A Total Scattering School on the Como Lake

Villa del Grumello, Como, May 29th- June 2nd, 2017

Lecturers
Simon J. Billinge (Columbia, USA)
Hans Beat Bürgi (UZH, CH)
Antonio Cervellino (PSI, CH)
Maksym Kovalenko (ETH, CH)
Jan Skov Pedersen (AU, DK)
Nora Ventosa (ICMAB-CSIC, ES)
Fabio Ferri (Insubria, IT)
Antonella Guagliardi (IC-CNR, IT)
Norberto Masciocchi (Insubria, IT)

Tutorials on DebUsSy and PDFgui

Federica Bertolotti (AU, DK), Ruggero Frison (UZH, CH)
Simon J. Billinge, Maxwell W. Terban (Columbia, USA)

Organizing Committee
Directors Norberto Masciocchi (Insubria, IT)
Antonella Guagliardi Antonella Guagliardi (IC-CNR, IT)
Norberto Masciocchi Fabio Ferri (Insubria, IT)
José M. Delgado-López (IACT-UGR, ES)
Federica Bertolotti (AU, DK)
 T O .S CA .L AKE S UM M ER S CHOOL

T OTAL S CATTERING FOR N ANOTECHNOLOGY

ON THE C OMO L AKE

A Hands-on Workshop on X-ray Total Scattering Techniques and Light Scattering

including Experimental and Computational Aspects

V ILLA DEL G RUMELLO

C OMO , I TALY , M A Y 2 9 TH - J UNE 2 ND 201 7

F INAL S CIENTIFIC P ROGRAM

Monday, May 29th 2017

AFTERNOON (14:00 – 19:00)

14:00 – 15:00 REGISTRATION
15:00 – 15:30 OPENING
15:30 – 17.00 Single Crystal X-ray Diffraction - From Standard Crystal Structure Models to
Quantum Crystallography
Hans-Beat Bürgi (Uni-Bern and Uni-Zurich, CH)
17.00 – 18.00 Powder Diffraction beyond Bragg Scattering
Norberto Masciocchi (Uni-Insubria, IT)
18:00 – 19.00 Debye Scattering Equation and Experiments @ X04SA-MS, Swiss Light Source
Antonio Cervellino (Paul Scherrer Institut, SLS, CH)

19:00 – 21.30 WELCOME PARTY AT THE VILLA DEL GRUMELLO

Tuesday, May 30th 2017

MORNING (9:00 – 13:10)
9:00 – 10:30 Pair Distribution Function – Theory and Applications
Simon Billinge (Uni-Columbia, US)
10:30 – 11:00 COFFEE BREAK
11:00 – 12:30 Debye Scattering Equation – From Modeling to Applications
Antonella Guagliardi (IC-CNR, IT)
12:30 – 13:10 COMMERCIAL PRESENTATIONS
12:30 – 12:50 Structure analysis with lab systems
Geert Vanhoyland (Bruker)
12:50 – 13:10 PANalytical solutions for Total Scattering experiment
Marco Sommariva (Panalytical)
13:10 – 14:30 LUNCH

AFTERNOON (14:30 – 19:00)

14:30 – 16:30 Parallel Hands-on session on DebUsSy Suite
Federica Bertolotti (Uni-Aarhus, DK)
Ruggero Frison (Uni-Zurich, CH)
Parallel Hands-on session on PDFGui
Simon Billinge (Uni-Columbia, US)
Max Terban (Uni-Columbia, US)

16:30 – 17:00 COFFEE BREAK

17:00 – 19:00 Parallel Hands-on session on DebUsSy Suite
Federica Bertolotti (Uni-Aarhus, DK)
Ruggero Frison (Uni-Zurich, CH)
Parallel Hands-on session on PDFGui
Simon Billinge (Uni-Columbia, US)
Max Terban (Uni-Columbia, US)

Wednesday, May 31st 2017

MORNING (9:00 – 13:10)
9:00 – 10:30 Inorganic/Hybrid Colloidal Nanocrystals: From Synthesis to Devices
Maksym Kovalenko (ETH, CH)
10:30 – 11:00 COFFEE BREAK
11:00 – 12:30 Single Crystal Diffuse Scattering – Measurements, Data Processing, 3D-
delta-PDF and MC Modeling
Hans-Beat Bürgi (Uni-Bern and Uni-Zurich, CH)
12:30 – 13:10 COMMERCIAL PRESENTATIONS
12:30 – 12:50 Today’s possibilities in modern lab-based XRD
Jürgen Grässlin (Rigaku-Assing)
12:50 – 13:10 Structure Analysis of Drug Delivery Systems with SAXS in the Laboratory
Alexander Pilcher (Anton Paar)
13:10 – 14:30 LUNCH

AFTERNOON (14:30 – 19:00)

14:30 – 16:30 Parallel Hands-on session on DebUsSy Suite
Ruggero Frison (Uni-Zurich, CH)
Federica Bertolotti (Uni-Aarhus, DK)

Parallel Hands-on session on PDFGui

Simon Billinge (Uni-Columbia, US)
Max Terban (Uni-Columbia, US)

16:30 – 17:00 COFFEE BREAK

17:00 – 19:00 Parallel Hands-on session on DebUsSy Suite
Ruggero Frison (Uni-Zurich, CH)
Federica Bertolotti (Uni-Aarhus, DK)

Parallel Hands-on session on PDFGui

Simon Billinge (Uni-Columbia, US)
Max Terban (Uni-Columbia, US)
 Thursday, June 1st 2017
MORNING (9:00 – 13:00)
9:00 – 10:30 Molecular Materials for Nanomedicine: Preparation and Characterization
Challenges
Nora Ventosa (ICMAB-CSIC, ES)
10:30 – 11:00 COFFEE BREAK
11:00 – 12.00 Basics and Applications of SAXS
Jan Skov Pedersen (Uni-Aarhus, DK)
12:00 – 13:00 Basics and Applications of SALS/LASL/DLS
Fabio Ferri (Uni-Insubria, IT)
13:00 – 14:30 LUNCH

AFTERNOON (14:30 – 19:00)

14:30 – 16:30 Short Oral Presentations by Young Attendees
14:30 Characterizing synthesis and processing effects in nanostructured
molecular materials
Maxwell W. Terban, Columbia University (NY, US)
14:45 Connection between structural and optical properties of fluorescent
Carbon nanodots doped with different amounts of Nitrogen
Alice Sciortino, University of Palermo (Italy)
15:00 Local and average structure of BiREWO6 (RE=Eu & Tb) nano-photocatalyst
Pradeep P. Shanbogh, Poornaprajna Institute of Scientific Research (India)
15:15 Structural analysis of defective CdSe colloidal quantum-dots through
synchrotron X-Ray Total Scattering Techniques
Daniele Moscheni, University of Insubria & To.Sca.Lab (Italy)
15:30 In-situ reduction of as-prepared γ-Iron Oxide nanoparticles
Pelle G. Garbus, Aarhus University (Denmark)
15:45 Hydrothermal synthesis of magnetic spinel ferrite nanocrystallites
Henrik Lyder Andersen, Aarhus University (Denmark)
16:00 Hybrid organic-inorganic inks flatten the energy landscape in colloidal
quantum dot solids
Mengxia Liu, University of Toronto (Canada)
16:15 Electrical conductivity of the thin films grown by random shaped clusters
Zhaleh Ebrahiminejad, Islamic Azad University (Iran)

16:30 – 17:00 COFFEE BREAK

17:00 – 18:00 Short Oral Presentations by Young Attendees
17:00 New iron telluride obtained by Mechanical alloying
Carlos E.M. Campos, Universidade Federal de Santa Catarina (Brazil)
17:20 Liquid PDF – CdTe detectors revolutionize data quality
Mirijam Zobel, Bayreuth University (Germany)
17:40 Structural investigation of hydrogenated alkali-cluster fullerides with
high-energy X-ray diffraction
Daniele Pontiroli, University of Parma (Italy)

18:00 – 19.00 Demo on SAXS Data Analysis

Jan Skov Pedersen (Uni-Aarhus, DK)
 Friday, June 2nd 2017
MORNING (9:00 – 13:00)
9:00 – 10.00 A Live DLS Experiment
Fabio Ferri (Uni-Insubria, IT)

10:00 – 12.00 Short Oral Presentations by Young Attendees

10:00 Quantifying stacking disorder in idealized metal nanoparticle ensembles by
modelling the PDF
Robert J. Koch, Alfred University (NY, US)
10:15 Coupling synchrotron radiation powder X-Ray diffraction and
thermodynamic modelling on complex Hydrides for energy storage
Erika M. Dematteis, University of Turin (Italy)
10:30 The interaction of electrons with clusters of inert and molecular gases
Olena Tkachenko, V. N. Karazin Kharkiv National University (Ukraine)
10:45 Operando scattering studies of Vanadium Oxide Nanotubes as cathodes for
rechargeable batteries
Christian K. Christensen, Aarhus University (Denmark)
11:00 Spin reorientation, magnetization reversal and negative thermal expansion
observed in RFe0.5Cr0.5O3 (R=Lu, Yb and Tm) perovskites
Fernando Pomiro, Universidad Nacional de Córdoba (Argentina)
11:15 Investigation of colloidal systems by Small Angle X-ray Scattering and X-
ray Photon Correlation Spectroscopy
Alexander Schavkan, PTB Physikalisch-Technische Bundesanstalt (Germany)
11:30 Probing the subtle local structure modifications in thermoelectric
materials by variable temperature total scattering
Hazel Reardon, Aarhus University (Denmark)
11:45 Bone microstructure revealed by sub-micron resolution Diffraction
Scattering Computed Tomography
Nina K. Wittig, Aarhus University (Denmark)

12:00 – 13.00 CLOSING AND LIGHT LUNCH

WE ARE GRATEFUL TO ALL THE SPONSORS

   

 
   
     

 
PATRONAGE OF  
       

   
 
Courtesy of Maxwell Terban, Columbia University, New York, USA

Title: Characterizing synthesis and processing effects in nanostructured molecular 
materials

Due largely to substantial developments at x­ray producing facilities and in software 
tools, the rapid collection of x­ray data for high precision, high resolution pair 
distribution function (PDF) analysis has become quite routine. This has allowed for 
successful applications toward understanding phenomena such as broken symmetry 
states in crystals, structures of ultra small nanoparticles, and nucleation pathways 
during nanoparticle synthesis in a wealth of inorganic systems. The PDF is also 
increasingly finding use in characterizing molecular materials. Such systems often 
contain increased structural complexity necessitating modified modeling techniques. 

Such techniques for molecular materials will be discussed in terms of small molecule 
compounds with applications in developing amorphous and nanocrystalline 
pharmaceutical formulations.1,2 Important  targets of such research include 
characterizing the behavior of drug­excipient mixtures and understanding how to 
engineer disordered formulations which remain stable at ambient conditions. Extensions 
to synthetic and natural polymeric materials will also be discussed, for example, to 
identify chain conformation and packing in nanocrystalline hard segments 3 or 
crosslinking through ion­complex formation.

1. MW Terban, M Johnson, M Di Michiel, SJL Billinge. (2015). Nanoscale 7 (12), 5480­
5487.
2. MW Terban, EY Cheung, P Krolikowski, SJL Billinge. (2016). Crystal Growth & 
Design 16 (1), 210­220.
3. MW Terban, R Dabbous, A Debellis, E Poselt, SJL Billinge. (2016). Macromolecules, 49
(19), 7350–7358.
 Connection between structural and optical properties of fluorescent Carbon nanodots
doped with different amounts of Nitrogen
A. Sciortino
Dipartimento di Fisica e Chimica, Università degli Studi di Palermo, Palermo, Italy.
Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Catania, Italy.
Institute of Applied Physics, University of Bern, Bern, Switzerland.

Carbon dots are a class of optically-active carbon-based nanomaterials, consisting in sub-10 nm

nanoparticles composed by carbon, oxygen, nitrogen and hydrogen. They are capable of a strong
fluorescence which can be tuned in the visible range. Such a property, combined with ease of synthesis,
water solubility, low cost and lack of toxicity, is very interesting for applications in different fields such as
bioimaging and optoelectronics. The structure of carbon nanodots is synthesis-dependent and often
consists in a nanocrystalline, carbon-rich core, decorated by a variety of polar functional groups on the
surface. The literature suggests that doping the structure by different atoms as Nitrogen or Sulphur both
changes the fluorescence quantum yield and the structure of these nanodots, but the connection between
the structure and the optical properties is rather unclear so far.

We used different techniques (such as XRD, HRTEM, time-resolved fluorescence, UV/VIS) to carry out an
extensive study on the influence of nitrogen-doping on the structure and optical properties of microwave-
synthesized carbon nanodots. In particular, we synthesized carbon nanodots with different amounts of
Nitrogen and, in order to study the changes in the structure, we performed XRD measurements using
synchrotron radiation at ESRF. The role of Nitrogen turns out to be critical for the core structure, which
follows a regular trend with the amount of doping. In order to gain a deeper understanding of the problem,
we also performed HRTEM measurements which are very helpful to study the crystalline structure at the
single-dot level. Combining the results from all these techniques, we succeeded in tuning the core of the
dots from having a β-C3N4 nanocrystalline structure to a graphitic one. Similarly to the core structure, also
the optical properties follow a regular trend with the amount of nitrogen and this opens the possibility of
using N-doping to control not only the structural properties, but also the optical characteristics of these
nanomaterials.
Local and Average Structure of BiREWO6 (RE=Eu & Tb) Nano-
Photocatalyst.
Pradeep P. Shanbogh1, Diptikanta Swain2, Rajamani Raja2, Michael Fegenson3, Chandrabhas
Narayana4, Jasper Plaisier5and Nalini G. Sundaram1*
1
Functional Nanomaterials Group, Materials Sciences Division, Poornaprajna Institute of Scientific Research,
Bengaluru 572064, India.
2
Solid State and Structural Chemistry Unit, Indian Institute of Science, Benagluru-560012
3
NOMAD beamline, Oakridge National Laboratory, Oak Ridge, TN, USA
5
Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur,
Bengaluru-560064
4
MCX Beamline, Elettra Synchrotron facility, Area Science Park, Basovizza, Trieste, Italy.
E-mail: nalini@poornaprajna.org
Key Words: Layered Perovskite, average & local structure, pair distribution function

Bi2WO6 shows temperature-dependent phase transitions,: The room temperature orthorhombic phase
(Pca21) undergoes phase transition to another orthorhombic phase with space group B2cb at 650oC and
further a monoclinic phase (A2/m) at T> 950oC 650oC, at above it [1]. In the present work, the
monoclinic phase of Bi2WO6 has been stabilized by Eu & Tb substitution at the Bi position using a
simple one step hydrothermal method for the first time. As synthesized nanomaterials are characterized
by p-XRD, FE-SEM, DRS, TGA, & BET surface analysis measurements. Photocatalytic activity of as
synthesized BiEuWO6 & BiTbWO6 nanoparticles was established for Congo-red dye degradation under
visible light source. Rietveld refinement using GSAS-EXPGUI[2] suite has been carried out on these
nanoparticles using combined synchrotron X-ray and spallation Neutron data obtained from Elettra,
Trieste and ORNL, Oakridge respectively. Additionally, local structural analysis using atomic pair
distribution function has been carried out on high Q data collected from NOMAD, ORNL by using
PDFgui program [3].

Structures are refined in the A2/m space group

using the BiNdWO6 model. The Tungsten
octahedra are distorted and the oxygen were
refined by a split atom model indicating that there
is a disorder in the rare earth substituted analogue.
Structural parameters obtained from Rietveld
refinement were used as initial model to fit the
local structure of BiEuWO6 and BiTbWO6 and a
good fit is obtained for low r range 1.5 to 5Å.
Positional disorder observed in average structure
is also present in local structure. DFT calculations
for band gap analysis and Raman studies were
also carried out. As compared to Bi2WO6, the Figure: Average and Local structure refinements of
BiEuWO6 & BiTbWO6 nanoparticles showed BiEuWO6 and BiTbWO6 plots using GSAS-
superior Photocatalytic activity for the degradation EXPGUI and PDFgui.
of Congo red dye in the visible region. The detailed
Crystal Structure-Local Structure implications on the Photocatalytic activity is discussed. Such studies
are essential for the generation of new materials possessing improved properties.

References:
[1] Watanabe, A., Polymorphism in Bi2WO6. Journal of Solid State Chemistry 1982, 41 (2), 160-165.
[2] Toby, B. H., EXPGUI, a graphical user interface for GSAS. Journal of applied crystallography 2001, 34
(2), 210-213.
[3] Farrow, C., et al., PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals.
Journal of Physics: Condensed Matter, 2007. 19(33): p. 335219.
 Structural Analysis of Defective CdSe Colloidal Quantum-Dots
through Synchrotron X-Ray Total Scattering Techniques

Daniele Moscheni,a Federica Bertolotti,a,b Loredana Protesescu,c Dmitry N. Dirin,c Laura

Pivateau,c Maksym V. Kovalenko,c Norberto Masciocchi,a Antonietta Guagliardid
a
Università degli Studi dell’Insubria and To.Sca.Lab, Como, Italy
b
Aarhus University, Aarhus, Denmark
c
ETH Zürich and EMPA, Dübendorf, Switzerland
d
Istituto di Cristallografia, CNR, Como, Italy.
d.moscheni@studenti.uninsubria.it

In the last years, pushed by a large scientific and technological interest, the knowledge of
nanocrystalline materials has enormously increased. The functional properties of
semiconductors depend on the crystal structure, particle size and shape, their distributions and
on the presence of various kind of defectiveness. Several synthetic approaches have been
addressed to control these fundamental parameters playing on kinetic and thermodynamic
criteria, but robust characterization methods at the nanoscale are still missing [1,2].
Not being restricted to ideally periodic and ordered materials, Wide Angle X-ray Total
Scattering methods (WAXTS) and particularly the Debye Scattering Equation (DSE) approach,
can suitably model diffuse scattering, between and below very broad Bragg peaks, which is
normally neglected in conventional powder diffractometry. This feature makes DSE a powerful
tool for characterizing nanosized and defective materials [3,4].
Here the DSE method has been used for deriving important structural and microstructural
properties of organic-ligand-capped CdSe colloidal quantum-dots (QDs) and nanoplates (nPLs)
[5]. These materials are stable in different crystal forms (cubic and hexagonal) but, due to
kinetic effects and growth conditions, often contain numerous faults of the planar type (stacking
faults, SF) [5]. The presence of SF affects the diffraction pattern of the colloidal suspension in
different ways, modifying the peak positions, widths and shapes in a still to be fully understood
manner, which can be easily confused with effects form nanocrystals size, shape, distribution
and surface relaxation.
Using the DSE approach, we investigated the effect of different SF probabilities in populations
of atomistic clusters of variable size and shape (QDs and nPLs) aiming at modeling the
synchrotron experimental data collected on CdSe QDs of 2÷5 nm in diameter and nPLs of
1.5÷2.5 nm in thickness.
Modeling aspects and results will be presented and discussed in comparison with those from
other techniques, including PDF, UV-Vis Absorption spectroscopy, HRTEM, SAXS and NMR.

[1] D.V Talapin, J. Lee, M.V. Kovalenko, E.V. Shevchenko, Chem. Rev., 2010, 110, 389-458.
[2] G.H. Carey, A.L Abdehady, Z. Ning, S.M. Thon, O.M. Bakr, E.H. Sargent, Chem. Rev., 2015, 115, 12732-12763.
[3] A. Cervellino, R. Frison, F. Bertolotti, A. Guagliardi, J. Appl. Cryst. 2015, 48, 2026-2032.
[4] F. Bertolotti, D.N. Dirin, M. Ibanez, F. Krumeich, A. Cervellino, R. Frison, O. Voznyy, E.H. Sargent, A. Guagliardi,
N. Masciocchi, Nat. Mater. 2016, 15, 987-994.
[5] M. Nasilowski, B. Mahler, E. Lhuillier, S. Ithurria, B. Dubertret, Chem. Rev., 2016, 116, 10936-10982.
[6] Y. Gao, X. Peng, J. Am. Chem. Soc. 2014, 136, 6724-6732.
 15 minutes presentation at To.Sca.Lake PhD-School

In-situ reduction of as-prepared γ-Iron Oxide Nanoparticles

Pelle Gorm Garbus1, 2, Jakob Ahlburg1, Henrik L. Andersen1, Lukas Keller2 and Mogens
Christensen1
1
Center for Materials Crystallography, iNANO & Department of Chemistry, Aarhus University, Langelandsgade
140, 8000 Aarhus C.
2
Laboratory for Neutron Scattering and Imaging (LNS), Paul Scherrer Institut, 5232 Villigen PSI.
E-mail: garbus@inano.au.dk

Magnetic materials are a hot topic among energy-materials and they find applications in nearly
all everyday consumer electronics. Advances in magnetic performance have in particular been
made for thin film and nanosized particles because the magnetic properties are strongly related
to the size. Bulk iron is relatively unreactive, however nanosized iron particles are highly reactive
as a result of their enlarged high surface area and the oxidation potential of iron.
Iron oxides are cheap and unreactive precursors for the production of nanosized iron particles.
Understanding the mechanisms behind the structural development [1, 2] adds to the fundamental
understanding of materials’ formation and can lead to new synthesis pathways. In this study, iron
oxide (γ-Fe2O3) particles were heated to 400°C under a flow of H2/Ar mixture, while the process
was followed by in situ synchrotron powder X-ray diffraction measurement. The as-prepared
maghemite nanoparticles were synthesized by the continuous decomposition of solutes in
supercritical hydrothermal flow synthesis [3, 4]. The reagent used was ferric ammonium citrate
(C6H8O7•xFe(III)•yNH3) that under hydrothermal flow synthesis decomposes into the γ-iron
oxide Fe2O3. The reduction of maghemite to body centered cubic (BCC) iron does not go through
a detectable intermediate state.

1. Jensen, K.M., et al., Mechanisms for iron oxide formation under hydrothermal
conditions: an in situ total scattering study. ACS nano, 2014. 8(10): p. 10704-10714.
2. Andersen, H.L., et al., Size and Size Distribution Control of γ-Fe2O3 Nanocrystallites:
An in Situ Study. Crystal Growth & Design, 2014. 14(3): p. 1307-1313.
3. Bondesgaard, M., et al., Guide to by-products formed in organic solvents under
solvothermal conditions. The Journal of Supercritical Fluids, 2016. 113: p. 166-197.
4. Bremholm, M., M. Felicissimo, and B.B. Iversen, Time‐Resolved In Situ Synchrotron
X‐ray Study and Large‐Scale Production of Magnetite Nanoparticles in
Supercritical Water. Angewandte Chemie, 2009. 121(26): p. 4882-4885.
Hydrothermal synthesis of magnetic spinel ferrite nanocrystallites

Henrik Lyder Andersen, Center for Materials Crystallography, Dept. of Chemistry and iNANO, Aarhus
University, DK-8000 Aarhus C, Denmark

Magnetic spinel ferrites, MFe2O4 (M= Zn2+, Mn2+, Ni2+, Co2+,[ ] , etc.) are important magnetic materials
with many modern technological applications. Their magnetic properties depend on the constituent
elements, their positions within the crystal structure, as well as the size of the crystallites. Controlling
the crystal- and nanostructure allows manipulation of the magnetic properties of the materials.
Hydrothermal synthesis in near- or supercritical water is a relatively simple, cheap, energy efficient
and easily scalable preparation method in which material characteristics, such as crystal structure,
size and physical properties, often can be tuned by performing simple adjustments to the reaction
parameters, e.g. temperature, heating rate, precursor concentration, pH, pressure and reaction time.
Hydrothermal reactors are generally ‘black box’ systems and the identification of optimal synthesis
parameters has traditionally been done via extensive trial-and-error based ex situ studies. In the
pursuit of deeper understanding of the mechanisms governing the formation and growth of materials
during solvothermal synthesis, a number of research groups have developed the means for studying
chemical reactions as they happen, i.e. in situ, by powder X-ray diffraction and other techniques. Using
Rietveld refinement, time-resolved quantitative information can be extracted from the obtained
diffraction patterns, and the evolution of crystallite size, size distribution and crystal structure of the
synthesised nanocrystallites can be followed. The development of total scattering techniques and pair
distribution function analysis opens up the possibility for advanced modelling and structural
refinement of amorphous precursor clusters. This means that the entire process from precursor to
product can be described structurally. The flexibility added by fully understanding the processes in
play, will enable us to apply the ideal conditions to synthesize crystallites with certain characteristics
optimized for specific applications.
Courtesy of Megxia Liu, University of Toronto, Toronto, Canada

Hybrid Organic-Inorganic Inks Flatten the Energy

Landscape in Colloidal Quantum Dot Solids

Bandtail states in disordered semiconductor materials result to losses in open-circuit

voltage (Voc) and inhibit carrier transport in photovoltaics. For colloidal quantum dot
(CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are
determined by CQD synthetic polydispersity and inhomogeneous aggregation during the
ligand exchange process. Here we introduce a new method that produces solution-phase
ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously
high packing density. In the solid-state, these materials exhibit a sharper bandtail and
reduced energy funneling compared to the previous best CQD thin films for
photovoltaics. Consequently, we demonstrate solar cells with higher Voc and more
efficient charge injection into the electron acceptor, allowing the use of a closer-to-
optimum bandgap to absorb more light. These enable the first certified report of CQD
solar cells made via a solution-phase ligand-exchange, with a certified power conversion
efficiency of 11.3%. The devices are stable when stored in air, unencapsulated, for over
1000 hours.
Key  words:  Energy  landscape,  colloidal  quantum  dot,  bandtail,  solar  cells  
New iron telluride obtained by Mechanical alloying

K.F. Ulbricha,, F. L. Faitaa, E. Girottob, H. Gallardob, C.E.M. Camposa*

a
Departamento de Física, Universidade Federal de Santa Catarina, Campus Trindade, 88 040-
900 Florianópolis, Santa Catarina - SC, Brazil

b
Departamento de Química, Universidade Federal de Santa Catarina, Campus Trindade, 88
040-900 Florianópolis, Santa Catarina - SC, Brazil

*Corresponding author email: carlos.campos@ufsc.br tel: +55 4837212868 fax:

Abstract

New nanocrystalline iron telluride Fe3Te2 was prepared by mechanical alloying

starting from Fe60Te40 powders mixture. Thermal treatments were performed to test stability and
to improve crystallinity by increasing the crystals size domain. X-Ray Powder Diffraction
(XRPD) and Transmission Electron Microscopy (TEM) were carried out to characterize the
micro/structure of the samples. Magnetization and FC-ZFC measurements were employed to
characterize the products. The Fe3Te2 phase has an unknown structure but nanometric character
can be attested by the broad Bragg peaks observed in the XRPD patterns and in the TEM
images. Magnetizations of both as-milled and treated samples increase with temperature
decreasing and at 2 K they show hysteresis, suggesting a ferromagnetic behavior at low
temperature. The ZFC curves present blocking temperatures around 150 K (H = 200 Oe) and the
very small magnetic remanence directly demonstrate that the samples are superparamagnetic at
room temperature. Structural determination and complete microstructural characterization using
Rietveld and total scattering methods are in view of next steps in this scientific project.
Figure Captions

Fig. 1. (a) XRPD patterns of Fe60Te40 alloy for 0 hours (solid solution) and for 9 hours of
milling (first and second batch) before and after thermal treatments at 450 oC and 500 oC. The
symbols (red bars) represent the peak positions of Fe3Te2 phase reported on file PDF (number
00-041-0759). (b) First and second runs (heating and cooling) DSC curves of Fe60Te40 alloy.
The gray lines represent the second run.

Fig. 2. TEM images (a and b) and SAED (c and d) of the Fe60Te40 mechanical alloyed for 9
hours before and after thermal treatments at 500 oC, respectively.

Fig.3 (a) Temperature dependence of magnetization of the Fe60Te40 mechanical alloyed for 9
hours before (gray symbols/lines) and after (black symbols/lines) thermal treatments at 500 oC
in FC (filled symbols) and ZFC (open symbols) process under an applied field of 200 Oe. (b) M
– H curves at 2 K and 300 K.
 Electrical conductivity of the thin films grown
by random shaped clusters
Zh. Ebrahiminejad, S. Farhad Masoudi, H. hamzehpour

Abstract— In the present work, using Monte Carlo

Zh. Ebrahiminejad, is with the Faculty of Science, Islamic Azad University
technique, a rough and porous surface recently (West branch), 41, Tehran, Iran (phone: (+98) 21 23064364; fax: (+98) 21
23064218; e-mail: zhl.ebrahimi@gmail.com).
simulated by deposition of randomly shaped clusters S. Farhad Masoudi, is with the Department of Physics, K.N. Toosi
University of Technology, Shariati Ave, Mojtabaee St, Kavian Street, 41,
with different sizes on an initially flat substrate. The Tehran, Iran (e-mail: masoudi@kntu.ac.ir).
H. Hamzehpour, is with the Department of Physics, K.N. Toosi University
scaling exponents are calculated and found to agree of Technology Shariati Ave, Mojtabaee St, Kavian Street, 41, Tehran, Iran
(hamzehpour@kntu.ac.ir).
with the ballistic deposition model. Then, effect of
cluster size on the scaling exponents is studied.
Moreover, the bulk porosity and its dependence on
time and cluster size are also surveyed. As the
behavior of film’s conductivity affects by its
morphology, in continue, the electrical conductivity of
these porous solid films which grown by random
shapes and sizes clusters is investigated. The
conductivity is computed as a function of several
relevant parameters. Based on our results, the
frequency-dependent effective conductivity is a
decreasing function of the cluster’s sizes, such as
porosity. The effective conductivity and dc
conductivity depends on the frequency and the
clusters sizes through a power law, respectively. As
the scattering process plays the key role in transport
properties through rough surfaces/interfaces, the
results can be used in semiconductor and magnetic
nanostructures.

Keywords— Electrical conductivity, Nanostructures, Porosity,

Random shaped clusters, Rough solids
Courtesy of Mirijam Zobel, University of Bayreuth, Bayreuth, Germany

To.Sca.Lake 2.0: Total Scattering for Nanotechnology on the Como Lake

Abstract for oral presentation

Liquid PDF – CdTe detectors revolutionize data quality

Keywords: CdTe detector, high-energy X-ray scattering, liquid PDF

Just recently, CdTe detectors became available as 2M pixel detectors at beamlines ID15 and ID31 at
the ESRF. They feature about triple the sensitivity for high-energy X-rays (70 keV) compared to
commonly used Perkin Elmer detectors. Furthermore, they have an almost negligible intrinsic
background, which makes them, at present, the ideal detector to measure liquid or other weakly
scattering samples. In this talk, a short overview of the CdTe detector will be given, alongside with data
collection strategies. Its data quality will be compared with data from Perkin Elmer detectors. For this
purpose, data on different liquids and nanoparticle dispersions will be shown, which was recently
collected at ID31, ESRF. Furthermore, the astonishingly low background of the CdTe detectors reveals
that the X-rays at synchrotrons are not perfectly linearly polarized, but that an additional polarization
correction is required during radial integration. A workaround to this new issue in data analysis will be
presented.
 Structural investigation of hydrogenated alkali-cluster fullerides
with high-energy X-ray diffraction
D. Pontiroli1*, M. Gaboardi1,2, G. Magnani1, C. Cavallari3, M. Riccò1

1 - Carbon Nanostructures Laboratory, DSMFI, Università degli Studi di Parma, Parma, Italy
2 - ISIS-RAL, Didcot, UK
3 - ESRF, Grenoble, France
*e-mail: daniele.pontiroli@fis.unipr.it

Hydrogen absorption in solid materials seems to be the most efficient strategy to overcome the limits
of the current hydrogen-storage devices, in terms of both gravimetric and volumetric energy densities
attainable [1]. However, among the systems investigated so far, none of them are still really
competitive with a conventional gasoline tank, either in terms of thermodynamic and kinetics, or
concerning the reversibility of the fuel loading/unloading process.
Carbon-based materials have been identified as promising hydrogen-storage systems, since they are
light and easily processable at the industrial level. In these compounds, hydrogen-storage is generally
obtained through the H2 physisorption onto the large carbon surface at low temperatures. However,
recently a new class of carbon based nanomaterials, namely the alkali-cluster intercalated fullerides,
have shown the ability to chemically absorb significant amount of hydrogen (up to 6 wt %) at
reasonable temperatures for practical applications. Surprisingly, this process also proved to be fully
reversible. Such results can be reached thanks to the catalytic effects of the intercalated alkali clusters
towards the H2 dissociation, followed by a sizeable hydrogenation of the C60 molecule [2].
In order to gain more knowledge on these systems, extensive structural investigation by means of
either in-situ or ex-situ synchrotron and neutron powder diffraction was performed on the
hydrogenated compounds [3,4]. However, the intrinsic structural disorder induced by the extremely
large number of possible isomers of hydrofullerenes (up to 1031 for C60H36) actually limits the
information which can be extracted from conventional powder diffraction and suggested the use of a
non-conventional approach. In particular, here we show how the study of the total scattering signal
with the extraction of the atomic pair distribution function can be a powerful method in order to gain
knowledge on the structure of such systems at the nanoscale.

References

[1] A. Züttel, A. Borgschulte, L. Schlapbach; Hydrogen as a future energy carrier, WILEY-VCH 2008.
[2] M. Aramini, M. Gaboardi, D. Pontiroli, M. Riccò, et al., Carbon 67, 92 (2014).
[3] P. Mauron, M. Gaboardi, D. Pontiroli, M. Riccò, et al., Int. J. Hydrogen Energy, 37, 14307 (2012).
[4] M. Gaboardi, S. Duyker, G. Magnani, D. Pontiroli, et al., J. Phys. Chem. C, 119, 19715 (2015).
 Quantifying stacking disorder in idealized metal nanoparticle ensembles by modelling the
PDF
Robert J. Koch,1, Peter Metz1 and Scott T. Misture1
1
Kazuo Inamori School of Engineering, Alfred University, 2 Pine Street, Alfred, NY 14802

Explicit atomic models for several different nanometallic systems with extensive stacking
disorder provide input into the Debye Scattering equation, yielding idealized I(Q) scattering data.
This data provides idealized pair distribution functions (PDFs), characteristic for these systems.
Traditional small-box periodic models fail to reproduce the observed PDFs over reasonable r-
ranges. Modelling this data with hierarchical ensembles of weighted stacking models is used to
improve the PDF fit over a large r-range and demonstrates model sensitivity of the PDF to
stacking vector and layer-layer transition probabilities. Monte Carlo Sampling of the posterior
distribution of parameters allows for accurate error estimates on refined values.
 Coupling Synchrotron Radiation Powder X-Ray Diffraction and
Thermodynamic modelling on Complex Hydrides for Energy Storage
Erika M. Dematteis,a)b) Eugenio R. Pinatel,a) Marta Corno,a) Torben R. Jensen b) and Marcello Bariccoa)
a)
Department of Chemistry and Inter-departmental Center Nanostructured Interfaces and Surfaces (NIS), University of Turin,
Via Pietro Giuria 7, 10125 Torino, Italy
b)
Department of Chemistry, Center for Materials Crystallography (CMC) and Interdisciplinary Nanoscience Center (iNANO)
Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark

Abstract
Key words: borohydride, phase diagram, assessment, mixtures, hydrogen

Hydrogen can be the next energy carrier for mobility and large scale stationary applications. The efficient
storage of hydrogen is the bottleneck towards a hydrogen society. Solid-state hydrogen storage in
complex hydrides (e.g. borohydrides) and their mixtures has been in the spotlight, owing to their high
gravimetric hydrogen content.1,2 However, the kinetic and thermodynamic limitations of hydrogen
sorption reaction for these compounds have to be addressed and different approaches have been
described in the literature so far.3 A full evaluation of the thermodynamics is indeed fundamental for
tailoring hydrogen storage materials.
In our research, we combine experimental characterization and theoretical modelling of mixtures of
borohydrides, in order to determine various thermodynamic properties and to identify possible
decomposition paths for hydrogen sorption reactions, in a wide temperature and composition range. As
an output of modelling, the values of the enthalpy of mixing in the liquid and solid solutions can be
obtained.4,5
The use of the in-situ high energy X-ray diffraction is helpful to investigate the mechanism of hydrogen
sorption reactions as a function of temperature and backpressure of hydrogen and to determine the
structure of new compounds or solid solutions. In the case of eutectic mixtures important information
can be obtained from Synchrotron Radiation Powder X-Ray Diffraction (SR-PXD) experiments as a
function of temperature, such as the determination of various transition temperatures (e.g liquidus,
eutectic). These data have been used to perform a thermodynamic assessment using the Calphad method.
The assessed binary and ternary phase diagrams in the LiBH4-NaBH4-KBH4 system will be presented,
underlining the role of the structural determination of the different phases in the system using SR-PXD.
Negative values for the enthalpy of mixing have been obtained for the liquid phase, suggesting attractive
interactions in the liquid state.

Bibliography
1 H. W. Li, Y. Yan, S. I. Orimo, A. Züttel and C. M. Jensen, Energies, 2011, 4, 185–214.
2 E. Callini, Z. Ö. K. Atakli, B. C. Hauback, S. I. Orimo, C. Jensen, M. Dornheim, D. Grant, Y. W. Cho, P. Chen, B.
Hjörvarsson, P. de Jongh, C. Weidenthaler, M. Baricco, M. Paskevicius, T. R. Jensen, M. E. Bowden, T. S. Autrey
and A. Züttel, Appl. Phys. A, 2016, 122, 353.
3 L. H. Rude, T. K. Nielsen, D. B. Ravnsbaek, U. Bösenberg, M. B. Ley, B. Richter, L. M. Arnbjerg, M. Dornheim,
Y. Filinchuk, F. Besenbacher and T. R. Jensen, Phys. status solidi, 2011, 208, 1754–1773.
4 E. M. Dematteis, E. Roedern, E. R. Pinatel, M. Corno, T. R. Jensen and M. Baricco, RSC Adv., 2016, 6, 60101–
60108.
5 E. M. Dematteis, E. R. Pinatel, M. Corno, T. R. Jensen and M. Baricco, to be submited, 2017.
Courtesy of Olena Tkachenko, V. N. Karazin Kharkiv National University, Kharkiv, Ukraine

THE INTERACTION OF ELECTRONS WITH CLUSTERS OF INERT AND

MOLECULAR GASES
Nanometer sized aggregates of matter – nanoclusters – have become compelling subjects to study
in different areas of science such as physics, chemistry, medicine, and materials science. Clusters
are vitally important for processes occurring in the atmosphere and even in space. Supersonic free
jets of rare gas clusters offer the possibility of isolating and characterizing molecules and
complexes at very low temperatures, which are not accessible by other techniques.

The experimental setup for investigation of free clusters, which has been designed, set up, tested,
and put into operation at the B. Verkin Institute for Low Temperature Physics and Engineering of
NAS of Ukraine, is presented in this report. Additionally, the most interesting results obtained on
this setup during the last years are given. The setup consists of a cluster beam, an electronographic
device (electronograph EMR-100M), and a spectroscopic device to study atomic and molecular
clusters over a wide wavelength range (1–800 nm). Using a conical supersonic nozzle, we are able
to produce heterogeneous and homogeneous clusters (Ar, Kr, Xe, N2, CO2, and CH4) with cluster
size ranging from 2 to 105 atoms/cluster. The presented experimental complex allows one to
answer some of the crucial questions on the structure of one- and multicomponent clusters, as well
as on the dynamics of their electron subsystems.

The interaction of clusters of inert and molecular gases with electrons is an important area of
research, because it provides a tool for a better understanding of cluster properties. The 50-100
keV electron scattering on clusters is used to define structure, temperature, and mean size of
clusters by means the electronographic method. The effectiveness of clusters studies by this
method is specified by the strong electron scattering in matter, and by a quite simple focusing of
an electron beam, which makes it possible to obtain the high resolution of the diffraction pattern.

The interaction of low-energy electrons (50-2000 eV) with atomic electron shells in clusters leads
to electron ionization and excitation, and can result in the emission of photons with different values
of energies. Spectroscopy device was applied to study luminescence spectra from pure and mixed
rare-gas clusters e.g., exciton-impurity luminescence features, phase segregation and emission
from neutral and charged excimer molecules in mixed clusters. It has also been used in the studies
of polarization bremsstrahlung arising from electron scattering on atoms and clusters.

Keywords: electron scattering, nanoclusters, diffraction pattern, luminescence spectra,

polarization bremsstrahlung
Operando scattering studies of Vanadium Oxide Nanotubes as Cathodes for
rechargeable batteries
a a b b,c
Christian Kolle Christensen, Daniel Risskov Sørensen, Espen Drath Bøjesen, Jette Mathiesen, Jonas
a b a
Hyldahl Kristensen, Bo Brummerstedt Iversen, and Dorthe Bomholdt Ravnsbæk
a
Departnemt of Physics, Chemistry, and Pharmacy, University of Southern Denmark, bDepartment of Chemistry, Aarhus University,
c
DTU Energy, Danish Technical University

Exchanging the active specie, Li+ in Li-ion batteries by multivalent, abundant and cheap cations,
such as Mg2+, are projected to boost the energy density and lower the cost per kilo-watt-hour
significantly, making the Mg-ion battery technology a promising candidate for one of the battery
technologies of the future.1 The increase in energy density is i.a. a result of the divalent Mg2+
carrying twice as much charge as the monovalent Li+.1 However, the higher charge also poses a
problem as it significantly increases the charge density of the ion, which results in stronger
interactions with the host lattice of the electrodes and hampers facile ion transport. Therefore,
development of novel electrode materials for effective Mg-ion storage is a vital step for the
realization of this battery technology.2 One way of enhancing electrode materials is nanosizing.3
Developments in the control of nanostructured morphologies have led to more advanced materials,
and recently vanadium oxide nanotubes (VOx-NT) were shown to perform well as a cathode
material for Mg-ion batteries.4 The VOx-NTs consists of multiwalled scrolls of crystalline VOx layers
with approximate composition V7O16 and primary amines in between the layers acting as spacer
molecules, which can be exchanged with metal cations with a subsequent change in layer
spacing.5
In this study we have synthesized a series of VOx-NTs with varying spacer molecules. The
mechanism for Mg-intercalation and deintercalation was studied by operando X-ray scattering
measured during battery operation.

References
1. Van Noorden, R. The rechargeable revolution: A better battery. Nature 507, 26–28 (2014).
2. Saha, P. et al. Rechargeable magnesium battery: Current status and key challenges for the future. Prog. Mater.
Sci. 66, 1–86 (2014).
3. Guo, Y. G., Hu, J. S. & Wan, L. J. Nanostructured materials for electrochemical energy conversion and storage
devices. Adv. Mater. 20, 2878–2887 (2008).
4. Jiao, L. et al. Electrochemical insertion of magnesium in open-ended vanadium oxide nanotubes. J. Power
Sources 156, 673–676 (2006).
5. Reinoso, J. M., Muhr, H.-J., Krumeich, F., Bieri, F. & Nesper, R. Controlled Uptake and Release of Metal Cations
by Vanadium Oxide Nanotubes. Helv. Chim. Acta 83, 1724–1733 (2000).
Spin reorientation, magnetization reversal and negative thermal expansion

observed in RFe0.5Cr0.5O3 (R=Lu, Yb and Tm) perovskites.

Fernando Pomiro,1 Rodol fo D. Sánchez,2 Gabriel Cuello,3 Antoine Maignan 4, Chris tine Ma rtin 4 and Raúl E. Ca rbonio 1

1
INFIQC (CONICET – Universidad Nacional de Córdoba), Departamento de Fisicoquímica, Facultad de Ciencias Químicas,

Universidad Nacional de Córdoba, Haya de la Torre esq. M edina Allende, Ciudad Universitaria, X5000HUA Córdoba,

Argentina.
2
Centro Atómico Bariloche, Comisión Nacional de Energía Atómica and Instituto Balseiro, Universidad Nacional de Cuyo,

(8400) San Carlos de Bariloche (RN), Argentina.

3
Institut Laue-Langevin, BP 156, F-38042 Grenoble Cedex 9, France.
4
Laboratoire CRISM AT, UM R 6508 CNRS/ENSICAEN/UCBN, 6 Boulevard M arechal Juin, 14050 Caen cedex, France.

Abstract

Three members of the perovskite family RFe0.5Cr0.5O3 (R=Lu, Yb and Tm) have been synthesized and

characterized. A systematic study of the crystal and magnetic structures was performed by neutron

powder diffraction combined with magnetization measurements. All these compounds crystallize in a

Pbnm orthorhombic unit-cell and they are already antiferromagnetic at room temperature. The study of

the magnetic structure vs. temperature showed the occurrence of a progressive spin reorientation from

Γ4TM to Γ2 TM for the transition metal sub-lattice, and in the Tm based-sample a long range magnetic order

of the Tm3+ sub-lattice was found (Γ8R). These results are in excellent agreement with the magnetic

susceptibility measurements. No spin reorientation is observed in the Lu-sample for which a

magnetization reversal with Tcomp.=225 K was detected. A clear magnetostrictive effect was observed in

the samples with R=Yb and Tm associated with a negative thermal expansion, assigned to a

magnetoelastic effect produced by repulsion between the magnetic moments of neighbor transition

metal ions.
Colloid suspensions play an important role in research as model and “real life” systems. Together with
deeper understanding of the properties of colloid suspensions and liquid crystals the industrial use of
these materials experienced a huge boost. Nowadays extensive research concentrates among others on
the topic of “smart nanoparticles”, which would enable a controlled switching between the states of a
suspension by tuning a chosen parameter. Small Angle X-ray Scattering method ensures the structural
investigation of colloid suspensions. It covers precise and reproducible measurement methods of size,
polydispersity and concentration for suspensions of different particles and forms, which is important for
industrial manufacturing. On the other hand particles of anisotropic shapes and high polydispersity
show enriched phase diagram and sometimes unusual behavior under influence of a controlling
parameter. For investigation of the structural details and the phase diagram the method of Small Angle
X-ray Scattering is indispensable, too. The appearing phases and phase transitions can be studied as a
function of the concentration and applied magnetic field. For this purpose, order parameters, ellipticity,
radial and azimuthal peak positions, width of scattering features, form factor as well as structure factor
can be investigated to clarify the structural properties.

Additionally X-ray Photon Correlation Spectroscopy can be used to investigate the underlying
microscopic dynamics of suspensions of nanoparticles to understand the behavior of the particles in
different phases in detail. For the analysis of the underlying dynamics, the relaxation rates and the
shape of measured time correlation functions is evaluated. The dependence on the concentration of
nanoparticles and the nature of the controlling parameter leads to different kinds of particle motion in
the suspensions with different characteristics. These induced differences influence the structural
properties of the suspension and liquid crystal phases formed by them.

The connection of both methods allows studying of different liquid crystal phases of colloid suspensions
and underlying microscopic dynamics, which can be combined through the establishment of models
based on particle interactions in order to describe the structural and dynamical properties of the colloid
suspensions and their unusual physical properties.
Probing the subtle local structure modifications in thermoelectric materials by variable temperature total
scattering

Hazel Reardon, Lasse R. Jørgensen, Christian B. Zeuthen, and Bo B. Iversen

Center for Materials Crystallography (CMC), Department of Chemistry and iNANO, Aarhus University,
Langelandsgade 140, Aarhus, 8000, Denmark

Abstract
The complex host-guest structure of Type-I inorganic clathrates has been studied fervently within the CMC
based on their low thermal conductivity and promising thermoelectric Figure of Merit (𝑧𝑇).i We have
recently been focused on understanding unusual features in the high temperature diffraction data
collected over a number of years on Ba8Ga16Ge30 (BGG), where numerous samples have been prepared in-
house using various synthesis methods. This led to a comprehensive thermal stability study of clathrate
powders, where PXRD revealed amorphous components in the samples treated at high temperature in air
(Figure 1a). PDF measurements were performed on data collected from ex situ annealed BGG samples. This
ex situ study (to be submitted), reveals that the seemingly subtle change in the clathrate structure and the
emergence of a significant amorphous phase observed from PXRD data is likely to be the result of
modifications in the cage configuration, but further data analysis is necessary to identify the specific
features of the cages that are affected.

Although the thermal stability of thermoelectric materials has been highlighted as a critical bottleneck in
their commercialization, the aim of this work is to understand how we may stabilize TE materials through a
thorough understanding of their high temperature structure reorientations and decomposition
mechanisms.ii

a) b)

c)

Figure 2 – a) PXRD (collected at BL44B2, SPring-8, Japan); b) representative unit cell of BGG, and c) example PDF fit of as
prepared BGG (un-annealed).

i
M. Christensen, et al., Dalton Trans., 39, 2010, 978.
ii
H. Yin et al., Eur. J. Inorg. Chem., 2011, 2733.
Bone microstructure revealed by sub-micron resolution Diffraction Scattering Computed
Tomography
N. K. Wittig, S. Frølich, M. E. Birkbak, J. Palle, M. Østergaard, K. Spiers, J. Garrevoet, H. Birkedal

Bone is a complex hierarchical material adapted to withstand applied loads. It has essential
structural features ranging from the nanoscale to the macroscopic. The link between bone
structure and function, and especially the contribution of the nanoscale structural elements on the
macroscopic properties is however still poorly understood. The osteon is an essential building
block in human long bones and contributes to highly anisotropic mechanical properties. In this
motif, mineralized collagen fibrils are arranged in a twisted plywood structure surrounding a
Haversian canal (Fig. 1). It has been shown that the indentation modulus varies periodically with
the osteon lamellae and that this is positively correlated with the mineral content (1), but exactly
how the mineral phase contribute to the mechanical properties of bone remains unanswered.
Here, we have applied Diffraction Scattering Computed Tomography (DSCT) at Petra-III, beamline
P06 with sub-micron resolution to investigate how the nanocrystalline component varies
throughout the osteon. This experiment combines the capabilities of diffraction with those of
computed tomography to allow for reconstruction of a
diffractogram in each volume element within the sample(2). The
resulting >1.5 million diffractograms were Rietveld refined using
MultiRef(3) to obtain typical crystallographic parameters,
including unit cell parameters, profile parameters etc. This
revealed a periodic variation of the crystal properties from the
center of the osteon and out. In addition we observed altered
crystal properties surrounding the cellular network lying buried
within the bone matrix, thus providing insight into yet another
open question within bone research.

Key words: Bone microstructure, Osteon, Diffraction Scattering

Computed Tomography, Synchrotron Figure 1. Section of long bone
displaying osteons; cylindrical
motifs with concentric lamellae
[1] Gupta et al. 2006 J Mater Res 21, 1913-1921
surrounding a central (Haversian)
[2] Birkbak et al. 2015 Nanoscale 7, 18402-18410
canal.
[3] Frølich, Birkedal 2015 J Appl Cryst 48, 2019-2025