PDF analysis of CdS Nanoparticles

Reinhard B. Neder Institut fr Mineralogie Universitt Wrzburg, Germany

Topics

Nanoparticles
Experimental determination of PDF Interpretation of PDF Simulation of PDF Results for CdS-Glutathion

Nanoparticles

Extended clusters ~1 nm to 300 nm Properties intermediate between molecule and crystal

Optical properties depend on size

Open topics for Nanoparticles

determination of size
TEM: XRD: Exciton: small angle:

preparation; core/shell; statistics Debye-Scherrer invalid: size + disorde depends on bulk theory available edges

Au particles scale = 5nm

Zanchet et al. J. Phys. Chem B (2000),104,11013

Invalidity of Scherrer equation

16
32

Dhkl =

0.9

sin

Open topics for Nanoparticles

determination of size
TEM: XRD: Exciton: small angle:

preparation; core/shell Debye-Scherrer invalid: size + disorde depends on bulk theory available edges

Open topics for Nanoparticles

structure
small crystal <=> glass <=> unique structure core = rim ? surface relaxation ?

homogeneous structure

heterogeneous structure

Open topics for Nanoparticles

structure
TEM: XRD: EXAFS: lattice planes ==> well ordered too few, broad peaks local order only

thiol passivated Au nanoparticles

Zanchet et al. J. Phys. Chem B (2000),104,11013

Open topics for Nanoparticles

structure
TEM: XRD: EXAFS: lattice planes ==> well ordered too few, broad peaks local order only

CeO2

Wu et al. J. Phys. Chem B (2000), 106, 4569

Open topics for Nanoparticles

structure
TEM: XRD: EXAFS: lattice planes ==> well ordered too few, broad peaks local order only

CeO2

Wu et al. J. Phys. Chem B (2000), 106, 4569

Open topics for Nanoparticles

structure
TEM: XRD: EXAFS: lattice planes ==> well ordered too few, broad peaks local order only

CdS-Glutathione
contradictory size information 15 to 30

Cd S

Bond length Cd-S - within core - to Glutathione molecule Structure

Synthesis
Precipitation form aqueous solution Glutathione + CdCl monodisperse powder

Data Collection
BW5, HASYLAB =0.088 E=140 keV T=15 K sealed capillary Qmax = 30 -1

Experimental Data
Inset corresonds to experiment with Cu-K Only three broad maxima

Normalized Structure Factor

Experimental PDF
narrow first maximum at 2.525 broad, asymmetric second maximum at 4.11

Experimental PDF
broad maxima

longest distance

Experimental PDF

weak maxima at ~1.5

Analysis of first Maximum

R = 2.525 ; = 0.063 N = 3.4 ONE Cd-S distance Cd-Sorganic

Cd-Sinorganic

Analysis of second Maximum

R = 4.13 ; = 0.15 R = 3.85 ; = 0.12 TWO Cd-Cd distances => two Cd-S-Cd angles N = 5.8 N = 2.7

Cd-Sorganic -Cd = 100 Cd-Sinorganic -Cd = 109

Summary of direct Interpretation

RAMAN spectroscopy No H-S modes ==> Glutathione bound to Cd

Chem. analysis
PDF 1. peak 2. peak

Cd1 S0.5 Glutathione0.5

Cd-S = 2.525 ; = 0.063 Cd-Sinorganic-S = 109(5) Cd-Sorganic -S = 100(4)

PDF longer distances highly disordered

PDF longest distances Diameter ~ 18

Aspects of PDF Simulation

Finite particle size Structure more cystal like? more glass like ?

Proper density Proper coordination distribution Proper distance distributions Best strategy trial and error RMC evolutionary algorithm

PDF of Nano versus Bulk

Bulk: Number of interatomic pairs increases with r2

4 0 r

DISCUS uses r !

PDF of Nano versus Bulk

Nanoparticle: A longest vector exists

DISCUS uses r ! 4 0 r 4 0 r tanh(shape(r-diameter))

Diameter

Crystal of nanoparticles

Periodic boundary conditions lead to PDF maxima well beyond the particle diameter.

Crystal of nanoparticles

Periodic boundary conditions with random orientation destroy PDF maxima beyond the particle diameter.

Individual nanoparticle

PDF with modified background function

Simulation of PDF
Experimental PDF Distorted zincblende structure

Simulation of PDF
Growth algorithm
Zincblende layer or S- or Cdterminated || all <111> Wurtzite layer

N(Cd) 50% S on surface fault probability starting group

Simulation of PDF
Relaxation of the structure by Monte Carlo
constrains: < Cd-Sorganic-C =100(4) Cd-S = 2.523(63)

< Cd-Sinorganic-C =109(5)

Simulation of PDF
Decoration by Glutathione

Calculated PDF
~70 Cd atoms ~16 diameter 60% fault propability average of many particles

Further Issues
Fit to data by evolutionary algorithm easy to adapt to multiple steps needed: growth, relaxation, glutathione, PDF calculation and averaging; different structures Fit to data by RMC requires large supercell to avoid inter-particle vectors ==> adjust 0, avoid shift of particle, limit movement to within particle starting model ? different particles ? to be learned...

Acknowledgements
V.I. Korsounski K. Hradil J.Neuefeind P. Jovari Ch. Barglik-Chory G. Mller Th. Proffen

Financial support by German Science Foundation SFB 410