Talia Gershon, IBM T. J. Watson Research Center
Svetlana B. Boriskina, Massachusetts Institute of Technology
Stephan Lany, National Renewable Energy Laboratory
Kevin Sivula, École Polytechnique Fédérale de Lausanne (EPFL)
EE1.1: MAPI Perovskites and Related Materials
Svetlana B. Boriskina
Tuesday PM, March 29, 2016
PCC North, 100 Level, Room 122 AB
2:30 PM - *EE1.1.01
Effects of Processing Conditions on Methyl Ammonium Lead Halide Perovskite Prepared by Two-Step Process: From Fundamental Materials Properties to Device Performance
Seong Ryul Pae 1,Daehan Kim 1,Hee Joon Jung 2,Oki Gunawan 3,Byungha Shin 1
1 KAIST Daejeon Korea (the Republic of),2 Pacific Northwest National Laboratory Richland United States3 IBM T. J. Watson Research Center Yorktown Heights United StatesShow Abstract
With the record power conversion efficiency surpassing 20%, inorganic-organic hybrid perovskite has been the center of attention for many researchers in the field of photovoltaics and in the related fields. Different approaches are being used to prepare perovskite films such as vacuum evaporation, one-step solution process, or two-step solution process. In each approach, a great number of variations in the processing conditions are noted in the literature. Narrowing down to two-step process of perovskite films, where precursor solutions (PbI2 and CH3NH3I solutions for CH3NH3PbI3 perovskite) are sequentially spin-coated, differing ratios of molar concentration and volume of precursor solutions have been reported but discussion of their impacts is often absent or limited to the performance of the final solar devices. Here, we report a comprehensive study of how processing conditions in two-step solution process affects structural, chemical, and electrical properties of the perovskite films as well as the device performance of the resultant solar cells. In contrast to common anticipation, we find that the presence of a small amount of remnant PbI2 that has not reacted with CH3NH3I to form perovskite helps improve the efficiencies as well as reduce hysteresis of current-voltage characteristics of the final solar cells. This is explained by the changes in fundamental materials properties of the perovskite films. Details of materials characterization of the perovskite by transmission electron microscopy, temperature-dependent capacitance and Hall measurements and the suggested links between materials properties and device performance will be discussed.
3:00 PM - EE1.1.02
Novel Iodide Semiconductors for Photovoltaic Applications
Rachel Kurchin 1,Riley Brandt 1,Robert Hoye 1,Prashun Gorai 3,Jeremy Poindexter 1,Vera Steinmann 1,Alex Polizzotti 1,Rupak Chakraborty 1,Vladan Stevanovic 2,Tonio Buonassisi 1
1 MIT Cambridge United States,2 Colorado School of Mines Golden United States,3 National Renewable Energy Laboratory Golden United States3 National Renewable Energy Laboratory Golden United States,2 Colorado School of Mines Golden United StatesShow Abstract
The recent success of methylammonium lead iodide perovskite solar cells has caused the photovoltaic research community to reconsider its criteria for what makes a promising absorber material. In particular, prior screening efforts have focused extensively on optical properties and often neglected transport. Our group has recently made an effort to further formalize selection criteria based not only on bandgap and absorption but also on computationally accessible properties that can enable improved carrier transport – even in the presence of defects. 
These properties include a high dielectric constant, disperse band edges (which can result from spin-orbit coupling prevalent in materials composed of heavier atoms), and antibonding character of the valence band maximum. The latter is observed in materials containing partially oxidized p-block cations, in which the cation lends antibonding s-orbital character to the VBM.
We have identified several classes of iodide materials predicted to exhibit these characteristics, in addition to the lead halide perovskites. In this work, we experimentally evaluate several of these compounds, including BiI3 , SbSI, and BiOI. We grow these materials by a variety of methods, including physical vapor transport, solution synthesis, and Bridgman growth. We perform both spectral and time-resolved photoluminescence measurements to assess optical properties as well as minority carrier lifetime. In the present work, we identify several candidates with carrier lifetimes ranging from >200 ps to the nanosecond scale. By performing measurements on bare films without the need to fabricate devices, we can both speed up the cycle of learning and minimize the convoluting effects of other device layers. This efficient experimental validation in tandem with a computational search focused on minority carrier transport properties, may help accelerate the discovery of new promising PV absorbers.
 Brandt, R. E., Stevanović, V., Ginley, D. S., & Buonassisi, T. (2015). Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites. MRS Communications, 5(2), 1–11. doi:10.1557/mrc.2015.26
 Brandt, R. E., Kurchin, R. C., Hoye, R. L. Z., Poindexter, J. R., Wilson, M. W. B., Sulekar, S., … Buonassisi, T. (2015). Investigation of Bismuth Triiodide (BiI 3 ) for Photovoltaic Applications. The Journal of Physical Chemistry Letters, 151012112305004. doi:10.1021/acs.jpclett.5b02022
3:15 PM - EE1.1.03
Studying Perovskite-Based Solar Cells with High Resolution in situ Microscopy
Jeffery Aguiar 1
1 National Renewable Energy Laboratory Golden United States,Show Abstract
Perovskite based solar technologies are generating a great deal of interest in the materials community. In this work, we plan to discuss our ongoing work to characterize new synthesis routines and processes to generate sustainable and reliable perovskite-based materials whose properties are significantly better than the current state of the art. In particular, we are utilizing the latest advances in high-resolution analytical and in situ microscopy to characterize these emerging photovoltaic materials and their interfaces, defects, and discrete paths to crystallization.
There are longstanding interests in the relation between growth, microstructure, defects, electronic structure, and electro-optical activity for two reasons. The first reason is studies suggest there is a great deal of variability in the growth of these materials. The fundamental origins however remain nascent due to the current novelty of these materials and the complexities associated with studying beam-sensitive materials. Furthermore, beyond static conditions, observing transient behavior associated with the growth of these materials is of increasing importance to set future research directions for generating next generation perovskite-based solar cells. The second reason is a more complete understanding of the microstructure, growth defects, and doping behavior and how they affect the efficiency of devices will be crucial in developing both sustainable and efficient perovskite-based solar technology in the future.
This talk will present the correlations between our current ongoing observations and measurement of the optical properties, microstructure, defects, and crystallization associated with perovskite-based solar cells. The guided use of the latest high-resolution state-of-the-art high resolution analytical and in situ (scanning) transmission electron microscopy (S/TEM) techniques to examine growth, crystallization, and material stability of this exciting class of materials will be discussed at length.
This work was supported by the National Renewable Energy Laboratory as a part of the Non-Proprietary Partnering Program under Contract No. DE-AC36-08-GO28308 within the U.S. Department of Energy. Other parts of the TEM work were performed at the LeRoy Eyring Center for Solid State science at Arizona State University.
3:30 PM - EE1.1.04
Methylammonium Bismuth Iodide as a Lead-Free, Stable Hybrid Organic-Inorganic Solar Absorber
Robert Hoye 1,Riley Brandt 1,Anna Osherov 1,Vladan Stevanovic 3,Samuel Stranks 4,Mark Wilson 1,Hyunho Kim 1,Austin Akey 1,John Perkins 3,Rachel Kurchin 1,Jeremy Poindexter 1,Evelyn Wang 1,Moungi Bawendi 1,Vladimir Bulovic 1,Tonio Buonassisi 1
1 MIT Cambridge United States,2 Colorado School of Mines Golden United States,3 NREL Golden United States1 MIT Cambridge United States,4 University of Cambridge Cambridge United Kingdom3 NREL Golden United StatesShow Abstract
Hybrid organic-inorganic materials have recently generated considerable interest for photovoltaics, owing to the rapid rise in efficiency of methylammonium lead halide perovskite solar cells. But the widescale deployment of these perovskites is currently limited by their decomposition in the presence of humid air and environmental concerns with the lead content. It is essential to develop lead-free alternatives that are stable and efficient. Traditional methods for designing new solar absorbers have been empirical and slow, with many materials not reaching their theoretical performance, often limited by short minority carrier lifetimes. We have recently developed new strategies for computationally identifying materials likely to have favorable optical and transport properties based on their electronic structure, effective mass and dielectric constant. One material we predicted is methylammonium bismuth iodide (MBI). In our work, we show that Rietveld refinement of the powder X-ray diffraction pattern of MBI reveals a monoclinic unit cell consisting of Bi2I93- groups alternating with (CH3NH3)+ cations. We synthesize MBI thin films by low-temperature solution processing. These thin films are stable under ambient air (61±4% relative humidity and 21.8±0.7 °C temperature) for a month, whereas methylammonium lead iodide degrades to PbI2 after only five days. Thermogravimetric analysis, X-ray photoelectron spectroscopy and X-ray diffraction are used to examine the causes for the differences in stability between the two materials. We also find that MBI has a high absorption coefficient approaching 105 cm-1 and indirect bandgap of 2.04 eV, which is suited to forming an efficient tandem with Si. MBI luminesces at room temperature, and we find that the photoluminescence decay times can be increased by treating the films with pyridine and using higher temperature vapor conversion to form larger grains. We use vapor growth to produce long-lifetime, continuous MBI thin films that we explore in devices. The features of MBI amenable to stability and long lifetimes are shared by other hybrid ternary bismuth halides, and this work identifies this family of materials as promising alternatives to the perovskites to produce efficient, lead-free, stable solar absorbers.
3:45 PM - EE1.1.05
17.6% Stabilized Efficiency in Low-Temperature Processed Planar Perovskite Solar Cells: The Role of Interface Engineering
Annamaria Petrozza 1,Chen Tao 1,Srinivasa Maruthi Ajay Ram Srimath Kandada 1,Stefanie Neutzner 1
1 Istituto Italiano Tecnologia Milano Italy,Show Abstract
One of the most promising approaches to boost efficiency in photovoltaics is to make tandem solar cells. The challenge is to find a way to make this approach economically viable. Over the past few years, organic–inorganic lead halide perovskites have emerged in the PV technology scenario. The rapid progress in the field has led to certified solar energy conversion efficiencies above 20%, which brings this technology to the cohort of highly performing solar cells, while keeping the promise of low cost energy production. All-perovskite-based tandem solar cells may represent the ultimate goal considering the relatively easy tunability of the semiconductor’s bandgap. However, on a shorter term, the realization of hybrid systems which couple perovskite devices with market-leading technologies is highly attractive. For achieving these targets we need to obtain perovskite solar cells with high steady state efficiency (and thus reliable) and to deliver a device architecture and fabrication process that enables multi-layered structures.
We present1 here a planar perovskite solar cell with a stabilized power conversion efficiency (PCE) of 17.6% at the maximum power point and a PCE of 17% extracted from quasi-static J–V with an open-circuit voltage of 1.11 V. Such excellent figures of merit can be achieved by engineering a solution-processed electron buffer layer that does not require high temperature steps. A compact thin film of perovskite absorber is grown onto a PCBM-based electron extraction layer by implementing a novel two-step procedure which preserves the soluble organic interlayer during the deposition of successive layers. . This has a broader impact on the design and optimization of future charge extracting layers as their choice will not be limited anymore by the processing of the top layers.
By using transient absorption spectroscopy we also evidenced the role of charge extraction in reducing the detrimental effects related to slow transient phenomena. Efficient charge extraction achieved with the use of 60-PCBM as electron extracting layer makes the device much less sensitive to the device polarization, thus producing an inherently more stable device. On the other hand, in the presence of a flat TiO2 layer, the electron extraction is strongly dependent on the pre-polarization conditions, thus undermining device stability.
1. Chen Tao et al, Energy Environ. Sci., 2015, 8, 2365--2370
EE1.2: Kesterites I
Tuesday PM, March 29, 2016
PCC North, 100 Level, Room 122 AB
4:30 PM - *EE1.2.01
Industrial Perspectives on Earth Abundant, Multinary Photovoltaics and How We Can Make Them Better
Richard Haight 1
1 IBM TJ Watson Research Ctr Yorktown Heights United States,Show Abstract
Numerous requirements are imposed on photovoltaic materials subject to their specific applications. Above all, high efficiency is of paramount importance. But beyond that, myriad issues such as production costs, temperature budgets that impact compatibility with flexible substrates, toxicity, availability and cost of constituent elements, and industrially expedient methods of fabrication can populate the list. While it is clear that no one specific photovoltaic technology can provide the answers to all these issues, earth abundant multinaries such as CZTS,Se and its variants are a sub-group of materials that hold great promise along with significant challenges. Comprised of relatively inexpensive and widely available elements, these materials were thought to provide the solution to terawatt level renewable energy generation. But, as we have come to understand, a high density of defects have conspired to limit open circuit voltage (Voc) and hence power conversion efficiency. In this talk I will review the status of our understanding of these voltage limiting defects. This knowledge has motivated our efforts along two lines; engineering of the back contact to increase Voc, and elemental substitution to reduce intrinsic defects. Back contacts consisting of high work function materials exploit electrostatics to drive higher Voc. These effects are supported by WXAMPS device simulations and confirmed with experimental results that show an increase in Voc when high work function back contacts are employed in conjunction with careful control of absorber thickness. In the realm of elemental substitution l will describe our recent results from alloying Ag with CZTS,Se over a range of concentrations. Both experiment and ab-initio calculations indicate that Ag provides as much as a 10X reduction in the density of Cu/Zn antisite defects that are primarily responsible for the low Voc that plagues CZTS,Se absorbers. Fundamental properties, electrical measurements and potential applications of multinary photovoltaic devices will be presented.
*Work done in collaboration with P. Antunez, T. Gershon, O. Gunawan, Y. Lee and T. Gokmen at IBM, A. Kummel, E. Chagarov and K. Sardashti at UC San Diego and D. Bishop at the University of Delaware. This work was carried out under support from the DoE Sunshot program under contract DE-EE0006334
5:00 PM - EE1.2.02
Structural Characterization of Cu2Zn(Sn1-xGex)Se4 by Neutron Diffraction
Galina Gurieva 1,Alexandra Franz 1,Susan Schorr 2
1 Helmholtz-Zentrum Berlin Berlin Germany,1 Helmholtz-Zentrum Berlin Berlin Germany,2 Institute of Geological Sciences Free University Berlin Berlin GermanyShow Abstract
Cu2ZnGeSe4 and Cu2ZnSnSe4 are quaternary semiconductors belonging to the adamantine compound family, contain only abundant elements, which makes these materials promising candidates for engineering on their base of different high-efficient and low-cost devices: solar cells, optical filters and are considered as very interesting, also due to their possible applications in optoelectrics and non-linear optics [2,3]. Cu2ZnSn(S1-xSex)4 solar cells with Ge alloying recently reached efficiency of 8.4% . Cu2ZnSnSe4 crystallizes in the kesterite type structure which can be derived from the cubic sphalerite type structure by doubling the unit cell in the direction of the crystallographic c-axis and an ordering of the cations . X-ray diffraction used for structural characterization of Cu2ZnGeSe4 was reported in the literature, and it suggests that Cu2ZnGeSe4 shows the tetragonal stannite type structure  In contrast to these findings recent first principal calculation predicts the kesterite type phase to be the ground state structure for this material . A differentiation between the isoelectronic cations Cu+, Zn2+and Ge4+ and consequently kesterite and stannite is not possible using X-ray diffraction due to their similar scattering power. But neutrons diffraction can solve this problem; the coherent scattering lengths are sufficiently different . By this method our group could show that both Cu2ZnSnSe4 and Cu2ZnGeSe4 occur in the kesterite structure. [4, 8].
A detailed structural analysis of Zn rich off-stoichiometric (B-F and F-D type mixtures) Cu2Zn(Sn1-xGex)Se4 powder samples with x=0, 0.02, 0.16, 0.5, 0.55, 0.70, 0.76, 0.90, 1, grown by solid state reaction, was performed by neutron diffraction at the fine resolution neutron powder diffractometer E9 at BER II (λ = 1.7986 Å, RT). Rietveld refinement of diffraction data using the FullProf suite software  lead to accurate values of a and c lattice constants and site occupancy factors. The latter have given insights into the cation distribution within the crystal structure of Cu2Zn(Sn1-xGex)Se4 solid solutions with different x values. The correlated information about changes in lattice parameters and cation site occupancies, details on the existing intrinsic point defects and their concentrations will be discussed.
This research was supported by KESTCELLS 316488, FP7-PEOPLE-2012 ITN, Multi-ITN project.
 K. Tanaka et. al., Sol. Energy Mater. Solar Cells 91 (2007) 1199
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 M. Ibañez et al., J. Am. Chem. Soc. 134 (2012) 4060.
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 G. Gurieva, D.M.Többens, M. Valakh, S.Schorr, Phys and Chem of Solids. Submitted.
 Juan Rodriguez-Carvajal and Thierry Roisnel, www.ill.eu/sites/fullprof
5:15 PM - EE1.2.03
Thermal Dependence of Cu/Zn Ordering in CZTSe Kesterites by Anomalous Diffraction
Daniel Toebbens 1,Galina Gurieva 1,Susan Schorr 2
1 Helmholtz-Zentrum Berlin Berlin Germany,1 Helmholtz-Zentrum Berlin Berlin Germany,2 Institute of Geological Sciences Freie Universität Berlin Berlin GermanyShow Abstract
We demonstrate by means of direct determination of the site occupancies from anomalous X-ray powder diffraction data at the Cu and Zn absorption edges the ordering of Cu+ and Zn2+ in B-type Cu2ZnSnSe4 (CZTSe) kesterite upon annealing at temperatures below 180°C.
Cu2ZnSn(S,Se)4 (CZTSSe) semiconductor material is a promising alternative for absorber layers in thin film solar cells. One structural property of particular interest is the distribution of the cations Cu1+ and Zn2+ in the crystal structure. In a recent paper  ordering of Cu and Zn in the CZTS structure was reported at temperatures below 533 K; similar results were found for CZTSe below 473 K . The implications of such a low critical temperature would be significant. CZTSSe is normally grown at 720–830 K, far above the critical temperature. The exact extent of ordering by the end of the synthesis will depend only on the part of the cooling that occurs below the critical temperature, in a temperature region in which cooling history often is neither controlled nor reported. Thus the concentration of CuZn and ZnCu antisite defects in CZTSSe and from these the electrical properties of CZTS could be modified by relatively low temperature processes. Indeed, low temperature postdeposition annealing has been shown to increase photovoltaic power conversion efficiency significantly . However, the low temperature ordering effects were only deducted indirectly, from changes in the Raman spectrum , from anomalous lattice parameter expansion , and from kinetics simulations .
Cu1+ and Zn2+ cannot be distinguished by conventional X-ray diffraction, since they have essentially the same scattering factor for X-rays (same number of electrons). Anomalous diffraction has been used to overcome this, but currently published papers either restrict themselves to qualitative changes [5,6] or used single crystal data  with limited explanatory power for realistic samples. We used anomalous X-ray diffraction on the Cu- and Zn- K absorption edges to determine the distribution of Cu and Zn over the crystallographic sites in a B-type CZTSe kesterite (Cu1.949Zn1.059Sn0.983Se4) powder. Rietveld refinement allowed the quantitative determination of both Cu- and Zn-occupancy for all relevant sites. From this, the temperature dependency of a structure-based, quantitative order parameter could be determined. The critical temperature of the phase transition was confirmed at 460±10 K. The ordering mechanism is in agreement with a transition from disordered to ordered kesterite.
 J. J. S. Scragg et al., Appl. Phys. Let. 2014, 104, 041911
 G. Rey et al., Appl. Phys. Let. 2014, 105, 112106
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 T. Washio et al., J. Appl. Phys. 2011, 110, 074511
 A. O. Lafond et al., Acta Crystallographica B 2014, 70, 390
5:30 PM - EE1.2.04
Solution-Based Deposition of Silver-Alloyed Cu2ZnSn(S,Se)4 Solar Cells
Priscilla Antunez 1,Talia Gershon 1,Oki Gunawan 1,Yun Lee 1,Douglas Bishop 2,Ravin Mankad 1,Brian McCandless 2,Richard Haight 1
1 IBM T.J. Watson Research Ctr Yorktown Heights United States,2 University of Delaware Institute of Energy Conversion Newark United StatesShow Abstract
Thin film solar cell absorbers composed of earth-abundant elements such as Cu2ZnSn(S,Se)4 (CZTSSe) are particularly relevant due to their low toxicity and their record maximum power conversion efficiency of 12.6%. Despite promising results, further work is needed to understand how to improve this technology and enable its commercial-scale implementation. Recent efforts have identified the need to remove defect states by deliberate passivation or the introduction of dopants in order to improve upon the voltage deficits (compared to theoretical limits) exhibited by CZTSSe. The inclusion of Ag could reduce tail states that are introduced by the disorder caused in the random alternation of copper and zinc in the kesterite lattice (the copper cation is only 5% larger than the zinc cation). Herein we use a hydrazine solution growth procedure to deposit the CZTSSe absorbing layer, and use different alloying levels of Ag to substitute Cu. Compositional profiling across the absorber layer shows an almost homogeneous distribution of Ag, and the electrical characterization of the Ag-alloyed devices gives a record power conversion efficiency of 8.1% without the use of an antireflective coating. Changes in band gap, carrier density concentrations, and minority carrier lifetimes (measured by time-resolved photoluminescence, TRPL) are also used to assess the effects of Ag alloying. In addition, this study compares the use of Na and different Li salts and their effects on the absorber’s crystal grain structure, size, and overall device performance. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), time-resolved photoluminescence, and photoluminescence imaging are used to characterize the Ag-alloyed CZTSSe devices. This work is supported by the U.S. Department of Energy under DE-EE0006334.
5:45 PM - EE1.2.05
Phase Transformation during Cu2Znsns4 Synthesis by Reactive Magnetron Co-Sputtering
Pierre-Antoine Cormier 1,Rony Snyders 2
1 University of Mons Mons Belgium,1 University of Mons Mons Belgium,2 Materi Nova Mons BelgiumShow Abstract
Cu2ZnSnS4 (CZTS) has attracted significant attention for thin film solar cells because it is composed on earth abundant and non-toxic elements and, has an optimal band gap of 1.5 eV. CZTS absorbers are currently synthesized by annealing metallic precursors in sulfur atmospheres. Foreseeing large scale applications, one step processes, for example based on reactive magnetron sputtering, are currently developed [1-3]. The control of the film stoichiometry is critical during the CZTS growth since it influences the electrical properties of the material and its phase constitution. Indeed, it has been shown, based on phase diagram, that the experimental windows allowing to grow CZTS is very narrow [4,5]. Nevertheless, these diagrams are not relevant for low pressure processes operating outside the thermodynamical equilibrium. Therefore, the aim of the present work is to go further in the understanding of the influence of the Cu, Zn, Sn and S concentrations on the film phase constitution by drawing a phase diagram scalable to one step magnetron sputter processes.
We previously reported the growth of close to stoichiometric and phase pure CZTS thin films by sputtering a Zn and a CuSn alloy targets in Ar-H2S atmospheres by magnetron sputtering . The amount of metallic species (Cu, Zn, Sn and S) provided to the growing film is modified by varying: (i) the CuSn target composition and (ii) the power applied to this target, while the other experimental parameters are kept constant. The film phase constitution is determined by combining multi-wavelengths Raman spectroscopy and X-Ray diffraction analysis whereas the atomic concentration is measured by Energy-dispersive X-ray spectroscopy.
All the synthesized films are regrouped in a phase diagram which exhibits three groups of phase compositions: CZTS-ZnS, CZTS-SnS-ZnS and SnS-ZnS-Cu4Zn-S6. The main factor affecting the phase transformation is the sulfur concentration in the films. An atomic sulfur concentration < 50 % was found to be necessary to synthesize CZTS films. Its decrease associated to the increase of the Sn amount leads to the disappearance of CZTS to the profit of SnS phase. The electrical properties of the films have been evaluated by Hall effect measurements. All the films exhibited a p-type conductivity with a high hole concentration between 1017 and 1020 cm-3. The CZTS films have the highest holes concentration which could be explained by a high amount Cu or by the presence of the ZnS phase. A very low Hall mobility is found in comparison with the value usually reported in the literature. This is explained by a small grain size and defects in the film microstructure.
 Cormier et al., Acta Materiallia, 96 (2015) 80-88
 Liu et al., Sol. Energy Mater. Sol. Cells 94 (2010) 2431–2434.
 T. Ericson et al., Thin Solid Films 520 (2012) 7093–7099.
 C. Platzer-Bjorkman et al., Sol. Energy Mater. Sol. Cells 98 (2012) 110–117.
 Mitzi et al., Solar Energy Materials & Solar Cells 95 (2011
EE1.3: Poster Session I
Wednesday AM, March 30, 2016
Sheraton, Third Level, Phoenix Ballroom
9:00 PM - EE1.3.01
Structural Investigations on the Solid Solution Series CH3NH3PbI3 – CH3NH3PbCl3
Alexandra Franz 1,Julia Steckhan 2,Daniel Toebbens 1,Susan Schorr 3
1 Helmholtz -Zentrum Berlin Berlin Germany,1 Helmholtz -Zentrum Berlin Berlin Germany,2 Universität Potsdam Potsdam Germany1 Helmholtz -Zentrum Berlin Berlin Germany,3 Freie Universität Berlin Berlin GermanyShow Abstract
Hybrid perovskites became of high interest in the recent years due to their huge variety of element substitutions on both cation and anion sites and thus the tailoring of new materials for solar energy conversion. Our work is mainly focused on the solid solution CH3NH3PbI3 – CH3NH3PbCl3 which shows on the one iodine end member fast rising efficiencies of more than 20% solar conversion efficiencies.
The solid solution shows in case of 2.2% chlorine ratio a bandgap of about 1.1eV and additionally a higher air stability  which is still a problem in case of the iodine perovskite.
The CH3NH3PbI3 (MAPbI3) shows a tetragonal crystal structure (s.g. I4/mcm) while the chlorine perovskite (MAPbCl3) belongs to the cubic space group Pm-3m. Both structures consist of corner linked PbX6 – octahedra (X=I, Cl). However due to different electronic effects the iodine perovskite shows an octahedral tilting and disordering of the anions which influences the orientation of the organic methylammonium molecule and therefore photovoltaic properties.
Therefore we investigated as well the solid solution end members as systematically the solid solution possibilities with regard to the degree of substitution and miscibility.
The iodine end member was prepared by precipitation from hydroiodic solution  while MAPbCl3 was prepared by precipitation of lead(II) acetate from a methyl amine solution . Polycrystalline MAPbI3-xClx was synthesized from an equimolar mixture of methylammonium halide and lead(II) halide in a mixture of γ-butyrolactone and N,N-dimethylformamide . For structural investigations synchrotron X-ray and neutron diffraction experiments were performed at the Helmholtz-Zentrum Berlin für Materialien und Energie. In the presentation the main results of this complementary study concerning detailed structural parameters, especially the hydrogen positions and the orientation of the methylammine molecule, will be discussed.
1. Boix, P.P., et al., Current progress and future perspectives for organic/inorganic perovskite solar cells. Materials Today, 2014. 17(1): p.16-23.
2. Poglitsch, A. and D. Weber, Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter wave spectroscopy. The Journal of Chemical Physics, 1987. 87(11): p. 6373-6378.
3. Leguy, A.M.A., et al., Reversible hydration of CH3NH3PbI3 in films, single crystals, and solar cells. CHEMISTRY OF MATERIALS, 2015. 27(9): p. 3397-3407.
4. Baikie, T., et al., Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications. Journal of Materials Chemistry A, 2013. 1(18): p. 5628-5641.
9:00 PM - EE1.3.02
Surface Charge Recombination in Hybrid Perovskite Single Crystals: Implication in Applications for Photovoltaics and Narrow Band Photodetectors
Yanjun Fang 1,Qingfeng Dong 1,Yuchuan Shao 1,Yongbo Yuan 1,Jinsong Huang 1
1 University of Nebraska - Lincoln Lincoln United States,Show Abstract
Methylammonium lead trihalide perovskite (MAPbX3 X is Cl, Br, or I) has emerged as a new generation of solution-processable optoelectronic materials for photovoltaics, light emitting diodes, lasers, and photodetectors. Most of these applications, however, are based on perovskite thin films which usually contain large density of charge traps at the grain boundaries. Since single crystals possess no grain boundaries, it is anticipated that perovskite single crystal based devices can possess much better optoelectronic performance. Recently, we have demonstrated that the carrier diffusion length in solution-grown MAPbI3 single crystals is larger than 175 μm, more than two orders of magnitude longer than the thin film counterpart, which resulted in a nearly 100% internal quantum efficiency (IQE) near band edge in the thick perovskite single crystal solar cells.1 However, the largely suppressed IQE at short wavelength range indicates the existence of severe surface charge recombination on the perovskite single crystals that would hinder the efficient charge collection.
Here, we first studied the surface charge recombination velocity of perovskite single crystals via photoconductivity measurement, and illustrated its origin and possible ways to reconcile it for photovoltaic application. Moreover, the surface charge recombination was intentionally utilized to fabricate highly narrow band perovskite single crystal photodetectors with full-width-at-half-maximum (FWHM) < 20 nm, and continuously tunable response spectra from blue to red by changing the halide composition and consequently, the bandgap of the single crystals.2 The narrow-band photo-detection can be explained by the strong surface charge recombination of the excess carriers close to the crystal surfaces generated by short wavelength light. The excess carriers generated by below bandgap excitation locate away from the surfaces and can be much more efficiently collected by the electrodes assisted by the applied electric-field. To the best of our knowledge, this is the first time that perovskite single crystals were utilized for photodetector application and exhibited the unique narrow band light response in contrast to the thin film analogues. These are also the narrowest band photodetectors reported with a continuously tunable response spectrum. The new design paradigm presented in this work provides an alternative approach to realize the optical filter free UV, visible, or IR narrow band photodetection, and it is not limited to any specific material system.
Q. Dong, et al. "Electron-hole diffusion lengths> 175 μm in solution-grown CH3NH3PbI3 single crystals." Science 347, 967-970 (2015).
Y. Fang, et al. "Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination." Nature Photonics 9, 679–686 (2015).
9:00 PM - EE1.3.03
NH4Cl Regulated Crystallization and Film Formation of CH3NH3PbI3-xBrx for Efficient Planar Heterojunction Solar Cell
Jian He 1,Tao Chen 1
1 Physics The Chinese Univ. of Hong Kong Hong Kong Hong Kong,Show Abstract
Organic-inorganic hybrid CH3NH3PbI3 perovskite solar cells have been investigated intensely in the past few years with efficiency exceeding 20%. The substitution from I to Br in CH3NH3PbI3 was proven to tune the band gap from 1.50 eV to 2.20 eV conveniently. This feature makes CH3NH3PbI3-xBrx very attractive in terms of fabricating colorful and semi-transparent devices. It was also found that CH3NH3PbI3-xBrx displays excellent photovoltaic property with improved long-term stability.
However, it is not easy to fabricate uniform and well crystalized CH3NH3PbI3-xBrx planar films. Reaction between PbX2 (X=Br or I) and CH3NH3X (X=Br or I) usually leads to films with rough surface and low coverage, resulting in poor performance of the solar cells. Here we report a one-step solution method to fabricate more uniform and crystalized CH3NH3PbI3-xBrx (x=0, 0.45, 0.51, 0.60, 1, 2, 3) film on FTO/TiO2 by using NH4Cl additive. The films with improved coverage and crystallization were confirmed by SEM and XRD. UV-vis spectrum showed that the absorbance of the films using NH4Cl was greatly enhanced comparing to those without NH4Cl. Efficiencies of the resulting planar solar cells can be largely improved. Especially when x = 0.60, the efficiency increased from 6.40% to 12.10% by 89%. As far as we know, this is the highest efficiency of planar heterojunction solar cell based on CH3NH3PbI3-xBrx. Furthermore, we also conducted in-situ XRD to explore the role played by NH4Cl in the film formation.
To sum up, this work provides a convenient approach for the fabrication of high efficiency CH3NH3PbI3-xBrx based planar heterojunction solar cells.
1. Zhou, H., et al., Interface engineering of highly efficient perovskite solar cells. Science, 2014. 345(6196): p. 542-546.
2. Noh, J.H., et al., Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. Nano Lett, 2013. 13(4): p. 1764-9.
3. Zhao, Y. and K. Zhu, Efficient planar perovskite solar cells based on 1.8 eV band gap CH3NH3PbI2Br nanosheets via thermal decomposition. J Am Chem Soc, 2014. 136(35): p. 12241-4.
9:00 PM - EE1.3.04
Epitaxial Thin Film Cu2O Photovoltaic Devices
Yulia Tolstova 1,Stefan Omelchenko 1,Harry Atwater 1
1 California Inst of Technology Pasadena United States,Show Abstract
In this study we fabricate the first epitaxially grown Cu2O thin film photovoltaic devices, incorporating a Zn(O,S) buffer layer. We start by depositing 50 nm thin films of Au and Pt with sub-nanometer roughness on single crystalline MgO substrates. This ohmic back contact, which serves as a heteroepitaxial template, is then used to deposit phase pure, oriented Cu2O thin films of 5 μm thickness by plasma-assisted molecular beam epitaxy (PA-MBE). Then, a 30 nm Zn(O,S) buffer layer is sputtered to form a stoichiometric Cu2O-Zn(O,S) interface crucial for achieving high open circuit voltages, followed by an 80 nm layer of ITO as a top contact. Zn(O,S) has been developed as a Cd-free, earth-abundant, and scalably manufacturable window layer material for CIGS solar cells, and has a conduction band tunable by the relative O and S concentrations. Its thermodynamic properties make it a great heterojunction partner for Cu2O.
We report current-voltage, spectral response, and light beam-induced current characteristics of thin film Cu2O solar cells and correlate device performance with material structure and quality. The film and interface structure and defects are analyzed by high-resolution cross-sectional transmission electron microscopy and x-ray diffraction. Our material system has achieved open circuit voltages above 1 V, as well as short circuit currents of a few milliamps. We also demonstrate a scheme for replacing the precious metal contacts currently employed in Cu2O photovoltaic devices.
We conclude by discussing the outlook for epitaxial Cu2O thin film photovoltaic devices considering current trends in the PV market. Cu2O has been regarded as a promising photovoltaic material for many decades, and most of the device results have been achieved on thermally oxidized, polycrystalline Cu2O foils. Cu2O’s bandgap of 2.1 eV makes it a strong wide bandgap candidate for a tandem solar cell with a crystalline Si bottom cell. The Cu2O cell efficiency required to improve upon the efficiency of a crystalline Si cell in such a tandem configuration is around 8%. While the theoretical efficiency for a Cu2O solar cell is around 21%, the experimental record efficiency for a Cu2O device has tripled in the past few years and recently surpassed 6%. Our work presents a path to create an entirely earth-abundant, high efficiency tandem solar cell.
9:00 PM - EE1.3.05
Defect Behavior in Cu2SnS3: Point Defects, Disorder, and Alloying Investigated via Theory and Experiment
Lauryn Baranowski 1,Pawel Zawadzki 2,Stephan Lany 2,Eric Toberer 1,Andriy Zakutayev 2
2 National Renewable Energy Laboratory Golden United States,1 Colorado School of Mines Golden United States,2 National Renewable Energy Laboratory Golden United States1 Colorado School of Mines Golden United StatesShow Abstract
As the world’s demand for energy grows, the search for cost competitive and earth abundant photovoltaic materials becomes increasingly important. Cu2SnS3 (CTS) is a promising earth abundant absorber with demonstrated 4% device efficiency , and interest in this material has increased rapidly in the past few years. Our work on CTS has focused on understanding the defect physics of this material, and how these defects affect the carrier transport. Here we present a summary of our experimental and theoretical findings, including insights on the roles of point defects, cation disorder, and alloying in CTS.
We initially investigated defect behavior in CTS from the perspective of point defects. Theoretical calculations determined that the dominant acceptor defect in CTS is the Cu vacancy (VCu), which would be expected to control the hole concentration . Experimentally, we control the VCu concentration by varying the S chemical potential during film growth . Additionally, we observed that the as-grown films were cation disordered, as opposed to the theoretical predictions of a cation ordered structure.
Because of the importance that cation disorder has in similar materials such as CZTS, we investigated this issue in CTS. Theoretically, we found that cation disorder in CTS can cause regions of compositional inhomogeneity, or “clusters” of specific coordination motifs. These clusters may lead to electronic potential fluctuations and band tailing, ultimately affecting photovoltaic device performance . Experimentally, we used terahertz spectroscopy to evaluate the minority carrier transport in ordered and disordered CTS. We found that even the ordered films showed poor minority carrier transport, including picosecond decay times and carrier localization. We couple this data with high-resolution TEM to conclude that even very low levels of structural defects (such as stacking faults or twins) can dominate the carrier transport in CTS .
Further theoretical investigations of disorder in Cu2SnS3 have revealed that cation disorder can significantly lower the formation energy of CuSn antisite defects . This can ultimately result in alloying with a semi-metallic Cu3SnS4 phase. Experimental spectroscopy techniques (Raman and NEXAFS) were used to detect changes in S and Cu bonding environments that result from formation of the predicted Cu2SnS3-Cu3SnS4 alloy.
 Kanai, et al. J. Journal of Appl. Phys 54, 08KC06 (2015).
 Zawadzki, et al. Appl. Phys. Lett. 103, 253902 (2013).
 Baranowski, et al. Chem. Mater. 2014, 26, 4951-4959.
 Zawadzki, et al. Phys. Rev. Appl. 3, 034007 (2015).
 Baranowski, et al. Phys. Rev. Appl. In press (2015).
 Zawadzki, et al. Submitted, 2015.
The project “Rapid Development of Earth-Abundant Thin Film Solar Cells” is supported as a part of the SunShot initiative by the U. S. Department of Energy, Office of Energy Efficiency and Renewable Energy under Contract No. DE-AC36-08GO28308 to NREL.
9:00 PM - EE1.3.06
Toward Improving the Prospects of Antimony Chalcogenide Solar Cells
Geovanni Vazquez-Garcia 1,Fabiola De Bray-Sanchez 1,Jose Diego Gonzaga-Sanchez 1,Diego Perez-Martinez 1,M.T. Santhamma Nair 1,P.Karunakaran Nair 1
1 IER UNAM Temixco Mexico,Show Abstract
Among prospective thin film solar cell materials, antimony chalcogenides have a place owing to their availability, low toxicity and low cost. Even though the current production of antimony is concentrated in a few countries, antimony may be recovered more profitably once its solar cell application is developed. We used in this work antimony sulfide and antimony sulfide-selenide powder obtained by chemical precipitation of antimony salt, sodium thiosulfate, thioacetamide and sodium selenosulfate. Typical solar cell structure is simple: (i) TCO/Sb2S3/C-Ag or (ii) TCO/CdS/Sb2S1.2Se1.8/C-Ag. Here TCO is a commercial SnO2:F coating on 3 mm glass, CdS is chemically deposited thin film of 80 nm in thickness, the antimony chalcogenide film is 400 nm in thickness produced by thermal evaporation of the precipitate. Carbon electrodes are of 0.5 – 1 cm2 in area, painted using colloidal graphite and heated at temperatures of 280-300 oC. Colloidal silver paint is applied on C-electrode after the heating. In cell (i), the open circuit voltage is 0.7 V, the short circuit current density is 9 mA/cm2, fill factor, 0.37 and conversion efficiency, 2.3%. In cell (ii), these values are 0.53 V, 11 mA/cm2, 0.36 and 2.1%. Together, the absorber films might improve upon these cell characteristics in a cell structure (iii) TCO/CdS/Sb2S3-Sb2S1.2Se1.8/C-Ag.
9:00 PM - EE1.3.07
Photovoltaic Performance of Solid State Heterojuntions with Sb2SxSe3-x Sensitized Mesoporous TiO2 Layers
Araceli Hernandez-Granados 1,Jose Escorcia-Garcia 3,Diego Perez Martinez 1,Hailin Hu 1,Elsa Menchaca-Campos 2,J. Garcia-Cerrillo 1
2 Centro de Investigacion en Ingenieria y Ciencias Aplicadas Universidad Autonoma del Estado de Morelos Cuernavaca Mexico,1 Instituto de Energias Renovables Universidad Nacional Autonoma de Mexico Temixco Mexico,3 Cinvestav-Unidad Saltillo, Av. Industria Metalúrgica 1062, Parque Industrial Coahuila Mexico1 Instituto de Energias Renovables Universidad Nacional Autonoma de Mexico Temixco Mexico2 Centro de Investigacion en Ingenieria y Ciencias Aplicadas Universidad Autonoma del Estado de Morelos Cuernavaca MexicoShow Abstract
Titanium dioxide (TiO2) is considered one of the most promising semiconductors in sensors, solar cells, photodetectors, photocatalysis, etc. Due to its n-type conductivity and wide band gap (3.2 eV), it has been an important component in the dye sensitized solar cells (DSSC) during the last 25 years. However, the use of organic dyes to sensitize the mesoporous TiO2 layers of the DSSCs make them unstable under continuous solar radiation. In order to avoid this, new inorganic sensitizers such as semiconductors have been developed to fabricate high efficient semiconductor-sensitized solar cells (SSSCs). In this work is presented the fabrication and optimization of SSSCs using a solid solution of antimony sulfide-selenide (Sb2SxSe3-x). For the fabrication of the SSSCs an electron blocking layer of TiO2 (bl-TiO2) with 60 nm in thickness is deposited by spin-coating onto a conductive glass substrate (F-doped SnO2, FTO). Then, a mesoporous TiO2layer (mp-TiO2) of about 300 nm is obtained by spin coating on the top of bl-TiO2. Later, the mp-TiO2 is sensitized with cadmium sulfide (CdS) and antimony sulfide-selenide by successive ionic layer absorption. The SSSCs are completed by placing graphite/silver contacts on the top of the Sb2SxSe3-x absorber with a post-heating of the entire cell at 300 °C in nitrogen. The optical and electrical measurements of these cells indicate that the sensitizing process with CdS and Sb2SxSe3-x absorbers improve significantly the light absorption and photogenerated current of the mp-TiO2 layers, with respect to those SSSCs without CdS or Sb2SxSe3-x. Furthermore, the presence of CdS between the mp-TiO2/Sb2SxSe3-x interface plays an important role to obtain solar cells with better photovoltaic parameters. The best solar cell showed an power conversion efficiency above of 1% under AM 1.5G solar radiation. Improvement of the photovoltaic characteristics of the SSSCs by optimizing the deposition of CdS and Sb2SxSe3-x absorbers as well as increasing the porosity of the mp-TiO2 layer are discussed.
9:00 PM - EE1.3.08
Structure-Property Relationships Study of CdTe Grain Boundaries via Wafer Bonding
Tadas Paulauskas 1,Fatih Sen 2,Cyrus Sun 3,Edward Barnard 4,Maria Chan 2,Moon Kim 3,Sivananthan Sivaligham 1,Robert Klie 1
1 University of Illinois at Chicago Chicago United States,2 Argonne National Laboratory Argonne United States3 University of Texas at Dallas Dallas United States4 L Berkeley National Laboratory Berkeley United StatesShow Abstract
Poly-crystalline CdTe-based photovoltaic (PV) devices are the forerunners in commercialized thin film solar cell technology. Despite the commercial success, present laboratory champion cells achieve ~21% power conversion efficiency and hence are still ~10% shy of its theoretical limit. Current research efforts are mainly focused on improving the open circuit voltage, Voc, which is just 60% of CdTe band-gap /e in the most efficient solar cells. In this collaborative study we investigate effects of numerous randomly oriented grain boundaries and their role in limiting further improvements. It is very challenging to examine individual behavior of these sub-micrometer crystallites within as-grown poly-CdTe and to decouple surface effects. To overcome these difficulties we fabricate a number of artificial grain boundaries by CdTe wafer bonding which allow us to study CdTe interfaces in isolation. To reveal atomic structures of the interfaces we use aberration-corrected scanning –transmission electron microscope (STEM) and atomic-column resolved X-ray spectroscopy. Electronic and thermodynamic properties of these selected interfaces are then calculated using first-principles density-functional theory (DFT). To investigate role of the interfaces on charge carrier lifetimes 2-photon time-resolved photo-luminescence (TRPL) experiments are carried out which allow probing the crystals deep below influence of surface effects. Finite elements analysis simulations are used to extract interface recombination velocities based on the TRPL data and correlate with STEM imaging and DFT calculations to identify detrimental structures and ways to passivate them. A number of previous studies suggested that Cl segregation at grain boundaries after CdCl2 treatment might be transforming the interfaces into effective charge carrier channels which assist their collection. We investigate the effects CdCl2 treatment on these artificial grain boundaries using TRPL and DFT calculations.
Supported by Department of Energy SunShot BRIDGE Program (DOE DEEE0005956)
9:00 PM - EE1.3.09
Atomistic Level Characterization of Grain Boundaries in CdTe Using STEM and DFT
Fatih Sen 1,Christopher Buurma 2,Tadas Paulauskas 2,Cyrus Sun 3,Moon Kim 3,Sivananthan Sivaligham 2,Robert Klie 2,Maria Chan 1
1 Argonne National Laboratory Lemont United States,2 University of Illinois at Chicago Chicago United States3 University of Texas at Dallas Richardson United StatesShow Abstract
CdTe is a widely-used photovoltaic material, due to its high efficiency and low manufacturing cost. However, the practical efficiencies of polycrystalline CdTe photovoltaic cells are still well below the theoretical limit, indicating possible room for improvement. A fundamental understanding of the role of vacancies, interstitials, dislocations and grain boundaries on the electronic structure of CdTe may lead to efficiency improvements. Atomistic-level characterization, including microscopy and first principles modeling, is crucial in developing such a fundamental understanding. In the present work, we manufactured selected bicrystals of CdTe and revealed the grain boundary and dislocation core structures. We constructed atomistic models of grain boundaries and dislocation cores from image analysis and crystallographic information from STEM and modeled using first principles density functional theory (DFT) calculations. In addition, we carried out high-throughput search for twist and tilt grain boundary structures that have low interfacial energy using empirical potentials. We report the electronic density of states (DOS) and planar-averaged electrostatic potential profiles of different CdTe grain boundaries to understand charge interactions. We also present the results of point defects and pairs of point defects that are present on or near several representative grain boundary models. We discuss the thermodynamics of point defect and complex formation, as well as resultant changes in electronic structures. The implications of these electronic structure changes at grain boundaries on photovoltaic performance, and corresponding strategies to improve performance, are discussed.
ACKNOWLEDGEMENT: We acknowledge funding from the DoE Sunshot program under contract # DOE DEEE005956. Use of the Center for Nanoscale Materials was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The submitted abstract has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.
9:00 PM - EE1.3.10
Carbon Nanotube/Silicon Heterojunction Solar Cells Fabricated by Solution-Based Mild Process
Eri Muramoto 1,Yuhei Yamasaki 1,Feijiu Wang 2,Kei Hasegawa 1,Kazunari Matsuda 2,Suguru Noda 1
1 Department of Applied Chemistry Waseda University Tokyo Japan,2 Institute of Advanced Energy Kyoto University Kyoto JapanShow Abstract
Solar cells fabricated by simply coating n-type mono-crystalline silicon with carbon nanotubes (CNTs) have been reported . Photovoltaic conversion efficiencies (PCE) exceed 11% and 17% with pristine and MnOx-coated SWCNT films, respectively . Such high PCEs, however, are achieved using highly crystalline SWCNT films captured on membrane filters by floating catalyst chemical vapor deposition (CVD) or SWCNT films processed in superaicd. Mild solution process of mass-produced CNTs is more promising for large-scale production of CNT films.
In this work, we studied the surfactant-based mild solution process for CNT films with a focus on removal of contaminated surfactants. Two kinds of CNT powders, MEIJO eDIPS (Meijo Nano Carbon Co., Ltd.) produced by enhanced Direct Injection Pyrolytic Synthesis method , and vertically aligned SWCNTs produced by on-substrate CVD , were used. Their dispersions were prepared by ultrasonication in 0.5 wt% sodium dodecylbenzene sulphonate aqueous solution and centrifugation. The dispersion was filtered onto a hydrophilic membrane filter, which was slowly immersed into purified water to let CNT film detach and float on the water surface. Water was heated to and held at ~70 °C for 3 h to remove surfactant residue from the film, and then the film was transferred onto SiO2/n-Si substrate with a bare Si window of 1-2 mm in diameter. Gold anode and indium cathode were connected to the CNT film and n-Si, respectively. The as–fabricated cell with eDIPS CNT film of 80% optical transmittance showed a short-circuit current density of 30.0 mA/cm2, an open-circuit voltage of 0.565 V, and a fill factor of 0.600, leading to a PCE of 10.2% (drastically improved from <5% without careful surfactant removal). Further doping of and impurity removal from the CNTs with 1 M HNO3 considerably improved the fill factor, resulting in a PCE of 12.6%. The cells with on-substrate-produced SWCNTs showed a PCE of 9.1% despite of their inferior crystallinity than the eDIPS CNTs. Effective removal of surfactant is the key to realize solar cells using solution-processed CNT films.
9:00 PM - EE1.3.11
Cadmium Oxysulfide (CdSxO1-x) as Novel High Transmittance Buffer Layer Formed by Surfactant Mediated Chemical Bath Deposition for Thin-Film Heterojunction Solar Cells
Faruk Ballipinar 2,Naoki Kitamura 2,Abhishek Nandur 2,Alok Rastogi 2
1 Electrical and Computer Engineering Binghamton University, SUNY, Binghamton Binghamton United States,2 Center for Autonomous Solar Power (CASP) Binghamton University, SUNY, Binghamton Binghamton United States,Show Abstract
Polycrystalline <100 nm thin CdS films used as n-type window layer play an important role in developing high efficiency heterojunction CuInSe2, Cu2ZnSnS4, and CdTe solar cells. Though CdS film is formed by vacuum evaporation, electrodeposition and atomic layer deposition, by far the best efficiency results for these solar cells are obtained with the CdS buffer layer deposited by the chemical bath deposition (CBD) method. A key requirement for the window layer is high transmittance in the visible spectrum. This enables more photons reaching the absorber and thereby increase the photocurrent and quantum efficiency of solar cells. Though the high band gap materials ZnS or ZnO1-x Sx meet this criterion, as a buffer layer these showed no improvement in solar cell performance.
In the present work, we propose an alternative window layer for the heterojunction solar cells based on cadmium oxysulfide (CdOxS1-x) thin films formed by the CBD method. The 100 nm thin CdOxS1-x films deposited by alloying CdS with CdO, which is a direct band gap n-type degenerate transparent conductor, we obtained high >90% optical transmittance over 550-1000 nm region. Corresponding pure CdS films show low ~ 70% transmission. It requires a ~20 nm thin CdS film to increase optical transmission for a gain of ~1.5 mA.cm-2 in photocurrent density. The difficulty lies in depositing continuous CdS film without shunting paths at 20 nm thickness. We show that a CdOxS1-x film of ~100 nm thickness formed with highly conformal coverage over p-type absorber surface can easily meet the optical criterion. Direct optical band gap of CdOxS1-x films determined from Tauc plots is 2.25-2.3 eV (x=0.58-0.45) within the acceptable range for a buffer layer. Obeying the Vegard’s Law, it lies between the optical gaps of CdS (2.42 eV) and CdO (2.16 eV).
The CBD growth of CdS is via controlled release of S2- and Cd2+ ions in an alkaline medium through complexing to prevent CdS or Cd(OH)2 as colloids in the solution phase. In the present method, by altering the substrate conditions in which Cd2+ ions sheathed within micelle or surrounded by hydrophobic groups of sodium dodecyl sulfate surfactant, we carried out controlled Cd(OH)2 deprotonation reaction to form CdO over the substrate concurrently with CdS to deposit CdOxS1-x films. These films are polycrystalline having cubic CdS structure identified by (111), (220) and (311) x-ray diffractions. Formation of CdOxS1-x phase is confirmed by Raman spectra which besides characteristic CdS LO A1 and A2 modes at 300 and 600 cm-1, also show Raman lines from CdO at 432 and 925 cm-1 assigned to 2LA and 2LO phonon modes. CdOxS1-x films show higher electrical conductivity and better structural stability compared to the CdS due to lesser S vacancy defects. This paper will present CBD growth, mechanistic aspects, structure, optical and electrical properties and evaluation of CdOxS1-x as a buffer layer in heterojunction solar cells.
9:00 PM - EE1.3.12
Direct Plasmon-Driven Photoelectrocatalysis
Hossein Robatjazi 1,Shah Mohammad Bahauddin 1,Chloe Doiron 3,Isabell Thomann 4
1 Department of Electrical and Computer Engineering Rice University Houston United States,1 Department of Electrical and Computer Engineering Rice University Houston United States,3 Applied Physics Program Rice University Houston United States1 Department of Electrical and Computer Engineering Rice University Houston United States,2 Department of Chemistry Rice University Houston United States,4 Department of Materials Science and NanoEngineering Rice University Houston United StatesShow Abstract
Harnessing the energy from hot charge carriers is an emerging research area with the potential to improve energy conversion technologies.1−3 Here we present a novel plasmonic photoelectrode architecture carefully designed to drive photocatalytic reactions by efficient, nonradiative plasmon decay into hot carriers. In contrast to past work, our architecture does not utilize a Schottky junction, the commonly used building block to collect hot carriers. Instead, we observed large photocurrents from a Schottky-free junction due to direct hot electron injection from plasmonic gold nanoparticles into the reactant species upon plasmon decay. The key ingredients of our approach are (i) an architecture for increased light absorption inspired by optical impedance matching concepts,4 (ii) carrier separation by a selective transport layer, and (iii) efficient hot-carrier generation and injection from small plasmonic Au nanoparticles to adsorbed water molecules. We also investigated the quantum efficiency of hot electron injection for different particle diameters to elucidate potential quantum effects while keeping the plasmon resonance frequency unchanged. Interestingly, our studies did not reveal differences in the hot-electron generation and injection efficiencies for the investigated particle dimensions and plasmon resonances.
KEYWORDS: Plasmonic solar energy conversion, hot-electron, quantum efficiency, solar water splitting, Au/NiOx, selective transport layer.
(1) Moskovits, M. Nat. Nanotechnol. 2015, 10 (1), 6.
(2) Brongersma, M. L.; Halas, N. J.; Nordlander, P. Nat. Nanotechnol. 2015, 10 (1), 25−34.
(3) Linic, S.; Christopher, P.; Ingram, D. B. Nat. Mater. 2011, 10 (12), 911−921.
9:00 PM - EE1.3.13
Nano-Level Characterization of Optical Properties and Defect States in TiO2 and Ta2O5 Based Photocatalysts
Qianlang Liu 1,Liuxian Zhang 1,Katia March 2,Toshihiro Aoki 1,Peter Crozier 1
1 Arizona State Univ Tempe United States,2 Université Paris-Sud Orsay Cedex FranceShow Abstract
TiO2 and Ta2O5 are both earth-abundant materials and efficient UV absorption semiconductors due to their large bandgaps and have shown interesting photocatalytic water-splitting behaviors when functionalized with suitable co-catalysts [1,2]. Characterization of these particulate catalyst systems is challenging since heterogeneity exists in the structure and performance of these nanoparticles. For water splitting applications, understanding surface hydroxylation processes on the surfaces of nanoparticles is also difficult. Electron energy-loss spectroscopy (EELS) in the electron microscopy has a unique advantage of studying materials’ response at high resolution allowing correlation of local optical and electronic properties with structural information including composition, morphology and surface facets. Recent advances in monochromation now allows EELS to achieve ultra-high energy resolution of 15 meV or better with spatial resolution below 1 nm . This opens up the opportunity of detecting vibrational signals, inter-band and surface states and subtle bandgap changes at the nano-level, which is valuable to understand charge transfer and reaction mechanism at the interfaces/surfaces. Here we present results on the surface states that form on oxide nanoparticle surfaces. The effects of water and defects of the electronic structure of oxides is probed with EELS. Localized bandgap measurements at the co-catalyst-oxide interface is also discussed. To interpret the spectra, simulation of inter-band states and bandgap onset were performed using both dielectric models and density of states calculation.
 L. Zhang et al, J. Phys. Chem. C 119.13 (2015), 7207.
 Q. Liu et al, Appl. Catal. B: Environ.172 (2015), 58.
 O.L. Krivanek et al, Nature 514 (2014), 209.
 The support from US Department of Energy (DE-SC0004954) and the use of the microscope at John M. Cowley Center for High Resolution Microscopy at Arizona State University is gratefully acknowledged.
9:00 PM - EE1.3.14
The Effect of Critical Thickness on the Photovoltaic Performance of InGaN/GaN Multiple Quantum Wells in a p-i-n Junction Solar Cell
Alec Fischer 1,Hongen Xie 4,Shuo Wang 1,Heather McFavilen 2,Chantal Arena 2,Stephen Goodnick 3,Fernando Ponce 1
1 Physics Arizona State University Tempe United States,4 Material Science and Engineering Arizona State University Tempe United States2 Soitec Phoenix Labs Inc Tempe United States3 Engineering Research Center Arizona State University Tempe United StatesShow Abstract
We have studied the optical, electrical, and structural properties of InGaN/GaN multiple quantum wells (MQWs) in a p-i-n solar cell grown by metalorganic chemical vapor deposition (MOCVD). Four equivalent structures were grown with 9, 20, 40, and 60x QWs in order to understand the limiting factors of the device performance. First, the onset for plastic relaxation as the total QW thickness increases from 40 to 60x (i.e. 120 to 180 nm) is observed by the opening of threading dislocation cores at a given thickness, when the film can no longer store the accumulated misfit strain energy between InGaN and GaN. The estimated critical thickness of ~129 nm is similar to that of a thick InxGa1-xN film with x=0.12 grown on GaN, according to the People and Bean model. Second, we observe an increase in the integrated absorption (from 280 nm to InGaN band gap) with an increase in the number of QWs. The integrated absorption does not improve considerably despite the increase in number of QWs from 40 to 60x, reaching a maximum of ~84%. This may be due to the degradation of the material quality beyond the critical thickness of InGaN which plays an important role in the absorption. Despite the higher absorption for the device with 60x QWs, the best cell performance under 300x suns is for 9x QWs with measured short-circuit current Jsc = 516 mA/cm2, open-circuit voltage Voc = 1.7 V, calculated fill factor of 0.71, and power of 623 mW/cm2. Piezoelectric polarization fields and the non-radiative recombination centers limit the Jsc and Voc, with the latter having a stronger effect for higher number of QWs due to material degradation. The correlation of these properties with the microstructure will be discussed.
9:00 PM - EE1.3.15
Combinatorial Synthesis and High-Throughput Photoelectrochemical Assessment of Fe-W-Ti-O Thin-Film Materials Libraries for Solar Water Splitting
Helge Stein 1,Chinmay Khare 1,Kirill Sliozberg 2,Robert Meyer 1,Wolfgang Schuhmann 3,Alfred Ludwig 3
1 Institute for Materials Ruhr-Universität Bochum Bochum Germany,2 Analytical Chemistry, Center for Electrochemical Sciences (CES) Ruhr-Universität Bochum Bochum Germany2 Analytical Chemistry, Center for Electrochemical Sciences (CES) Ruhr-Universität Bochum Bochum Germany,3 Materials Research Departement Ruhr-Universität Bochum Bochum Germany1 Institute for Materials Ruhr-Universität Bochum Bochum Germany,3 Materials Research Departement Ruhr-Universität Bochum Bochum GermanyShow Abstract
Discovery and optimization of metal oxide based semiconductors for photoelectrochemical water splitting that are abundant, stable and non-toxic is challenging. The predominantly investigated binary oxides Fe2O3, TiO2 and WO3 do not show sufficient stability, a suitable bandgap, efficient light absorption, high catalytic activity or long charge carrier lifetimes so that new materials need to be identified. As the number of possible multinary mixtures of yet to be found materials is enormous, new methods of rapid synthesis and high-throughput/high-quality evaluation and optimization need to be implemented. Using this approach, synthesized Ti-W-O, Fe-W-O and Ti-Fe-W-O materials libraries were thoroughly characterized for potential photoelectrode materials by automated EDX, XRD, thickness and PEC measurements. For the Ti-W-O system exhibiting a compositional range between (Ti80W20)Ox and (Ti97W3)Ox, the PEC measurements revealed a maximum quantum efficiency of 37.5 % (at λ = 350 nm) and a maximum peak photocurrent density of 70.3 µA/cm2 at 94.4 at.% Ti. Extensive phase analysis in the case of Fe-W-O indicated the presence of a ternary phase Fe2O6W at the local photocurrent maxima, while the sub-stoichiometric W5O14 phase (with 15 at.% Fe) demonstrated a maximum quantum efficiency of 45 % at λ = 300 nm and photocurrent densities of 65 µA/cm2. Utilizing new ways for visualization of the obtained multidimensional datasets correlations between composition, morphology, thickness, crystallinity and PEC properties were made. An overview of optimization routes implemented in our combinatorial materials science framework by variation of deposition pressure, substrate temperature using an actively controlled step heater, and glancing angle deposition for nanostructuring will be shown.
9:00 PM - EE1.3.16
Optimizing New Type Nano-Composite Infrared-to-Ultraviolet Up-Conversion Luminescence Layer for Efficient Anatase Titania Film-Based Dye-Sensitized Solar Cells Dye Sensitized Solar Cells
Halil Yavuz 1,Idris Candan 2,Serkan Yetkin 1
1 Mechanical Engineering Yuzuncu Yil University Van Turkey,2 Center for Solar Energy Research and Applications Ankara TurkeyShow Abstract
Many research works reported that the rare earth ions is an advanced doping elements for optoelectronic ceramic materials which have potential applications on data storage, color display, multiplexed bio-imaging devices due to its excellent properties of having rich energy levels and their upconversion luminescence spectra are in a wide range from infrared to ultraviolet and tunable. However upconversion materials can be used for visible light producer via absorbtion of unabsorbed-infrared solar radiation for solar cells. Dye-sensitized solar cells (DSSC) have attracted great interest due to their large potential applications as a cheap alternative candidate to replace conventional silicon-based p–n junction solar cells. For many years, TiO2 and ZnO absorber nanomaterials such as nanoparticles, nanowires and nanotubes and the organometallic ruthenium dye families such as N719, N3 and C101 are well known suitable most efficient materials to obtain highly efficient photo anodes. However, the maximum light conversion efficiency of DSSC has a barrier around 10% recorded. To alter this barrier, using light v layer, which is new subject matter to extend the light path, is performed to enhance the light harvesting efficiency. The suitable converter layer should be composed of Ba2YbF7 or doping whit Tm3+ or Er3+. In this study, to better understand of the up conversion emission effect on solar cell harvesting of Yb3+ concentration of Ba2YF7:xYb3+,0.02Er3+ (x = 0.2, 0.4, 0.6, 0.8, 0.98) used as upconversion layer to improve photo conversion efficiency of DSSC. Average size of converter layer particules is found as 10 nm by TEM. 45 % total improvements has been recorded on photovoltaic efficiency. In addition, highest IPCE value obtain DSSC whit upconversion layer than traditional DSSC. Surprisingly 25% improvements has been seen on decreasing serial resistance on photo anode. Positive improvements effect was seen on lifetime measurements by EIS. Applied upconversion layer obtains nearly two times higher recombination time. In addition, upconversion layer cells have higher diffusion length than conventional DSSC. in the light of this study, Ba2YF7:xYb3+,0.02Er3+ can be candidate an alternative material for upconversion layer applications for highly efficient dye sentized solar cell.
9:00 PM - EE1.3.17
High Efficient Inverted Bulk-Heterojunction Solar Cells with a Gradiently-Doped ZnO Layer
Sungho Nho 1,Shinuk Cho 1
1 University of Ulsan Ulsan Korea (the Republic of),Show Abstract
We demonstrate a highly efficient inverted bulk heterojunction (BHJ) polymer solar cell using a wet-chemically prepared doped ZnO with a self-organized ripple nanostructure as an electron extraction layer and a blend of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)-carbonyl]-thieno-[3,4-b]thiophenediyl]] (PTB7) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) as an active light absorbing layer. In order to enhance the electron extraction efficiency, the ZnO ripple surface was modified with various alkali metal carbonate materials including Li2CO3, K2CO3, Na2CO3, Cs2CO3, and (NH4)2CO3. The inclusion of an additional metal carbonate layer led to gradient doping of the ZnO ripple layer and improved the electron extraction properties by modifying the energy level without destroying the ZnO ripple structures. The highest performing solar cells were fabricated with Li2CO3 and yielded a maximum PCE of 10.08%; this value represents a ~14% increase in the efficiency compared to solar cells without a metal carbonate treatment.
9:00 PM - EE1.3.18
Thermochemical Solar to Fuel Conversion Efficiency Based on CALPHAD Data for Lanthanum Manganite Perovskites Doped with Strontium and Chromium
Alexander Bork 1,Erwin Povoden-Karadeniz 2,Sebastian Schweiger 1,Jennifer Rupp 1
1 ETH Zurich Zurich Switzerland,2 Materials Science and Technology Vienna University Technology Vienna AustriaShow Abstract
Finding new strategies for transition away from dependence of fossil fuels is a global challenge of the 21st century. Two-step thermochemical production of syngas, is an energy technology utilizing solar power to convert water and carbon dioxide into syngas, an attractive renewable fuel that can replace fossil fuels. Recently, perovskites have attracted much attention due to impressive solar fuel yields surpassing state-of-the-art material ceria.1 Although higher yields can be obtained, it does not imply that it is the best choice for solar to fuel reactor. It is critical to compare the thermochemical fuel conversion efficiency, because it defines the actual useful chemical energy per input of solar energy.2, 3 Typically, this is calculated from oxygen nonstoichiometry equilibrium data derived from thermogravimetric measurements in the relevant temperature range, or extrapolations of data at lower temperatures. Performing experiments to test a few selected compositions is useful but time consuming and it does not give the best estimate of the thermochemical efficiency. We calculate thermochemical fuel conversion efficiency based on CALPHAD descriptions of defect chemistry of multi-component perovskites, based on critical review of all available experimental phase stability data. It is found that this defect chemistry model based on the weighted sum of optimized energies of various ionic compounds assembling the perovskite phase extrapolates well over the whole technologically relevant temperature and oxygen partial pressure range. Further, the thermodynamic properties are determined for a continuous variation of the doping concentration x, so a large compositional space can be tested. We compare and highlight advantages of this approach to previous predictions of thermochemical efficiency. The efficiency analysis is exemplified by using data on the perovskite composition La0.6Sr0.4Mn1-xCrxO3-δ. Finally, we discuss how the presented approach can be generalized to effectively screen other dopants and select the most efficient material for various operating conditions.
1. A. H. McDaniel, E. C. Miller, D. Arifin, A. Ambrosini, E. N. Coker, R. O'Hayre, W. C. Chueh and J. Tong, Energy & Environmental Science, 2013, 6, 2424-2428.
2. A. H. Bork, M. Kubicek, M. Struzik and J. L. Rupp, Journal of Materials Chemistry A, 2015, 3, 15546-15557.
3. J. R. Scheffe, D. Weibel and A. Steinfeld, Energy & Fuels, 2013, 27, 4250-4257.
9:00 PM - EE1.3.19
Cubic SnxGe1-x Nanoalloys: Beyond Bulk Composition Limit
Karthik Ramasamy 1,Jeffrey Pietryga 1,Sergei Ivanov 1
1 Los Alamos Nat'l Laboratory Los Alamos United States,Show Abstract
Semiconductor germanium (Ge) is an extensively studied element and widely used in the semiconductor industry. However, its use as an active medium in photovoltaics is significantly hampered by its inefficient light absorption due to the indirect band gap. It has been proposed that the indirect band gap of germanium can be switched to direct band gap by alloying with tin and thereby make them a better light absorber. However, the large lattice strain and low solubility of tin in germanium makes it challenging to obtain their alloys in bulk. Nonetheless, utilizing the nanocrystals’ ability to relax large lattice strain combined with a particular selection of precursor molecules, we have already achieved1 the synthesis of SnxGe1-x alloy nanocrystals with x up to 0.4. Here we report further improvements in the synthesis of SnxGe1-x nanoalloys that yielded the product with tin content up to 95% pushing the composition limit, which has not been possible earlier. X-ray diffraction, TEM and EDX mapping analysis have confirmed the presence of homogenous alloys over the full composition range. Mechanistic and computational studies of the material formation point to the reaction pathway through the formation of intermediate cubane-like Sn-Ge imide clusters. Absorption spectroscopy of NCs of varying composition demonstrates a pronounced red-shift and increase in molar absorptivity as a more direct indicator of changes in the electronic structure toward direct band gap behavior with increasing Sn-content. The details of the synthetic approach together with results of the structural, optical characterizations and mechanistic investigation will be presented. Mechanistic implications of Sn-Ge nanoalloy formation allowed us to introduce silicon into the alloy composition and the preliminary results on the synthesis of SixGeySn1-x-y nanoalloys will also be discussed.
1. Ramasamy, K.; Kotula, P. G.; Fidler, A. F.; Brumbach, M. T.; Pietryga, J. M.; Ivanov, S. A. Chem Mater. 2015, 27, 4640-4649.
9:00 PM - EE1.3.20
Effect of Thickness on Photo Response Behavior in Si/MoS2 Heterojunction Solar Cells
Sangram Pradhan 1,Bo Xiao 1,Aswini Pradhan 1
1 Center For Materials Reserach Norfolk State Univ Norfolk United States,Show Abstract
High quality ultrathin transition-metal dichalcogenide films and their Vander Waals heterostructures are very promising for fabrication of optoelectronic devices for their superior photovoltaic performance, extreme flexibility and long lifetime due to suitable band gap and excellent light absorption capability. Designing the appropriate and suitable band structures of these materials is crucial for its promising applications. Especially, thin molybdenum disulfide (MoS2) film is fu