Yabing Qi, Okinawa Institute of Science and Technology Graduate University
Hyun Suk Jung, Sungkyunkwan University
Selina Olthof, University of Cologne
Kai Zhu, National Renewable Energy Laboratory
Borun New Material Technology Co., Ltd.
M. Braun Inc.
EN02.01: Flexible, Hysteresis, Interface, Passivation and 2D Perovskites
Monday PM, April 02, 2018
PCC North, 100 Level, Room 129 A
8:15 AM - EN02.01.02
Understanding and Quantifying the Efficiency Loss of Perovskite Solar Cells
Wallace Choy1,Wei E.I. Sha1,Hong Zhang1,Zi Shuai Wang1,Hugh L. Zhu1,Xingang Ren1
University of Hong Kong1Show Abstract
Due to interesting features of direct band gap, high and balanced carrier mobility, long electron-hole diffusion length, low non-radiative Auger recombination, and high internal quantum efficiency, perovskite solar cells (PVSCs) have been consideration as the great potential candidate for the next-generation high-performance photovoltaics. Various approaches have been proposed to improve device performances, and enhance power conversion efficiency (PCE) up to 22%. However, limited works discuss the loss mechanism and quantify the efficiency loss for perovskite solar cells.
In this work, we will unveil the loss mechanism and quantify the loss factors of perovskite solar cells. Through investigating the device performance of various fabricated perovskite solar cells, the three dominant loss factors of optical loss, non-radiative recombination loss, and ohmic loss are identified quantitatively. The perovskite-interface induced surface recombination, ohmic loss, and current leakage are also analyzed. Our theoretical and experimental results show that for experimentally optimized perovskite solar cells with the power conversion efficiency of 19%, optical loss of 25%, non-radiative recombination loss of 35%, and ohmic loss of 35% are the three dominant loss factors for approaching the 31% efficiency limit of perovskite solar cells. We also find that the optical loss will climb up to 40% for a thin-active-layer design. Moreover, a misconfigured transport layer will introduce above 15% of energy loss. Finally, the perovskite-interface induced surface recombination, ohmic loss, and current leakage should be further reduced to upgrade device efficiency and eliminate hysteresis effect. Consequently, the work offers a guideline to the researchers for optimizing perovskite solar cells and ultimately approaching the Shockley-Queisser limit of photovoltaics .
 W.E.I. Sha#, H. Zhang#, Z.S. Wang, H.L. Zhu, X. Ren, F. Lin, A.K.-Y. Jen, W.C.H. Choy*, Adv. Energy Mater., in press.
8:30 AM - EN02.01.03
Progress of Perovskite Photovoltaics Exploring for Ultra-Thin Lightweight Power Source
Tsutomu Miyasaka1,Trilok Singh1,Youhei Numata1
Toin University of Yokohama1Show Abstract
A major industrial application of perovskite photovoltaic cells will be large area fabrication of extremely lightweight flexible power sources in demand of electric vehicles and self-charging small devices in IoT society. Such application is not easy for Si solar cell, in particular for the purpose of power devices useful under weak indoor light. Perovskite solar cell capable of high voltage output can work with high performance even under very low light intensity. We fabricated Cs-doped FAMA perovskite photovoltaic cells on glass substrate  and plastic film substrate (125 um); the latter works with efficiency 15-18% exhibiting relatively small ideality factor <1.5 in intensity dependence of Voc . The cell maintains high voltage under indoor illumination, indicating the usefulness of the device as power source to the circuitry of wireless IoT devices. The plastic film perovskite device showed robust stability against mechanical bending over 1000 times. Device was fabricated by low temperature preparation of metal oxide electron transporting layer (ETL). By tuning the composition of ETL at junction structure, hysteresis was successfully removed. Heat-resistant and hydrophobic hole transport materials replaced spiro-OMeTAD to improve the device stability against ambient air and long-term light exposure. We focused on use of low temperature-prepared AM-free FA/Cs perovskite absorber in glass-based and plastic-based cells to enhance thermal resistance. The FA/Cs P3HT perovskite cell was tolerant of large temperature changes (-80 to +100C). The device durability against thermal impacts is a significant issue in R&D but it is improving by tuning the perovskite and hole transporting materials. Perovskite cells were also subjected to stability examination against exposure to high energy particle radiation such as electron and proton for the purpose to know radiation tolerance in comparison to Si, GaAs-based commercial solar cells. Based on these data, versatile applications of lightweight perovskite photovoltaic devices in IoT and smart sustainable system industries will be discussed.
 T. Singh and T. Miyasaka, Adv. Energy Mat. 2017, DOI: 10.1002/aenm.201700677
 T. Singh and T. Miyasaka, submitted.
9:00 AM - EN02.01.04
Resolving Issues in Perovskite Solar Cells
Sungkyunkwan University1Show Abstract
Since the first report on the solid-state perovskite solar cell with power conversion efficiency (PCE) of 9.7% and 500 h-stability in 2012 by our group, perovskite photovoltaics have received great attention. As a result, the highest PCE of 22.1% was reported in 2017. It is believed that perovskite solar cell is promising next-generation photovoltaics due to superb performance and very low cost. Although high photovoltaic performance was demonstrated, perovskite solar cell is suffering from current-voltage hysteresis. Since hysteric perovskite solar cell cannot guarantee long-term stability, development of methodology toward hysteresis-free perovskite solar cell is important. The hysteresis in perovskite solar cell is especially pronounced in normal mesoporous structure having TiO2 electron transfer layer. Inverted structure was proved to show non-hysteric behavior, which is however inferior to the normal structure in terms of PCE. Thus, it is important to explore effective ways to remove hysteresis in normal perovskite solar cell employing TiO2. In this talk, defect, both bulk and surface defects, is emphasized as origin of the hysteresis. Interfacial engineering is found to be one of effective methods to reduce hysteresis and improved improve stability simultaneously. However, interfacial engineering might not be sufficient to remove hysteresis completely. We successfully discovered a universal approach toward hysteresis-free perovskite solar cell, which will be discussed in detail.
9:30 AM - EN02.01.05
Process Development for Roll-to-Roll Production of Perovskite Solar Cells
Doojin Vak1,Jueng-Eun Kim1,2,Youn-Jung Heo1,2,Chuantian Zuo1,3,Dechan Angmo1,Liming Ding3,Dong-Yu Kim2,Mei Gao1
CSIRO Manufacturing1,GIST2,University of Chinese Academy of Sciences3Show Abstract
Organic-inorganic hybrid perovskite solar cells (PeSCs) are a promising solar technology with rapidly increasing power conversion efficiency (PCE). One of the key advantages of PeSCs is their solution processability. This allows PeSCs to be manufactured by cost-effective industrial roll-to-roll processes. However, rapid progress in the technology has been predominantly made by spin coating, a laboratory process that is not compatible/transferable to the roll-to-roll process. Typically, only a small fraction of reported processes developed by spin coating are applicable to the roll-to-roll process and, therefore, process re-optimization is required for the roll-to-roll process. CSIRO has been developing deposition processes by roll-to-roll compatible deposition methods and actual roll-to-roll processes. In this presentation, various approaches used in slot die coating of perovskite layers in batch and roll-to-roll processes will be presented. To realize a defect-free uniform perovskite layer, various deposition parameters including deposition temperature, coating speed, additives and drying methods are optimized. The sequential deposition process was modified to be suitable for the roll-to-roll process, producing PeSCs on flexible substrate with up to 11% PCE. The more ideal one-step deposition was also developed by additive and blowing-assisted slot die coating, and roll-to-roll produced PeSCs showed over 11% PCE without hysteresis. Hot deposition has also been found to be suitable in the roll-to-roll process. Recent progress on this process will be also presented.
10:15 AM - EN02.01.06
Electronic Structure of a Series of Two-Dimensional Metal Halide Perovskites
Antoine Kahn1,Scott Silver1
Princeton University1Show Abstract
Two-dimensional metal halide perovskites (2D-MHP), first synthesized in the 1990’s , have recently been the subject of considerable attention. In addition to interesting (opto)electronic properties linked to their reduced dimensionality, they appear to exhibit higher resistance to the environment, e.g., moisture, than their 3D-MHP counterparts, thereby offering great potential for various applications. The importance of these materials warrants in-depth investigations of their electronic properties.[2–4] Here we present recent electronic structure measurements of a series of solution-processed films of 2D butylammonium methylammonium lead iodide compounds, BA2MAn-1PbnI3n+1, n=1 - 4. XRD, AFM, UV-vis absorption, and ultra-violet and inverse photoemission spectroscopies are used to investigate these compounds. We measure valence and conduction band spectra, and determine ionization energy (IE), electron affinity (EA) and single particle gap as a function of n. We find that the single particle gap decreases from 2.77 eV for n=1 to 1.87 eV for n=4 (and 1.6 eV for the 3D-MHP MAPbI3), with IE decreasing and EA increasing in a nearly symmetric fashion, in contrast to previous results. We use the single particle gap and the onset of optical absorption at the exciton peak to calculate the exciton binding energy EB. In agreement with previous results, EB is found to be large for n=1 and 2 (390 and 110 meV, respectively). However, we find that the exciton binding energy decreases very rapidly thereafter, reaching below 50 meV by n=3. Finally, a simple model is presented to justify the electron and hole levels and the single particle gap in these quantum wells structures.
 D. B. Mitzi, C. A. Feild, W. T. A. Harrison, A. M. Guloy, Nature 1994, 369, 467.
 D. H. Cao, C. C. Stoumpos, O. K. Farha, J. T. Hupp, M. G. Kanatzidis, J. Am. Chem. Soc. 2015, 137, 7843.
 K.-G. Lim, S. Ahn, Y.-H. Kim, Y. Qi, T.-W. Lee, Energy Environ. Sci. 2016, 9, 932.
 K. Yao, X. Wang, Y. Xu, F. Li, L. Zhou, Chem. Mater. 2016, 28, 3131.
10:45 AM - EN02.01.07
Perovskite Solar Cells—Crystal Structure and Interface Architecture with High Resolution TEM Observation
Satoshi Uchida1,Tae Woong Kim1,Ludmila Cojocaru1,Takashi Kondo1,Hiroshi Segawa1
The University of Tokyo1Show Abstract
Recently, organometal halide perovskite solar cells (PSCs) have received great attention. The power conversion efficiency (PCE) of PSCs have shown a dramatic increase and certified PCEs adopting mixed organic cations and halide anions have reached up to 22%. The PCE is considerably affected by photovoltaic property of each component of a PSC. Particularly, because crystal quality of materials is strongly concerned with the electronic properties such as carrier transport, investigation of detailed crystallographic information of the perovskite light absorber is essential. In spite of the significance in the crystallographic information, however, microstructural observation for crystal structure analysis of the perovskite layer has not been actively conducted. In this talk, we will report a microstructural observation about phase coexistence in the perovskite light absorber through transmission electron microscope (TEM) observation.
To obtain the crystallographic information of the perovskite light absorber, a pure methylammonium lead iodide (MAPbI3) layer was formed through spin-coating method assisted by antisolvent in a planar type PSC (Au/Spiro-MeOTAD/MAPbI3/TiO2/FTO/Glass). MAPbI3 precursor solution used is 1.4 M and the spin-coated MAPbI3 film was annealed at 100 oC for 30 min.
Surprisingly, during the high resolution (HR) TEM observation, we found the coexistence of tetragonal and cubic structures in the perovskite layer. Additionally we found such a mixture condition affetcs on the photovoltaic peroformance of the perovskite solar cells. This new observation is expected to be an important clue of the enhancement of perovskite crystal quality for highly efficient PSCs.
11:00 AM - EN02.01.08
Passivation Schemes for Perovskite Solar Cells
Nina Vaidya1,Jing-Shun Huang1,Harry Atwater1
California Institute of Technology1Show Abstract
Perovskite solar cells have emerged as a prominent candidate in the field of photovoltaics. With their efficiency comparable to silicon solar cells and easy of fabrication involving low temperature solution processing and self-assembly, Perovskites are an attractive prospect to reduce costs and implement large scale solar energy adoption. However, the main hurdle in the way of success of Perovskites is their sensitivity to moisture. We present passivation schemes to protect organic–inorganic lead halide perovskite solar cells from degradation when exposed to moisture and also encapsulation schemes for vacuum environment like space applications. In specific, hydrophobic BAI (Butyl Ammonium Iodide) that has been used for passivation of 2D layered perovskite solar cells  improves perovskite stability and efficiency even in solution processed 3D perovskites [2, 3]. The device architecture in our experiments is ITO Indium tin oxide/ NiO Nickle Oxide/ MAPbI3 Methyl Ammonium Lead Iodide/ BAI/ PCBM [6, 6]-phenyl-C61-butyric acid methyl ester/Ag Silver. For fabrication of the passivated cells, a layer of BAI solution was span at 4000 rpm for 20 seconds followed by heat at 100°C for 10 minutes, over the perovskite layer. The concentrations of the BAI solutions varied from 2mg/ml to 10mg/ml. 2mg/ml gave the best results so far with efficiency of 12.1% after 18 days for passivated cells as compared to 12.3% for as-fabricated cells without passivation which degraded to about 9% efficiency after the 18 day interval (measured under solar simulator spectra of AM 1.5G). The suggested hypothesis of the mechanism of the BAI passivation, which will be studied in this paper, is that the long chains of the butyl group extend outwards from the perovskite layer blocking other molecules to react with the perovskite layer and in effect passivating the perovskite surface. In x-ray diffraction (XRD) analysis, there is a pronounced peak for PbI2 seen for 6-day old cells without passivation which is not present in the 6-day old passivated cells, further providing evidence for passivation using BAI. The absorption between 500 nm and 1000 nm wavelength for as-grown perovskite and 6-day old passivated perovskite agree with each other and the curves are almost identical. We further investigate the passivation scheme, structure, and potential improvements using x-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and opto-electronic measurements.
Success of passivation schemes will propel the promising perovskite solar cell technology from research in inert glove boxes to industry-wide adoption.
11:15 AM - EN02.01.09
The Critical Role of Titanium Dioxide (TiO2) Surface Chemistry on the Nucleation, Growth, Bulk Composition and Energetics of Hybrid Perovskite Films
R. Shallcross1,Selina Olthof2,Leo Hamerlynck1,S. Saavedra1,Klaus Meerholz2,Neal Armstrong1
University of Arizona1,University of Cologne2Show Abstract
We elucidate how the surface chemistry of compact TiO2 electron-selective contacts dramatically affects the nucleation, growth, bulk composition and energetics of device-relevant hybrid perovskite (PVSK) thin films that are processed via solution- and vacuum-based deposition methods. The surface chemistry and energy level alignment of compact TiO2 thin films, which are grown by either chemical vapor deposition (CVD) or sol-gel methods, is systematically modified by combinations of annealing temperature/environment, plasma activation and end-functional silane modification. The TiO2 surface chemical composition (e.g., stoichiometry, hydroxyl concentration, monolayer composition, etc.) is quantified by high-resolution, monochromatic X-ray photoelectron spectroscopy (XPS), and the frontier orbital energetics are determined using ultraviolet photoelectron spectroscopy (UPS), which shows that the work function and energy level alignment of the TiO2 contact can be tuned by approximately 1 V depending on the treatment conditions. In situ XPS and UPS measurements of incrementally co-evaporated methylammonium lead triiodide (MAPbI3) films reveal that initial nucleation and subsequent growth of MAPbI3 PVSK films strongly depends on the chemical functionality of the TiO2 surface, where silane-modified surfaces surpress chemical reactions between the PVSK precursors (e.g., methylammonium iodide) and TiO2 surface species (e.g., hydroxyls). X-ray diffraction (XRD) studies of solution-processed PVSK films based on methylammonium (MA) and formamidinium (FA) organic cations reveal that the bulk film composition and crystallinity are controlled by the TiO2 work function and surface energy, where low work function and low surface energy TiO2 contacts show enhanced conversion of the precursors to the PVSK phase and higher crystallinity. In addition, scanning electron microsope (SEM) images show that the TiO2 surface free energy, which is tailored by end-functional silane monolayers and plasma activation, and processing conditions have a strong influence on the morphology (e.g., grain size) of both vacuum- and solution-processed PVSK films based on MA and FA organic cations. These combined studies show how the formation mechanism, interfacial/bulk energetics, chemical composition, crystallinity and morphology of device-relevant PVSK active layers is critically dependent on the surface chemistry and energetics of TiO2 contacts, which have significant consequences related to the processing, stability and operation of next-generation optoelectronic device platforms.
11:30 AM - EN02.01.10
Highly Promising Strategies to Mitigate the Instability Issues Associated with Perovskite Solar Cells
M. Ibrahim Dar1,Neha Arora1,Shaik Mohammed Zakeeruddin1,Michael Grätzel1
Ecole Polytechnique Federale de Lausanne1Show Abstract
Organic-inorganic perovskites solar cells have emerged in a short span of time as a potential photovoltaic technology. However, the instability of these PSCs under operational conditions has impeded their large-scale deployment. Such instability issues could arise from the degradation of absorber layer itself or by virtue of the charge extraction layers. To mitigate these issues, we have explored the following promising strategies. 1) Crystal cross-linking to passivate the perovskite surfaces and grain boundaries; as the ionic nature of organic-inorganic perovskites renders them inherently sensitive towards reactive species, such as water molecules present in the form of a moisture. 2) Identification of new absorber material which contains less electrophilic organic cations and thermodynamically more stable inorganic frame work, and 3) Using all-inorganic charge extraction layers which are extremely cheap and stable. In my presentation, how one could achieve extraordinary operational stability by employing these highly promising strategies will be discussed.
1. Li, X.; Dar, M. I. et al. Nat. Chem. 2015, 7, 703-711.
2. Arora, N., Dar, M. I.* et al. Science 2017, 358, 768-771
3. Arora, N., Dar, M. I.* et al. Nano Letters 2016, 16, 7155-7162.
11:45 AM - EN02.01.11
Tin-Based Perovskite with Improved Coverage and Crystallinity Through Tin-Fluoride-Assisted Heterogeneous Nucleation
Nanjing University1Show Abstract
Tin fluoride (SnF2) is widely used as an effective additive for lead-free tin-based perovskite solar cells. However, the function of SnF2 and the mechanism in improving the film morphology are still not clear. In this work, it is clearly demonstrated that SnF2 can play a crucial role in the crystal nucleation process. Due to the limited solubility, SnF2 creates more nucleuses for the crystal growth and therefore enables more uniform thin film with high coverage. It is confirmed that this mechanism can be applied to the growth of both thin film and single crystal. As a result of tin fluoride-assisted heterogeneous nucleation, an MASnIBr2-based perovskite solar cell with a high and stable power conversion effciency of 3.70% is demonstrated.
 Min Xiao, Jia Zhu et al, Adv. Opt. Mater. 2017, 1700615.
EN02.02: Tandem, Mixed Cations, 2D Perovskites, Stability and HTM
Monday PM, April 02, 2018
PCC North, 100 Level, Room 129 A
1:30 PM - EN02.02.01
Perovskite—A Wonder for Photovoltaic and Optoelectronic Applications
Shengzhong (Frank) LiuShow Abstract
A new type perovskite, a hybrid material with both organic and inorganic components, has appeared to be a wonder for its excellent optical absorption, long range charge-carrier diffusion and apparent tolerance to defects. In the last few years, it has been emerged as a primary candidate material for various photovoltaic, optoelectronic and photoelectronic applications. In just a few years, the power conversion efficiency (PCE) of the perovskite solar cells has been improved from 3.8% to >22%. Moreover, the solar cell fabrication processes based on the planar architecture have been particularly enthusiastic thanks to their low temperature fabrication and compatibility with a range of substrates. Comparing solution deposition and vacuum deposition, the vacuum processes for thermal co-deposition and sequential deposition of PbCl2 and CH3NH3I materials are recognized as efficient means to prepare perovskite film with good uniformity and high surface coverage.
A vacuum deposition process has been developed to fabricate high efficiency perovskite solar cells with high stability using alternating layer-by-layer vacuum deposition. The new deposition process allows us to relax the strict deposition monitoring and control measures, while realizing superior uniformity in film morphology, surface coverage and smoothness, together with crystalline phase purity. The power conversion efficiencies for the planar device is as high as 19.6% on rigid glass substrate, the highest reported at the time. More importantly, we have developed a superior low temperature TiO2 coating and transferred the cell fabrication process onto lightweight flexible polymeric substrate. The highest cell efficiency achieved was over 16%, it is also the highest efficiency among the flexible perovskite cells reported. Our current status for the rigid thin film cell efficiency is over 21.5% and that for the flexible device over 18.3%, both are the highest for their respective category. Meanwhile, the devices show very good stability over long term exposure in ambient with very low degradation. After a representative cell was exposed in ambient lab condition for a year, its final cell efficiency is as high as over 95% of its initial efficiency with its degradation accounts for only smaller than 5%. Further analysis on the stability of the perovskite solar cells will be discussed.
We have also developed a series of single-crystalline perovskites with superior stability and optoelectronic performance.
 D. Yang, R. Yang, X. Ren, X. Zhu, Z. Yang, C. Li, S. Liu*, Advanced Materials, http://dx.doi.org/10.1002/adma.201600446.
 D. Yang, R. Yang, J. Zhang, Z. Yang, S. Liu, C. Li, Energy Environ. Sci. 2015, 8, 3208.
 D. Yang, Z. Yang, W. Qin, Y. Zhang, S. Liu, C. Li, J. Mater. Chem. A 2015, 3, 9401.
2:00 PM - EN02.02.02
Stability Enhancement of Perovskite Solar Cells
University of North Carolina at Chapel Hill1Show Abstract
One critical issue related perovskite solar cells is their relatively low stability compared with other thin film solar cell technologies. In htis talk, I will present our progress in understanding the intrinsic stability of perovskite materials related to material structure and operation conditions, including strain, ferroelastic domain boundaries, light, and defects. Many of these properties are unique to halide perovskites in good and bad way in terms the impact to solar cell stability. And our pregress on stability enhancement will also be presented in ehnahcing the overall device stability under real device operation condition. It is shown that efficient perovskite devices (PCE>20%) can be made stable for over six months under one sun illumination at evevrated temperatures.
2:45 PM - EN02.02.04
Wrinkling in Perovskite Films for Improved Light Harvesting in Perovskite-Silicon Tandems
Kevin Bush1,Nicholas Rolston1,Jakob Hausele2,Zhengshan Yu2,Salman Manzoor2,Rongrong Cheacharoen1,Zachary Holman2,Reinhold Dauskardt1,Michael McGehee1
Stanford University1,Arizona State University2Show Abstract
The rapid progress in metal halide perovskites has generated great interest in the fabrication of tandems on silicon to enable the next generation of solar cells. Optimized light harvesting is essential to achieve the highest current density and efficiency in tandems. Specifically, high infrared transmission through the perovskite top cell is critical. We show here that texturing the top surface of the perovskite considerably reduces coherent reflections in the infrared.
The antisolvent method we use to deposit perovskite films results in a film with a rippled surface that micron-wide ridges with 300-nm-deep trenches. For comparison, we fabricate smooth perovskites using a two-step interdiffusion method. The smooth perovskites appear shiny, indicative of highly specular reflection. In contrast, the textured perovskites are grey on top and angle resolved transmission measurements confirm a significant increase in haze. To understand the mechanism behind the formation of this textured perovskite surface, we performed stress measurements and found that this morphology is caused by wrinkling that occurs because a compressive stress of ~20 MPa arises after the antisolvent drip. However, perovskites fabricated without an antisolvent are shown to remain in tension throughout processing, and no texturing is observed in the films. Experiments are underway to understand the factors that determine whether there is compressive or tensile stress in the films. We will point out examples in the literature in which scanning electron microscope images revealed the same buckling pattern we have observed, but the mechanism of the patterns formation was not identified.
To evaluate the effect of the textured perovskite surface, we fabricated 4-terminal perovskite-silicon tandems. When comparing perovskites with smooth and textured surfaces, we observed a ~1 mA/cm2 increase in current density in the silicon bottom cell under the textured surfaces. Reflectance measurements confirm a decrease in infrared reflections by the textured perovskite, leading to higher transmittance and an increased EQE in the silicon. With this higher current density, we achieve >25% efficient perovskite-silicon tandems.
3:30 PM - EN02.02.05
Bilayer 2D/3D Perovskites and Surface Passivation for Enhanced Solar Cell Stability
Subodh Mhaisalkar1,Nripan Mathews1,Tze Chien Sum1,Cesare Soci1,Tim White1
Nanyang Technological University1Show Abstract
Since the first reports of metal halide perovskite solar cells, intense research focus has centered on CH3NH3PbI3, and related family of materials. Although the initial priority of research was on increasing solar cell efficiencies, focus has now shifted to improve the stability of these solar cells, especially for long-term atmospheric exposures.
The hydrophilicity and volatility of methylammonium cations (MA+) turn the archetypical metal halide perovskite vulnerable to degradation through humidity and thermal exposure. The prospects for advancing device stability are contingent upon exploring structural variants, including bilayer 2D/3D perovskites and surface passivation approaches which yield more environmentally stable PSCs. Through molecular design of organic A-site cations, we developed a series of Ruddlesden-Popper perovskites, (CHMA)2(MA)n-1PbnI3n+1, in which a thin lower dimensional perovskite was formed over the 3D perovskite layer in one-step deposition. The bilayer 2D/3D hybrid perovskites possess striking moisture resistance and displayed high ambient stability up to 65 days. In order to modulate the formation of bilayer 2D/3D perovskites for high efficiency PSCs, top surface of well-formed 3D perovskite is converted into 2D perovskite in two-steps deposition, resulting a better bilayer perovskite layer in term of perovskite quality, morphology and interfacial contacts. Not only the enhanced moisture tolerance from the hydrophobicity of long chain organic cations, this approach could also suppress surface defects and vacancies of solution-processed perovskite which in turn results in higher power conversion efficiency (PCE) with excellent moisture stability.
Surface passivation approach is another way to improve the stability of PSCs. Different from conventional organic cations, utilization of hydrophobic fluorinated organic salt to passivate highly efficient triple-cations perovskite without triggering the formation of 2D perovskite has been demonstrated. The passivated perovskite thin film displays narrower band gap (halide substitution), longer PL lifetime and a notable improvement in PCE. More importantly, the passivated PSCs show remarkable stability for more than 169 days under ambient conditions at an average relative humidity (RH) of 55% without any significant change in its initial PCE. These findings provide new insights into intrinsic bilayer perovskite formation and passivation through careful design of the organic components in the perovskite structure to achieve a more stable and highly efficient perovskite material for photovoltaics.
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4:00 PM - EN02.02.06
Study on Fabricating High-Efficiency and Highly Stable Perovskite Solar Cells
Baomin Xu1,Chun Cheng1,Yanqing Tian1
Southern University of Science and Technology1Show Abstract
Perovskite solar cells (PSCs) have been received great interest in recent years due to the rapid increase of their solar power conversion efficiency (PCE). However, in order to commercialize PSCs there are still many challenges need to be solved, including fabricating high efficiency and highly stable PSCs using simple, scalable, affordable and eco-friendly process technologies. In this talk, I will introduce several efforts our team have done towards this objective. First, by simply adding 4-tert-butylpyridine (tBP) into the PbI2 precursor solution to enhance its hydrophobicity, we can fabricate highly stable PSCs in ambient air with PCE > 12.5% using spin coating method. Then I will present our work on improving PSCs performance and stability using inorganic perovskite quantum dots (QDs). All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, I) nanocrystals (NCs) have been prepared, which exhibit near-unity photoluminescence (PL) quantum yields, narrow emission peak widths and anion-tunable absorption/emission wavelengths. By introducing stable α-CsPbI3 QDs as an interface layer between the perovskite film and the hole transport material (HTM) layer to improve the energy band matching, the PCEs of devices have been increased from 15.17% to 18.56%, with substantial improvement on stability as well. Thirdly, we have developed a heat assisted spin-coating (HASP) process to fabricate PSCs with inverted structure and using PbAc2 as the precursor. This new process allows us to avoid using the toxic anti-solvents such as toluene and chlorobenzene. The PCEs can reach 19.12% on glass substrate and 14.87% on flexible PEN substrate. Over 80% of the initial PCEs can be remained for 20 days in air without encapsulation, and for 60 days under simple encapsulation. Finally, I will introduce our work on developing new hole transporting materials to replace Spiro-OMeTAD in order to fabricate high-efficiency and stable PSCs with much lower cost.
4:15 PM - EN02.02.08
A Generic Interface to Reduce the Efficiency-Stability-Cost Gap of Perovskite Solar Cells
Yi Hou1,C. Brabec1
Friedrich-Alexander University Erlangen-Nuremberg1Show Abstract
Thin-film solution-processed solar cells based on a hybrid organohalide lead perovskite semiconductor have achieved certified power conversion efficiencies (PCEs) exceeding 22%. Early efforts to bring this technology from the lab to the market quickly revealed certain disadvantages of perovskites, including the use of toxic lead, the diffusion of ionic defects causing a hysteresis effect, long-term stability, water sensitivity, the complexity of the ink formulation, as well as the cost efficiency and compatibility of the interface materials. Of these, a critical limitation on commercializing this technology is the absence of suitable hole-transporting materials (HTMs) that offer full performance without sacrificing long-term stability, and with low material costs and printability from green solvents.
In this work1, we present a generic interface architecture that combines solution-processed, reliable, and cost-efficient hole-transporting materials, without compromising efficiency, stability or scalability of perovskite solar cells. Tantalum doped tungsten oxide (Ta-WOx)/conjugated polymer multilayers offer a surprisingly small interface barrier and form quasi-ohmic contacts universally with various scalable conjugated polymers. Using a simple regular planar architecture device, Ta-WOx doped interface-based perovskite solar cells achieve maximum efficiencies of 21.2% and combined with over 1000 hours of light stability based on a self-assembled monolayer. By eliminating additional ionic dopants, these findings open up the whole class of organics as scalable hole-transporting materials for perovskite solar cells.
1. Yi Hou. et al. A generic interface to reduce the efficiency-stability-cost gap of perovskite solar cells. Science, In press.
4:30 PM - EN02.02.09
New Hole-Transporting Materials for Low-Cost and High-Efficient Perovskite Solar Cells
Yanqing Tian1,Jianchang Wu1,Xiang Deng1,Chang Liu1,Baomin Xu1
Southern University of Science and Technology1Show Abstract
In recent few years, the efficiency of organic-inorganic metal halide perovskite-based solar cells (PSCs) has been improved rapidly, because of the significant efforts in materials development and device fabrications. Hole transporting materials (HTMs) play an important role to the PSCs in charge extraction and interface modification. Currently, the most extensively studied and applied HTM for perovskite devices is 2,2’,7,7’-tetrakis(N,N’-di-p-methoxyphenylamine)-9,9’-spirobifluorene (Spiro-OMeTAD),[2-4] which is expensive because of its relative long synthesis and purification processes. For achieving large area solar cells, devices with satisfactory efficiencies and low-cost materials are urgently required. Thus, the development of high efficient and low-cost HTMs is very necessary for promoting PSCs from lab scale experimentation towards industrial scale application.
We have been working on the development of new organic and polymeric HTMs. For example, two HTMs were synthesized by connecting the arylamine side groups to the both sides of thiophene and/or benzene moieties, named as HTM1 and HTM2, respectively, in which the synthesis procedures are much shorter and simpler than those of Spiro-OMeTAD. When applied in the PSCs devices, the thiophene-based HTM1 and benzene-based HTM2 showed short circuit photocurrent densities (Jscs) of 21.08 mA cm-2 and 15.83 mA cm-2 , open circuit voltages (Vocs) of 1.01 V and 0.79 V and fill factors (FFs) of 0.59 and 0.46 respectively. The devices with the two HTMs showed average power conversion efficiencies (PCEs) of 13.7% and 6.4 % with best PCEs of 14.7% and 7.5%, while the device with Spiro-OMeTAD has a best PCE of 15.8% under the similar device preparation method and measurement conditions. These observations indicated that thiophene-based HTM1 has a comparable performance to the Spiro-OMeTAD. These results showed that selecting a proper π-linker is important for the performance of the HTMs. And the simple material of HTM1 is a promising HTM with the potential to replace the expensive Spiro-OMeTAD due to its comparable performance with much simpler synthesis route and much reduced cost (less than 1/10 folds of that of Spiro-OMeTAD).
1. Calió, L.; Kazim, S.; Grätzel, M.; Ahmad, S., Angew. Chem. Int. Ed. 2016, 55, 14522-14545.
2. Ding, I. K.; Tétreault, N.; Brillet, J.; Hardin, B. E.; Smith, E. H.; Rosenthal, S. J.; Sauvage, F.; Grätzel, M.; McGehee, M. D., Adv. Funct. Mater. 2009, 19, 2431-2436.
3. Jeon, N. J.; Lee, H. G.; Kim, Y. C.; Seo, J.; Noh, J. H.; Lee, J.; Seok, S. I., J. Am. Chem. Soc. 2014, 136, 7837-40.
4. Liu, D.; Kelly, T. L., Nat. Photon. 2014, 8, 133-138.
4:45 PM - EN02.02.10
Tri-Halide and 2D/3D Hybrid Structure of Tin Perovskites Applied as Lead-Free Perovskite Solar Cells with a Mesoscopic Carbon Electrode
Cheng-Min Tsai1,Eric Wei-Guang Diau1
National Chiao Tung University1Show Abstract
All-solid-state organic-inorganic lead perovskites have attracted much attention, due to its rapid and tremendous development within the photovoltaic field. However, toxic lead-containing still a big issue of this field. We developed and characterized methylammonium tri-halide tin perovskites (MASnIBr2-xClx) for carbon-based mesoscopic solar cells free of the hole-transporting layers. There is a question whether iodide and chloride co-crystalize together in a perovskite structure. We found that the iodide and chloride can form the stable single phase, but based on certain amounts of bromide within the structure. Three different halides (Cl, Br and I) co-crystalized inside the crystal of tin perovskites, MASnIBr2-xClx, according the stoichiometric ratios, from x = 0 (SnBr2/SnCl2 = 100/0) to x = 0.5 (SnBr2/SnCl2 = 75/25). When the SnCl2 ratio was higher than 25 % (x > 0.5), phase separation occurred to generate MASnI3-yBry and MASnCl3-zBrz these two phases. The MASnIBr1.8Cl0.2 (SnCl2 = 10 %) device showed the best device performance with VOC/mV = 380, JSC/mA cm-2 = 14.0, FF = 0.573 and PCE/% = 3.1 with great long-term stability and reproducibility. Transient PL decay measurements were carried out to show the intrinsic problem of tin-based perovskites with the averaged lifetimes less than 100 ps, for which the MASnIBr1.8Cl0.2 film featured the longest lifetime over the others to account for its greater device performance than the others. What is more, we also investigated the effect of a bi-functional ammonium cation, EOAI, on structure and energy levels of a tin-based perovskite, FASnI3. Following the increase of EOAI ratio within the EOAyFA(1-y)SnI3, the valence band maximum of tin perovskite can be modified linearly from deficient -4.91 eV to appropriated -5.50 eV and the crystal structure will transform from 3D to a 2D/3D hybrid structure. Finally, the power conversion efficiency of tin-based carbon electrode perovskite solar cells improved 5 times, which that compared with the FASnI3 reference device. X-ray diffraction (XRD) analysis, ultraviolet photoelectron spectra (UPS) and electrochemical impedance spectra (EIS) were performed to understand the crystal structures and the photovoltaic performances of the devices for this series of tin perovskite solar cells.
Yabing Qi, Okinawa Institute of Science and Technology Graduate University
Hyun Suk Jung, Sungkyunkwan University
Selina Olthof, University of Cologne
Kai Zhu, National Renewable Energy Laboratory
Borun New Material Technology Co., Ltd.
M. Braun Inc.
EN02.03: Photodetector, 2D Perovskites, Fundamental, Efficiency and Stability
Tuesday AM, April 03, 2018
PCC North, 100 Level, Room 129 A
10:30 AM - EN02.03.00
The Role Alkali Metal Distribution on the Electronic Properties of Organic-Inorganic Perovskites
Juan-Pablo Correa-Baena1,Mallory Jensen1,Sarah Wieghold1,Barry Lai2,Tonio Buonassisi1
Massachusetts Institute of Technology1,Argonne National Laboratory2Show Abstract
Perovskite solar cells have shown remarkable efficiencies beyond 21%, through organic and inorganic cation alloying. However, the role the inorganic cations plays is not well-understood. By using synchrotron-based micro X-ray fluorescence, we show that alkali metals K, Rb and Cs, mostly segregate into well-defined pockets without fully incorporating. In this presentation I will show how these alkali metals influence the distribution of other elements and how that improves electronic dynamics, including lifetimes above 3 µs and homogenous photobleaching in transient absorption visualized by ultrafast microscopy. Solar cell performance is compromised by large amounts of Rb/K and high efficiency is seen with small amounts of the alkali metal. Remarkably, the high concentration of Rb and K agglomerations do not affect the open-circuit voltage, average lifetimes and photoluminescence distribution, further indication of perovskite’s defect tolerance.
10:45 AM - EN02.03.01
Reduced Interfacial Recombination in Au-Decorated ZnO Nanoarrays for Perovskite Photovoltaics
Tulus TulusShow Abstract
We fabricated ZnO nanorod arrays decorated with Au nanoparticles for use as the electron transport layers in perovskite solar cells. We show with current-voltage measurements, impedance analysis and photoluminescence spectroscopy that the Au nanoparticles reduce recombination losses at the ZnO-perovskite interface. We compare the performance of double cation-mixed halide and triple cation-mixed halide perovskites in this architecture. The use of Au nanoparticles in the solar cells resulted in an increase in the open circuit voltage (Voc) and fill factor, leading to an increase in the maximum power conversion efficiency from 11.52 % to 12.62 % (double cation) and from 11.9 % to 12.66 % (triple cation). We discuss these results in terms of trap filling and surface passivation by the Au nanoparticles at the ZnO-perovskite interface.
11:00 AM - EN02.03.02
Functionalizing Grain Boundaries/Surfaces Confocally in Organic-Inorganic Halide Perovskite Thin Films
Yuanyuan Zhou1,Nitin Padture1
Brown University1Show Abstract
Grain boundaries (GBs) and grain surfaces (GSs) are the most prominent microstructural features that play significant roles in determining the physical properties and photovoltaic functions of the organic-inorganic halide perovskite (OIHP) thin films. While enormous effort has been devoted to modifying/functionalizing the OIHP GBs and GSs and making them benign, the microstructures in these modified/functionalized OIHP thin films have been somehow random and/or uncertain. Herein, we demonstrate several unique chemical approaches to functionalize the OIHP GBs and GSs confocally at the nanoscale. The key to the unprecedent success of the confocal functionalization is the strong molecular interaction between OIHPs grains and functionalizing agents. Microscopic characterization methods including analytical transmission electron microcopy have been employed to confirm the precisely controlled microstructures in our OIHP thin films. Combined experimental and theoretical studies have showed that the confocal functionalization of OIHP GBs and GSs not only leads to electronic passivation of defects, but also protects OIHP grains from moisture/oxygen ingression and unfavorable phase transformation. As a result, highly efficient and stable perovskite solar cells are demonstrated. The concept of confocal functionalization of the OIHP GBs and GSs is paving the way for developing higher-performance perovskite solar cells of the future.
11:15 AM - EN02.03.03
Fully Printable Large Area Monolithic Perovskite Solar Cells with High Stability
Nripan Mathews1,Anish Priyadarshi1,Jia Haur Lew1,Sudhanshu Shukla1,Subodh Mhaisalkar1,Frederick Prehn1
Nanyang Technological University1Show Abstract
To date, solid-state perovskite solar cells (PSCs) have been developed with power conversion efficiency exceeding 22%<span style="font-size:10.8333px">.</span> PSCs comprise entirely of Earth-abundant elements, can be manufactured in various geometries, can be solution-processed, and possesses ideal solar cell material characteristics. This meteoric rise in PCEs has created a renaissance in studies on perovskites for light-emitting diodes, lasing, photodetectors etc. In addition to its outstanding performance, perovskite solar cell have a simple and low-cost solution-based fabrication process which opens the possibility of commercialization. We have demonstrated upscaling of monolithic perovskites solar device with high efficiency and stability using solution based processing and low cost electrode materials. Monolithic devices of size 10cm x 5cm (active area 30cm2) and 10cm x 10cm (active area 70cm2) with efficiency 10.5% and 10.74% have been realized. Fabrication of large area solar cells were done by fully screen-printed process along with slot die coating of perovskite solution. Perovskite infiltration process and quality of carbon (conductivity and surface area) plays key roles in improving the device performance. Recent progress in the pursuit of 900 cm2 monolithic devices and a 3S-3P module comprised of 10x10 substrates encapsulated in a window with junction box will also be covered.
11:30 AM - EN02.03.04
Exciton Dissociation Through Surface States in Layered 2D Perovskites Enable High-Efficiency Solar Cells
Jean-Christophe Blancon1,Wanyi Nie1,Hsinhan Tsai2,Constantinos Stoumpos3,Mikael Kepenekian4,Sergei Tretiak1,Pulickel Ajayan2,Mercouri Kanatzidis3,Jacky Even5,Claudine Katan4,Jared Crochet1,Aditya Mohite1
Los Alamos National Laboratory1,Rice University2,Northwestern University3,Université de Rennes 14,INSA de Rennes5Show Abstract
Understanding and controlling charge and energy flow in state-of-the-art semiconductor quantum-wells has enabled high-efficiency optoelectronic devices. Two-dimensional Ruddlesden-Popper layered perovskites (RPPs) have recently emerged as an alternative to the classic bulk organic-inorganic hybrid perovskites, mainly due to significantly improved photo- and chemical-stability in optoelectronic devices . Few recent encouraging developments in optoelectronic applications, notably in energy harvesting and light emitting [1-3], have already been demonstrated in these two-dimensional layered perovskites. RPPs are solution-processed quantum-wells wherein the band gap can be tuned by varying the perovskite layer thickness, which modulates the effective electron-hole confinement. We report that, counterintuitive to classical quantum-confined systems where photo-generated electrons and holes are strongly bound by Coulomb interactions or excitons, the photo-physics of thin films made of Ruddlesden-Popper perovskites with a thickness exceeding two perovskite crystal-units (>1.3 nanometers) is dominated by lower energy states associated with the local intrinsic electronic structure of the edges of the perovskite layers . These states provide a direct pathway for dissociating excitons into longer-lived free-carriers that significantly improve the performance of solar cell devices.
 Tsai et al., Nature (2016), 536, 312-316.
 M. Yuan et al., Nat. Nanotechnol. (2016), 11, 872-877.
 Blancon et al., Science (2017), 355, 1288-1292.
11:45 AM - EN02.03.05
Molecular Engineering of Low Cost Hole Transporting Materials for Highly Efficient and Stable Printable Perovskite Solar Cells
Prashant Sonar1,Hong Duc Pham1,Sagar Jain2,Yeng Ming Lam3,Yabing Qi4
Queensland University of Technology1,Swansea University Bay Campus2,Nanyang Technology University3,Okinawa Institute of Science and Technology Graduate School (OIST)4Show Abstract
Perovskite solar cells (PSCs) technology has attracted a big attention in the solar cell community due to their exceptional performance as the power conversion efficiency (PCE) surged to world record 22%. Though the highest PCE of 22.1% up to date used PTAA as polymeric hole transporting material (HTM) but it has some disadvantages such as super high cost and reproducibility. In contrast to polymers, small molecules possess advantages, e.g. batch-to-batch reproducibility, easy purification, high purity & definite structure. Among small molecular HTMs for PSCs, Spiro-OMeTAD has been employed intensively as standard HTM. Despite of the remarkable performance (20.8%), some main drawbacks of Spiro-OMeTAD, including high cost and multistep synthesis, can hamper the progress of low cost and large area flexible PSCs.1, 2
Herein, six new simple cost efficient solution processable small molecular HTMs, namely TPA-BPV-TPA, TPA-BP-TPA, TPA-TVT-TPA, TPA-NAP-TPA, TPA-ANT-TPA, and ACE-ANT-ACE, using triphenylamine(TPA) and acenaphthylene(ACE) as end-capping groups with different cores are reported. The variation in cores is aimed to change the highest occupied molecular orbital (HOMO) energy level of each HTM to match ot with the HOMO level of perovskite, enhancing the hole extraction and efficient performance.3-6 Thereafter, TPA-ANT-TPA, ACE-ANT-ACE, TPA-BPV-TPA and TPA-BP-TPA were implemented in mesoporous perovskite devices whereas TPA-TVT-TPA and TPA-NAP-TPA were fabricated in inverted ones. In case of conventional layouts, while doped TPA-BPV-TPA based devices give efficiency around 16.42%, dopant-free TPA-ANT-TPA ones achieves an overall efficiency of 17.5%. Notably, both TPA-BPV-TPA and TPA-ANT-TPA exhibits an impressive stability compared to Spiro-OMeTAD under identical aging condition. Additionally, TPA-ANT-TPA possesses the low synthetic cost of $67/g compared to that of Spiro-OMeTAD ($91/g). For inverted architecture, the devices based on pristine TPA-TVT-TPA and TPA-NAP-TPA as HTMs are found to be of 16.32% and 14.63%, respectively. The cut-price and straightforward synthesis with elegant scale up makes these classes of materials important for the industry to produce high-throughput printed perovskite solar cells for large area applications.
. D. Bi, W. Tress, M. I. Dar, P. Gao, J. Luo, C. Renevier, K. Schenk, A. Abate, F. Giordano, J.-P. C. Baena, J.-D. Decoppet, S. M. Zakeeruddin, M. K. Nazeeruddin, M. Grätzel, A. Hagfeldt, Sci. Adv. 2016, 2, e1501170
 N. J. Jeon, J. H. Noh, W. S. Yang, Y. C. Kim, S. Ryu, J. Seo, S. I. Seok, Nature 2015, 517, 476
 H. D. Pham, Z. Wu, L. K. Ono, S. Manzhos, K. Feron, N. Motta, Y. Qi, P. Sonar, Adv. Electron. Mater. 2017, 3, 1700139
 H. D. Pham, H. Hu, K. Feron, S. Manzhos, H. Wang, Y. M. Lam, P. Sonar, Solar RRL. 2017, 1, 1700105
 Patent filed
 H. D. Pham, T. T, Do, J. Kim, C. Charbonneau, S. Manzhos, K. Feron, W. C. Tsoi, J. Durrant, S. M. Jain, P. Sonar, manuscript submitted to Adv. Ener. Mater.
EN02.04: 2D Perovskites, Fundamental, Efficiency and Stability
Tuesday PM, April 03, 2018
PCC North, 100 Level, Room 129 A
1:30 PM - EN02.04.01
Two-Dimensional Organic-Inorganic Perovskite from Nanostructures to Solar Cells
Hebrew University1Show Abstract
Perovskite is a promising light harvester for use in photovoltaic solar cells. In recent
years, the power conversion efficiency of perovskite solar cells has been dramatically
increased, making them a competitive source of renewable energy.
This work will discusses new directions related to organic inorganic perovskite and their applications in solar cells.
In low dimensional systems, stability of excitons in quantum wells is greatly enhanced due to the confined effect and the coulomb interaction. The exciton binding energy of the typical 2D organic-inorganic perovskites is up to 300 meV and their self-assembled films exhibit bright photoluminescence at room temperature.
In this work we will show the dimensionality in the perovskite structure. The 2D perovskite structure should provide stable perovskite structure compare to the 3D structure. The additional long organic cation, which is added to the perovskite structure (in the 2D structure), is expected to provide hydrophobicity, which will enhance the resistivity of the perovskite to humidity. Moreover we will demonstrate the use of 2D perovskite in high efficiency solar cells.
Organometal halide perovskite is used mainly in its “bulk” form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this work, we present facile low temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs, demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier Transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g. octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light emitting diodes, lasing, solar cells and sensors.
2:00 PM - EN02.04.02
Efficiency Improvement of the Lead Acetate Solution Derived Perovskite Solar Cells by Introduction of Nitrogen Flow and Pre-Aging Process
Yuanqing Chen1,2,Aditya Yerramilli1,Yuxia Shen1,Zhao Zhao1,Yang Song2,1,N. David Theodore1,3,Terry Alford1,4
Arizona State University1,Xi'an University of Technology2,NXP Semiconductors3,African University of Science and Technology4Show Abstract
In this study, we explored the formation of Pb-Sn binary perovskite solar cells using Pb(CH3COO)3 and SnI2 as starting materials. We successfully fabricated CH3NH2Pb0.75Sn0.25I3 perovskite solar cells with a power-conversion efficiency (PCE) of nearly 10%, using a fast crystallization process. The effects of annealing time and temperature on the film properties were investigated. We found that a short-duration annealing at 100-105oC facilitated the crystallization of the CH3NH2Pb0.75Sn0.25I3 phase. We also found that the molar ratio of MAI: (Pb+Sn) influenced the film properties. The incorporation of excessive Pb and Sn ions improved the power conversion efficiency of the perovskite solar cells.
2:15 PM - EN02.04.03
High Efficiency Perovskite Solar Cells Based on Kinetic Control of Cs-Mixed Intermediate States During the Crystallization
Gyu Min Kim1,Trilok Singh1,Yoshitaka Sanehira1,Tsutomu Miyasaka1
Toin University of Yokohama1Show Abstract
Perovskite solar cells (PVSCs) have attracted great attention recently due to their high power conversion efficiency (PCE) with low cost despite their short history. Development of engineering method of perovskite crystallization has boosted the PCE of PVSCs up to 22.7% recently. Among the several fabrication methods, dripping anti-solvents to perovskite precursors in DMF:DMSO mixed solvents is one of the promising way to high quality perovskite films, leading to superior performances. It is known that lewis base and acid interaction by using DMSO forming intermediate states prevents abrupt crystallization. On the other hand, anti-solvents which are casted to perovskite precursors such as chlorobenzene and ethyl ether accelerate crystallization of perovskites by super-saturation. It is considered that kinetics of perovskite precursor during the formation of perovskite crystals directly result in optical and electrical properties of PVSCs. In this sense, we tried to focus on the kinetic control of Cecium (Cs)-mixed intermediate states during the formation of perovskite crystals. By putting the petri-dish on the perovskite substrates right after spin-coating with lower temperature for certain time (stage 1) and further annealing without petri-dish for 1h at 100 celsius (stage 2) for complete conversion to black phase of perovskite, evaporation kinetics of intermediate states can be easily controlled. The remaining DMF and DMSO vapors inside petri-dish decelerate decomposition of intermediate states at stage 1. The optimum temperature at stage 1 depends on types of perovskite compositions. The addition of cation dopants such as Cs, Rubidium (Rb) and Potassium (K) decreases intermediate state binding energy. Thus, for adequate control of intermediate states, lower temperature at stage 1 is required especially for cations-doped perovskite precursors. The mirror-like color, which is indicative of intermediate states, is retained for several seconds or minutes depending on the annealing temperature with petri-dish at stage 1. From the measurement of AFM and SEM, the grain sizes and the surface roughness are largely affected by the time at which intermediate states are retained at stage 1. Photoluminescence (PL) measurement also reveals that adequate control of vaporization kinetics of intermediates enhances the PL intensity, indicating that non-radiative recombination is suppressed. The engineering of kinetic control at stage 1 has resulted in high PCE recording 21.3% with negligible hysteresis for Cs-mixed PVSCs.
3:30 PM - EN02.04.04
2D Chalcogenide Perovskite—A Promising Semiconductor Material
Shanghai Institute of Ceramics, Chinese Academy of Sciences1Show Abstract
The past several years have witnessed a burgeoning of the research on halide perovskite photovoltaic (PV) materials. These materials are structurally distinct from all previous high-efficiency PV materials, such as Si, GaAs, CdTe, and CIGS. Recently, the halide perovskites have also been explored for other optoelectronic devices, such as LEDs. These breakthroughs have motivated us to study other perovskite materials that are potentially semiconductors, instead of dielectrics. Recently, we explored the chalcogenide perovskite materials in quest of suitable ones for PV applications. A number of promising candidates have been identified. In this talk, I will further explore two-dimensional chalcogenide perovskites. In particular, I will discuss the possibility of existence of such materials, including their structures, thermodynamic and kinetic stabilities from a density-functional-theory point of view. I will also discuss their electronic and optical properties in the context of nanoelectronic and optoelectronic applications.
4:00 PM - EN02.04.05
Printable Low-Temperature TiO2 Nanoparticles for High Efficiency Stable Perovskite Solar Cells
Ihteaz Hossain1,2,Florian Mathies2,3,Tobias Abzieher2,Somayeh Moghadamzadeh2,Bryce Richards1,2,Uli Lemmer1,2,Damien Hudry1,Ulrich W. Paetzold1,2,Afshin Hadipour4
Institute of Microstructure Technology, KIT1,Light Technology Institute, KIT2,InnovationLab GmbH3,IMEC v.z.w.4Show Abstract
Perovskite solar cells (PSC) exhibit the potential to be the next-generation thin-film photovoltaic technology, having already reached power conversion efficiencies (PCEs) of >22% for lab-scale devices within a few years. State-of-the-art PSCs utilize high temperature (> 450 °C) processed TiO2 as the electron transport layer. However, upscaling techniques such as roll-to-roll processing on flexible substrates or inkjet printing on large area devices demand low temperature fabrication routes. In this work, we tackle this challenge using TiO2 nanoparticles (TiO2-np) instead, which are synthesized at only 72 °C. The TiO2-np are crystalline in nature and the process allow precise control over particle size, doping, as well as dispersing capability in different solvents. Our results show that TiO2-np can form compact films upon spin-coating, thus reducing recombination processes at the interfaces. When spin-coated CH3NH3PbI3 is used as the perovskite absorber, devices exhibiting a high initial efficiency (> 19%) and a stabilized PCE of 18.2% (measured at constant voltage) can be realized. Furthermore, the synthesized nanoparticles demonstrate high compatibility (in terms of efficiency) with other perovskite absorber layers, including co-evaporated CH3NH3PbI3 and triple cation perovskite, Cs0.1(MA0.17FA0.83)0.9Pb(I0.83Br0.17)3. We also show that TiO2-np can be used to achieve efficient PSCs both in thin (30 nm) and thick (75 nm) layer configurations. In addition, the doping of the TiO2-np with niobium (Nb) results in a significant improvement for the thicker layers. Moreover, when dispersed in appropriate solvents, we demonstrate both inkjet printing and slot die coating processes for the TiO2-np. PSCs fabricated with such processes show high initial PCE of >17%, paving the way for high throughput and digitally printed PSCs.
4:15 PM - EN02.04.05.5
A Proposal for Mesoscopic CH3NH3PbI3/bR/TiO2 Heterojunction Solar Cells Based on Band-Gap Measurement
Subhabrata Das1,Bernardo Barbiellini-Amidei2,Xingyu Gao3,Steve Harvey4,Shinichiro Muramoto5,Kai Zhu6,Ponisseril Somasundaran1,Venkatesan Renugopalakrishnan7
Columbia University1,Lappeenranta University of Technology2,Chinese Academy of Sciences3,Materials Science Center | National Renewable Energy Laboratory4,National Institute of Standards and Technology5,National Renewable Energy Laboratory6,Northeastern University7Show Abstract
Bacteriorhodopsin (bR) has been deposited on TiO2 and gold substrates separately. An ultraviolet photoemission experiment (UPS) reveals the energy-level alignment and the Fermi energy of the bR/TiO2 system while combined x-ray absorption measurements (XANES) and X-ray photoemission spectroscopy (XPS) indicate that in bR the lowest unoccupied molecular orbital (LUMO) is located about 2 eV above the highest occupied molecular orbital (HOMO). A separate Time of Flight Secondary In Mass Spectrometry (TOF-SIMS) study, conducted to characterize the attachment of bR to Au substrate, confirm successful Thiol-Gold bond formation with films thicker than 10 nm. Principal component Analysis (PCA) of TOF-SIMS data further separated the samples based on ratio peak intensities of C2H3+, C2H5+ to that of Ca2+, Cu2+.The HOMO-LUMO gap of retinal was spectroscopically determined to be 2.49 eV. For comparison, we also performed DFT calculations to determine the HOMO-LUMO gap of free retinal and Spiro OMe-TAD. Using the G-311G basis set, the calculated HOMO-LUMO gap was 2.69 eV for Retinal and 1.1 eV for Spiro respectively. The chromophore can be stabilized in the bR protein by the HOMO-LUMO interaction with the protein environment. Based on these spectroscopy results and DFT calculations, new solar cell architectures combining perovskite and bR are proposed and discussed.
4:30 PM - EN02.04.06
Room Temperature Processable Growth of Lead Halide Perovskites Catalyzed by Alcohols
Muge Acik1,Fangmin Guo1,Yang Ren1,Sergei Ivanov2,In Kee Park3,Geunsik Lee3,Todd Alam4
Argonne National Laboratory1,Los Alamos National Laboratory2,Ulsan National Institute of Science and Technology3,Sandia National Laboratories4Show Abstract
Methylammonium lead trihalides (MAPbX3) have great potential as light harvesters for perovskite solar cells due to their unique optical and electronic properties. In general, conventional growth techniques apply spin-coated precursors on a substrate followed by annealing for the processing of the lead halide perovskites; however, use of toxic solvents and high temperature hinder device stability and performance. To avoid annealing processes, the solution-based methods have been developed, which involve the formation of perovskite colloidal particles in solution. I will introduce a new one-step solution technique to facilitate in situ crystal formation of methylammonium lead bromide and methylammonium lead chloride perovskites at the micron (~1-10 µm) to nano scale (< 500 nm).1 As a substrate-free approach, the crystal pre-growth allows crystallization in alcohols (methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol) at room temperature followed by a direct precipitation of the perovskite material for a large-area deposition. This room-temperature processable technique, however, differs from the in situ growth method of methylammonium lead iodide in alcohols that eliminates treatment at the boiling point of the alcohols.2
The techniques used to characterize the perovskite crystals involve high-energy synchrotron XRD, wide angle x-ray scattering (WAXS), Fourier transform infrared (FTIR) in reflection (ATR, % R), UV-Vis-NIR (% R), micro Raman spectroscopy, and the solid state 1H, 13C, and 207Pb –MAS NMR. Based on the analysis results, the perovskites show improvement in air/moisture for their chemical stability (<1.5 months, in a fume hood under varying humidity level). Thermogravimetric analysis and in situ techniques of powders also determine their thermal stability (~150°C -MAPbCl3, ~250°C -MAPbl3, ~350°C -MAPbBr3). The poor yield of methylammonium lead iodide in toluene confirms that the alcohols catalyze the growth process through a substitutional reaction mechanism but the mechanism in toluene follows a different path. Indeed, the theoretical calculations reveal that the growth reaction in alcohols is exothermic. Moreover, I will discuss the role of solvent polarity (polar, apolar, non-polar), the type of solvent (protic vs. aprotic), the reactivity order of the alcohols, effect of their different binding affinity, and other reaction parameters on the growth mechanisms. 1M. Acik, et al. in prep., 2M. Acik, et al. Adv. Energy Mater., 1701726 (2017).
4:45 PM - EN02.04.07
Charge Transfer Mechanism of Cs2SnI6-Based Photovoltaic Devices
HyeonOh Shin1,Byung-Man Kim1,Deok-Ho Roh1,Tae-hyuk Kwon1
Ulsan National Institute of Science and Technology1Show Abstract
We examined the charge transfer mechanism of Cs2SnI6 and clarified the function of its surface state in photovoltaic devices. From a cyclic voltammetry study, we found that the faradaic reactions of the iodine species derived from Cs2SnI6 induce charge transfer through a surface state of Cs2SnI6, mainly at +0.9 V vs. the normal hydrogen electrode. This potential is located in the mid-gap state of Cs2SnI6 and its surface state charging was confirmed by Mott-Schottky measurements. This mid-gap charge transfer was further proved in photovoltaic devices. More specifically, we developed dye-sensitized solar cells with quasi-solid Cs2SnI6-based regenerator, or conventional liquid electrolyte. The performances of the Cs2SnI6-based regenerator were strongly dependent on the highest occupied molecular orbital (HOMO) of the organic dyes. In particular, BT-HT featuring the lowest HOMO (−5.65 eV) provided a 79% enhancement in the photocurrent density (14.1 mA cm−2) in the Cs2SnI6-based regenerator compared to that of a conventional liquid electrolyte (7.9 mA cm−2). This unprecedented finding can be explained as follows: i) fast charge transfer through Cs2SnI6; ii) efficient charge regeneration owing to lower HOMO of BH-HT than mid-gap state (−5.43 eV); and iii) lesser early recombination in the Cs2SnI6-based regenerator. To further confirm this mid-gap charge transfer, we demonstrated a correlation between performance of Cs2SnI6 as a light absorber and the TiO2 conduction band by Sn doping in TiO2. Our findings confirm the importance of surface state engineering in future designs of Cs2SnI6 lead-free perovskite devices.