
0.64
10
Range of 0.62
8
experim.
0.60
 (cm )
-1

n (THz)
0.58

4 0.56

Typical pulse 0.54

2
spectral width
0.52
0
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 0.50
Wavelength (m) 1.40 1.45 1.50 1.55 1.60
Wavelength (m)

17 cm-1 to 20 cm-1
 Excitation and phase
Impulse K - change

Sine Cosine
0.2

0.1
Phase (rad)

0.0

-0.1

-0.2

1.40 1.45 1.50 1.55 1.60

Wavelength (m)

Phase  0o cosine Excitation

 Damping Time
Sphere Acoustic Modes APL 73, 2149-2151 (1998)

 u
2
 
 2       u  (l  2) (  u)  0
t

1.0

SAXS data
4.5 0.8
(b) Experimental data
n (THz)
4.0
Damp time (ps)

3.5 0.6
3.0 Anisotropic band
2.5
0.4 calculation
2.0

1.5
0.2 Parabolic band approximation
1.0

0.5 1.4 1.5 1.6

Wavelength (m)
1.40 1.45 1.50 1.55 1.60
Wavelength (m)
Coherent Phonons: pump & probe detection
 Coherent Phonons: amplitude
PdV  P 4r 2 dr  dEconf
1 dEconf
P
4r 2 dr
 r 3  A
P  K
DV
 K
(r 3  r03 )
  K    1   4.4  10 6
 r0  
3
V0 r0 A
r 1 60
  P
r0 3K 50

-6
 Econf r
40

DT/T ·10
Econf (r )  2 ,  2 30
43

r E0 r0 42

20 41
2
 E  40

 E0 
2 10
T A 1  E  1 2 4 6 8
      
T A 2  Tot  2  Tot 
0
 -2 0 2 4 6 8 10 12
 E 0  Delay (ps)
Critiscim to kp Models
Parabolic and kP Models are not good enough for very
small quantum dots
 Energy Dispersion

Bulk energy dispersion calculated by

Prof. Guimarães USP/UNICAMP
Modelo Unidimensional
com solução analítica
Cadeia de poços unidimensionais
Solução analítica
Estrutura de bandas
Estados confinados
Energia de confinamento
Heuristic Model
 n
j  ka   0  k n  e

ke
 n
j  ka   0  k n  e

k SO

E
 No 9 j1  k HH a  j3  k LH a  + Yes
+j3  k HH a  j1  k LH a  = 0 ?? E

k HH k LH

E
 FCS

Fluorescence Correlation Spectroscopy

 Fluorescence Correlation Spectroscopy FCS
(1 m)3 = 1 femtoliter mass spectrometry?
Hydrodynamic radius Rodamine
extracted from
diffusion time

Home made CdSe Quantum dot

R = 1.9 nm
Quantum Dot Fabrication
 Fluxo de
Argônio
Alvo

532 nm
Laser
giratório

NaBH4
Te Te2- Cd(ClO4)2+ AMA Cd2+ + AMA- Etanol + MPS

Lâminas de
microscópio
Agitador magnético
+ Aquecimento
Lente
cilíndrica

Ambas precisam de estabilização:

CH3O
CH3O Si SH
CH3O

AMA (solúvel em água) MPS (solúvel em etanol)

Laser Ablation in Liquids
Vaccum versus liquid laser ablation

SAITO, K. et al. Appl. Surf. Sci. 197, 56-60, ( 2002)

Laser Ablation in Vacuum
 Experimental set up

Ti:Sapphire, 800 nm,

(30mJ/pulse, 100fs, 10Hz)
~ 38 TW/cm2
 Lower bkg pressure
Higher nr. of pulses
QD growth on
substrate

COALESCENCE

Higher bkg pressure

Lower nr. of pulses

QD Growth at vapor
phase
target

substrate
HRTEM (LME-LNLS) PbTe QDs images
Quantum dot doped Glass
 Growth Kinectics: How to Control Size and Dispersion
Glass and QD elements Thermal annealing 460 - 560 oC:
melted together 1200 oC: QD’s development - time
transparent glass

Size dispersion vs time:

0.35
SAXS study
Results
0.30 CdTe S
0.6 0.4
CdTe S
0.3 0.7 SAXS show nucleation&growth
0.25
happening simultaneously
Size Dispersion [ln 2]

0.20

Double annealing method suggested:

0.15
first (460oC): only nucleation
0.10
second (560oC): only growth

0.05
- New method produced 6% size
0.00
dispersion QD’s
0 10 20 30 40 50 60

Heat Treatment Time [min]

 The End!!

Thanks for the attention