Quantum Simulations of Nano-

Materials for Renewable Energy

Zhigang Wu
zhiwu@mines.edu
Department of Physics
Colorado School of Mines, Golden, CO 80401

Extra Lecture in Modern Physics

Class, CSM, 05/04/2010
 Outline


Introduction


Renewable energy


Nanomaterials and nanotechnology


Quantum Simulation Methods


Density functional theory, Quantum Monte Carlo


Challenges for simulating nanomaterials for energy


My Research Work


Complex-structured silicon nanowires


Energy-level alignment at hybrid nano-interfaces


MgH2 nano-clusters for hydrogen storage
1
Why Do We Care About Renewable Energy?

The possibilities of renewable energy are limitlessWeve heard promises

about it in every State of the Union for the last three decades. But each and
every year, we become more, not less, addicted to oil a 19th-century fossil
fuel.
Barack Obama
2
 What is Renewable Energy?
Renewable energy comes from
natural resources such as sunlight,
wind, tides, biological materials,
geothermal heat, etc.

3
 What is Non-Renewable Energy?
Fossil fuels: petroleum, coal, natural
gas, formed by buried organism
through anaerobic decomposition with
millions of years.

4
 The Greenhouse effect
The greenhouse effect occurs because
windows are transparent in the visible but
absorbing in the mid-IR, where most materials
re-emit. The same is true of the atmosphere.

Greenhouse gases:
Sun
carbon dioxide
water vapor
methane
nitrous oxide

Methane, emitted by
microbes called
methanogens, kept
the early earth warm.

5
Why Do We Care About Renewable Energy?

6
USA Energy Consumption in 2008

7
 Is Renewable Energy Enough?
There is more energy in sunlight striking on the surface of earth
for 1 hour than total global energy consumption per year.

8
 U.S. Renewable Resources

(100 miles)2 solar

panels (10% efficiency)
in Nevada would
power the U.S.

Turner, Science 285, 687

(1999).

$20 Trillion using

Si solar panels.

9
 A Challenge with Solar Energy
For comparison: the cost of coal/oil/gas is 1-4/kWh
3-4

20
3
6-7
5

Need major improvement in efficiency and cost to take

advantage of solar energy: Nanotechnology
10
There is Plenty Room at the Bottom
Why cannot we write the entire 24 volumes
of the Encyclopedia Brittanica on the head
of a pin?

Now, the name of this talk is There is

Plenty of Room at the Bottom---not just
There is Room at the Bottom. What I
have demonstrated is that there is room---
that you can decrease the size of things
in a practical way. I now want to show
that there is plenty of room. I will not now
discuss how we are going to do it, but only
what is possible in principle---in other
words, what is possible according to the
laws of physics. We are not doing it now
simply because we haven't yet gotten
around to it.

Dec. 29, 1959, Annual APS Meeting

Richard Feynman (1918
1988) 11
Nanoscience and Nanotechnology

1 nm = 10-9 m = 10

Nanoscale: ~ 1
100 nm

Nanomaterials: at least one

Nanoparticle Ant Motor Speedway
dimension in the nanoscale.
4 nm diameter 4 mm long 4km per lap

Nanoscience is the study of phenomena and manipulation of nanomaterials.

Nanotechnology is the design, characterization, production and application of

structures, devices and systems by controlling size and shape at nanoscales.

http://www.nano.gov

12
 Applications of Nanotechnology
. . . nanoscience and nanotechnology will change the nature of almost every
human-made object in the next century.
The Interagency Working Group on Nanotechnology, 1999

$1 trillion market by 2011-2015 (NSF 2004)

Anti-cancer drug Cheap and clean Next-generation

delivery system energy computer

Michigan Center for Biological Nanotechnology

UCSB Bazan Group

13
 Quantum Effects at the Nanoscale

= 729 nm

UV UV
light light CdSe

A bulk materials properties are

fixed.

Properties of nanomaterials can

be tuned by varying the size.
http://nanocluster.mit.edu/

14
 Complex Structures of Nanomaterials
Nature Nanotech. 1, 186 (2006)
CdSe Tapered Si Nanowires
Properties of nano-
materials are affected by
their shapes significantly.

Exp. characterization of
nanomaterials is
Thermoelectricity: Good Poor
extremely challenging.

Theory and simulations

are in critical need for
advancing nanotech.
Rough Si Nanowire
4nm Smooth Si Nanowire 3nm
Hochbaum et al., Nature 451, 163 (2008)
15
 Quantum Mechanical Simulations


First-principles (or ab initio): no experimental input
and start from beginning solving the many-electron
Schrdinger Equation:
H
= E



Explain key processes and mechanisms from
fundamental theory.


Empirical models need experimental data.

Materials properties depend strongly on atomistic

details.

Predict new materials with better properties.

16
Solving Many-Electron Schrdinger Equation

2 2            

 ( r1 , r2 ,..., rN ) + V ( r1 , r2 ,..., rN )( r1 , r2 ,..., rN ) = E( r1 , r2 ,..., rN )
2m
3N-dimensional problem
Interacting
Interacting N- Exponential wall: the time t needed
Electron System to solve this equation is prop. to eN.
N = 1, t = 1 s

- - - N = 2, t = 7 s

- - N = 10, t = 2.2
104 s = 6.1 h

N = 20, t = 4.9
108 s = 15 years
- - -
N = 100, t = 2.7
1043 s
= 8.5
1035 years!
17
Density Functional Theory

18
 Density Functional Theory


Many-body Schrdinger equation:




H
= E
, where
=
( r1, r2 ,..., rN ) Intractable 3N-dimentional equation
t
eN


Hohenberg-Kohn (HK) theorem1: ground-state total energy can be
expressed in terms of electron density n(r), instead of wave functions.


E0 = E[n( r )]


Kohn-Sham (KS) theory2: mapping an interacting many-body system
to a non-interacting single-particle system in a mean field.

Interacting Non-interacting H  =
 


where   =   ( r )
- - -
- - - Solvable 3-dimentional equation!
- - - t
N3
[1] Phys. Rev. 136, B864 (1964)
[2] Phys. Rev. 140, A1133 (1965)
19
 KS Single-Particle Equation

2 2    

2m + vKS ( r )  i ( r ) =  i i ( r )

   
where vKS ( r ) = vext ( r ) + vH ( r ) + vxc ( r )

 n( r ') 
with vH ( r ) =
  dr '
|r
r'|

  Exc [n( r )] Need approximation,
vxc ( r )=  but simple form
 n( r ) works pretty well.
 OCC  2
and n( r ) =  |  i ( r ) |
i
20
 The Triumph of DFT

Methanol inside a cage of the zeolite Clathrate Sr8Ga16Ge30

sodalite (Blue: Si; Yellow: Al; Red: O) (Red: Sr; Blue: Ga; white: Ge)

N = O (1000)
21
 Challenges
Nanomaterials are complicated.

CdSe Nano-
particle with
d = 4 nm

~ 2,000 atoms
~ 20,000 electrons

Solution: better scaling scheme: t
N.

22
 Challenges
Accuracy is limited by the approximation for the exchange-




Exc [n( r )]
correlation energy:
vxc ( r )=


n( r )
Solution: better Exc guided by results obtained
from more accurate methods.

23
 Challenges
Excitations: DFT is NOT a theory for excited properties.

Band gap problem

Si: EgDFT = 0.6 eV

EgEXP = 1.2 eV

Solution: go beyond the

single-particle method to
include the many-body
interactions due to
excitation.
24
 Quasiparticle
Bare particle Quasiparticle

Excitations of many-electron
system can often be described
in terms of weakly interacting
quasiparticles. - -
Quasiparticle (QP) = bare
particle + polarization clouds.

EQP = E0+

: response of system to the

excitation(self-energy)

25
 Beyond DFT


Quantum chemistry post-HF methods:
CI, CC, MCSCF, MP2, etc.


Very accurate for small systems


But very bad scaling of N5-7

Many-body perturbation methods: GW/BSE

Accurate for excitations, scaling as N4-7

Quantum Monte Carlo (QMC) methods

Fully-correlated many-body calculation
Stochastic solution to Schrdinger equation


Scaling as N3: most accurate benchmarks for
medium-size systems
26
 Monte Carlo Technique
Random numbers can be used to help solve complicated
problems in physics.

27
 Diffusion Monte Carlo (DMC)

Ref: Foulkes et al., RMP 73, 33 (2001)

28
How to Perform the Projection?

29
G(R, R,
) as a Transition Probability
H=T+V

V=0

V
0

30
Diffusion and Branching

31
A Toy Model: 1D Harmonic Oscillator

t DMC ~ O(100
1000) t DFT

DMC is Intrinsic parallel.
32
An Analogy of QM Methods
DFT Post-HF, GW/BSE

QMC

33
Complex-Structured Si Nanowires
Wu, Neaton & Grossman, PRL 100, 246804 (2008)
Wu, Neaton & Grossman, Nano Lett. 9, 2418 (2009)

34
 Tapering in Nanowires

Chan et al., Nature Nanotech. 1, 186 (2006)

Nanowires (NWs) are often tapered rather than straight.

The tapering can be as large as 2 nm reduction in d for 10 nm in L.

35
 Tapering in Nanowires
GaAs

Nature Nanotech. 1, 186 (2006)

Nanowires (NWs) are often tapered rather than straight.

The tapering can be as large as 2 nm reduction in d for 10 nm in L.


The tapered tip can be grown gradually into a few nm in d.


Previous theory only considers straight NWs.
36
 Modeling Tapered Nanowires


Wire axis along [011] direction with periodic boundary
condition.


H-passivation.


More than 1600 atoms or 5000 electrons in the unit-cell.
Tapered Si NW 2.2 nm
1.7 nm 1.9 nm
d = 1.2 nm 1.4 nm

L = 10 nm

Method: DFT with atomic-orbital basis (SIESTA1 code).

Linear-scaling code [1] http://www.icmab.es/siesta/

37
 Near-Gap States

hole

electron

Spatial separation of the valence band maximum (VBM) and the

conduction band minimum (CBM) states in the tapered nanowire.
38
Finite-Length Model: Tapered Nanorod

The highest occupied (HOMO) and lowest unoccupied

(LUMO) molecular orbitals are separated along axis.
39
 A New Route for Solar Cells

Separating charge carriers

p-n Junction Type-II Hetero-Junction No Junction
n-type p-type CB LUMO

Simple and cheap

HOMO
new type of PV
VB
40
Level-Alignment at Hybrid Interfaces
Wu, Kanai & Grossman, PRB 79, 2013(R) (2009)

41
 Level-Alignment at Hybrid Interfaces
LUMO
CBM

VBM
HOMO

Bent Group at Stanford

Hybrid interface is crucial for LUMO LUMO
molecular electronics and opto- CBM CBM
electronics, e.g. organic PV cells.


Design interfaces with appropriate
HOMO
energy-level alignment:
HOMO VBM


Modify molecular gap

Control semiconductor band-gap

VBM
by tuning quantum confinement
42
 Si (001)
TTF Interface
DFT calculation
Type-II Junction
Interface

1.91
0.44
1.79

Tetrathiafulvalence: TTF Type-II junction is very

interesting and useful.

43
Interface-Type vs. Quantum Confinement
DFT-KS

Type "III"

Type III
Type II
LUMO
LUMO LUMO
CBM CBM CBM
Type I HOMO
HOMO HOMO
VBM VBM VBM

4 8 12 16 20 24 28 32
bulk
Number of Layers

DFT: This junction can be

tuned by quantum confinement.

44
 Many-Body Correction
 = QP
DFT
Bare Particle Quasiparticle

 is the many - body correction

CBM LUMO
- -
CBM CBM

VBM HOMO
VBM VBM

DFT has successfully predicted accurate band-offsets at

semiconductor interfaces1,2 due to error cancellation of

.


However, for hybrid interfaces composed of two distinct
materials,

 can be different significantly.
[1] Walle et al., PRB 35, 8154 (1987)
[2] Wei & Zunger, APL 72, 2011 (1998)
45
Many-Body Corrections to Level-Alignment
DFT
DFT-KS
QMC-DMC
Interface 2.5

1.1 1.91
0.44
1.79

0.5 2.8

DFT: Type-II QMC: Type-I

LUMO LUMO
CBM CBM

HOMO
VBM VBM
HOMO 46
Interface-Type vs. Quantum Confinement
DFT-KS
QMC - DMC
Type "III"

Type II

Type I

4 8 12 16 20 24 28 32
bulk
Number of Layers

QMC: The junction type CAN NOT

be tuned by quantum confinement.

47
MgH2 Nanoscale Cluster for H Storage
Wu, Allendorf & Grossman, JACS 131, 13918, (2009)

48
 Motivation

C + O2 = CO2
H2 + O2 = water

Chemical storage: the reversible absorption of H into

another material.


Bulk materials are often too stable.


E.g. MgH2: 7.7wt%,
Ed = 75 kJ/mol, Td ~ 300 oC

Desirable
Ed = 20
50 kJ/mol

Ed can be tuned by the size of nanoparticles.
49
Mg and MgH2 Crystal Lattices

Rutile: P42/mnm
HCP: P63/mmc
50
Chemical Accuracy for
Ed is Required
Chemical accuracy: 1 kcal/mol = 4.2 kJ/mol = 0.043 eV

51
MgH2 Clusters

52
Desorption Energy of MgH2 Clusters
100

Ed (kJ/mol H2)

50
Expt.: bulk
CCSD(T)
DMC
0 DFT-LDA
DFT-PBE

20 40 60 Bulk
(MgH2)N 53
Desorption Energy of MgH2 Clusters

(MgH2)N 54
Size-Dependent DFT Error

55
 Size-Dependent DFT Error
20
(kJ/mol H2)

0
LDA
PBE
DMC
-
Ed

-20
DFT

Ed

-40

0 20 40 60 Bulk
(MgH2)N 56
 Summary
Nanostructured PV Hybrid Nano-Interfaces

Computational
Hydrogen Challenges
Storage in
Nanoparticles

57
 Acknowledgements

Department of Energy (DOE)

National Science Foundation (NSF)


Molecular Foundry, NERSC, and Teragrid

Thank you very much for your attention!

58