Program

International Symposium & School
on Crystal Growth Fundamentals"New Insights into Crystal Growth Fundamentals:
A tribute to Profs. Ichiro Sunagawa and Pieter Bennema”

November 3-7, 2018
Convention Hall of Hotel Sakan, Akiu, Sendai, Japan

Organizers
Katsuo Tsukamoto (chair): Tohoku Univ./Osaka Univ., JapanJim De Yoreo: PNNL, USA
Peter Vekilov (program): University of Houston, USA
Elias Vlieg: Radboud Univ., The Netherlands
Michihiko Nakamura (education): Tohoku Uni., Japan

Organizing Committee
Gen Sazaki (program), Koichi Kakimoto (internationals), Hitorshi Miura (secretary registration,
website), Andrew Putnis (education), Juanma García-Ruiz (education), Satoshi Uda (education),
Junpei Yamanaka (treasurer), Toru Ujihara (treasurer), Mihoko Maruyama (ceremony), Takeshi
Miyata (general), Masayuki Kawasaki (poster), Shigeya Naritsuka (poster report), Etsuro
Yokoyama (poster report), Yoshihisa Suzuki (publicity), Harutoshi Asakawa (publicity), Yuki
Kimura (secretary local), Ken Nagashima (registration)

3(Sat.)14:40
Taketoshi Hibiya
Keio University

Memory of Piet Bennema for the discussion of garnet
morphology on a boat

I met Prof. Bennema in Stuttgart, Germany, where the ICCG-7 was held. I presented a paper onmorphology control for liquid phase epitaxial growth of magneto-optic iron garnets. During theconference a boat excursion was held along the Marbach am Neckar. On boat Prof. Bennema
and I talked lots about morphology of garnets; at that time he was engaged in calculation for
periodic-bond-chain of crystals in particular for the garnet system and I was faced to difficultyin morphology control of garnets. I learned from him not only the latest scientific research result
but also his experience in Indonesia during the Second World War.

1

3(Sat.)16:40
Jim De Yoreo
Pacific Northwest Laboratory

Classical vs non-classical pathways of crystal nucleation andgrowthRecent observations have shown that crystallization occurs along a rich set of hierarchicalpathways involving species of higher order than simple monomers, ranging from multi-ion
clusters to dense liquid droplets to transient amorphous or crystalline particles. The extent towhich these pathways can be understood using well-known concepts of classical nucleation
theory or require alternative “non-classical” models is a matter of current debate. Here I use anumber of examples from in situ AFM and TEM studies of nucleation and growth to illustrate
the diversity of pathways seen during crystallization and provide a holistic picture of that relates
non-classical dynamics to classical concepts.

2

3(Sat.)17:20
Geun Woo Lee
Korea Research Institute of Standards and Science

Crystal nucleation and growth in a deep metastable liquids
using electrostatic levitation and dynamic diamond anvilcell
We develop a novel device, a combination of electrostatic levitation, and x-ray and Raman
scattering, so that we can achieve extremely high supersaturated solutions, and its atomic andmolecular structure and thermodynamics. Using this new device, here, we will demonstratethat a levitated KH2PO4 (KDP) aqueous solution shows two different nucleation paths with thedegree of supersaturation, while (NH4)H2PO4 (ADP) solution (a family materials with KDP) doesnot. Moreover, by measuring molecular structure and its evolution in the highly supersaturated
solution prior to nucleation, we find a solution-solution transition in short range order which
underlies the different nucleation path.

3

4(Sun.)8:00
Juan Manuel García-Ruiz
CSIC-University of Granada

Patterns on the rocks: An overview of mineral growth
patterns

Understanding howcrystals, their morphology and their texture are related to growth
conditions is the gate to revealingbygone geochemical environments when no other proxies areavailable. In this lecture I invite you to join me on a personal journey through rock patterns,
from those controlled by the mineral crystal structure, as those currently forming giant crystalsof gypsum, to patterns with non-crystallographic symmetry, as those controlled by interactionof transport and chemical precipitation leading to mineral self-organization.

44(Sun.)8:40
Teruki Sugiyama
National Chiao Tung University

Crystallization controlled by optical trapping

Optical trapping in solution increases solution concentration locally at laser focus, triggering
spatiotemporally-controlled crystallization. Ever since we firstly succeeded in demonstrating
optical trapping-induced crystallization of an amino acid in 2007, we have explored novel opticaltrapping-controlled phenomena such as crystal growth and polymorphism for amino acids andproteins. In this presentation, we will first make a brief introduction of the principle of opticaltrapping and then present these research results. In addition, recent results about chirality
control in chiral crystallization utilizing plasmonic optical trapping will be also presented.

5

4(Sun.)9:40
Koichi Kakimoto
Kyushu University

Numerical investigation and experimental validation of
crystal growth of semiconductors

This paper reports the synergy effect of both experimental results and numerical validation on
crystal growth of semiconductor crystals. The paper contains quantitative comparison between
experimentally obtained defect density and numerically calculated data in semiconductor
crystals. The paper also contains the results on interface shape and stress distribution in a
growing bulk crystal. The quantitative discussion will be discussed based on the experimental
and numerical results.

6

4(Sun.)10:40
Elias Vlieg
Radboud University

Structures of interfaces

The growth of crystals takes place at the interface with its growth medium and (nearly) always
atom by atom (or molecule by molecule). A complete understanding of crystal growth therefore
requires an atomic-scale knowledge of the processes and structure at the interface. At thegrowth interface, both the crystal and the growth medium will typically have a structure that isdifferent from the bulk. Assessing such interfaces, in particular when growing from a solution
or melt, is quite difficult, but a combination of techniques like AFM, computer simulations and
X-ray diffraction, has yielded significant insights.

7

4(Sun.)11:20
Takeshi Fukuma
Kanazawa University

Visualizing atomic-scale structures and dynamics at solidliquid interfaces by high-speed frequency modulation AFM

Atomic force microscopy (AFM) has been widely used for imaging nanoscale step flows during
crystal growth and dissolution. However, it has been difficult to visualize atomistic events at thestep edges. To overcome this limitation, we recently developed high-speed frequency
modulation atomic force microscopy (FM-AFM) and imaged atomistic events at the step edges
during the calcite dissolution. These images revealed the formation of Ca(OH)2 monolayer along
the step edges as an intermediate state of the dissolution. In this lecture, I will overview the
recent progress in the development of in-liquid FM-AFM and its applications to crystal growthstudies.

84(Sun.)14:00
Teruyasu Mizoguchi
University of Tokyo

Machine learning for atomic-resolution analysis of interface

Interface plays important roles for materials properties, such as mechanical strength, electric
conductivity, and crystal growth. Thus, the modeling of the interface structure is one of themost important subjects for the materials research. On the other hand, the modeling theinterface is usually difficult due to its geometrical freedoms. Here, we have applied machinelearning techniques to accelerate the interface structure determination. I will talk on our
method, virtual screening, kriging and transfer learning, for the interface structure searching,in my presentation.

9

4(Sun.)14:40
Qiu-Sheng Liu
Chinese Academy of Sciences

Solutal convection of liquid in alloy directional solidification
with porous dendrite mush

Alloy solidification commonly takes place with a cellular or dendritic microstructure, i.e., with aregion of intimately co-existing liquid and solid phase named as "the mushy layer". During alloy
solidiﬁcation, there always exists a mushy layer sandwiched between pure liquid and solid
phases. In this lecture, theoretical study of the onset of solutal convection during the directional
solidiﬁcation of Bridgman type on liquid Al-3.5wt%Li is presented. In the double-layered system
where the liquid layer on the top of mush is considered, the depth ratio and the porosity at theliquid-porous interface are both relevant with the pulling rate. A mode transition between thetwo modes of instability convection is also predicted to occur under the increase of pulling rate,
which varies the depth ratio together with the permeability of the porous layer.
10

4(Sun.)15:40
Toru Ujihara
Nagoya University

Machine learning for SiC crystal growth (modeling,
optimization and visualization)

In this study, we constructed prediction model of CFD result by using machine learningtechnique as follows: (1) we prepare 300 results of CFD simulations as training data for machinelearning and (2) we produce the prediction model on neural network. Figure 1 shows thesimulation result of supersaturation distribution and fluid velocity distribution and thepredicted result based on the prediction model. Surprisingly, both results are very similar toeach other. Moreover, the average calculation time of the simulation and that of the prediction
model are about 3000 s and 0.003 s, respectively. Using this prediction model, it is also possible
to decide an optimized condition11

4(Sun.)16:20
Noriko Akutsu
Osaka Electro-Communication University

Introduction to deep learning with a software Keras: A
guide for end-to-end users

Deep learning has led to remarkable achievements in recent years.
It offered better
performance on many problems. Deep learning also makes problem-solving much easier,because it automates feature engineering. By this automation, machine-learning workflows
are simplified from the multistage pipelines to a single end-to-end deep-learning model. In
addition, the rise of user-friendly libraries such as Keras is driven by TensorFlow which is atensor-manipulation framework for Python. In order to apply this new method to our own
problems, a guide of the software Python with Keras for end-to-end users is shown.

12

4(Sun.)17:20
Hiroaki Imai
Keio University

Formation of mesocrystal: classical and non-classical crystal
growthSophisticated architectures consisting of oriented small crystalline blocks are observed inbiological and biomimetic minerals. Recently, these hierarchical structures are categorized into
mesocrystal as intermediate between single crystals and polycrystals that are randomarrangements of small grains. Here, artificial formation processes of mesocrystals are discussed
on the basis of the growth mechanism. Various hierarchical crystalline architectures areconstructed through classical routes including nucleation and growth that are controlled byorganic agents. Several mesocrystals are also produced through nonclassical routes including
oriented attachment of specific nanoscale blocks.

13

5(Mon.)8:00
Hiroshi Ohmoto
Pen State University

New model for the condensation of minerals in the Solar
Nebula and the origin of Earth based on the meteorites
discovered in 3.46 Ga-old submarine basalts

Geochemists have estimated the bulk compositions of the early Solar System and of the Earthfrom the compositions of: (1) meteorites (e.g., CI chondrites) that have fallen on Earth during
the past ~300,000 yrs, and (2) the present-day Solar Winds. Yet, the possibility that the earlySolar System had significantly different composition than these materials has not beenquestioned. Based on the results of mineralogical, geochemical and geological investigations of
the recently discovered 3.46 Ga-old meteorite fragments in Australia, I will discuss a new modelfor the Earth formation.
14

5(Mon.)8:40
Noriaki Ozaki
Akita Prefectural University

Silica biomineralization in rice plants

Biogenic amorphous silica (biosilica) is widely found in diatoms, marine sponges, some higher
plants and bacteria. Biosilicas in diatom and sponge, are formed under mild condition andneutral pH using organic matrices (unique proteins and long-chain polyamines). Although rice
plants produce large quantity of biosilica in their leaves and rice hulls, the molecularmechanisms of silica biomineralization is still unclear. Here we report some preliminary resultson the characterization of several proteins, extracted from the biosilica of the rice plants (Oryza
sativa). As far as we know, this is the first report of protein identification existed within biosilicaof the rice plants.

15

5(Mon.)9:40
Chaorong Li
Zhejiang Sci-tech University

Morphology control and applications of Cu2O nanoparticles

Cu2O has many applications in photo-electronic areas. The morphology of Cu2O nanoparticles
plays important role in their property performance. For instance, different crystalline surface
shows different catalysis behavior, due to their different surface energy. In this talk, we will
shall how to obtain cubic, octahedral, truncated cubic and truncated octahedral morphologies
by some simple controlling ways during fabrication, and then investigated their properties andintroduce several applications of the fabricated Cu2O nanocrystals.

16

5(Mon.)10:20
An-Pang Tsai
Tohoku University

Growth of quasicrystals

Quasicrystals display diffraction patterns with symmetries forbidden in crystallography, andquasi-periodicity, have been found to be stable phases in several alloy systems. Thanks to theirstability, one can grow single grained quasicrystals with large scale. In this talk, we will firstmake a brief introduction to quasicrystals and describe the state of the art of structure foricosahedral quasicrystal. The morphologies of icosahedral quasicrystals are discussed in termsof atomic structures, surface structures and crystal growth mechanism.

17

5(Mon.)15:00
Michihiko Nakamura
Tohoku University

Magma crystallization and volcanic eruptions

In volcanic eruptions, crystallization of magmas is driven by decompression-induced degassing
rather than by cooling. Groundmass microlites record magma ascent rate from the magma
reservoir to the shallow conduit, which is a fundamental factor controlling eruption explosivity.
However, microlites do not record the explosive-effusive transitions in some eruptions, whensuch transitions are governed by the decrease of exsolved volatile pressure in the shallow
conduit. Instead, the difference in the slope of crystal size distributions (CSDs) down to 1 nm
among the eruption styles may be interpreted by considering the difference in magma
residence time and fragmentation pressure.

18

5(Mon.)15:40
Etsuro Yokoyama
Gakushuin University

Morphology, roughening and instability

This talk is focused on the stability of a growing interface and the relation between the stability
and interface structures, such as kinetic roughening and smooth interface. For example, agrowing ice disk in supercooled water has two distinguish instabilities, in which growth of theradius is controlled by transport of latent heat, on the other hand, disk thickening is governedby the generation and lateral motion of steps on the basal faces. The morphological instability
occurs at the edge of the basal face, while the instability of facet occurs on the basal face. We
discuss the difference between morphological instability and facet instability.

19

5(Mon.)16:40
Yuki Kimura
Hokkaido University

Application of liquid TEM to various crystallization

Transmission electron microscope (TEM) is a powerful tool to observe a material innanoscale. Unfortunately, however, there is some limitations on a sample. Particularly,
samples must be dry, because it is exposed to a vacuum environment in TEM. Therefore liquidsamples are not able to observe as is. Recent years, several techniques using MEMS liquid cell,graphene cell and ionic liquid have been developed to observe liquid samples. Here, I will
introduce several techniques and example results, such as nucleation and growth of several
nanoparticles including behaviors of defects, a concretion process and dissolution processes.

20

5(Mon.)17:20
Junpei Yamanaka
Nagoya City University

Self assembly of colloidal particles

Uniformly shaped colloidal particles dispersed in liquid media self assmble into ordered crystal
structures. We introduce crystallization in various colloidal systems, including hard spheresystems, charged colloid, and depletion attraction systems (colloid + polymer). In the hard
sphere colloids the crystallization is purely entropic. The charged colloids crystallize due toelectrostatic repulsion between the particles, while the driving force of the depletion system is
an attraction due to difference in osmotic pressures between those in bulk and in a gap of two
particles. We also report clustering of small number of colloidal particles, and further clusteringof the clusters.

21

6(Tue.)8:00
Mu WangNanjing University

The mechanism leading to the long range ordering in theinterfacial aggregation

Nucleation is an important step in crystallization, and many self-organized patterns are
mediated by the very unique spatial environment for nucleation process. Here we take someexamples to show the significance of concave-corner-mediated nucleation in both selforganized formation of long-range-ordering crystalline structures and in self-assembly of
metallic nano wire arrays.

22

6(Tue.)8:40
Xiang-Yang Liu
National University of Singapore

Kinetic and control of spider silk crystallization

To re-engineer the hierarchical structure of soft materials， ie. silk fibroin, and to functionalize
the materials can be achieved by controlling nucleation at the mesoscale. In this talk, I will cover
the principles and strategies of mesoscopic structural re-engineering and functionalization ofsilk fibroin materials based on Intra/inter molecular nucleation. This allows in the design andintegration of high-performance bio-integrated devices for future applications in consumer,
biomedical diagnosis, and human–machine interfaces.

23

6(Tue.)9:40
Tetsuo Okutsu
Gunma University

Light induced crystallization of proteins and organic
molecules

We discovered a phenomenon in which protein crystallization is induced by surface plasmon
resonance, and elucidated its mechanism. Protein molecules adsorb onto the surface of gold
nanoparticles with high density. Molecules present in gaps between gold nanoparticles aretrapped by the electric field of light and stay for a certain time. There another protein molecule
is carried in by diffusion and forms a cluster. In this state, when a covalent bond is formed byphotochemical reaction using quinone, a tetramer of protein is observed. Nucleation requires
time to gather certain molecules, and plotting nuclear appearance against light irradiation time
gave a relation indicating induction time.

24

6(Tue.)10:40
Satoshi Uda
Tohoku University

Growth of new congruent oxide crystals with extended
stoichiometric compositions

The new concept of stoichiometry is discussed. The unity of activity for all constituent elements
is essential to a material being stoichiometric since the unity of activity leads to zero mixing
term in chemical potentials. The activity of an element to be unity needs the standard-statechemical potential equal to the chemical potential itself and one degree of freedom is basicallyrequired for each of constituent elements. The degree of freedom is examined for each crystal
site by the subtraction of number of constraints from that of constituent elements. Based on
the new stoichiometry, we have developed MgO-doped LiNbO3 and LiTaO3 that issimultaneously congruent and stoichiometric.

25

6(Tue.)11:20
Hitoshi Miura
Nagoya City University

Fundamentals of step dynamics

Surfaces of polyhedral crystals may seem flat by naked eye, but they are not perfectly flat andtake some structures in atomistic scale. When the crystal grows, the growth units such as atoms
or molecules are incorporated into the surface structure. The incorporation kinetics determines
the rate of crystal growth. Therefore, you should learn the incorporation mechanism in orderto understand crystal growth. In my lecture, I will lecture how the growth units are incorporated
into the crystal lattice for beginners of crystal growth. You will find the fundamental process of
crystal growth -the step dynamics- and how the rate of crystal growth depends on the driving
force of crystallization.

26

6(Tue.)14:00
Masaru Tachibana
Yokohama City University

Perfection of protein crystals by X-ray diffraction

X-ray topography is a non-destructive technique for imaging microscopic structural defects innearly perfect crystals. It has been applied to a large variety of inorganic and organic materials
and undoubtedly has played a major role in the search of defect-free crystals for thesemiconductor industry. In my lecture, it is shown that X-ray topography can be a valuable toolin the study and understanding of protein crystal growth and diffraction properties. Recent
report on the first observation of dynamical diffraction in protein crystals, which has been
observed only in perfect crystals such as Si crystals, is also shown in the lecture.

27

6(Tue.)14:40
Matthias Konrad-Schmolke
University of Gothenburg

Reactive fluid fluxes through solid rocks – constraints onmechanisms and element transport

Reactive fluids are interacting with crystalline rocks at every depth in the Earth’s lithosphere.
This fluid-rock interaction induces mineral reactions with implications ranging from nutrienttransport for plants to element exchange between mantle and atmosphere in subduction zones.
Furthermore, fluid-rock interactions influence the rocks’ shear strength thus playing afundamental role in the earthquake cycle. I will present several examples from subduction zone
rocks that excellently preserve information about the mechanisms of fluid migration and fluidmediated mineral dissolution and re-precipitation reactions. Such knowledge is crucial for thequantification of global scale element fluxes, but also for the understanding of fluid migrationin subduction zones.
28

6(Tue.)15:40
Zhisen Zhang
Xiamen University

Ice nucleation in hydrogel matrix

Water freezing remains a perennial topic of great relevance to many important aspects of ourlives. One of unsolved puzzles of freezing is the question of how cooled of the idea pure water
can withstand before freezing to ice. Commonly, -40 °C is regarded as the homogeneous
nucleation temperature. However, previous work of our group has proved that water freezing
is affected by dust particles even at a temperature as low as -40 °C. Here we report a new findingof water freezing water in hydrogel, in which the dust particles were embedded by the gelation
process. And hence, the heterogeneous nucleation effect by the dust particles can be minimized.
The observed effective nucleation temperature of ice in the hydrogel is -50 °C, suggesting that,instead of -40 °C, the homogeneous nucleation temperature of pure water could be lower than
-50 °C.
29

6(Tue.)16:20
Gen Sazaki
Hokkaido University

The surface melting of ice crystals

We are studying thin water films, so called quasi-liquid layers (QLLs), that cover ice crystal
surfaces at subzero temperature. Using laser confocal microscopy combined with differential
interference contrast microscopy (LCM-DIM), we so far revealed that there exist two types of
QLLs with different morphologies: a droplet type and a thin-layer type. In the symposium, we
will show that the existence of such two types of QLLs can be explained by the transition of thewetting state of QLLs on ice surfaces. We found that such QLLs are kinetically formed as ametastable phase. We will also show the uptake of HCl in ice crystals: this triggers the ozone
depletion.

30

6(Tue.)17:20
Katsuo Tsukamoto
Tohoku University/Osaka University

Optical in-situ observation of crystal growth interfaces

Mineral surfaces reflect the history how fast and where the crystals grew because these areclosely related to the crystal growth mechanism. So as to understand the relationship, we havebeen using varieties of in-situ observations of crystal surface and the environments in various
environments at low temperature to high temperature as high as 2000 K. The molecular-scaleobservation of crystal surface has been realized by using various techniques, AFM, STM and also
phase-sensitive optical microscopy and interferometry. We show some examples how thegrowth history of minerals and crystals have been analyzed based on the knowledge of crystal
growth mechanism.

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