Symposium Organizers
Feng Bai, Henan University
Ying-Bing Jiang, Angstrom Thin Film Technologies LLC
Binsong Li, Tsinghua Innovation Center in Dongguan
Dong Qin, Georgia Institute of Technology
Symposium Support
Dongguan-RITS Innovation Center
Henan University
ED5.1: Photocatalysis I
Session Chairs
Tuesday AM, April 18, 2017
PCC North, 100 Level, Room 129 A
10:30 AM - *ED5.1.01
Interfacial Self-Assembly of Hierarchically Structured Nanoparticles with Photocatalytic Activity
Hongyou Fan 1 2
1 , Sandia National Laboratories, Albuquerque, New Mexico, United States, 2 , University of New Mexico, Albuquerque, New Mexico, United States
Show Abstract
Design and engineering of the size, shape, and chemistry of photoactive building blocks enable the fabrication of functional nanoparticles for applications in light harvesting, photocatalytic synthesis, water splitting, phototherapy, and photodegradation. Here, we report the synthesis of such nanoparticles through a surfactant-assisted interfacial self-assembly process using optically active porphyrin as a functional building block. The self-assembly process relies on specific interactions such as π–π stacking and ligand coordination between individual porphyrin building blocks. Depending on the kinetic conditions, resulting structures exhibit well-defined one- to three-dimensional morphologies such as nanowires, nanooctahedra, and hierarchically ordered internal architectures. At the molecular level, porphyrins with well-defined size and chemistry possess unique optical and photocatalytic properties for potential synthesis of metallic structures. On the nanoscale, controlled assembly of macrocyclic monomers leads to formation of ordered nanostructures with precisely defined size, shape, and spatial monomer arrangement so as to facilitate intermolecular mass and energy transfer or delocalization for photocatalysis. Due to the hierarchical ordering of the porphyrins, the nanoparticles exhibit collective optical properties resulted from coupling of molecular porphyrins and photocatalytic activities such as photodegradation of methyl orange (MO) pollutants and hydrogen production. The capability of exerting rational control over dimension and morphology provides new opportunities for applications in sensing, nanoelectronics, and photocatalysis.
Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.
11:00 AM - *ED5.1.02
Effects of Nano-Scale Surface Modifications on Photoelectrochemical Solar Fuel Production
Tsutomu Minegishi 1 2 , Kazunari Domen 1
1 Department of Chemical System Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan, 2 PRESTO, JST, Bunkyo-ku, Tokyo, Japan
Show AbstractSunlight driven fuel production is the key technology for the construction of sustainable energy society. Hydrogen has been regarded as a promising fuel derived from only water and renewable energy, and can be utilized in devices such as fuel cells and combustion engines. On the other hand, investigations about the hydrogen carriers such as ammonia and methylcyclohexane (MCH) also have arisen as one of the most important research issues.
Photocatalytic and photoelectrochemical (PEC) reactions are the promising way to produce fuels such as hydrogen and/or hydrogen carrier directly utilizing solar energy, and development of photocatalytic materials and construction of reaction sites are of crucial for these techniques. BaTaO2N (BTON) is one of the attractive photocatalytic materials owing to the relatively long absorption edge of <660 nm and a preferable band structure for water splitting. BTON photoanode prepared by particle transfer method shows relatively large photocurrent and stable water oxidation. [1] A solid solution of ZnSe and CuIn0.7Ga0.3Se2 (CIGS) with composition of (ZnSe)0.85(CIGS)0.15 is the recently reported promising candidate for photocathode because of a preferable absorption edge of ~900 nm with an outstanding onset potential of cathodic photocurrent, 0.9 VRHE.[2]
In the present study, PEC properties of surface modified particulate BTON photoanode and (ZnSe)0.85(CIGS)0.15 thin film photocathode on overall water splitting and/or overall MCH production were investigated in detail. BTON based photoanode sequentially modified with Co-species and Ir-species showed enhanced photocurrent contributing oxygen evolution. The improved PEC properties are due to both the enhanced charge separation by Co-species and high oxygen evolution activity of Ir-species. PEC hydrogen evolution reaction from water over (ZnSe)0.85(CIGS)0.15 based photocathode is clearly enhanced by introduction of multilayer structure. A surface modification with Pt and CdS enhanced both photocurrent value and an onset potential because of a modulated band diagram at solid-liquid interface and enhanced hydrogen evolution reaction. Furthermore, introduction of bilayer structure composed of In-rich and Ga-rich layer into the (ZnSe)0.85(CIGS)0.15 layer largely increased cathodic photocurrent under simulated sunlight. A cross-sectional electron beam-induced current (EBIC) mapping analysis clarified that the enhancement of the photocurrent is because of improved structural properties rather than of enhanced charge separation by varied band diagram.
[1] K. Ueda, T. Minegishi, J. Clune, M. Nakabayashi, T. Hisatomi, H. Nishiyama, M. Katayama, N. Shibata, J. Kubota, T. Yamada, and K. Domen, J. Am. Chem. Soc. 2015, 137, 2227−2230.
[2] H. Kaneko, T. Minegishi, M. Nakabayashi, N. Shibata, Y. Kuang, T. Yamada, and K. Domen, Adv. Funct. Mater. 2016, 26, 4570–4577.
11:30 AM - ED5.1.03
Ferroelectric Field Tuned Photoelectrochemical Water Splitting Using Graphene as Electrode
Xiaobo Chen 1 2 , Matthew Starr 1 , Yanhao Yu 1 , Jihye Bong 3 , Zhenqiang Ma 3 , Yong Qin 2 , Xudong Wang 1
1 Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, Wisconsin, United States, 2 School of Physical Science and Technology, Lanzhou University, Lanzhou, Gansu, China, 3 Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin, United States
Show AbstractPhotoelectrochemical (PEC) water splitting is a promising strategy for converting solar energy to chemical fuels. To accomplish efficient fuel production, the photoelectrode desirably need following characteristics: broad-band light absorption, rapid electron-hole separation and effective Faradic surface reaction. Prevailing strategies to promote the charge separation includes reducing the crystal size to the scale of the hole diffusion length; and increasing the carrier conductivity by morphology and crystallography control. Nevertheless, both strategies are restricted by the limit of synthesis procedures. Recently, permanent electric polarization (e.g., piezoelectric and ferroelectric potentials) were discovered to be an effective approach to tune the charge separation property of PEC electrodes beyond the limitation of structure and chemistry optimizations, known as piezotronics. The main challenge of this technology is how to sufficiently delivering free charges to the out circuit without screening out the electric polarizations. The trade-off between the charge collection and the electric polarization severely constrains the materials selection, film thickness and structural design of polarization-enhanced PEC electrodes, which synergistically jeopardizes the piezotronic enhancement.
Graphene is a two dimensional carbon material with unique electric and mechanical properties. The semimetal characteristic of graphene endows it a moderate free electron density, which is settled between metals and semiconductors. This unique property makes graphene a promising electrode selection for balancing the charge collecting and piezopotential screening in a piezotronic PEC system. Here, we demonstrated a ferroelectric polarization-enhanced PEC performance of TiO2 photoanode with graphene as the charge collection electrode sandwiched between the photoactive TiO2 and ferroelectric single crystalline lead magnesium niobate-lead titanate (PMN-PT). Both theoretical and experimental results show that the ferroelectric field is able to penetrate through graphene and further altering the depletion width and amplitude of photoactive TiO2. As a consequence, the photocurrent density and onset potential of TiO2 electrodes can be manipulated by controlling the polarization condition of PMNPT. By poling PMNPT with forward bias, the light current density increased from 0.08 mA/cm2 to 0.12 mA/cm2 at potential of 0 V vs. Ag/AgCl, and the onset potential decreased from -0.82 to -0.91 V. Reversely, backward bias induced a reduction of photocurrent density from 0.08 mA/cm2 to 0.06 mA/cm2 at potential of 0 V vs. Ag/AgCl, and an increase of onset potential from -0.82 to -0.74 V versus RHE. This study suggests graphene is a promising electrode material for piezotornic-enhanced PEC cells for its good conductivity and low charge density.
11:45 AM - ED5.1.04
Twin Defects Control the Shape of Ternary Silver Halide Nanocrystals for Photocatalytic Reactions
Bo Yin 1 2 , Xing Huang 3 , Rohan Mishra 4 1
1 Institute of Material Science and Engineering, Washington University in St. Louis, St. Louis, Missouri, United States, 2 Chemistry, Washington University in St. Louis, St. Louis, Missouri, United States, 3 Department of Biomedical Engineering, Washington University in St. Louis, St. Louis, Missouri, United States, 4 Department of Mechanical Engineering and Materials Science, Washington University in St. Louis, St. Louis, Missouri, United States
Show AbstractSilver halide particles with small clusters of reduced silver metal on their surface are active photocatalysts for both the degradation of organic molecules and the reduction of carbon dioxide to produce methanol and ethanol. We demonstrate that the anion composition of ternary silver bromoiodide, AgBr1-xIx, nanocrystals determines their shape through the introduction of twin defects as the nanocrystals are made more iodide-rich. AgBr1-xIx nanocrystals grow as single-phase, solid solutions with the rock salt crystal structure for anions compositions ranging from 0 ≤ x < 0.38. With increasing iodide content the morphology of the nanocrystals evolves from cubic to truncated cubic to hexagonal prismatic. Structural characterization indicates the cubic nanocrystals are bound by {100} facets whereas the hexagonal prismatic nanocrystals possess {111} facets as their top and bottom surface. Our observations are consistent with a growth model in which the presence of multiple twin defects parallel to a {111} surface enhances lateral growth of the side facets, which changes the nanocrystal shape. Using these ternary silver bromoiodide nanocrystals of different controlled morphologies, we are able to study the facet-dependence of photocatalytic reactions, such as CO2 reduction.
ED5.2: Nanocrystal I
Session Chairs
Tuesday PM, April 18, 2017
PCC North, 100 Level, Room 129 A
1:30 PM - *ED5.2.01
Gold Nanocages as Photothermal Transducers for Controlled Release and Sensing Applications
Younan Xia 1
1 , Georgia Institute of Technology, Atlanta, Georgia, United States
Show AbstractGold nanocages are hollow nanostructures with ultrathin (<2 nm) and porous walls. They have strong, highly tunable optical absorption in the visible and near-infrared regions, making them excellent photothermal transducers for a range of applications, including controlled release for drug delivery and optical sensing for detection and actuation. In this talk, I will start with a brief update on the recent progress in synthesis, including the preparation of gold nanocages as small as 15 nm in size, together with well-defined pores at the corner sites. I will then illustrate how gold nanocages can be integrated with other functional materials such as smart polymer, phase-change materials, and pyroelectric polymers for an array of technologically important applications.
2:00 PM - *ED5.2.02
Nanoscale Optical Interactions in Precise Assemblies
Paul Weiss 1
1 CNSI, Chemistry & Biochemistry, Materials Science & Engineering, University of California, Los Angeles, Los Angeles, California, United States
Show AbstractWe use molecular design, tailored syntheses, intermolecular interactions, and selective chemistry to direct molecules into desired positions to create nanostructures with controlled environments and dimensionality, to connect functional molecules to the outside world, and to serve as test structures for measuring single or bundled molecules and assemblies. We have developed and applied new multimodal nanoscale analysis tools based on the scanning tunneling microscope (STM) to measure structure, function, and spectra simultaneously. We are particularly interested in the interactions of photons with precisely assembled structures. The measured results of photoexcitation include photoconductivity and regioselective reaction. We apply this method to optimize molecules and materials for energy conversion and storage. Related imaging spectroscopies we have developed give access to the cooperative action of assembled molecular motors and the identification and orientations of parts of molecules such as amyloid-forming oligopeptides without averaging and without the need to crystallize the biomolecular assemblies. Concepts from sparsity and compressive sensing are developed and applied to guide efficient data acquisition and to accelerate data analysis and information assembly.
2:30 PM - ED5.2.03
Permanent Excimer Superstructures by Supramolecular Networking of Metal Quantum Clusters
Sergio Brovelli 1 , Angelo Monguzzi 1 , Beatriz Gonzalez 1 , Francesco Meinardi 1
1 , University of Milano Bicocca, Milano Italy
Show AbstractMetal quantum clusters are an important class of functional nanomaterials with growing applicative potential as size-tunable biocompatible luminescent probes for molecular theranostics and optoelectronic technologies. Here, we demonstrate for the first time that the optical properties of gold clusters (Au8), and in particular the energy separation between the emission and absorption spectra (Stokes shift), can be tuned by control of the inter-particle distance imposed by the capping ligands leading to the formation of inter-cluster excimers. Based on this newfound motif, we demonstrate a strategy for overcoming the intrinsic limitation to the use of molecular excimers in single-particle applications, that is, their nearly zero collisional formation probability in ultra-diluted solutions. To this aim, we use Au8 clusters as building blocks for fabricating permanent excimer-like colloidal superstructures (Au8-pX) held together by a network of hydrogen bonds between the capping ligands. In the ground state, unexcited clusters behave as individual photophysical entities, whilst optical excitation results in the formation of inter-cluster excimers featuring long-lived Stokes-shifted luminescence with no corresponding excitation transition. The obtained supramolecular architectures effectively represent a new aggregation state of matter conveying the photophysics of excimers into self standing individual particles that find their natural application as non-resonant emitters in cellular imaging and integrated photonic nanotechnologies. Importantly, in vitro confocal imaging experiments reveal the strong ability of Au8-pXs in scavenging cytotoxic reactive oxygen species responsible of premature cellular death, thereby further enhancing their potential for bio-medical applications.
Reference
Santiago-Gonzalez, B., Monguzzi, A., Azpiroz, J. M., Prato, M., Erratico, S., Campione, M., Lorenzi, R., Pedrini, J., Santambrogio, C., Torrente, Y., De Angelis, F., Meinardi, F. & Brovelli, S. Permanent excimer superstructures by supramolecular networking of metal quantum clusters. Science 353, 571-575 (2016).
2:45 PM - ED5.2.04
ALD-Grown Secondary Electron Emission Layer Studies for Microchannel Plates for Photodetection
Omkar Shende 1 2 , Anil Mane 1 , Jeffrey Elam 1
1 , Argonne National Laboratory, Lemont, Illinois, United States, 2 , Princeton University, Princeton, New Jersey, United States
Show AbstractRecent developments in the fabrication processes for microchannel plates (MCPs) using thin film functionalization methods, especially atomic layer deposition (ALD), allow precise and separate control over both resistive and electronic, namely secondary electron emission (SEE), properties of an MCP. By controlling the SEE material, thickness, and microstructure, it is possible to enhance the MCP’s SEE characteristics. These high gain MCPs can be used as electron multipliers in a variety of applications, including photodetectors, sensors, ToF mass spectrometers, in medical and scientific imaging, or any application where signal amplification is valued.
In particular, chemistries involving the oxides of magnesium and aluminum show promising results, yielding high gain values at coated thicknesses as low as 5-15 nm. We have assembled a high-vacuum-based MCP test setup to measure material parameters, including gain uniformity across samples via phosphor imaging on very short time scales (2 – 3 hrs). A systematic study of SEE layer thickness versus gain was performed using this newly assembled MCP test setup. Gain values on the order of 103 – 105 were observed and were shown to increase with secondary electron emission layer thickness, until a saturation point was reached for both Al2O3 and MgO coatings. Here, we present this behavior’s effects on MCP gain as a function of the thickness of precise ALD-grown SEE layer thickness.
3:30 PM - *ED5.2.05
Nanostructured Conjugated Polyelectrolyte Films—Properties and Applications
Kirk Schanze 1
1 , University of Texas, San Antonio, San Antonio, Texas, United States
Show AbstractConjugated polyelectrolytes (CPEs) are polymers that feature a pi-conjugated backbone that is functionalized with ionic charged units. These polymers feature the opto-electronic functionality characteristic of the conjugated backbone, with solubility in water. In addition, CPEs are polymer amphiphiles, and as such they undergo self-assembly to form nanostructured polyelectrolyte multilayer films at interfaces, and spontaneous self-assembly into nanoscale aggregates in aqueous solution. The talk will overview work which has characterized the structure and properties of the nanoscale CPE assemblies, and describe their application in hybrid solar cells and in light activated antimicrobials.
References:
Corbitt, T. S. et al. “Conjugated Polyelectrolyte Capsules: Light-Activated Anti-microbial Micro ‘Roach Motels’ “, ACS Appl. Mater. & Interfaces 2009, 1, 48-52, DOI: 10.1021/am800096q.
Fang, Z. et al. “Low Bandgap Donor-Acceptor Conjugated Polymer Sensitizers for Dye-Sensitized Solar Cells”, J. Am. Chem. Soc. 2011, 133, 3063-3069, DOI: 10.1021/ja109926k.
Parthasarathy, A. et al. “Conjugated Polyelectrolytes with Imidazolium Solubilizing Groups. Properties and Application to Photodynamic Inactivation of Bacteria”, ACS Appl. Mater. Interfac. 2015, 7, 28027-28034, DOI: 10.1021/acsami.5b02771.
4:00 PM - *ED5.2.06
Advanced Near-Infrared Fluorescence In Vivo Imaging—Seeing is Believing
Qiangbin Wang 1
1 , Chinese Academy of Sciences, Jiangsu China
Show AbstractFluorescent imaging in the second near-infrared window (NIR-II, 1.0~1.4 μm) is appealing in in vivo imaging due to minimal autofluorescence and negligible tissue scattering in this region, affording maximal penetration depth for deep tissue imaging with high feature fidelity. Herein, for the first time, we reported a new type of NIR-II QDs-Ag2S QDs and executed a series of in vivo imaging studies by using Ag2S QDs. The results show that, by using Ag2S QDs, the tissue penetration length can reach 1.5 cm, and the spatial and temporal resolution of the in vivo imaging can down to 25 µm and 50 ms, respectively, which are improved several to dozens of times in comparison with those using conventional fluorescence nanoprobes in the visible and the first near-infrared window (650-900 nm), facilitating in situ, real-time visualization of the biological events in vivo. With the advanced NIR-II fluorescence of Ag2S QDs, high signal to noise ratio imaging of tumor growth and angiogenesis, imaging-guided targeting drug-delivery and therapeutics, imaging-guided precision surgery of glioma, and stem cell tracking and regeneration in vivo, etc, have been achieved.
References
(1) Du, Y.; Wang, Q.; etc. J. Am. Chem. Soc. 2010, 132, 1470- 1471.
(2) Zhang, Y.; Wang, Q.; etc. ACS Nano 2012, 6, 3695-3702.
(3) Hong, G.; Wang, Q.; etc. Angew. Chem. Int. Ed. 2012, 51, 9818-9821.
(4) Li, C.; Wang, Q.; etc. Biomaterials 2014, 35, 393-400.
(5) Chen, G.; Wang, Q.; etc. Adv. Funct. Mater. 2014, 24, 2481- 2488.
(6) Chen, G.; Wang, Q.; etc. Biomaterials. 2015, 53, 265-273.
(7) Song, C.; Wang, Q.; etc. Adv. Funct. Mater. 2016, 26, 4192-4200.
4:30 PM - ED5.2.07
Phenoxazone-Based Pigments Isolated from Cephalopods Enhance Light Scattering in Bio-Derived Nanostructured Materials
Sean Dinneen 2 , Margaret Greenslade 2 , Leila Deravi 1
2 , University of New Hampshire, Durham, New Hampshire, United States, 1 , Northeastern University, Boston, Massachusetts, United States
Show AbstractCephalopods are arguably the most sophisticated, phototonic marine animals, as they possess the ability to rapidly adapt their dermal color and texture to their surroundings using both structural and pigmented coloration. While it is known that their pigmented chromatophore organs facilitate this process, the role of the pigments themselves in potentiating color change is not well understood. We hypothesize that the pigments, which are localized within nanostructured granules in the chromatophore, contribute to the scattering of light within the dermal tissue to enhance the color displayed during actuation. To test this, we first extracted the phenoxazone-based pigments from the chromatophore organ. We next extrapolated their complex refractive index (RI) from experimentally determined real and approximated imaginary portions of the RI and found that they possess uniquely high values (~1.99). Mie theory was used to calculate the absorbance and scattering cross-sections (cm2/particle) of the pigments across a broad diameter range at λ = 589 nm, where we observed that the pigments were more likely to scatter attenuated light than absorb it at particle sizes greater than 200 nm. These results are used inform the design of bio-inspired flexible displays built to efficiently absorb, scatter, and reflect all wavelengths of light using pre-packaged photonic nanoparticles.
4:45 PM - ED5.2.08
Energetic Alignment and Charge Transfer Excitation in Nanoassembly of Qyantum Dot and Metalorganic Dye
Svetlana Kilina 1
1 , North Dakota State University, Fargo, North Dakota, United States
Show AbstractRecent studies show organic or inorganic dyes retain as efficient hole mediators to quantum dots (QDs). Although the mechanism is yet to be determined, there exists an inclination in science and engineering communities to interpret the experimental charge transfer based on the energetic alignment between QD and dye. Here, we use the density functional method to simulate Cd33Se33 QD/tris(2,2’-bipyridine)Me(II) dye nanocrystal composite with different metal ion, Me=Cd, Cr, Fe, Os and Ru. Our results show: (1) the highest occupied molecular orbital (HOMO) energy level of dye is deep inside the valence band (VB) of QD; (2) increasing the electronegativity of metal ion reduces the energy separation between HOMO of dye and VB edge, on the contrary, the energy separation between LUMO of dye and CB edge is increased; (3) A substitution of Ru(II) ion with Cr(II) or Os(II) ion brings the dye states closer to the VB edge due to a smaller metal-ligand interaction in these two dyes than the other dyes. In addition, there is a significant increase of charge transfer (CT) characters in Cr(II) or Os(II) dye-functionalized Cd33Se33 QD upon photoexcitation. We further use the embedded fragment potential model to expand the QD’s electrostatic potential as multipole terms included in dye’s Hamiltonian, and found the dipole energies between QD and these two dyes are relatively larger than the other dyes, while the energy gaps between these two dye’s HOMOs and VB edge are relatively smaller than the other dyes, which collectively increases the resonant interaction between tris(2,2’-bipyridine)Me(II) dye and QD’s surface states, thus increases the probability of charge-transfer excitation.
ED5.3: Poster Session I
Session Chairs
Tuesday PM, April 18, 2017
Sheraton, Third Level, Phoenix Ballroom
8:00 PM - ED5.3.01
Solution-Based Self-Assembly and Nanoengineering of Multifunctional Nanoparticle Coatings
Kaifu Bian 1 , Zaicheng Sun 2 , Huimeng Wu 1 , C. Jeffrey Brinker 1 2 , David Burckel 1 , Hongyou Fan 1
1 , Sandia National Laboratory, Albuquerque, New Mexico, United States, 2 Chemical and Biological Engineering, University of New Mexico, Albuquerque, New Mexico, United States
Show AbstractOptical coatings/films are widely used in consumer electronics, semiconductor devices, and high-performance glass and ceramic materials. Presently most of these films are manufactured using complicated and costly processes such as sputter deposition and chemical vapor deposition (CVD), which requires high temperature and/or high vacuum. Seeking a simpler and less expensive fabrication process, we have developed a rapid and versatile self-assembling process that employs nanotechnology to overcome the limitations of the conventional CVD and sputtering. In our method, multifunctional nanoparticles are synthesized and then assembled into three-dimensional ordered arrays forming optical films at an interface with the aid of polymers. The versatility of our method can be further expanded by combining it with top-down micro-fabrication methods such as lithography to achieve coatings of hierarchical structures and desirable functions at multiple length scales. As an example, a near infrared reflector with improved performance, comparing with traditional CVD or sputtered counterparts, was developed by quarter wave stacking of self-assembled nanoparticle films. Theoretical modeling shows very good consistency with our experimental results and addresses key manufacturing challenges.
Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.
8:00 PM - ED5.3.02
Construction of Enhanced Photocurrent Generation Systems by Nanocomposite Layers of Silver Nanoparticles and Dyes
Katsuhiko Kanaizuka 1
1 , Yamagata University, Yamagata Japan
Show AbstractConstruction of artificial photo-excited electron-transfer systems on electrodes is one of the important issues for the creation of high performance solar cells, electroluminescent displays, catalytic devices, and so on. Metal nanoparticles (NPs) e.g., Ag, Au, Cu, and their alloys, have received much attention as light-harvesting materials due to the plasmonic effect. In addition, photo-excited efficiencies of molecules localized near metal NPs are remarkably improved by the near-field effect (enhanced electric fields caused by localized surface plasmon resonance). In this study, we have constructed porphyrins – Ag NPs composite layers on a transparent indium-tin oxide (ITO) electrode by using a bottom-up method and have evaluated their photocurrent generation.
An ITO electrode was immersed in a methanol solution of 3-mercaptopropyl trimethoxysilane (MPTS) to form self-assembled monolayers (SAMs) on the surface. Ag NPs (ca. 10 nm) were fixed on the ITO/MPTS film via thiol residues. 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrins, CPP, was embedded on the ITO/MPTS/Ag NPs electrode by its simple immersion into a chloroform solution of CPP. In addition, we also prepared ITO/CPP and ITO/Ag NPs/CPP. We measured atomic force microscope (AFM), UV-vis absorption spectra, cyclic voltammetry (CV), and photocurrent generation of these hybrid films. AFM was used for observation of surface morphology of Ag NPs of the electrodes. Photocurrent generation was measured in a 0.1 M Na2SO4 aqueous solution. The photocurrent was remarkably enhanced in the case of ITO/MPTS/Ag NPs/CPP. This enhancement is probably caused by near-field effect of Ag NPs.
8:00 PM - ED5.3.03
Pyrolysis of Self-Assembled Iron Porphyrin on Carbon Black as Core/Shell Structured Electrocatalysts for Highly Efficient Oxygen Reduction in both Alkaline and Acidic Medium
Yujiang Song 1
1 , Dalian University of Technology, Dalian China
Show AbstractWe report simple carbonization of evaporation-induced self-assembled iron(III) porphyrin (FeP) layers uniformly coated on carbon black, leading to an unprecedented core/shell structured nonprecious metal electrocatalysts (NPMEs) composed of N-doped graphene-like layers uniformly coated on carbon. The thickness of graphene-like shell can be readily adjusted up to about 6.6 nm by varying the amount of FeP loaded on carbon. Interestingly, the obtained NPME exhibited one of the highest oxygen reduction reaction (ORR) activity in both alkaline (half-wave potential of 0.87 V vs. RHE) and acidic (half-wave potential of 0.75 V vs. RHE) medium. In particular, the core/shell structured NPME demonstrated a remarkable durability in acidic conditions superior to that of commercial Pt/C, which likely comes from exposure of inner active sites after the outermost layer is consumed. Furthermore, the core/shell NPME displayed direct 4e and indirect 4e process toward ORR in alkaline and acidic medium, respectively. This study pointed out a new avenue for the design of high-performance NPMEs in both alkaline and acidic media, which may have potential applications in polymer electrolyte membrane fuel cells (PEMFCs), metal-air batteries, and electrolyzers.
8:00 PM - ED5.3.04
Graphene Quantum Dots in High Performance Organic Photovoltaic Devices
Zheling Zhang 1 2 , Xiaogang Xue 1 , Xiaoling Zhang 2 , Jian Zhang 1
1 School of Material Science and Engineering, Guilin University of Electronics and Technology, Guilin China, 2 School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing China
Show AbstractIn the past few years, there has been an ongoing enthusiasm on graphene quantum dots (GQDs) and study the new phenomena from GQDs, e.g. quantum confinement and edge effects. These dots are usually biocompatible, strongly luminescent and well dispersed in various solvents, showing bright promise for integration into devices of bioimaging, photovoltaic and light emitting applications [1]. It’s also can be applied in organic photovoltaic devices. For example, comparing with traditional hole extraction layer (HEL), the self-assembly of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) organogel films incorporating with GQDs and other similar combonations as the HEL can increase the device’s power conversion 26% [2].
Here we synthesis a series of amino-group modified GQDs by the widely used thermal route. These modified GQDs can help reduce the work function of transparent electrodes and can be applied in organic photovoltaic devices as electron transport layer.
Acknowledgement: This research was financially supported by the National Natural Science Foundation of China (61564003), and the Guangxi Natural Science Foundation (2015GXNSFGA139002).
Reference
[1] Mitchell Bacon, Siobhan J. Bradley, and Thomas Nann, Graphene Quantum Dots , Part. Part. Syst. Charact. 2014, 31, 415–428
[2] Jung Kyu Kim, Sang Jin Kim, Myung Jin Park, Sukang Bae, Sung-Pyo Cho, Qing Guo Du, Dong Hwan Wang, Jong Hyeok Park, Byung Hee Hong , Surface-Engineered Graphene Quantum Dots Incorporated into Polymer Layers for High Performance Organic Photovoltaics. Sci. Rep. 5, 14276; doi: 10.1038/ srep14276 (2015).
8:00 PM - ED5.3.05
Highly Stable Transparent Electrode Based on Copper Nanowire@Graphene Core@Shell Nanostructure
Yumi Ahn 1 , Donghwa Lee 1 , Youngu Lee 1
1 , Daegu Gyeongbuk Institute of Science and Technology, Daegu Korea (the Republic of)
Show AbstractTransparent electrodes (TEs) have been known and well-studied as an essential element of various optoelectronic devices. Vacuum-deposited Indium tin oxide (ITO) has been widely used in a variety of optoelectronic devices because of low sheet resistance and high optical transmittance. However, it has critical drawbacks such as brittleness, high production cost, high processing temperature, and low optical transmittance in near-infrared (NIR). Recently, silver nanowire (AgNW) TE showed outstanding physical performances such as high electrical conductivity, high transparency, and excellent flexibility. However, the mass production of AgNWs is limited due to its scarcity and high price. Copper is one of the earth-abundance elements. Copper is 80 times cheaper than silver. Furthermore, the electrical conductivity of copper (58.5 x 106 S/m) is as high as the electrical conductivity of silver which has the highest electrical conductivity (62.1 x 106 S/m). Thus, a copper nanowire (CuNW) has been considered as a promising alternative to AgNW. Recently, some research groups have proven the great performance of CuNW TE such as excellent optical transparency, electrical conductivity, and mechanical flexibility. However, it still has a long-term stability issue which makes it difficult for practical use. For instance, CuNW TEs are easily oxidized when exposed to air even at room temperature, leading to a sharp increase of their sheet resistance values. Thus, it is necessary to prevent the oxidation of CuNW in order to enhance the long-term stability of CuNW TE. To enhance the long-term stability of CuNW based TEs, we developed a CuNW@G core@shell nanostructure by a low temperature plasma enhanced chemical vapor deposition (LT-PECVD) process at temperatures as low as 400 °C for the first time. Furthermore, we have fabricated highly stable and conductive TEs based on a copper nanowire@graphene (CuNW@G) core@shell nanostructure. The CuNW@G core@shell nanostructure was systematically characterized by SEM, TEM, XRD, RAMAN, and XPS measurements. The CuNW@G TE exhibited excellent optical and electrical properties comparable to conventional ITO TE. In addition, the CuNW@G TE exhibited highly enhanced oxidation and chemical stability because of excellent moisture and gas barrier property of the graphene shell layer. The sheet resistance of the CuNW-G TE increased slightly less than 9% even after 30 days in air while that of the CuNW TE increased over 1800 times within 2 days. Furthermore, polymer solar cells with CuNW@G TE exhibited higher power conversion efficiency than those with CuNW TE because of significantly enhanced anti-corrosion property.
8:00 PM - ED5.3.06
Low Dimensional Multilayered Nanostructures for Plasmonic Applications
Ezgi Abacioglu 1 , Alpan Bek 1
1 , Middle East Technical University, Ankara Turkey
Show AbstractOptical properties of materials can be enhanced by tailoring their plasmonic properties. Plasmons are collective electron oscillations inside metals that can be coupled with light. Forming surface plasmon polaritons, this coupling creates strong optical and electrical fields within nanostructures. Plasmon resonance frequency is affected by intrinsic and morphological features of nanostructures; therefore, design holds great importance. Since they support the production of complex hybridized resonances, 1D coaxial nanowires of several metal-dielectric layers are promising in this manner. In addition, noble metals are generally preferred for plasmonic applications since their resonance frequency is in the visible and near-IR region. Scattering peaks of multilayered nanostructures depend on the thicknesses of the layers, i.e. thin coaxial nanowires exhibit strong plasmon mixing. Thus, dielectric and metal layers should be deposited as thin films. In this study atomic layer deposition (ALD) technique is used to fabricate coaxial nanowires. ALD is an important thin film deposition technique consisting of sequential surface reactions. Due to its self-limiting nature it has the best conformality compared to other thin film techniques, especially for high aspect ratio nanostructures. In this work high aspect ratio silver nanowires that are synthesized by polyol process are used as core nanostructures. On core Ag nanowires, oxides of titanium or aluminum are deposited as spacer dielectric layer which is succeeded by silver deposition. As the multilayered low dimensional plasmonic structures bear hybrid plasmon modes due to mixing, some of these modes are found to be subject to very low attenuation, thus long range, and long lifetime. We expect beneficial qualities as light management interfaces from the resultant nanostructures in thin film photovoltaic devices. The material properties, process optimization and optical characterization of these structures will be discussed in this context.
8:00 PM - ED5.3.07
Porphyrin-Based Composites Controllable Self-Assembly and Photodynamic Therapy Research
Jiefei Wang 1 2 , Yong Zhong 1 2 , Feng Bai 1 2
1 , Henan University, Kaifeng, AE, China, 2 , Key Laboratory for Special Functional Materials of the Ministry of Education, Kaifeng, Henan, China
Show AbstractPhotodynamic therapy is a kind technology of oxygen molecules participate in and photosensitizer mediated and produce biological effects. Porphyrin-based photosensitizers has attracted much attention on account of higher singlet oxygen productivity and very low toxicity, but most of them have a poor water solubility. Here we adopted an acid-base neutralization micelle confinement self-assembly method to simultaneously achieve the self-assembly of zinc porphyrin (ZnTPyP) and the hydrolysis condensation of tetraethoxysilane (TEOS), and one pot obtained core-shell type and blend type porphyrin @ SiO2 composite nanomaterials. The nanocomposite materials have realized on HeLa cells target recognition after further modification of BSA and folic acid and have good fluorescent tags learned from a confocal laser scanning microscope imaging. The cells were irradiated by laser irradiation at 660 nm and a power density 100 mW/cm2 for different time shown a very good kill efficiency and without dark toxicity and a good time- and concentration-dependent.
8:00 PM - ED5.3.08
3D Core-Shell Porous Structures for Photoelectrochemical Water Splitting
Kiwon Kim 1 , Jun Hyuk Moon 1
1 Chemical and Biomolecular Engineering, Sogang University, Seoul, Seoul, Korea (the Republic of)
Show AbstractPhotoelectrochemical cells which convert solar energy into hydrogen are a promising energy conversion technology for substituting fossil fuel and producing hydrogen. For photoelectrochemical cell photoanode, BiVO4 has become the top performer among the metal oxide due to its visible light absorption up to 520nm and relatively negative energy level. This advantage, however, is compensated by high electron-hole recombination property of BiVO4. Here, we fabricate 3D BiVO4-based core-shell inverse opal structure for photoelectrochemical water splitting application. The core-shell morphology and crystallinity of core-shell oxides are characterized. The electrode film and BiVO4 shell thicknesses are controlled and then, the effect of them on the water splitting efficiency is evaluated. Our heterojunction inverse opal structure exhibit the improvement of light harvesting and charge separation efficiencies compared to 1D planar bilayer electrode.
8:00 PM - ED5.3.09
Enhanced Optical Stability of All-Inorganic Perovskite Nanocrystals Embedded in Polymer
Yuan Chih Chang 1 , Fu-Song Ye 1 , Ing-Chi Lue 1
1 Department of Materials Science, National University of Tainan, Tainan Taiwan
Show AbstractCesium lead halide (CsPbX3, X=Cl, Br, I) perovskite nanocrystals prepared by solution process have shown great potential as a new class of optoelectronic material. Because they have high luminescence quantum yields, broad emission spectra tunablility, narrow emission bandwidth, and short radiative lifetimes. But their application is hindered by a low chemical and structural stability. In order to enhance their stability we introduce polymethylmethacrylate (PMMA) into the synthesis of the CsPbX3 perovskite nanocrystals. It is found that CsPbX3 perovskite nanocrystals can be stabilized by PMMA with the formation of ligand shell, and can also be embedded in the PMMA film to prevent them from the attack of water in the ambient environment. We can fabricate polymer composite films with different colors by using CsPbX3 nanocrystals with different compositions. In addition, we successfully attached the CsPbBrI2 nanocrystal-embedded PMMA films onto the commercial white LED chips to make them warmer. Finally we studied the durability of the CsPbBrI2 nanocrystal-embedded polymer films, and found their optical performance could maintain for more than one week in the ambient condition and could be operated at 70 degree Celcius without degradation.
8:00 PM - ED5.3.10
Synthesis and Characterization of Novel Copper-Manganese Based Oxides
Chun-Yi Lu 1 , Tri-Rung Yew 1
1 Materials Science and Engineering, National Tsing Hua University, Hsinchu, Choose a State or Province, Taiwan
Show AbstractOxide materials have played an important role in optoelectronic and sensing devices benefited from their various optical and electrical properties. In this work, earth-abundant cupric oxide and manganese dioxide were used according to the Gibbs free energy rule and fabricated into copper-manganese based oxide materials via a standard ceramic process. By varying the molar ratio of cupric oxide to manganese dioxide and ceramic processing conditions, different phases of Cu-Mn based multi-element oxides were formed and characterized to study their potential applications.
The prepared copper-manganese based oxides were fabricated into targets, followed by the oxide films deposition using RF sputtering. Thin film deposition parameters such as ambient pressure, working power, post-annealing temperature were optimized and the structural, electrical and optical properties of the oxide thin films were characterized. The morphological, compositional and structural properties of the films were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and X-ray diffraction (XRD), respectively. The electrical and optical properties of the thin films were also measured by Hall-effect measurement system and ultraviolet-visible spectroscopy (UV-Vis), respectively.
8:00 PM - ED5.3.11
Hierarchical TiO2-Based Nanostructures for Photoelectrochemical Water Splitting
Luca Mascaretti 1 , Simona Ferrulli 1 , Beatrice Bricchi 1 , Piero Mazzolini 1 3 , Carlo Casari 1 3 , Valeria Russo 1 , Roberto Matarrese 2 , Isabella Nova 2 , Giancarlo Terraneo 4 3 , Andrea Li Bassi 1 3
1 Micro and Nanostructured Materials Laboratory, Department of Energy, Politecnico di Milano, Milano Italy, 3 Center for Nanoscience and Technology - IIT@Polimi, Istituto Italiano di Tecnologia, Milano Italy, 2 Laboratory of Catalysis and Catalytic Processes, Department of Energy, Politecnico di Milano, Milano Italy, 4 Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Milano Italy
Show AbstractTitanium dioxide (TiO2) is one of the most studied materials for both photocatalytic and photoelectrochemical (PEC) water splitting, nonetheless it presents some limitations, such as poor absorption of visible light and low quantum efficiency. Recent innovative approaches towards the extension of its absorption range consist in the hydrogenation or reduction of TiO2, leading to the so-called black titania [1], and in the combination of TiO2 with noble metal nanoparticles, which exhibit plasmonic effects [2]. In both cases, remarkable enhancement for the water splitting reaction have been obtained, even though the comprehension of the involved mechanisms still presents some open issues. In addition, hierarchical TiO2 nanostructures, combining large surface area and anisotropic morphology, are object of intense research for the development of more efficient photoanodes [3].
In this work we present an explorative combined approach aimed at extending to the visible range the photoresponse of a TiO2 photonaode with optimized morphology and structure. First, hierarchical TiO2 nanostructures were prepared by Pulsed Laser Deposition (PLD) controlling both the deposition atmosphere and the post-annealing atmosphere with the aim to achieve hydrogenation or reduction of the material. This was performed by using an oxygen-poor deposition atmosphere and/or by annealing in a Ar/H2 mixture. Second, an investigation on plasmonic-enhanced water splitting was undertaken by studying the synthesis of Au nanoparticles (NPs) with PLD and exploring different strategies to efficiently combine them with the aforementioned hierarchical TiO2 nanostructures: growth of Au nanoparticles on top or below the TiO2 film, or dispersion of Au NPs in TiO2 by a co-deposition approach. SEM, Raman spectroscopy, XRD and UV-vis-NIR spectroscopy were employed as characterization techniques, whereas photocurrent measurements under solar simulator illumination with a three-electrode cell were employed to assess the materials photoresponse.
We discuss how the structure and consequently the photoresponse of hierarchical TiO2 can be tuned by playing with the deposition and annealing atmospheres. In particular, a thermal treatment in Ar/H2 results in the appearance of an optical absorption tail towards the visible region, and the material photoresponse is significantly enhanced after Ar/H2 annealing if an oxygen-poor deposition atmosphere is employed (i.e. Ar/O2 mixture) and if it is preceded by thermal sintering in air. Furthermore, we show how PLD permits to achieve dispersion and size control of Au NPs from few nm to about 20 nm. A detailed investigation of the plasmonic and photoelectrochemical properties of the Au/TiO2 films is currently being carried out.
[1] X. Chen et al. Chem. Soc. Rev. 2015, 44, 1861-1885.
[2] S. C. Warren, E. Thimsen Energy Environ. Sci. 2012, 5, 5133-5146.
[3] F. Di Fonzo et al. Nanotechnology 2009, 20, 015604; R. Matarrese et al. Chem. Eng. Trans. 2014, 41, 313-318.
8:00 PM - ED5.3.12
Tunable-Photoluminescence 2D Materials Quantum Dots
Bedanga Sapkota 1 , Abdelkrim Benabbas 1 , Paul Champion 1 , Meni Wanunu 1 2
1 Department of Physics, Northeastern University, Boston, Massachusetts, United States, 2 Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts, United States
Show AbstractBedanga Sapkota†, Abdelkrim Benabbas†, Paul Champion†, and Meni Wanunu*,†,‡
†Department of Physics, Northeastern University, Boston, Massachusetts 02115 United States
‡Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115 United States
Graphene quantum dots (GQDs) have garnered an increasing interest for bioimaging and biotargeting applications, due to merits such as their optical properties, reduced toxicity, small size that is commensurate with biomolecules, and ease of functionalization. However, despite their mild chemical composition, toxicity is GQD-size dependent. It is well known that ultra-small particles are able to enter mitochondria (<6 nm) and nucleus (<10 nm), and these can produce physical cytotoxic effects. Here, we report on GQD synthesis with mean diameters that are controllable in the range 15-35 nm. These quantum dots maintain strong visible light fluorescence (mean quantum yield of 0.64) and a high two-photon cross section (6,500 Göppert-Mayer units). Furthermore, by virtue of their mesoscopic size, the quantum dots exhibit good cell permeability into living epithelial cells, while they do not enter the cell nucleus. We also report on synthetic routes to metal dichalcogenide quantum dots (MDCQDs). To date, very few works have been reported on MDCQDs such as MoS2 and WS2, all of which involve complicated preparation steps and have resulted in low-quantum yield materials. Here, we employ a straightforward sonication method to prepare water-soluble MoS2 QDs. Further, we obtain eight-fold enhancements in their quantum yield by passivating their surface with amine groups. We demonstrate peptide binding to these particles using fluorescence resonance energy transfer (FRET). Finally, we demonstrate strong antimicrobial activity of MoS2 nanosheets (NS).
Acknowledgement: This work was supported by NSF grant EFMA-1542707.
8:00 PM - ED5.3.13
A Quantitative Analysis of the Reduction Pathways of a Salt Precursor in the Synthesis of Metal Nanocrystals
Tung Han Yang 1 2 , Younan Xia 1 3 4
1 The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta, Georgia, United States, 2 Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu Taiwan, 3 School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, United States, 4 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia, United States
Show AbstractMetal nanocrystals have received ever increasing interest owing to their fascinating properties for a variety of applications, including catalysis, electronics, photonics, sensing, and medicine. A typical synthesis involves the reduction of a salt precursor. Despite the remarkable progress, it is still unclear how the salt precursor is reduced to atoms for their evolution into nuclei, seeds, and then nanocrystals. It has been challenging to resolve such a process due to the lack of characterization tools. Specifically, the salt precursor can be reduced to an atom in the solution phase, followed by its deposition onto the surface of a growing nanocrystal. Alternatively, the precursor can adsorb onto the surface of a growing nanocrystal, followed by reduction through an autocatalytic surface growth process. With Pd as a typical example, here we design a set of kinetic experiments to shed light on the reduction pathway undertaking by a salt precursor during the growth of metal nanocrystals. Based on the quantitative analysis, we demonstrate that the pathway has a strong dependence on the reduction kinetics involved. We found that the precursor was reduced on the surface of a growing nanocrystal through an autocatalytic surface growth process under a slow kinetic whereas it was reduced in the reaction solution at faster reaction rates. Most significantly, we also demonstrate the switching of reduction pathway by manipulating the reaction parameters such as the type of precursor used and the reaction temperature, to modulate the reaction kinetics. This work represents a major step forward toward the achievement of a quantitative understanding of the reduction pathways of a salt precursor in the synthesis of metal nanocrystals.
8:00 PM - ED5.3.14
Optical Properties of Nano-Structured Semiconductors Fabricated by Ion Implantation
Angelica Hernandez 1 , Yuriy Kudriavtsev 1 , Georgina Ramirez 1
1 , CINVESTAV, Mexico City, FDM, Mexico
Show AbstractGermanium and silicon crystals were implanted with Ge+ ions at 25 and 50 keV, respectively and high ion dose (1x1016 ions/cm2). A subsequent thermal annealing was carried out with nitrogen and oxygen atmospheres in order to determine its effect in the optical properties. The annealing time and temperature were optimized in each case.
Structural characterization was performed by using Raman spectroscopy. The obtained results show the vibrational modes of the implanted element and the implantation matrix as the presence of germanium and silicon oxides as well as the crystalline properties of the lattice before and after annealing. The implanted elements were re-arranged into the crystal lattice due to the thermal process. Formation of a near surface binary layer was confirmed, among other.
A SIMS depth profile of the as implanted and thermally treated samples were obtained in order to study diffusion of the elements along the totally amorphized and the partially amorphized layer (caused by ion implantation). Of special interest is the concentration of the oxygen in the border between the amorphized layer and the crystal since the defects may act as a traps for oxygen.
The optical properties of the as implanted and thermally treated samples were studied at excitation wavelength of 325 nm at room temperature. The white light emission was observed in the as implanted samples and the PL intensity increased after the annealing. The de-convolved PL spectra reveal that several mechanisms gather in the photon-emission process. The spectrum can be considered a mixture of photonic effects that include the formation of nano-crystals and recombination of electrons in the oxygen vacancies of the germanium oxides.
Due to its technological importance, the fabrication of germanium and silicon-based luminescent materials has been explored through the development of several techniques which involve chemical and physical mechanisms. However, the ion implantation is an undoubtedly favorable cost-effect technique to fabricate nano-structured materials with optical properties in an uncomplicated and strongly controllable process.
8:00 PM - ED5.3.15
Tip-Enhanced Photovoltaic Effects in Pd Substituted PZT Thin Films
Shalini Kumari 1 , Dhiren Pradhan 1 , Ashok Kumar 2 , Ram Katiyar 1
1 , University of Puerto Rico, San Juan, Puerto Rico, United States, 2 , National Physical Laboratory (CSIR), Delhi India
Show AbstractDriven by the worldwide requirement for inexhaustible energy and clean fuel sources, considerable research attempts have been focused towards solar energy harvesting considering various photovoltaic (PV) effects. Ferroelectric materials have recently attracted much attention as promising candidates for use in photovoltaic devices, and for the coupling of light absorption with other functional properties. Breaking of strong inversion symmetry due to spontaneous polarization in these materials develop a desirable separation of photo-exited carriers and produces voltages higher than its band gap. However, a big challenge faced by ferroelectric-photovoltaic devices is to overcome the very low output photocurrent. Theoretically, it has been proposed by some research groups that metallic defects and/or doping/substitutions of transition metals and/or metal ions can reduce the band gap of ferroelectric materials which is the basic requirements for their applications in photovoltaic devices. We have synthesized Palladium substituted PZT (Pb(Zr0.20Ti0.80)0.70Pd0.30O3-δ (PZTP30)) thin films on ITO coated glasses and La0.67Sr0.33MnO3 (LSMO) coated LSAT (100) substrates utilizing pulsed laser deposition technique. X-ray diffraction showed that the PZTP30 thin films on ITO coated glass are polycrystalline and exhibit a random orientation with strong (101) diffraction peak whereas in the XRD spectrum of LSAT/LSMO/PZTP30, only (00l) diffraction peaks are visible, indicating a (00l) oriented growth of the films. The existence of ferroelctricity and switching of polarization are confirmed from the band excitation Piezo Force Microscopy (PFM) in PZTP30 thin films. XPS studies confirmed the existence of Pd in thin films. The frequency dependent dielectric constant and loss tangent of LSAT/LSMO/PZTP30 films show almost constant dielectric constant around 3000 and relatively low loss tangent (<0.2) at frequencies below 10 kHz. Well saturated ferroelectric loop with remanent polarization ~40 μC/cm2 confirmed the presence of ferroelectricity in this material. Optical properties were investigated by UV-visible spectrometer of PZTP30 films on glass/ITO, it exhibits 60% transmittance at 600 cm-1, with a reduction of only 30% compared with pure ITO/glass substrate. A decrease in direct-Eg value was observed from 3.8 eV to 3.1 eV as the thickness of the films increased from 5 nm to 400 nm. A decrease in indirect-Eg value was also observed from 3.4 eV to 2.2 eV as the thickness of the films increased from 5 nm to 400 nm. The tip induced photovoltaic studies were carried out on PZTP30 thin films using c- AFM measurements and significant amount of current were observed when the blue drive was on. The structural, dielectric, ferroelectric, tip induced photovoltaic, and bulk photovoltaic properties will be discussed in details.
8:00 PM - ED5.3.16
A Systematic Study of the Effect of CdS Shell Thickness on the Complex Index of Refraction of CdSe/CdS Core/Shell Nanocrystal Solids
Mayank Puri 1 , Dana Dement 1 , Vivian Ferry 1
1 , University of Minnesota, Minneapolis, Minnesota, United States
Show AbstractA deep understanding of the factors that affect the complex index of refraction of quantum dot (QD) solids is essential towards tailoring QD-containing photonic and optoelectronic devices, such as photovoltaic cells and LEDs. This is particularly true for carrying out computational models on these systems, where knowledge of the complex index is a requirement. We have undertaken a systematic study on the effect of CdS shell thickness on the index of CdSe/CdS core/shell QD films, using spectroscopic ellipsometry to derive the complex refractive index directly from fabricated films. This data set ultimately allows us to control optical interactions inside these materials with greater precision.
Measuring the complex index of QD solids is made challenging by multiple variables including the QD chemical composition, shape, size and packing, as well as the supporting ligand identity and surface coverage. The use of CdSe/CdS heterostructures provides many advantages over plain CdSe QDs, including increased quantum yield and stability, as well as the ability to tune the size and shape of the QD through the thickness of the CdS shell, resulting in synthetic control over optical properties such as emission wavelength, Stokes shift and non-blinking behavior.
We have successfully synthesized zinc-blende CdSe QDs on a multigram scale through a reproducible non-hot-injection synthesis, yielding monodisperse particles with an average diameter of 3.5 nm and standard deviation of 10%. The large scale of this synthesis is critical to allow us to maintain the same CdSe core particles while systematically varying the thickness of the CdS shell, leading to a family of spherical CdSe/CdS QDs of varying diameters dependent only on the monolayers of CdS shell grown. We have realized 3, 5 and 9 monolayers of CdS growth, producing a range of CdSe/CdS particle sizes from 3.5 nm to 9.4 nm and emission wavelengths ranging from 585 nm to 637 nm.
Dip-coating a solution of the CdSe/CdS QDs onto an Al2O3 surface forms thin films with thicknesses ranging from 10 nm – 40 nm, depending on the coating conditions. Variable angle spectroscopic ellipsometry measurements on films containing CdSe/CdS QDs with 5 monolayers of CdS shell provides refractive index, n, and extinction coefficient, k, values of 1.92 and 0.075, respectively, at 500 nm, with appropriate dispersion throughout the full spectrum characterized. The ellipsometry model includes a Cauchy fit at energies below the band gap and multiple Loretz oscillators to model the QD absorption features. Importantly, quantum confinement is observed in the ellipsometry data, where the first excitonic peak of the CdSe/CdS QDs is visible. A systematic trend between the CdS shell thickness and the solid index will be presented and ultimately this systematic study will inform the development of computational models incorporating CdSe/CdS QDs, and enable the design of tailored optoelectronic devices using nanophotonic elements.
8:00 PM - ED5.3.17
Development of Al3+ and Fe3+ Co-Doped TiO2 Compact Films and their Application in Hybrid Solar Cells with a Mixed Tin-Lead Perovskite and Sb2S3 Photoabsorbing Nanoparticles
Jose Garcia Cerrillo 1 , Claudia Martinez-Alonso 2 , Asiel Neftalí Corpus Mendoza 1 , Araceli Hernandez-Granados 1 , Paola Moreno Romero 1 , Omar-Armando Castelo-Gonzalez 1 , Hailin Zhao Hu 1
1 Instituto de Energías Renovables, Universidad Nacional Autónoma de México, Mexico (UNAM), Temixco Mexico, 2 Facultad de Química, Universidad Autónoma de Querétaro, Querétaro, Querétaro, Mexico
Show AbstractPerovskite-based photovoltaic technology is promising in terms of competitive performance and cost, as intensive and exciting research and development have recently demonstrated. Although their entrance into the photovoltaic market is imminent, perovskite solar cells still have many fundamental issues to be addressed, like the interfacial processes that occur between the perovskite absorber and the electron selective contact, in particular titanium dioxide (TiO2) compact layers. The surface morphology and chemistry of this electron transport layer (ETL) could influence the charge recombination phenomena, whereas its electrical conductivity is related to the device charge collection. In this work, co-doping with aluminum (Al3+) and iron (III) (Fe3+) is explored as a means to enhance the charge transfer and transport characteristics of the TiO2 compact layer, which is integrated into planar and mesoscopic devices employing an associated photoabsorber, e.g. a tin-lead organohalide perovskite and antimony sulfide (Sb2S3) nanoparticles. The effect of three co-dopant Al3+/Fe3+ molar ratios (1.0/0.4, 0.7/0.7 and 0.4/1.0) as well as individual impurifications is analyzed in terms of the photovoltaic parameters delivered by complete hybrid devices. It is concluded that the localization of dopants on the surface of the ETL improved the transference of electrons coming from the associated absorber and their distribution in the inner TiO2 structure facilitated their transport until reaching the charge collector, as reflected in an enhanced solar cell energy conversion efficiency.
8:00 PM - ED5.3.18
A Porphyrin Protein Maquette-Based Photovoltaic Device
David Officer 2 , Christopher Hobbs 3 , Nicholas Roach 3 , Rhys Mitchell 3 , Klaudia Wagner 3 , Pawel Wagner 2 , Jonathan Barnsley 1 , Keith Gordon 1 , Goutham Kodali 4 , Christopher Moser 4 , P. Leslie Dutton 4
2 ARC Centre of Excellence for Electromaterials Science and the Intelligent Polymer Research Institute, University of Wollongong, Wollongong, New South Wales, Australia, 3 Intelligent Polymer Research Institute, University of Wollongong, Wollongong, New South Wales, Australia, 1 Department of Chemistry, University of Otago, Dunedin, Otago, New Zealand, 4 Department of Biochemistry & Biophysics, The University of Pennsylvania, Philadelphia, Pennsylvania, United States
Show AbstractThe emulation of photosynthesis, the efficient and sustainable utilization of solar energy using renewable materials to produce hydrogen and oxygen from water or convert carbon dioxide into a chemical feedstock represents one of the great scientific challenges of the 21st Century. Creating photosynthetic-like processes in devices could not only provide a new generation of economical photovoltaic devices but also lead to sustainable hydrogen production through water splitting as well as fuel and food production through carbon dioxide fixation.
The challenge in building a useful ‘artificial photosynthetic’ assembly is not in simply mimicking the natural photosynthetic apparatus but utilizing new materials to create and, if possible, improving the structural properties and functionality of the biological system. In 1994, Dutton et al. developed the methodology for the facile production of de novo synthetic protein helices (maquettes), structurally simpler analogs of natural redox proteins, which have proved extremely useful for the study of porphyrin behaviour and interactions in proteins.1 It has been demonstrated that not only is a maquette bound porphyrin more efficiently photo oxidized than a free porphyrin but also that light induced electron transfer between the porphyrin complex and an acceptor is faster and higher yielding. As the maquettes can be assembled on a variety of surfaces such as gold or titanium dioxide, they provide a unique platform on which to build and study a light harvesting reaction center replica.
Over the last 10 years, we have developed syntheses of single porphyrins and porphyrin arrays and utilized the resulting materials as light harvesters in dye sensitized solar cells bound through carboxyl based linkers to titanium dioxide.2 However, the introduction of porphyrins into water soluble maquettes requires the development of amphiphilic porphyrins and porphyrin arrays. We have synthesized and incorporated carboxylated porphyrins and amphiphilic porphyrin dimers into maquettes. As a first step in the practical application of these artificial photosynthetic reaction centers, we have bound a porphyrin maquette to titanium dioxide in a dye sensitized solar cell (DSSC) to create the first artificial protein based dye sensitized solar cell. The current–voltage characteristics of the porphyrin maquette DSSC exhibits an excellent fill factor of 0.73, an open circuit voltage of 652 mV, photovoltaic current density of 2.69 mA cm−2 and power conversion efficiency of 1.28%, which remarkably is more than 50% of the value for the DSSC directly sensitised with five times more of the porphyrin itself.
1. B. M. Discher, R. L. Koder, C. C. Moser, P. L. Dutton, Curr. Opin. Chem. Biol. 2003, 7, 741.
2. A. J. Mozer, M. J. Griffith, G. Tsekouras, P. Wagner, G. G. Wallace, S. Mori, K. Sunahara, M. Miyashita, J. C. Earles, K. C. Gordon, L. Du, R. Katoh, A. Furube, D. L. Officer, J. Am. Chem. Soc. 2009, 131, 15621.
8:00 PM - ED5.3.19
Nitrogen-Doped Carbon Nanodots for Photoacoustic Imaging and Photothermal Therapy
Songeun Beack 1 , Changho Lee 1 , Woosung Kwon 2 , Shi-Woo Rhee 1 , Chulhong Kim 1 , Sei Kwang Hahn 1
1 , POSTECH, Pohang Korea (the Republic of), 2 , Sookmyung Women's University, Seoul Korea (the Republic of)
Show AbstractMultifunctional nanoparticles have been widely investigated for biomedical applications, such as imaging, therapy, and drug delivery. Especially, photo-activated nanoparticles have received attention as theranostic agents because of their heat-generating abilities after laser irradiation. Unfortunately, photostability and safety issues have been critical problems. Here, we designed nitrogen (N)-doped carbon nanodots (N-CNDs), which have strong absorption in the near-infrared region, high photostability, and excellent biodegradability, by regulating their N-doped content. Optimized N-CNDs not only can be utilized as a new photoacoustic (PA) imaging agent but also as a superior photothermal therapy (PTT) agent in vivo because of their strong optical absorption at a specific wavelength. We used N-CNDs to perform in vivo/ex vivo noninvasive PA imaging of sentinel lymph nodes via local delivery and performed PTT for cancer ablation therapy. Finally, biodegradation and renal clearance were demonstrated by performing whole-body PA monitoring and a degradation test.
[Keywords] Carbon nanodot; Heat generation; Photoactivate nanoparticle; Photoacoustic Imaging; Photothermal therapy
8:00 PM - ED5.3.21
Microwave—Assisted Synthesis and Characterization of SnS Nanoparticles with Different Morphologies
Evelyn B. Diaz-Cruz 1 , Concepcion Arenas 2 , Hailin Zhao Hu 1
1 , UNAM, Temixco, Morelos Mexico, 2 , Escuela Nacional de Estudios Superiores, Leon, Guanajuato, Mexico
Show AbstractThe metal sulfide semiconductor nanostructures have attracted much attention in recent years due to their exceptional physico-chemical properties. Tin sulfide (SnS) has been reported with a direct optical band gap of 1.1–1.3 eV. This material exhibits excellent properties such as high absorption coefficient, high mobility, non-toxic nature and low cost, which makes it widely used in near-infrared detectors, photovoltaic materials and electrochemical capacitors. Various methods are available in the literature for the synthesis of SnS, however the synthesis of nanoparticles by microwave (MW) irradiation has the advantage of being effective, economical and environmentally friendly. Furthermore, the performance of nanomaterials in different fields of applications, depends largely on their morphology and 3D architecture. For example, morphologies of wires or rods are desirable for solar cell applications, and for hydrogen storage it is expected to be porous materials. During the microwave reaction process, the types of sulfur precursor and solvent are very important to the structural and morphological properties of SnS nanoparticles. In this work SnS nanoparticles under microwave irradiation were synthesized with thioacetamide and tin chloride as raw materials in different solvents. Different washing processes with ethanol, deionized water and ammonia were also conducted to improve the product purity. The reaction temperature was varied between 100 and 200°C. The crystal phase, morphology, binding energy and optical properties of the as-synthesized SnS products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectra (XPS), UV–vis diffuse reflection spectroscopy (UV–vis DRS), respectively. The obtained products gave an orthorhombic phase of SnS (PDF: 39-0354). The SEM results show that with water as solvent a morphology of spherical like flakes of 1 – 2 µm in diameter was obtained, while with ethylene glycol (EG) the morphology of the products was of square plates of 1 – 1.5 µm in diameter. The setting temperature generates an effect on the thickness of the plates obtained in EG; at lower temperatures plates of 150 nm were obtained, and at higher temperatures the plates were much thinner (10 – 20 nm). Finally, the asymmetrical nanowire morphology of MW synthesized Bi2S3 could be obtained by controlling the tin source and type of solvent, which is interested for their application in hybrid solar cells.