Symposium ES16 : Perovskite Photovoltaics and Optoelectronics

Perovskite solar cells promise to yield efficiencies beyond 30% by further improving the quality of the materials and devices. Electronic defect passivation, and suppression of detrimental charge-carrier recombination at the different device interfaces has been used as a strategy to achieve high performance perovskite solar cells.
In this presentation, I will discuss the role of electronic defects and how these can be passivated to improve charge-carrier lifetimes and to achieve high open-circuit voltages. I will discuss the characterization of 2D and 3D defects, such as grain boundaries, crystal surface defects, and precipitate formation within the films, by synchrotron-based techniques. The importance of interfaces and their contribution to detrimental recombination will also be discussed. As a result of these contributions to better understanding 2D and 3D defects, the perovskite solar cell field has been able to improve device performance. Albeit the rapid improvements in performance, there is still a need to improve these defects to push these solar cells beyond the current state-of-the-art.

Non-radiative recombination loss specially at the interfaces is a big challenge in the perovskite solar cells (PSCs) and affect the performance, stability, reproducibility of devices. Engineering the interfacial regions of the PSCs using an interface layer or additives is an effective strategy to address this issue. Our new findings report on a major breakthrough in the PSCs research. We discovered amazingly effective ways to mitigate the radiationless recombination of charge carriers at the interfaces of the perovskite with either electron transporting layer (ETL) or the hole transporting layer (HTL). In terms of ETL modification, we treat the surface of ETLs in the PSCs using SnO₂ and graphene, results in drastically improved the charge transfer properties, retarded the recombination rate and reduced the unwanted interfacial reactions at the interfaces with perovskite film. Moreover, we found that incorporation of the molecular modulators such as adamantanes either at the interface of perovskite with HTL or into the HTL solution prevents non-radiative recombination drastically, resulting in a highly efficient and stable PSC. Based on these techniques, we achieved PSCs (for both planar and mesoporous structures) with electric to power conversion efficiency (PCE) of ~22%, an open circuit voltage of up to 1245 mV, external electroluminescence yield of 2.5% and a great operational stability, which are the records for triple A-cation PSCs with respect to the band gap (1.61 eV). Our proposed approaches open up a promising route for fabrication of cost-effective solar cell and pave the way for the development and commercialization of the PSCs.

Understanding defects in perovskite films is key to improving device performance and stability. It has been hypothesized that vacancy defects enable ion migration¹, which has been implicated to cause current-voltage hysteresis and long-term material degradation. Additionally, defects at the surface of the perovskite film may affect the interfaces in a device, and interface engineering is seen as an important avenue for improving device performance. Scanning tunneling microscopy (STM) offers the ability to probe the surface of OHPs with atomic resolution, including resolving individual vacancy defects.^2-4 Scanning the same area multiple times allows for observation of dynamic events. Here, multiple types of defects were resolved and dynamic ion migration to and from the surface was imaged at the atomic scale. DFT calculations indicate vacancy defects are MABr vacancies and that vacancy defects at the surface of the film change the local work function, which has important implications for energy level alignment and charge transfer between layers in a photovoltaic device.

References
¹ J. Azpiroz, E. Mosconi, J. Bisquert and F. De Angelis, Eng. Environ. Sci. 8, 2118 (2015).
² L. She, M. Liu, D. Zhong, ACS Nano. 10, 1126 (2016).
² R. Ohmann, L.K. Ono, H.S. Kim, H. Lin, M.V. Lee, Y. Li, N.G. Park, Y.B. Qi, J. Am. Chem. Soc. 137, 16049 (2015).
⁴ Y. Liu, K. Palotas, X. Yuan, T. Hou, H. Lin, Y. Li and S.T. Lee, ACS Nano. 11 2060 (2017).

Abstract. Organic and inorganic cation alloying on the A-site in mixed halide perovskites solar cells has enabled remarkable improvements in efficiency and environmental stability. However, the added compositional complexity may lead to undesired phase segregation that detracts from optoelectronic performance. To clarify this balancing act, we assess the nanoscale chemical and electronic impacts of alkali-metal cation addition by means of synchrotron-based nanoprobe X-ray fluorescence and induced current. We find that the halide distribution homogenizes upon the addition of CsI and RbI precursors for films prepared with stoichiometric or excess lead halide. The halide homogenization coincides with long-lived charge carrier decays and spatially homogenous carrier dynamics visualized by ultrafast microscopy. At the same time, we observe Rb-rich clusters that phase separate within the film. We identify these Rb aggregates as recombination active sites using X-ray and E-beam induced current microscopy. Based on our microscopy investigations upon careful tuning of precursor stoichiometry, we will share quantitative precursor design strategies for preparing high-performance alloyed perovskite films that take advantage of the beneficial effects of alkali cations on homogenizing the lead-halide electronic backbone while minimizing secondary phase formation. These insights provide a more comprehensive understanding of the role of alkali cations in alloyed perovskite and indicate directions to further improve the performance and stability of perovskite optoelectronic devices.

Grain boundaries (GBs) are the most prominent microstructural features that play significant roles in determining the physical properties and photovoltaic functions of halide perovskite (HP) thin films. While enormous effort has been devoted to modifying the HP GBs and making them benign, the microstructures in these modified/functionalized HP thin films have been somehow random and/or uncertain. Herein, we demonstrate several unique chemical approaches to functionalize the HP GBs in a continuous, precisely-controlled manner. The key to the unprecedent success of the confocal functionalization is the strong molecular interaction between HPs grains and functionalizing agents. Microscopic characterization methods including analytical transmission electron microcopy have been employed to confirm the microstructures in our HP thin films. Combined experimental and theoretical studies have showed that the confocal functionalization of HP GBs not only leads to electronic passivation of defects, but also prevents HP grains from moisture/oxygen ingression and unfavorable phase transformation. As a result, highly efficient and stable perovskite solar cells are demonstrated. The concept of continously functionalization of the HP GBs is paving the way for developing higher-performance perovskite solar cells of the future.

We are developing effectively transparent superstrates for perovskite solar cells. These superstrates incorporate triangular-shaped grid fingers with thin transparent conductors, which mitigate shading losses associated with conventional grid fingers and/or thick TCO layers. We have investigated various types of polymers for use as superstrates in both rigid (glass-backed) and flexible applications. We have developed an electroplating process to fabricate the triangular gridlines, which improves their conductivity vs. prior silver ink printing approaches. We will present a summary of perovskite solar cells that were fabricated on these effectively transparent superstrates, including a discussion of their photovoltaic efficiency, spectral response, and LBIC mapping. The results demonstrate that effectively transparent superstrates enable an improvement in the short-circuit current density and fill factor for large-area perovskite solar cells.
Perovskite solar cells are of great interest due to their potential for low cost and high performance. One of the challenges to attaining high photovoltaic conversion efficiency, particularly for large-area cells, is the tradeoff between the optical and electrical performance of the top contact. Because perovskite absorbers and selective electrode materials provide very little lateral conductivity for current collection, a transparent conductive oxide (TCO) such as indium tin oxide (ITO) must be used for the front contact. However, TCOs offer a tradeoff between transparency and conductivity, resulting in a compromise between short-circuit current density (due to optical losses) and fill factor (due to resistive losses) for solar cells. A solution is to increase the density of the grid fingers such that thinner TCOs can be used; however, this increases the shading losses.
Recently, a method to produce effectively transparent front contact grids has been described (Adv. Optical Mater. 4 (10), 1470-1474 (2016); Photovoltaic Specialists Conference (PVSC) IEEE 43rd, 3612-3615, (2016); Sustainable Energy and Fuels, 1 (3), 593-598, (2017)). This approach yields a relatively dense array of high-aspect-ratio, triangular-shaped front contact fingers, in which light striking the metal is reflected towards the cell. Our current work pertains to the application of this technology to perovskite solar cells.

Solution processable hybrid organic-inorganic perovskites such as CH₃NH₃PbI_3-zCl_z have attracted enormous fundamental and applied interest because of their outstanding optoelectronic properties. There is considerable interest in establishing methods to control perovskite film morphology, for example, using micropatterning. Here, hydrophilic poly(N-vinylformamide)-based swellable colloidal sponge-like particles were dispersed in perovskite precursor solution which was then spin coated to deposit CH₃NH₃PbI_3-zCl_z films for the first time. Remarkably, the CH₃NH₃PbI_3-zCl_z films formed disordered inverse opal (DIO) films. Our unique approach enables micropatterning of the perovskite capping layer in a single step. The CH₃NH₃PbI_3-zCl_z pore wall thickness is shown to be controlled by the concentration of sponge-like colloid particles used. The particles not only caused CH₃NH₃PbI_3-zCl_z to be more efficiently deposited but also increased light absorption and photoluminescence intensity. Results from demonstration solar cells constructed containing the DIO CH₃NH₃PbI_3-zCl_z films are discussed. A mechanism for DIO film formation is also presented[1]. We also present recent results obtained by extending this approach to prepare semi-transparent perovskite solar cells.

[1] Dokhan et al, Phys. Chem. Chem. Phys., DOI: 10.1039/c8cp05148h.

The efficiency of perovskite solar cells has skyrocketed from 3.8% to 23.3% in the past few years. For the best MAPbI₃ perovskites, the open-circuit voltage deficit, defined as the difference between bandgap and open-circuit voltage (V_oc), is only 0.37 V, approaching other best technologies such as GaAs [1]. However, similar to III-V materials, higher bandgap perovskites tend to have larger V_oc deficits. For example, for 1.64-eV and 1.7-eV perovskites, the best V_oc deficits are 0.49 V and 0.51 V, respectively [2]. This voltage loss limits the performance of wide-bandgap perovskites, and their applications on, for instance, tandem solar cells.
The V_oc of photovoltaic devices is governed, hierarchically, by recombination in the absorber and the carrier-selective contacts of the devices. Grain engineering has been proven to be an effective way to reduce defect density and, thus, suppress recombination to enhance the V_oc [2][3]. In our work, we focus on exploring different carrier-selective contact materials for perovskites.
With inverted architecture, we have replaced PTAA hole contact with boron-doped a-Si:H material. Our first device shows a V_oc of 1.02 V on a 1.6-eV CsMAFABr perovskite, and 0.92 V on a 1.67-eV perovskite. These numbers are very close to the PTAA control devices with V_oc of ~1.1 V. Although the FF is rather poor due to shunts and possible large series resistance due to band misalignment. We are in the process of making new devices without shunts, and characterizing the band alignment between our a-Si:H hole contact and perovskite absorber. By the time we present, we believe we’ll have such information. In addition to the current-voltage measurement, we will use surface photovoltage and XPS/UPS etc technique to obtain the band information, and also use a Suns-V_oc tool that we developed to probe the series-resistance-free fill factor of the device with a-Si:H contacts. We’ll also further employ phosphorous-doped a-Si:H as an electron contact to perovskite, and perform a through analysis on that as well.

To maximize the scalable deployment of perovskite PV, we investigate low-temperature organic monolayer-based morphologies to chemically and electrically glue perovskites to their contacting phases while maintaining a “soft”, flexible interface and carrier selectivity. We have covalently grafted vertically oriented perylene dianhydride overlayers on TiO₂ through and imide linkage to a surface-bound silane. Secondary functionalization with a diamine to the terminal anhydride yields A-type cation moieties that serve as a chemical hook for perovskite deposition. UPS-quantified HOMO and LUMO levels of perylene diimide molecules aligned to facilitate electron transport to the TiO₂ substrate while blocking holes. Reflection-Absorption Infrared Spectroscopy (RAIRS) and X-ray photoelectron spectroscopy revealed a high coverage of vertically oriented perylene diimides. Perylene interfacial monolayers yield improved energy conversion relative to TiO₂/perovskite interfaces that we ascribe to enhanced interfacial carrier selectivity and transport, and reduced recombination. We discuss the present results in the context of other morphologies relevant to tandem photovoltaics.

Perovskite solar cells are surprising the photovoltaic community as unconventional behaviors have been reported. In most of the cases the origin of these behaviors is not completely understood and also, very important for the final application, how them influence the final performance of the device. On the other hand Impedance spectroscopy is a non-destructive characterization technique that can help in the understanding of these devices. Impedance spectroscopy is a characterization method in the frequency domain that allows to decouple physical processes with different characteristic times at the working conditions i.e. under illumination and applied bias. Despite the huge potentiality of this technique for the characterization of perovskite solar cell a complete model of impedance for this kind of cells applicable in all the conditions and configuration has been elusive for the moment. Undoubtedly, the combined action of electron and holes and ions in perovskite solar cell is at the base of the complex behavior observed in this kind of devices. In this talk we compare the well know dye sensitized solar cells with the perovskite solar cells highlighting similarities and differences. In addition the interest of impedance characterization of different types of perovskite solar cells is discussed.

Mobile ions in hybrid perovskite semiconductors introduce a new degree of freedom to electronic devices suggesting applications beyond photovoltaics. An intuitive device model describing the interplay between ionic and electronic charge transfer is needed to unlock the full potential of the technology. We describe the perovskite-contact interfaces as transistors which couple ionic charge redistribution to energetic barriers controlling electronic injection and recombination. This reveals an amplification factor between the out of phase electronic current and the ionic current. Our findings suggest a strategy to design thin film electronic components with large, tuneable, capacitor-like and inductor-like characteristics. The resulting simple equivalent circuit model, which we verified with time-dependent drift-diffusion simulations of measured impedance spectra, allows a general description and interpretation of perovskite solar cell behaviour.

arXiv:1805.06446

Photo-induced phase separation has been reported for a range of mixed-halide perovskites, which limits the available band-gap energies for photovoltaic applications [1,2]. An enhanced understanding of the phase separation mechanism is essential to rationalize limitations and design stable perovskite semiconductors. Up to now, phase separation and segregation has been detected by means of X-ray diffraction (XRD), photoluminescence (PL) and cathodoluminescence experiments [3,4].
During electron microscope experiments, the electron beam may cause changes in halide perovskites [4, 5] and we here show that phase separation can be induced by electron beam irradiation of the sample. Inorganic CsPb(Br_xI_1-x)₃ thin films were deposited by spin-coating and the phase separation investigated in-situ by using transmission electron microscopy (TEM). By this approach, it was possible to directly monitor the phase separation of CsPb(Br_0.5I_0.5)₃ thin films on the nanoscale into CsPbI₃ and probably PbBr₂ domains. We discuss the comparability of the interactions of electrons and photons with the halide-perovskite thin film and correlate the in-situ TEM with XRD and PL measurements of the same samples. Furthermore, we present different approaches of sample preparation for this in-situ TEM investigation.


[1] E. T. Hoke et al. “Reversible photo-induced trap formation in mixed- halide hybrid perovskites for photovoltaics”, Chem. Sci.,2015, 6, 613
[2] E. L. Unger et al. “Roadmap and roadblocks for the band gap tunability of metal halide perovskites,” J. Mater. Chem. A,2017, 5, 11401
[3] Barker et. al “Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films”, ACS Energy Lett. 2017, 2, 1416−1424
[4] W. Li, et al. “Phase Segregation Enhanced Ion Movement in Efficient Inorganic CsPbIBr2 Solar Cells”, Adv. Energy Mater. 2017, 7, 1700946
[5] Z. Dang et al. “In Situ Transmission Electron Microscopy Study of Electron Beam-Induced Transformations in Colloidal Cesium Lead Halide Perovskite Nanocrystals”, ACS Nano 2017, 11, 2124−2132

In recent years, the organic-inorganic hybrid perovskite has gained an increasing research interest in academia for applications in thin film solar cells, due to rapidly increased efficiency (from 3.8 to 23.3% within a decade) [1], high absorption coefficient [2], low-cost fabrication process, and material availability [3]. Among the hybrid perovskites, MAPbI₃ (CH₃NH₃PbI₃) based solar cells have shown high power conversion efficiencies but with several obstacles such as thermal instability, hysteresis loss at room temperature. Therefore, the commercialization of these solar cells is still a challenge. Understanding and resolving these issues necessitate the investigation of the sample at the atomic scale to determine the underlying fundamental processes.
Here, we present the growth and experimental characterization of thin MAPbI₃ films on Au (111) under ultra-high vacuum conditions (UHV=1x10^-10 Torr). The thin films were prepared by vacuum evaporation of the precursor molecules MAI and PbI₂ with a thickness of a few monolayers (approx. 4 nm). We characterize the sample with scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS), obtaining information about the atomic structure, and chemical composition. For the electronic properties analysis, we used ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPES). Our study will provide the basis for further understanding ion incorporation and stability at the atomic scale.

Mixed halide lead perovskites offer a useful strategy for continuous tuning of semiconductor bandgap. Based on their tunable optical properties these mixed halides are being considered as attractive candidates to develop single junction and multijunction tandem solar cells. The ease of halide ion exchange property poses a problem to create a tandem structure with layers of metal halide perovskites of different compositions. In order to keep the lead halide perovskite nanocrystals intact without undergoing exchange of halide ions and retain the original band structure one needs to suppress the halide ion migration across the nanocrystals. We have now successfully achieved this task by capping CsPbBr₃ and CsPbI₃ nanocrystals with PbSO₄-Oleate. Absorption measurements show that the nanocrystal assemblies maintain their identity as either CsPbBr₃ or CsPbI₃, for several days. Furthermore, we have electrophoretically deposited these assemblies as hierarchical structures on electrode surfaces and employ them in light emitting devices. The effectiveness of PbSO₄-Oleate capping of lead halide perovskite nanocrystals offers new opportunities to overcome the challenges of halide ion exchange and aid towards the tandem design of perovskite light harvesting assemblies.

Metal halide perovskites have sparked tremendous enthusiasm in the photovoltaic community with their promising performances. Currently holding a record power conversion efficiency of 23.3%, this exciting material class is approaching the mighty Si-powerhouse, concurrently opening encouraging avenues in (all-) perovskite multi-junction applications while approaching commercial exploitation.¹At the origin of these highly performing devices lie superior absorber properties that so far have been investigated by a plethora of characterisation techniques. Amongst all, electron microscopy (EM) remains one of the most extensively employed tools for studying the absorber in terms of crystallography, morphology, interfaces, lattice defects, compositions, and charge carrier collection and recombination properties. However, a crucial challenge upon using EM remains the beam sensitivity of the absorber, especially upon imaging with an increased electron dose. Resulting in structural and chemical changes in the light harvester in function of the total electron dose, it becomes extremely challenging to validate obtained results and those reported in literature.^3,4 Therefore, a quantitative characterisation of the beam damage is highly necessary to avoid, or at least mitigate, changes to the sample upon imaging in future analysis. Therefore, in this work, we investigate the current degeneration in multi-cation and –anion perovskite solar cells in function of the total electron dose by means of electron beam induced current (EBIC) measurements on rough cross-section of corresponding devices—providing an indirect yet quantitative route to characterise the electron beam induced damage to the absorber. Allowing the extraction of current decay profiles, various compositional perovskites are compared in terms of beam sensitivity, and operational parameters are indicated to avert (or at least mitigate) sample damage during imaging.

Halide perovskite solar cells (HPSCs) present a cutting-edge nanotechnology which has demonstrated remarkable power conversion efficiency increases to a recently reported value of 23% [1]. The high efficiency combined with low-cost production make HPSCs one of the most promising solar cell technologies but significant challenges related to their stability are yet to be solved. Exposure to oxygen, humidity, temperature, atmospheric pressure and UV light stimulates a complex set of degradation mechanisms such as diffusion of molecular oxygen and water, interfaces and the active material degradation, electrode reaction with the organic material to morphological and macroscopic changes[2]. For this reason, devices are encapsulated which prolongs their lifetime and also increases mechanical stability[3]. As the natures and timescales for each of these chemical reactions differ, it is challenging to elucidate the degradation processes. Secondary ion mass spectrometry (SIMS) is one of the few techniques that can offer valuable insights into potential degradation mechanisms by obtaining spatially resolved chemical analysis of organic and inorganic layers and interfaces. In this work, we present the high mass-resolving power depth profiling of HPSCs using the 3D OrbiSIMS[4].
The 3D OrbiSIMS comprises dual beam and dual analyser configuration by integrating a Q Exactive™ HF Hybrid Quadrupole-Orbitrap™ mass spectrometer with a high-resolution imaging ToF-SIMS platform. Advantages of this instrument include a significantly higher duty cycle compared with time-of-flight instruments (using pulsed ion beams), high-mass resolving power (>240,000) and high-mass accuracy (~ 1 ppm), up to 4 orders of magnitude dynamic range for organic materials and the ability to do MS/MS.
Here, we apply single beam depth profiling combined with high-mass resolving power to study the interface and interlayer chemistry in HPSCs and the degradation mechanisms that occur when exposed to air. Critical to achieving this is air-free transfer between a sample preparation glovebox and the 3D OrbiSIMS instrument. The air-free transfer protocol will be presented in this work.
[1] National Renewable Energy Laboratory, “Best Research-Cell Efficiencies”, 2018. https://www.nrel.gov/pv/assets/pdfs/pv-efficiencies-07-17-2018.pdf
[2] V. I. Madogni, B. Kounouhéwa, A. Akpo, M. Agbomahéna, S. A. Hounkpatin, and C. N. Awanou, “Comparison of degradation mechanisms in organic photovoltaic devices upon exposure to a temperate and a subequatorial climate,” Chem. Phys. Lett., vol. 640, pp. 201–214, Nov. 2015.
[3] A. Distler et al., “Effect of PCBM on the Photodegradation Kinetics of Polymers for Organic Photovoltaics,” Chem. Mater., vol. 24, no. 22, pp. 4397–4405, Nov. 2012.
[4] M. K. Passarelli et al., “The 3D OrbiSIMS—label-free metabolic imaging with subcellular lateral resolution and high mass-resolving power,” Nat. Methods, vol. 14, no. 12, pp. 1175–1183, Nov. 2017.

Organolead halide perovskites are a new class of photovoltaic materials for potential use in thin film solar cells, but suffer from rapid degradation under light and humidity, limiting their viability. Recently developed quasi-2D Ruddlesden-Popper phase perovskites show improved stability but, at present, the mechanism behind the stability is poorly understood. Here, we have used time-of-flight secondary ion mass spectrometry (ToF-SIMS), photoluminescence spectroscopy (PL), electrochemistry, and other techniques to study the chemistry and performance of 2D and 3D phases of methylammonium lead triiodide (MAPI) solar cells as a function of humidity exposure. ToF-SIMS depth profiles of both 2D and 3D MAPI planar solar devices (n-i-p, C₆₀/perovskite/PEDOT:PSS) show the formation of a significant hydrolysis-based degradation layer at the surface of only 3D MAPI devices after humidity exposure. Isotopic D₂O studies confirm the layer is caused by ambient humidity, while electrochemistry confirms it is directly related to loss of cell performance. The growth of this hydrolysis layer is found to be inhibited in 2D MAPI devices by the formation of a thin protective layer composed of more thermodynamically-stable 2D phases, clearly observed in PL spectra, which protects the less stable 2D bulk. To confirm that this newly formed 2D layer improves stability, we created solar cells consisting of 3D MAPI films coated with a thin layer of the 2D perovskite, and show that these cells are more stable that un-treated 3D MAPI devices. As a result, we conclude that using 2D perovskite as a protective interface may be a simple way to improve device stability.

Power conversion efficiency (PCE) of lead halide perovskite solar cell (over 23%) has surpassed those of CIGS and CdTe, approaching the top value of crystalline Si cell. Our group has been able to achieve PCE over 21% by low cost ambient fabrication. However, high PCE of single-cell enabled by lead halide-based perovskite absorbers are now being saturated, taking the Shockley Queisser (SQ) limit of open-circuit voltage (V_OC) (ca.1.32V) into account. Tandem cell making, which can further increases PCE up to 28% or more, leads to higher material and process cost and will raise a question if performance/cost ratio can be accepted in industry. Therefore, a smart way is to create a single cell which has high PCE comparable with that of GaAs (>28%) by reducing bandgap energy to <1.4 eV without accompaniment of increase in V_OC loss. This possibility will be in a family of metal halide perovskite out of those depending on use of lead. In addition to such efficiency issue, high performance of organo lead halide materials is not compatible with robust high stability required for practical use. Ensuring the intrinsic thermal stability (desirably >200^oC) of the perovskites is a key issue before industrialization. In addition, toxicity of lead-based perovskites are going to become the most formidable challenges for real use (commercialization), in particular, for applications to IoT society, which is one of the most promising field of perovskite photovoltaic device in terms of high voltage output even under weak illumination. These thoughts urge us to concentrate our next research of perovskite photovoltaics (PV) more on development of non-lead high efficiency absorbers. Sn perovskite is still a strong candidate because Sn(II) has been found to be stabilized against ambient air by metal doping method (such as Ge). Regarding Bi-based perovskites, we found AgBi₂I₇ as a promising all-inorganic absorber having high thermal and moisture stability. Stability also highly depends on the property of charge transport materials (CTMs), especially, the kind of hole transporter. Spiro-OMeTAD does not work at high temperature while P3HT, for example, is thermally stable. In our collaboration with JAXA, P3HT-based perovskite devices showed robust stability by exposure to high (100^oC) and low (-80^oC) temperatures and also to high energy particle radiations (iScience, 2018, 2, 148). Selection of CTMs is another important key in combination with non-lead perovskite materials. In conclusion, next direction of perovskite PV should be to enhance PV performance of non-lead all-inorganic semiconductor materials by extended compositional engineering, in parallel with developing thermally stable CTMs. Our on-going studies on non-lead perovskite materials in our group will be introduced in the talk.

Since the first report on the high efficiency, stable solid-state perovskite solar cell (PSC) in 2012 by our group, following two seed works on perovskite-sensitized liquid junction solar cells in 2009 and 2011, PSC demonstrated its power conversion efficiency (PCE) of 23.3% in 2018. According to Web of Science, publications on PSC increase exponentially since 2012 and total number of publications reaches already over 10,000 as of October 2018, which is indicative of a paradigm shift in photovoltaics. Although small area cell exhibited superb efficiency surpassing the performance of thin film technologies, scale-up technology is required toward commercialization. In addition, further higher efficiency toward Shockley–Queisser limit is required in parallel. In this talk, Large-area coating technology is introduced using perovskite cluster embedded coating solution, followed by brief introduction on history of perovskite solar cell. Bi-facial stamping method was developed for not only scale-up technique but also interface modification and low-temperature phase stabilization. For higher efficiency, managing recombination is critical. Methodology reducing recombination is developed via interface and bulk engineering. Current-voltage hysteresis is also discussed because hysteresis is related to the stability of perovskite solar cell. Ion migration is now visualized and confirmed to correlate with hysteresis.

Organic-inorganic perovskites enable a combination of useful organic and inorganic properties within a single molecular-scale composite and have attracted substantial interest for use within organic-inorganic electronic devices [1], in part due to the high carrier mobilities, long minority carrier lifetimes, tunable band gaps and relatively benign defects and grain boundaries for systems based on Group 14 metals (e.g., Ge, Sn and Pb) [2]. Indeed, these materials have enabled unprecedented rapid improvement in perovskite photovoltaic performance to levels above 20% power conversion efficiency and with open circuit voltages above 1V for a single junction photovoltaic (PV) device [3]. This talk will provide an historical perspective on foundational work related to the organic-inorganic perovskite semiconductors, including discussion of crystal structure flexibility [4,5], semiconducting properties, film deposition approaches and electronic device applications of the three-dimensional and lower-dimensional perovskite structures. Recent trends in the field, as they relate to application in photovoltaics and related devices, will also be coupled into this discussion.

[1] D. B. Mitzi, K. Chondroudis, C. Kagan, IBM J. Res. Develop. 45, 29 (2001).
[2] W.-J. Yin, T. Shi, Y. Yan, Adv. Mater. 26, 4653 (2014).
[3] W. S. Yang et. al., Science 356, 1376 (2017).
[4] B. Saparov and D. B. Mitzi, Chemical Reviews 116, 4558 (2016).
[5] D. B. Mitzi, Prog. Inorg. Chem. 48, 1 (1999).

In our work on perovskite solar cells (PSC) we have achieved efficiencies above 22% with a mixed composition of iodide/bromide and organic and inorganic cations. With the use of SnO₂ compact underlayers as electron acceptor contacts we have constructed planar perovskite solar cells with a hysteresis free efficiency above 20%. Through the compositional engieneering larger preovskite grains grown in a monolithic manner are observed and reproducibility and device stability are improved. With regards to lifetime testing, we have shown a promising stability at 85 ^oC for 500 h under full solar illumination and maximum power point tracking (95% of the initial performance was retained). Recently, we have also commented on the standardization of PSC aging tests.

Perovskite solar cell research continues to progress rapidly on various fronts. My group at OIST is making efforts to use surface science and advanced material characterization to obtain in-depth understanding about perovskite materials and solar cells [1]. In this talk, I will present our research progress on understanding the degradation mechanism of perovskite materials [2,3] as well as developing strategies to improve stability of perovskite solar cells [4-6].
[1] L. K. Ono, Y. B. Qi*, J. Phys. Chem. Lett. 7, 4764 (2016).
[2] S. Wang, Y. B. Qi* et al., Nature Energy 2, 16195 (2016).
[3] E. J. Juarez-Perez, Y. B. Qi* et al., J. Mater. Chem. A 6, 9604 (2018).
[4] Z. Wu, Y. B. Qi* et al., Adv. Mater. 30, 1703670 (2018).
[5] J. Liang, Y. B. Qi* et al., Adv. Energy Mater. 8, 1800504 (2018).
[6] Z. Liu, Y. B. Qi* et al., Nat. Commun. 9, 3880 (2018).

Tin oxide (SnO₂) is a promising material for the electron transport layer in planar perovskite solar cells (P-PSCs) due to its suitable energy level and high electron mobility. SnO2-based P-PSCs show the highest power conversion efficiency among planar structure devices, but the PCE remains still low compared to the mesoporous TiO₂-based PSCs and there is a lack of thermal stability study. In this study, we develop a simple interface engineering to improve optoelectronic properties and the thermal stability of the P-PSCs. The modified SnO2 shows high conductivity, effective charge extraction ability and high recombination resistance. Empirically, efficiencies of 21.43% and 20.5% were reached for the device with doped Spiro-OMeTAD and with dopant-free asy-PBTBDT, respectively, in the present study. The devices with modified SnO₂ show excellent stability under mild (humidity of 25%) and harsh conditions (humidity of 85%; temperature of 85°C). Thus, our newly developed method guarantees highly efficient and thermal stable P-PSCs.

Organic-inorganic hybrid perovskite solar cells show the promises as the next-generation photovoltaic technology. The efficiency has quickly increased from 3.8% [1] to 23.2% since 2009. [2] However, instability of perovskite solar cell is a big issue hindering its commercialization and practical applications. By combining thermal-insensitive organic-inorganic perovskite and moisture-resistant electrode, we report successful fabrication of stable organic-inorganic hybrid PSCs which shows enhances stability under tough aging condition. Surface contact is another critical factor affecting solar cell efficiency. After suitable surface modification, solar cell efficiency is significantly improved from 12.2% to 14.9%.
¹ A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, J. Am. Chem. Soc. 131, 6050 (2009).
² https://www.nrel.gov/pv/assets/images/efficiency-chart.png

Metal halide perovskites hold tremendous promise for next-generation solar cells, more than any other recently developed low-cost active PV material. To fulfill this promise, perovskites must first overcome the chemical and thermomechanical instability that has long been observed in them. While some promising results have recently been achieved in scalability with power conversion efficiencies (PCE) of 12% for 100 cm² perovskite devices, the thermomechanical instability of perovskites remains a significant challenge to producing module-scale perovskite solar cells with operational lifetimes comparable to c-Si and CdTe.

In particular, stresses are generated in perovskite films during processing and magnified in service by environmental effects such as thermal cycling, resulting in the formation of defects and propagation of fracture and delamination. Additionally, cracks that develop in the film are a source of accelerated degradation for the transport of gases, moisture, and other environmental species. Unfortunately, perovskite layers are exceptionally fragile and susceptible to delamination as measured by their fracture energy—less robust than organic photovoltaics (OPVs) by an order of magnitude and c-Si or copper indium gallium diselenide (CIGS) solar cells by two orders of magnitude. Despite the significance of film stresses for device stability, the origin and magnitude of stresses in perovskite films have been largely overlooked. In addition to causing fracture, stress accelerates the rate of photochemical degradation in many materials—such as fuel cell membranes, laser diodes, and encapsulants—and a recent report shows that perovskite are no exception.

Perovskites can accumulate residual stresses during processing through several pathways. For example, in solar cell devices, perovskites have much higher coefficients of thermal expansion (CTE) than the other device layers and the glass substrate. When perovskites are annealed after deposition and subsequently cooled back to room temperature, a lower-CTE substrate constrains the perovskite from contracting, an effect that generates lattice strain in the film. Given the extreme mechanical fragility of perovskite films, and the possibility for further stresses developing during fabrication and operation (e.g., exposure to environmental stressors such as thermal cycling), these residual stresses could contribute significantly to light, heat, and moisture-based chemical degradation as well as fracture in devices.

In this work, we report on an overlooked factor affecting stability: the residual stresses in perovskite films, which are tensile and can exceed 50 MPa in magnitude, a value high enough to deform copper. These stresses provide a significant driving force for fracture. Films are shown to be more unstable under tensile stress—and conversely more stable under compressive stress—when exposed to heat or humidity. Increasing the formation temperature of perovskite films directly correlates with larger residual stresses, a result of the high thermal expansion coefficient of perovskites. Specifically, this tensile stress forms upon cooling to room temperature, as the substrate constrains the perovskite from shrinking. No evidence of stress relaxation is observed, with the purely elastic film stress attributed to the thermal expansion mismatch between the perovskite and substrate. Additionally, the authors demonstrate that using a bath conversion method to form the perovskite film at room temperature leads to low stress values that are unaffected by further annealing, indicating complete perovskite formation prior to annealing. It is concluded that reducing the film stress is a novel method for improving perovskite stability, which can be accomplished by lower formation temperatures, flexible substrates with high thermal expansion coefficients, and externally applied compressive stress after fabrication.

Integrated circuits fabricated in the microelectronic industry heavily rely on complex interfaces which drive switching of the electrical components; i.e., transistors at the front end; capacitors & resistors at the back end. A combination of low resistive metal (Cu) and a low dielectric constant material (not limiting to SiO₂) are required to form a multi-level metallization scheme with electrical wiring to reduce the time constants (RC) at the back end. Such schemes facilitate faster and efficient signal and data processing to the front end. However, adhesion at these intricate interfaces and structures remain an issue under operational conditions resulting in a wide range of failure mechanisms at the back end of line. Mechanical probing using Cross-Sectional Nanoindentation (CSN) is a well-established method used to measure the fracture toughness and reliability of these interconnects. Subsequently electron microscopy is performed to identify the modes of failure mechanisms. On similar grounds, the perovskite and two-terminal silicon/perovskite tandem solar cells involve a variety of low resistive metals (Au, Ag, Al, carbon) and organic molecules/polymeric dielectric materials (Spiro-OMeTAD, PTAA etc), hence making it feasible to apply CSN method to characterize the mechanical reliability of these solar cells. Semi-quantitative assessment of the interfacial adhesion or cohesion in both single and multi-junction solar cells will be estimated from load-displacement curves and measuring the crack lengths using electron microscopy techniques (SEM, TEM). Modelling using non-classical finite element modelling will be used to generate load-displacement curves involved to predict the various modes of failure in such sub-micrometre single-junction perovskite solar cells and will be extended to multi-junction solar cells/modules. Understanding the failure mechanisms will facilitate better design and fabrication of reliable perovskite single-junction and multi-junction solar cells/modules.

In the current work, CSN testing method is extended to measure the interfacial delamination in perovskite and silicon/perovskite tandem solar cells (SPTS), which could lead to lowering of the fill factor (FF) under operating conditions of solar cells. In this test configuration, nanoindentation is performed on the substrate which is typically ~5-20 μm away from the electrode to air interface. The load-displacement curve obtained from the nanoindentation testing will be used to determine the fracture energy with the aid of a semi-quantitative analytical model to compute and compare adhesion and mechanical properties of samples with different interfaces.[2] At the conference, details pertaining to the CSN test and subsequent analytical analysis to get the fracture energy will be presented for various configurations of perovskite solar cells.

References
1. Sánchez, J.M., et al., Cross-sectional nanoindentation: a new technique for thin film interfacial adhesion characterization. Acta Materialia, 1999. 47(17): p. 4405-4413.

2. Mulmudi, H.K., Application and Further Development of Cross-Sectional Nanoindentation for Mechanical Stability Assessment of Complex BEoL Stacks with Cu/low-k, (Unpublished, Master Thesis, performed at the Center for Center for Complex Analysis, GLOBALFOUNDRIES, Dresden, 2009).

The issue of long-term stability in perovskite solar cells under atmospheric conditions remains at the forefront of making them viable technologies. To facilitate a firm understanding of the processes at stake and their influence, it is important to employ a systematic investigation of degradation [1]. The interactions between various degradation phenomena (e.g. the effect of load, atmosphere, etc.) can be substantial, warranting the use of multifactorial methodologies to extract dominant effects and their interactions. As such, we use a design of experiments (DOE) methodology, which allows us to identify salient confluent factors and their interactions as they affect the operation of the solar cells. Specifically, we observe the influence of the combination of temperature, humidity, perovskite type, and loading condition on electrical (I-V), crystallographic (XRD), and optical (UV-Vis) characteristics. We also track their impact on the concentration and activation energy of deep level traps in Cs_xFA_1-xPbI₃ and MAPbI₃ solar cells as a function of degradation via photo-induced conductivity transient spectroscopy. This study thus constitutes a framework upon which we can further our mechanistic understanding of degradation in perovskite solar cells.

Reference
[1] K. Domanski, E. A. Alharbi, A. Hagfeldt, M. Gratzel, and W. Tress, Nature Energy (2018), Vol. 3, pp. 61–67.

The wide and tunable bandgap of perovskites makes them attractive for use in tandem solar cells either as a top cell in perovskite/silicon and perovskite/thin film solar cells or as both top and bottom cells in all-perovskite tandem solar cells. For a tandem device, a transparent conducting electrode must be deposited on top of the perovskite solar cell to allow light transmission into the device. The conventional technique to deposit transparent conducting oxide (TCO) materials is sputtering. However, the high kinetic energy of the sputtered atoms and the UV radiation damages underlying layers of the cells (mainly the perovskite and hole contact layers), resulting in an S-shaped or shunted I-V curve with poor cell performance¹. Previously, a thin protective buffer layer of MoO_x² or SnO₂³ has been used before sputtering TCO, which places several processing constraints such as low-temperature deposition with mild precursors, high transparency of the buffer layer, and appropriate energy level alignment.

In this work, an aerosol-based technique is developed to deposit a uniform TCO thin film on perovskite solar cells without any damage to the other layers of the cell. The technique involves a two-step spraying process. In the first step, a colloidal solution of indium tin oxide (ITO) nanoparticles is sprayed through an ultrasonic atomizer nozzle generating droplets containing nanoparticles. Once the solvent from the droplet evaporates, in the second step, the dry nanoparticles are passed through a fine orifice nozzle along with a carrier gas, creating a spray of nanoparticles which then deposit on the substrate. The pressure downstream the orifice nozzle is almost 10-fold lower than the upstream pressure, which reduces the drag force on the fine nanoparticles and enables them to deposit on the substrate by impaction rather than flowing away along with the carrier gas. The absence of energetic atoms and radiation makes this technique suitable to deposit any kind of nanoparticle layer on top of perovskites without damage. The presentation will discuss this novel technique and its application in depositing a uniform layer of ITO nanoparticles as a top electrode in perovskite-based tandem solar cells to further boost their efficiency.

References:
1 Kanda, H. et al. Analysis of Sputtering Damage on I–V Curves for Perovskite Solar Cells and Simulation with Reversed Diode Model. The Journal of Physical Chemistry C 120, 28441-28447 (2016).
2 Duong, T. et al. Semitransparent perovskite solar cell with sputtered front and rear electrodes for a four-terminal tandem. IEEE Journal of Photovoltaics 6, 679-687 (2016).
3 Bush, K. A. et al. 23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability. Nature Energy 2, 17009 (2017).

Currently, perovskite solar cells (PSCs) with high performances greater than 20% contain bromine (Br), causing a suboptimal bandgap, and the thermally unstable methylammonium (MA) molecule. Avoiding Br and especially MA can therefore result in more optimal bandgaps and stable perovskites. We show that inorganic cation tuning, using rubidium and cesium, enables highly crystalline formamidinium-based perovskites without Br or MA. On a conventional, planar device architecture, using polymeric interlayers at the electron- and hole-transporting interface, we demonstrate an efficiency of 20.35% (stabilized), one of the highest for MA-free perovskites, with a drastically improved stability reached without the stabilizing influence of mesoporous interlayers. The perovskite is not heated beyond 100°C. Going MA-free is a new direction for perovskites that are inherently stable and compatible with tandems or flexible substrates, which are the main routes commercializing PSCs.

The major obstacles delaying the large scale commercialization of thin film solar cells based on hybrid organic halide perovskite are the complicated multi-step fabrication process, expensive materials, and environment and ion migration induced instability in the devices. In this research, we present a simple film-cover strategy to deposit light absorption layers (LALs) and hole transporting layers (HTLs) on a large area (4 x 4 cm²) through a single step process which is fundamentally based on polar and nonpolar interfacial induced self vertical phase separation between perovskite and HTLs. This process is highly saving material which is 3% Spiro-OMeTAD and 7.5% perovskite used compared to the traditional spin-coating process, it is dozens of times for the cost saving. Moreover, The specific gradient phase separation construction based on the doped-free Spiro-OMeTAD shows specific energy level and device construction, leading to efficient carrier transportation and higher power conversion efficiency (PCE). We further systematic studied the origin of stability in this phase separated film compared to the traditional layer by layer spin-coating film, it suggested that the gradient HTLs embed in perovskite crystal boundary which can effectively restrain ion migrate and moisture at the crystal boundary, providing an excellent environmental stability and retains 95% of the initial efficiency even after 68 days being stored in ambient condition without encapsulation. We believe that our strategy will pave a new way for simple, economical, efficient, stable, large-area and commercialized perovskite solar cells (PSCs) preparation, and provide more understanding on the nature of ion migrate in the PSCs devices.

Organic-inorganic hybrid perovskites are emerging as highly attractive materials for optoelectronic applications due to their high color purity, broadly tunable optical bandgap, facile solution process, and efficient narrow band emission. Due to these figure of merits, perovskite materials are highly utilized in the field of light-emitting diodes (LEDs) use as an active layer and have been successfully demonstrated to overcome the disadvantages of organic LEDs such as complex synthesis procedure, poor color purity, and high-cost processing. Because of these efforts, perovskite LEDs have recently reached external quantum efficiencies (EQEs) about 10 % for green and near-infrared emissions through reduce the grain size of the perovskite active layer. However, it still has the problem that increase the number of grain boundaries causing exciton quenching and nonradiative recombination, while reduce the grain size of the perovskites.
In this study, we investigated single-step solution-processed methylammonium lead-bromide (CH₃NH₃PbBr₃, MAPbBr₃) perovskite active layer for enhanced efficiency of LEDs. The single-step process contributed to strong exciton confinements inside the perovskite grain for improves the radiative recombination of the LEDs by achieving small grain size through a nanocrystal pinning method. In addition, the single-stepped perovskites can effectively reduced exciton quenching to the metallic Pb atoms by passivating the perovskite grain boundaries due to the MABr-rich molar proportion. As a result, the LED fabricated with single-step-processed MAPbBr₃ perovskite active layer (SSP LED) exhibited 33.8 % str