Solid State Chemistry for Physics, Information Technology Devices and Energy

Art Ramirez

Director Device Physics Research Bell Labs

SSC and Condensed Matter Physics

-Superconductivity : High, low, Superconductivity : High, low, symmetry symmetry

-Quantum phase transitionsQuantum phase transitions

-Magnetism : 1D, 2D, SDWMagnetism : 1D, 2D, SDW

-Charge Density, Heavy Fermion, Charge Density, Heavy Fermion, FerroelecticsFerroelectics

-Superconductivity : High, low, Superconductivity : High, low, symmetry symmetry

-Quantum phase transitionsQuantum phase transitions

-Magnetism : 1D, 2D, SDWMagnetism : 1D, 2D, SDW

-Charge Density, Heavy Fermion, Charge Density, Heavy Fermion, FerroelecticsFerroelectics

-Cross cutting themesCross cutting themes

-Artificial spatial dimensionalityArtificial spatial dimensionality

-Geometrical Frustration : Spin Geometrical Frustration : Spin Liquid, Spin Ice, Negative Liquid, Spin Ice, Negative thermal expansion in ZrWthermal expansion in ZrW22OO88

-Mixed valenceMixed valence

-MultifunctionalityMultifunctionality

-Cross cutting themesCross cutting themes

-Artificial spatial dimensionalityArtificial spatial dimensionality

-Geometrical Frustration : Spin Geometrical Frustration : Spin Liquid, Spin Ice, Negative Liquid, Spin Ice, Negative thermal expansion in ZrWthermal expansion in ZrW22OO88

-Mixed valenceMixed valence

-MultifunctionalityMultifunctionality

0 2 4 6 8 10 120.0

0.2

0.4

0.6

0.8

1.0

s = 1/2

W ~ +0.5K

Dy2Ti

2O7

Spi

n en

trop

y (R

ln2)

Temperature (K)

Pauling’s Ice Entropy

Ramirez et al, Nature 1999

MgB2

Akimitsu et al Nature 2001

Recent Major Discoveries based on SSC

Water-intercalated superconductivity – H2O:N aCoO2

Berry’s phase transport – Nd2Mo2O7

Multi-Ferroics from ISB magnetism– TbMnO3

Single-molecule metal – Ni(tmdt)2

3d Heavy Fermion Metal – LiV2O4

MgB2 2-band Superconductivity

p-wave Superconductivity in Sr2RuO4

Field-induced superconductivity in -BETS2FeCl4

Recent Major Discoveries based on SSC

Water-intercalated superconductivity – H2O:N aCoO2

Berry’s phase transport – Nd2Mo2O7

Multi-Ferroics from ISB magnetism– TbMnO3

Single-molecule metal – Ni(tmdt)2

3d Heavy Fermion Metal – LiV2O4

MgB2 2-band Superconductivity

p-wave Superconductivity in Sr2RuO4

Field-induced superconductivity in -BETS2FeCl4

SSC and CMP – Nation’s Status

Tanaka et al, Science 2001

Approach – materials discovery by crystal growthApproach – materials discovery by crystal growth

New Materials & Crystal Growth – NRC Proposal

- Crystals are new materials with technological importanceCrystals are new materials with technological importance

- Much of CMP physics originates with NMCGMuch of CMP physics originates with NMCG

- NMCG funding suffered from reduction of industrial labsNMCG funding suffered from reduction of industrial labs

- NMCG funding also not in line with major facility fundingNMCG funding also not in line with major facility funding

- Crystals are new materials with technological importanceCrystals are new materials with technological importance

- Much of CMP physics originates with NMCGMuch of CMP physics originates with NMCG

- NMCG funding suffered from reduction of industrial labsNMCG funding suffered from reduction of industrial labs

- NMCG funding also not in line with major facility fundingNMCG funding also not in line with major facility funding

Modern CMOSModern CMOS

Beginning ofSubmicron CMOS

Beginning ofSubmicron CMOS

Deep UV LithoDeep UV Litho

90 nm in 200490 nm in 2004

Presumed Limitto Scaling

Presumed Limitto Scaling

Moore's Law

10 um

1 um

100 nm

10 nm

1 nm1970 1980 1990 2000 2010 2020

34 Years of Scaling History

Every generation– Feature size shrinks by 70%– Transistor density doubles– Wafer cost increases by 20%– Chip cost comes down by 40%

Generations occur regularly– On average every 2.9 years over

the past 34 years– Recently every 2 years

Courtesy of D. Buss, TI

Scaling CMOS to the “End of Roadmap” will require sophisticated condensed matter physics.– Gate stack: Atomic and electron orbital understanding of

this complex material system– Quantum behavior of carriers

• High perpendicular E field• Stress

– Non-equilibrium Boltzmann transport– Tunneling: Gate insulator and Drain-to-Substrate– Simulation

Sophisticated condensed matter physics will also be required to invent and develop electronics beyond CMOS– Single Electron Transistor (SET)– Carbon Nano-tube (CNT)– Molecular Electronics– Spintronics– Quantum Computing

Scaling CMOS to the “End of Roadmap” will require sophisticated condensed matter physics.– Gate stack: Atomic and electron orbital understanding of

this complex material system– Quantum behavior of carriers

• High perpendicular E field• Stress

– Non-equilibrium Boltzmann transport– Tunneling: Gate insulator and Drain-to-Substrate– Simulation

Sophisticated condensed matter physics will also be required to invent and develop electronics beyond CMOS– Single Electron Transistor (SET)– Carbon Nano-tube (CNT)– Molecular Electronics– Spintronics– Quantum Computing

Courtesy of D. Buss, TI

SSC & CMOS Roadmap

SSC needed for new IT materials!

Micro- Electro- Mechanical Systems - MEMS

Lambda Router Mirror

MEMS microphone

- Mechanical device functionality : resonators, capacitors, microfluid, light control

- Silicon lithography : high “Q”, materials integratable

- Materials compatible

- Mechanical device functionality : resonators, capacitors, microfluid, light control

- Silicon lithography : high “Q”, materials integratable

- Materials compatible

Microcompass magnetometer

Solid-state Chemistry : Information Device Physics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

541 60 20 40 60 80 100

100

150

200

250

300

AF ins.

Charge-OrderedIns.

paramagnetic with polaron hopping

FM metal

AF/FMins.

% Ca

-Heterogeneous electronic phases, charge patterns

-Strongly coupled charge/ spin/lattice degrees of freedom

Solid-state Chemistry : Information Device Physics

541 6

CaCu3Ti4O12

Subramanian et al, 1999

ZrW2O8

SSC Challenge : to combine SSC Challenge : to combine local polarizability and strong local polarizability and strong interactions, but to interactions, but to destabilize long rage orderdestabilize long rage order

SSC Challenge : to combine SSC Challenge : to combine local polarizability and strong local polarizability and strong interactions, but to interactions, but to destabilize long rage orderdestabilize long rage order

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

Solid-state Chemistry : Information Device Physics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- Multiferroics Multiferroics

- OrganicsOrganics

541 6

Kimura et al, Nature 2003

Al, Cava, et al

Ni3V2O8 – A Kagome Staircase

TbMnO3 – IC magnetism

-large ME effect related to structures large ME effect related to structures that induce IC magnetismthat induce IC magnetism

-Large opportunities for materials Large opportunities for materials that combine AF, helical FM, and that combine AF, helical FM, and large polarizabilitylarge polarizability

-large ME effect related to structures large ME effect related to structures that induce IC magnetismthat induce IC magnetism

-Large opportunities for materials Large opportunities for materials that combine AF, helical FM, and that combine AF, helical FM, and large polarizabilitylarge polarizability

Multiferroics are Rare

Look at common mineral types that combine FE and FM ions

Spinel: AB2O4; Perovskite: ABO3; Pyrochlore: A2B2O7 - hard to find A4+ and B2,3+.

Solid-state Chemistry : Information Device Physics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- MultiferroicsMultiferroics

- OrganicsOrganics

- Colossal MR- Colossal MR

- FerroelectricsFerroelectrics

- MultiferroicsMultiferroics

- OrganicsOrganics

541 6

- Charge Transfer Salts

- Doping Carbon

- Carbon Nanotubes

- Plastic Electronics

- Charge Transfer Salts

- Doping Carbon

- Carbon Nanotubes

- Plastic Electronics

Structure of (EDT-TTF(CH2OH)2)2Mo6O19

From Batail et al.

Solid State Chemistry and Energy

Best Research-Cell EfficienciesBest Research-Cell EfficienciesEf

ficie

ncy

(%)

Universityof Maine

Boeing

Boeing

Boeing

BoeingARCO

NREL

Boeing

Euro-CIS

200019951990198519801975

NREL/Spectrolab

NRELNREL

JapanEnergy

Spire

No. CarolinaState University

Multijunction ConcentratorsThree-junction (2-terminal, monolithic)Two-junction (2-terminal, monolithic)

Crystalline Si CellsSingle crystalMulticrystalline

Thin Film TechnologiesCu(In,Ga)Se2

CdTeAmorphous Si:H (stabilized)

Emerging PVDye cellsOrganic cells(various technologies)

Varian

RCA

Solarex

UNSW

UNSW

ARCO

UNSWUNSW

UNSWSpire Stanford

Westing-house

UNSWGeorgia TechGeorgia Tech Sharp

NREL

Spectrolab

NREL

Masushita

MonosolarKodak

Kodak

AMETEK

Photon Energy

UniversitySo. Florida

NREL

NREL

NRELCu(In,Ga)Se2

14x concentration

NREL

United Solar

United Solar

RCA

RCARCA

RCA RCARCA

Spectrolab

Solarex12

8

4

0

16

20

24

28

32

36

University ofLausanne

University ofLausanne

Siemens

2005

Kodak UCSBCambridge

Groningen

University LinzBerkeley

Princeton

UniversityLinz

Art Nozik, DOE Solar Energy Workshop, 2005

Solid-state chemistry and energy

- Saving: solid state lighting O and inO

- Conversion: fuel cells, solar fuels, photovoltaics

- Storage: primary and secondary batteries

- Saving: solid state lighting O and inO

- Conversion: fuel cells, solar fuels, photovoltaics

- Storage: primary and secondary batteries

- Issues for OLEDs : conversion efficiency, operational life

- Small molecules : improve triplet harvesting, spectral range

- Issues for OLEDs : conversion efficiency, operational life

- Small molecules : improve triplet harvesting, spectral range

Luminous efficiency of monochrome OLEDS

Solid-state chemistry and O-Solar Cells

- Materials issues similar to OLEDs : injection efficiency, transport efficiency, emission efficiency

- Need new molecules that are : strong, light-absorbing, band-gap and exciton level tunable

- C60 : undergoes little structural distortion upon electron transfer

- Materials issues similar to OLEDs : injection efficiency, transport efficiency, emission efficiency

- Need new molecules that are : strong, light-absorbing, band-gap and exciton level tunable

- C60 : undergoes little structural distortion upon electron transfer

Solid-state chemistry and energy control

Conversion: High thermoelectric figure of merit in Na0.75CoO2

Conversion: High thermoelectric figure of merit in Na0.75CoO2

Cava, Ong, Science 2004

Solid-state chemistry and energy

•Transmission technologies: superconducting electric cables

•Fuel stream purification technologies : hydrogen separation membranes …. How to make hydrogen?

•Fuel transportation : containers, hydrogen storage materials

•Cuts across chemistry, materials science, chemical engineering, mechanical engineering

• Hybrid Organic/Inorganic

•Transmission technologies: superconducting electric cables

•Fuel stream purification technologies : hydrogen separation membranes …. How to make hydrogen?

•Fuel transportation : containers, hydrogen storage materials

•Cuts across chemistry, materials science, chemical engineering, mechanical engineering

• Hybrid Organic/Inorganic

Self-Assembled Materials and Organic Electronics

Semiconductor

GateDielectric

Source Drain

Substrate

drain

0.1 mchannelMarket Potential

- Flexible displays

- Smart Tags

- Photovoltaics

- $10B in 10 years

- Lucent has 25 patents

Potential Organic Materials Advantages:

–Printable/manufacturable–Flexible–Multi-functional materials/ molecular design (i. e. low-dielectric constant with high EO coefficient)–Low-cost

Potential Organic Materials Advantages:

–Printable/manufacturable–Flexible–Multi-functional materials/ molecular design (i. e. low-dielectric constant with high EO coefficient)–Low-cost

Tetracene

3 mm

TFT = semiconductor : Single crystal = insulator

Yang et al, APL 2002

Tetracene single crystal

- Polycrystalline thin film - Polycrystalline thin film transistorstransistors

-Semiconductor spun on or Semiconductor spun on or evaporatedevaporated

- Almost all of plastic electronicsAlmost all of plastic electronics

- Naturally occurring free-carrier Naturally occurring free-carrier density ~ 10density ~ 101717 carriers/cm carriers/cm33

- Polycrystalline thin film - Polycrystalline thin film transistorstransistors

-Semiconductor spun on or Semiconductor spun on or evaporatedevaporated

- Almost all of plastic electronicsAlmost all of plastic electronics

- Naturally occurring free-carrier Naturally occurring free-carrier density ~ 10density ~ 101717 carriers/cm carriers/cm33

- Single crystals grown from vapor Single crystals grown from vapor transport or melttransport or melt

- Insulating, free carrier density ~ 10Insulating, free carrier density ~ 10-12-12 carriers/cmcarriers/cm33

- No fundamental understanding of No fundamental understanding of doping or trapping in OFETsdoping or trapping in OFETs

- Similar situation in oxidesSimilar situation in oxides

- Single crystals grown from vapor Single crystals grown from vapor transport or melttransport or melt

- Insulating, free carrier density ~ 10Insulating, free carrier density ~ 10-12-12 carriers/cmcarriers/cm33

- No fundamental understanding of No fundamental understanding of doping or trapping in OFETsdoping or trapping in OFETs

- Similar situation in oxidesSimilar situation in oxides

Pentacene crystal

paralene 0.5 m

colloidal graphite

Ag-paint

Vg

Vs-d

Surface States in Single Crystals OFETs

The Role of Single Crystals for Organic Electronics

Single Crystal FETs :

–Easily fabricated–High purity*–Address issues of relevance for plastic systems: grain boundaries, deep traps, doping, reliability

Single Crystal FETs :

–Easily fabricated–High purity*–Address issues of relevance for plastic systems: grain boundaries, deep traps, doping, reliability pentacenepentacene

Purity :

–Commercial stock extremely dirty–E.g. in pentacene (to left) have few % dihydra, and quinone impurities–Need e.g. a pilot manu- facturing program

Purity :

–Commercial stock extremely dirty–E.g. in pentacene (to left) have few % dihydra, and quinone impurities–Need e.g. a pilot manu- facturing program

Palstra group, APL 2004

Identify individual H-related traps in pentacene

D. V. Lang et al, PRL, 2004

1 10 100 100010-14

10-13

10-12

10-11

10-10

10-9

10-8

10-7

10-6

Pentacene T = 297 K

600 V

300 V

100 V

30 V

600 V

300 V100 V

30 V

Cu

rre

nt

(A)

Bias Voltage (V)

0.26 eV PC @ 420 nm zero-field equilibrium bias polarized

Cu

rre

nt (

A)

Voltage (V)

Au pads on a Pentacene crystal

A

C

A

CEa = 0.21 eV

Ea = 0.55 eV

Average Ea = 0.38

Crystal FETs from many different molecules

Material Mobility [cm2/Vs] Type C60 ---- Benzoantracene ---- Dihydropentacene+Pentacene ---- TCNQ Ca. 1*10-6 n Perylene 4.3*10-3 p Br-tetracene 1.4*10-3 p Cl-tetracene 2.4*10-4 p Coronene 2*10-4 p Rubrene-(side product) 2.3*10-2 p Antracene 4.6*10-4 p Decapenlypentacene 1.4*10-3 p Tetraflurotetracene 2-7*10-3 p Rubrene 2-13 p Pentacene 0.2-2.24 p

C. Kloc, R. Zeis

PERIODIC TABLE OF THE ORGANICS

Benzene

B N

Napthalene

Symbol

Anthracene

A

Tetracene

T P

Pentacene

C

Coronene

picture

Py

Name

Perylene

Tc

TCNQCN

CN

NC

NC

C60

Fullerite

ET

BEDTS

S

S

S S

SS

S

Cl

Corannulene

Band gap

6 eV 5 eV

3.9 eV 3.1 eV 2.2 eV

2.3 eV

Blue = melts at atmospheric pressure

C2n

Fullerites

…

...Ru

Du

Durene

CH3

CH3

CH3

CH3

Vi

http://www.bell-labs.com/research/crystal.html

Bell Labs Crystal Bell Labs Crystal Growth ArchiveGrowth Archive

Many samples from Many samples from both our archives both our archives and from ongoing and from ongoing research projects are research projects are available for available for measurement by measurement by requestrequest

Bell Labs Crystal Bell Labs Crystal Growth ArchiveGrowth Archive

Many samples from Many samples from both our archives both our archives and from ongoing and from ongoing research projects are research projects are available for available for measurement by measurement by requestrequest

end