TGSW2016
Session 7: Green Innovation
19th September @ room 402
Energy Materials

Chair: Hideharu Niwa (UT)

13:30 - 14:00

Ching-Shun Ku and Di-Jing Huang (NSRRC, Taiwan)(invited)

Opportunities of Taiwan Photon Source for Energy Material Research

14:00 – 14:20 Venkatesha Rama Hathwar, Eiji Nishibori, Bo Iversen, Yutaka
Moritomo (UT)
Is the crystal structure of CH3NH3PbI3 so simple to understand?
14:20 – 14:50 Pirmin Ulmann (IMERYS Graphite & Carbon, Switzerland)(invited)

Carbon-based Negative Electrode Active Materials for Lithium-ion
Batteries –Past, Present and Trends towards the Future

14:50 – 15:10 break
Polymer Materials
15:10- 15:30

Chair: Yohei Yamamoto (UT)

Takaki Kanbara (UT)
Synthesis of fluorene-based conjugated polymers via direct arylation
polycondensation

15:30 – 16:00 Xike Gao (Shanghai Institute of Organic Chemistry, China)(invited)

Conjugated Diimides for Organic Optoelectronic Materials: Molecular
Design and Synthesis

16:00 – 16:30 Weishi Li (Shanghai Institute of Organic Chemistry, China)(invited)Poly(rod-coil) Polymeric Semiconductors: a new class of Organic
Optoelectronic Materials

18:00 – 20:00 Banquet

Opportunities of Taiwan Photon Source for Energy Material Research
Ching-Shun Ku and Di-Jing Huang
National Synchrotron Radiation Research Center (NSRRC), Hsinchu, TAIWAN
Recently the National Synchrotron Radiation Research Center (NSRRC) in Taiwan has successfully constructed a low-emittance 3 GeV synchrotron light source, the Taiwan Photon Source (TPS). The TPS witha circumference of 518 m is composed of 24 double-bend achromatic (DBA) cells connected by six 12-m
straight sections and eighteen 7-m straight sections. The natural emittance of the TPS is 1.6 nm．rad witha small dispersion in the straight sections. Figure 1 displays an aerial photograph of the NSRRC. The TPS
commissioning proceeded at a speedy pace, delivering its first synchrotron light in December 2014 andthe electron current in the storage ring reaching 100 mA in March 2015. In phase-I operation, the TPS
uses two sets of KEK-B type superconducting RF cavities to achieve an electron current of 500 mA in a
top-up injection mode.
Taking full advantage of the high-brilliance of TPS, the phase-I beamlines aim for the forefront of research to cover the diverse photon sciences in an energy range from soft to hard X-rays. These beamlines
are optimized for protein micro-crystallography, low-energy excitations of novel materials with atomic
specificity, spectroscopy and diffraction on the submicron and nanometer scales, scattering of coherent Xrays, and scanning nanoprobe studies that will resolve structures in a spatial resolution of tens nm. Currently four of the TPS phase-I beamlines are available to users; other three beamlines are scheduled todeliver photons in 2017.
In this talk, we will present the specifications and commissioning results of the TPS phase-I beamlines
for energy material research. In particular, we will discuss the of opportunities of using high-resolution Xray powder diffraction, X-ray nanodiffraction and coherent diffraction including ptychography, followedby an overview of future beamline plan.

Figure 1: An aerial photographof the NSRRC. This photographshows the recently completed
TPS and the 21-year-old Taiwan Light Source (TLS). The
proposal of the TPS project was
prepared in 2004. The civil construction of the TPS began in
February 2010, and was completed in December 2013. The
assembly of main accelerator
parts was completed in 2014.
The TPS project came to realization after ten years of efforts.

Is the crystal structure of CH3NH3PbI3 so simple to understand?
Venkatesha R. Hathwar,a Eiji Nishibori,a Bo B. Iversen,b Yutaka Moritomoa
aDivision of Physics, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki,305-8571, Japan.
bCenter for Materials Crystallography and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-

8000 Aarhus C, Denmark.

The hybrid inorganic−organic perovskite, CH3NH3PbI3 has become very promising
candidate for photovoltaic applications due to its high solar cell efficiency, evenexceeding 20%.1 The possibility of easy processing and solution based low cost synthesis
make it an attractive alternative to silicon based devices. Beside these continuous effort
on device improvements, an ambiguity about the crystal structure of tetragonal phase of
CH3NH3PbI3 is still not clear. The tetragonal crystal structure is reported in both polarand non-polar space groups,2 where respective claims were further supported by P-E loop
measurements and SHG efficiency. Recently, a piezoelectric force microscopy (PFM)
experiments show ferroelectric nano-domains in CH3NH3PbI3 thin films.3 In order toresolve the crystal structure contradictions, we have collected high resolution synchrotron
X-ray data at SPring-8 on single crystals (< 50 µm3) and the crystal structures are solvedin both polar and non-polar space groups. Measured synchrotron X-ray data and obtained
crystallographic results indicate a non-polar crystal structure for CH3NH3PbI3, which
seems to be preferable around room temperature with a coexistence of inversion twinningof micro-domains in the crystal. In my presentation, I will discuss our results in thecontext of sample size, quality of X-ray data and observation of twinning.
Refrences:
1. (a) M. A. Green, A. Ho-Baillie and H. J. Snaith, Nat. Photon. 2014, 8, 506-514.
(b) http://www.nrel.gov/ncpv/images/efficiency_chart.jpg
2 (a) C. C. Stoumpos, C. D. Malliakas and M. G. Kanatzidis, Inorg. Chem. 2013, 52, 9019-9038. (b) Y. Y.
Dang, et. al. CrystEngComm 2015, 17, 665-670. (c) Y. X. Ren et. al. Cryst. Growth Des. 2016 16, 29452951. (d) G. Sharada, P. et. al. J. Phys. Chem. Lett. 2016, 7, 2412-2419.
3. (a) H. S. Kim et. al. J. Phys. Chem. Lett. 2015, 6, 1729-1735. (b) M. Coll et. al. J. Phys. Chem. Lett.
2015, 6, 1408-1413.

Carbon-Based Negative Electrode Active Materials for Lithium-Ion
Batteries − Past, Present and Trends towards the Future
Pirmin A. Ulmann
IMERYS Graphite & Carbon / ulmann.net
Starting with a comparison of electrochemical characteristics exhibited by different
types of carbon that have historically been used as negative electrode materials inlithium-ion batteries (coke, hard & soft carbon, synthetic & natural graphite),1 recent
large format pouch cell results obtained based on a hydrophilic graphite active material
and water-processed electrodes will be presented (see Figure).2 Examples of Si, Sn andalloy-based active materials which are typically used in combination with conductive
carbons will be discussed as well.
Finally, some general considerations will be made as to how ‘frictions’ that slow down
development efforts made by lithium-ion battery researchers could potentially be

reduced by the use of ‘open innovation’3 and ‘open-source’4 concepts.
References:(1)a) Nishi, Y. Chem. Rec. 2001, 1, 405; b) Yoshino, A. Angew. Chem. Int. Ed.
2012,
51,
5798.
(2)
Kvasha, A.; Urdampilleta, I.; de Meatza, I.; Colombo, R.; Ulmann, P. A.; Gulas,M.; Gutiérrez, C.; Bengeoechea, M; Blázquez; Miguel, O.; Grande, H.-J. ECSTrans.
2016,
submitted.
(3)
Chesbrough, H. Open Innovation; Harvard Business Review Press: Cambridge,
2005.
(4)
Raymond, E. S. The Cathedral & the Bazaar; O’Reilly Media: Boston, 2008.

Synthesis of fluorene-based conjugated polymers via direct arylation
polycondensation
Takaki Kanbara
Tsukuba Research Center for Interdisciplinary Materials Science (TIMS),
Graduate School of Pure and Applied Sciences, University of Tsukuba,
Catalytic direct arylation of aromatic compounds via cleavage of C-H bonds ofaromatic compounds and the dehydrohalogenative cross-coupling reaction has attracted
increasing attention as a simple synthetic method because it allows for elimination of theuse of organometallic reagents and reducing undesired waste originating from theorganometallic reagents. Recently, several groups have attempted to utilize this reactionin polycondensation for the synthesis of π-conjugated polymers. We have envisioned
development of the direct arylation polycondensation as a general and reliable method;
expansion of this synthetic protocol allows for the polycondensation of various aromatic
monomers. This atom- and step-economical protocol also lends itself to practicalapplication for fabrication of organic devises such as organic photovoltaics cells, field
effect transistors, and light emitting diodes.
Firstly, we have focused on exploring the targeting aromatic monomers including
the highly active C-H bond for the metal-catalyzed functionalization. On the other hand,with respect to the coupling partner, 2,7-dibromo-9,9-dialkylfluorene is an appropriatemonomer because it possesses good reactivity toward the direct arylation
polycondensation and high selectivity against side reaction.
Consequently, theappropriate choices of monomers and detailed optimization of the reaction conditions
provided a variety of fluorene-based π-conjugated polymers via the direct arylation
polycondensation.
In this presentation, our recent activities on the facile synthetic protocol will also
be presented.
Conventional method:n X Ar X + n M Ar' M

cat. [MLn]

Ar

Ar'

n

e.g., SnBu3Br

e.g., M- = Bu 3 BrSn-

Direct arylationcat. [MLn]n X Ar X + n H Ar' H
use of nonpreactivated monomers+ 2n MX

Ar

Ar'

n

+ 2n HX
easily removableConjugated Diimides for Organic Optoelectronic Materials: Molecular
Design and Synthesis
Xike Gao
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic
Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, China
Organic thin film transistors (OTFTs) and organic photovoltaics (OPVs) have attracted
ever increasing attention due to their applications in low-cost, large-area, and flexible
semiconducting devices. In the field of OTFTs and OPVs, the n-type(electron-transporting) organic semiconductors (OSCs) are outmatched by theirburgeoning p-type (hole-transporting) counterparts [1]. Excellent n-type OSCs arehighly necessary for constructing low-power-consumption organic complementary
circuits and bulk-heterojunction OPVs with the p-type ones. In the past six years, wedeveloped a class of core-expanded naphthalene diimides (NDI), named as
NDI-DTYM2, and their-based solution-processed n-channel OTFTs showed highelectron mobility (0.1−3.5 cm2 V−1 s−1) and excellent device stability in air [2]. In
addition, NDI fused with two 2-(1,3-dithiol-2-ylidene)acetonitrile moieties(NDI-DTYA2), a novel strong electron-deficient monomer, was designed andsynthesized to develop n-type polymers [3]. Recently, we created a novel class ofazulene-based conjugated diimides, 2,2′-biazulene-1,1′,3,3′-tetracarboxylic diimides(BAzDIs), which have unique photophysical properties and are promising for organic
optoelectronic materials [4].
References:[1] (a) C. R. Newman, C. D. Frisbie, D. A. da Silva Filho, J.-L. Brédas, P. C. Ewbank, K.
R. Mann, Chem. Mater., 2004, 16, 4436.; (b) X. Gao, Y. Hu, J. Mater. Chem. C., 2014,
2, 3099.; (c) Y. Lin, X. Zhan. Mater. Horiz., 2014, 1, 470.
[2] (a) X. Gao, C. Di, Y. Hu, X. Yang, H. Fan, F. Zhang, Y. Liu, H. Li, D. Zhu. J. Am. Chem.
Soc. 2010, 132, 3697.; (b) F. Zhang, Y. Hu, T. Schuettfort, C. Di, X. Gao, C. R. McNeill,
L. Thomsen, S. C. B. Mannsfeld, W. Yuan, H. Sirringhaus, D. Zhu. J. Am. Chem. Soc.
2013, 135, 2338.
[3] Z. Zhao, F. Zhang, Y. Hu, Z. Wang, B. Leng, X. Gao, C. Di, D. Zhu, ACS Macro Lett.
2014, 3, 1174.
[4] H. S. Xin, C. W. Ge, X. D. Yang, H. L. Gao, X. C. Yang, X. K. Gao. Chem. Sci. 2016,
DOI: 10.1039/c6sc02514h.

Poly(rod-coil) Polymeric Semiconductors: a new class ofOrganic Optoelectronic Materials
Wei-Shi Li
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
E-mail: liws@mail.sioc.ac.cn
Owing to their features of light weight, flexibility, low cost, solution-processibility, and adaptabilty forlarge area device fabrication, organic electronics has attacted considerable attention from both scientificand industrial communities. With tremendous effort in material innovation in the past decades, a huge
number of organic semiconductors have been developed, some of which showed high performance inphotovoltaics, light-emitting diodes, and/or field-effect transistors. Although their chemical structures arein a wide diversity, most of them can be categorized into two classes: conjugated polymers and small
molecular compounds. In general, conjugated polymers have a good film-formation potential due to theirpolymeric nature. Moreover, conjugated polymers possess one-dimensional extended -conjugatedbackbones, which are favorable to transduction of charge carriers and excitons and benefit theiroptoelectronic performances. However, they are always the mixtures of homologues having different
lengths of conjugated backbones. It has been well documented that molecular weight and its polydispersity
have significant influence on optoelectronic performance of conjugated polymers. This causes a severe
problem for their real use: poor batch reproducibility. In contrary, small molecular semiconductors do nothave such batch-dependent problem because of their definite chemical structures. However, for achieving
efficient light absorption and good charge transportation among molecules, this kind of materials usually
have a large and rigid -conjugated core. As a result, they tend to aggregate or crystallize in film state andare hard to form a well-qualified homogenous film, particularly in a large size.
Recently, we proposed a new type of organic semiconductors, which is a kind of poly(rod-coil) polymers alternatively composed of definite conjugated and non-conjugated segments (Fig. 1).1-3 The conjugated segments are optoelectronically active and have a fixed chemical structure, like small molecular
semiconductors. Thus, it could be expected to have less molecular weight-dependent optoelectronic
properties. Moreover, their polymeric nature may endow them a good film formation behavior. In thispresentation, I will report several examples of this type of organic semiconductors and their applications inorganic solar cells and field-effect transistors.

Fig. 1 Schematic representation of proposed poly(rod-coil) organic semiconductors
Reference[1] H.-J. Li, J.-T. Wang, C.-Y. Mei, W.-S. Li, Chem. Commun. 2014, 50, 7720‒7722.
[2] W. Shao, L. Liang, X. Xiang, H.-J. Li, F.-G. Zhao, W.-S. Li, Chin. J. Chem. 2015, 33, 847‒851.
[3] X. Xiang, W. Shao, L. Liang, X.-Q. Chen, F.-G. Zhao, Z. Lu, W. Wang, J. Li, W.-S. Li, RSC Adv.
2016, 6, 23300‒23309.