Editorial Cite This: Chem. Rev. 2019, 119, 3033−3035
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Introduction: Perovskites
Chem. Rev. 2019.119:3033-3035. Downloaded from pubs.acs.org by 85.202.195.15 on 03/13/19. For personal use only.
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lthough known since the 19th century1,2 and vigorously pursued with respect to magnetic and optical/electronic properties and applications in the late 20th century (e.g., see refs 3−15), the last ten years have yielded an explosion of interest in the broad family of materials16,17 based on metal halide perovskite frameworks. Interest in these systems (most notably, those based on germanium, tin, and lead) derives from a confluence of attractive semiconductor traits, including: (1) electronic structures that provide direct tunable bandgaps, strong light absorption, relatively small and balanced electron/ hole effective masses, and defect resistance (i.e., dominant defects that do not cause substantial nonradiative recombination);18 (2) unprecedented flexibility to independently and synergistically tune structural, optical, and electronic properties using both organic and inorganic components of hybrid members of this family,19−23 pointing to outstanding promise for “organic−inorganic electronics” application;24 and (3) readily accessible synthesis of high-quality crystals and films, enabling facile structure−property correlation and rapid device prototyping/optimization. In an effort to capture some of the key contemporary directions of halide perovskite research, the current thematic issue has been assembled, with seven reviews provided by established and early career experts in the field: Demonstration of high-performance photovoltaic (PV) devices using (CH3NH3)PbI3-related materials as the absorber has provided the key spark initiating the current tidal wave of interest in halide perovskite optoelectronics. To celebrate the outstanding success of perovskite PV, A. K. Jena, A. Kulkarni, and T. Miyasaka review the advent, early evolution, and future prospects of perovskite PV. The rapid evolution of light-toelectricity power conversion efficiencies to a value of greater than 23% (similar to single crystal silicon devices) provides one underpinning of the interest in this materials family for PV devices, while issues of lead(II) toxicity and device stability represent directions of current study to enable future commercialization. Control over light emission provides a second highly promising direction of recent study, based on similar fundamentals to perovskite PVi.e., the existence of a wide degree of band structure tunability, coupled with defect tolerance and near-unity photoluminescence quantum yield (PLQY). M. D. Smith, B. A. Connor, and H. I. Karunadasa examine the connection between crystal/defect structure and the tuning of luminescence, from very narrow band edge emission to broad emission spanning the entire visible spectrum. The outstanding optoelectronic properties and tunability of halide perovskites make them particularly strong candidates for active layers in LEDs, photodetectors, X-ray detectors, and lasers, and these applications could rival PV as a prospective first commercial application for halide perovskites. The near-ideal properties of halide perovskites for use in optoelectronic semiconductor devices derive from the unique electronic structures arising within organic−inorganic hybrids and related metal halide perovskite semiconductors. To address this connection, C. Katan, N. Mercier, and J. Even © 2019 American Chemical Society
review the theoretical underpinnings of quantum and dielectric confinement in lower dimensional hybrid perovskite semiconductors. Despite the great successes of density functional theory (DFT) to describe the electronic structures of relatively simple 3D halide perovskites, the review examines recent directions and challenges for extending these models to more complex hybrid 2D and colloidal perovskites, particularly with respect to considering excited state properties. One unique attribute of the halide perovskites relates to the wide range of approaches for depositing high quality films i.e., generally a critically important prerequisite for successful device integration, but also important for property measurement. To highlight this point W. A. Dunlap-Shohl, Y. Zhou, N. P. Padture, and D. B. Mitzi provide a comprehensive review of the mechanisms and methods underlying successful solution, vapor-, and melt-phase thin-film deposition of halide perovskites. Despite the early stage in our understanding of the relatively complex halide perovskite film nucleation and growth processes, the review highlights the film deposition opportunities and challenges that arise from the relatively small formation energies and “soft” nature of the halide perovskites. Beyond thin-film deposition, nanocrystals represent another important synthesis direction and pathway for materials tailoring. As detailed in a review by J. Shamsi, A. S. Urban, M. Imran, L. De Trizio, and L. Manna, numerous approaches have been developed to prepare perovskite nanocrystals that offer a wide variety of compositions, shapes, sizes, and functionality. The resulting nanomaterials provide exceptional versatility for tailoring quantum confinement, linear and nonlinear optical response, and highly efficient light emission. While the intrinsic properties of halide perovskites provide far-reaching possibilities for properties and synthesis, interfaces between the halide perovskite and other prospective device layers or a substrate can play an equally critical role in determining material or device properties. The review by P. Schulz, D. Cahen, and A. Kahn examines interface issues for perovskite structures/devices, focusing on halide perovskite surface chemistry and energy level alignment, as well as prospective interfacial chemistry occurring between the perovskite and prevalent materials used for passivation, charge extraction, or film termination. A central question addressed in this review is how optoelectronic function within halide perovskite devices is determined or limited by interfaces. The low formation energies that provide for facile formation in bulk, single crystal, and thin-film forms also imply an ease of pulling the halide perovskites apart, therefore pointing to the importance of considering stability in films/devices based on these materials. C. C. Boyd, R. Cheacharoen, T. Leijtens, and M. D. McGehee review this important issue in the context of degradation mechanisms and stability concerns in perovskite PV devices (a technology that is particularly sensitive to the issue of device longevity). Despite expected challenges Special Issue: Perovskites Published: March 13, 2019 3033
DOI: 10.1021/acs.chemrev.8b00800 Chem. Rev. 2019, 119, 3033−3035
Chemical Reviews
Editorial
Biography
surrounding this issue in perovskite-based devices, the review points to the remarkable progress that has been made so far in addressing stability. Although not part of the current thematic issue on halide perovskites, two recent Chemical Reviews articles provide further coverage of the important space of halide perovskite chemistry and application. B. Saparov and D. B. Mitzi17 contributed a comprehensive overview of organic−inorganic perovskite crystal structures in the context of functional materials design, and J. S. Manser, J. A. Christians and P. Kamat25 provided a detailed review of photophysical properties of the metal halide perovskites. Additionally, given the rapidly evolving nature of the halide perovskite field, it should be pointed out that numerous emerging areas of inquiry have not been included (or only very briefly touched upon) in the current issue. These include, for example, examining the unique opportunities afforded by halide perovskites in terms of controlling spin (with possible implications for spintronics),26−28 as well as the issue of how structural “softness” of the halide perovskite family impacts mechanical, thermal, optical, and electrical properties.29−32 Finally, putting together a thematic issue requires substantial dedication from many sides and special thanks go out to the editorial staff at Chemical Reviews and to all of the authors for their contributions. As seen from the above discussion and the included reviews in the thematic edition, the halide perovskite field has been dramatically accelerated by the advent of perovskite photovoltaics and related optoelectronics. Despite this, the versatility provided by the metal halide framework and possibility of incorporating a wide range of functional organic cations (i.e., for “organic−inorganic electronics”24), coupled with recent advances in computational/theoretical screening, provide an unprecedented paradigm for materials design, rendering it difficult to predict where the most important properties/applications will lie in the future. With this paradigm in mind, it is expected that halide perovskites will provide exciting opportunities for materials discovery and development for many years to come.
David Mitzi is the Simon Family Professor of Engineering at Duke University, with appointments to the Department of Mechanical Engineering and Materials Science and the Department of Chemistry. He received his B.S. in Electrical Engineering and Engineering Physics from Princeton University in 1985 and his Ph.D. in Applied Physics from Stanford University in 1990. Prior to joining the faculty at Duke in 2014, Dr. Mitzi spent 23 years at IBM’s T. J. Watson Research Center, where his focus was on the search for and application of new electronic materials, including organic−inorganic hybrid perovskites and inorganic materials for photovoltaic, LED, transistor, and memory applications. For his final five years at IBM, he served as manager for the Photovoltaic Science and Technology Department, where he initiated and managed a multicompany program to develop a lowcost, high-throughput approach to deposit thin-film chalcogenidebased absorber layers for high-efficiency solar cells. Dr. Mitzi’s current research interests involve making emerging solar energy conversion materials more effective, cost-efficient, and competitive for the energy market. He has been elected a fellow of the Materials Research Society (MRS) and has authored or coauthored more than 200 papers and book chapters.
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David B. Mitzi* Department of Mechanical Engineering and Materials Science and Department of Chemistry, Duke University
AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. ORCID
David B. Mitzi: 0000-0001-5189-4612 Notes
Views expressed in this editorial are those of the author and not necessarily the views of the ACS. 3034
DOI: 10.1021/acs.chemrev.8b00800 Chem. Rev. 2019, 119, 3033−3035
Chemical Reviews
Editorial
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(9) Mitzi, D. B.; Wang, S.; Feild, C. A.; Chess, C. A.; Guloy, A. M. Conducting Layered Organic-Inorganic Halides Containing < 110>Oriented Perovskite Sheets. Science 1995, 267, 1473−1476. (10) Mitzi, D. B.; Feild, C. A.; Schlesinger, Z.; Laibowitz, R. B. Transport, Optical, and Magnetic Properties of the Conducting Halide Perovskite CH3NH3SnI3. J. Solid State Chem. 1995, 114, 159− 163. (11) Papavassiliou, G. C.; Koutselas, I. B. Structural, Optical and Related Properties of Some Natural Three- and Lower-Dimensional Semiconductor Systems. Synth. Met. 1995, 71, 1713−1714. (12) Fujita, T.; Sato, Y.; Kuitani, T.; Ishihara, T. Tunable Polariton Absorption of Distributed Feedback Microcavities at Room Temperature. Phys. Rev. B: Condens. Matter Mater. Phys. 1998, 57, 12428− 12434. (13) Kondo, T.; Azuma, T.; Yuasa, T.; Ito, R. Biexciton Lasing in the Layered Perovskite-Type Material (C6H13NH3)2PbI4. Solid State Commun. 1998, 105, 253−255. (14) Chondroudis, K.; Mitzi, D. B. Electroluminescence from an Organic-Inorganic Perovskite Incorporating a Quaterthiophene Dye within Lead Halide Perovskite Layers. Chem. Mater. 1999, 11, 3028− 3030. (15) Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D. OrganicInorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors. Science 1999, 286, 945−947. (16) Mitzi, D. B. Synthesis, Structure, and Properties of OrganicInorganic Perovskites and Related Materials. Prog. Inorg. Chem. 2007, 48, 1−121. (17) Saparov, B.; Mitzi, D. B. Organic−Inorganic Perovskites: Structural Versatility for Functional Materials Design. Chem. Rev. 2016, 116, 4558−4596. (18) Yin, W. J.; Shi, T.; Yan, Y. Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance. Adv. Mater. 2014, 26, 4653−4658. (19) Mitzi, D. B.; Chondroudis, K.; Kagan, C. R. Design, Structure, and Optical Properties of Organic-Inorganic Perovskites Containing an Oligothiophene Chromophore. Inorg. Chem. 1999, 38, 6246−6256. (20) Liu, C.; Huhn, W.; Du, K.-Z.; Vazquez-Mayagoitia, A.; Dirkes, D.; You, W.; Kanai, Y.; Mitzi, D. B.; Blum, V. Tunable Semiconductors: Control over Carrier States and Excitations in Layered Hybrid Organic-Inorganic Perovskites. Phys. Rev. Lett. 2018, 121, 146401. (21) Ema, K.; Inomata, M.; Kato, Y.; Kunugita, H.; Era, M. Nearly Perfect Triplet-Triplet Energy Transfer from Wannier Excitons to Naphthalene in Organic-Inorganic Hybrid Quantum-Well Materials. Phys. Rev. Lett. 2008, 100, 257401. (22) Braun, M.; Tuffentsammer, W.; Wachtel, H.; Wolf, H. C. Tailoring of Energy Levels in Lead Chloride Based Layered Perovskites and Energy Transfer Between the Organic and Inorganic Planes. Chem. Phys. Lett. 1999, 303, 157−164. (23) Passarelli, J. V.; Fairfield, D. J.; Sather, N. A.; Hendricks, M. P.; Sai, H.; Stern, C. L.; Stupp, S. I. Enhanced Out-of-Plane Conductivity and Photovoltaic Performance in n = 1 Layered Perovskites through Organic Cation Design. J. Am. Chem. Soc. 2018, 140, 7313−7323. (24) Mitzi, D. B.; Chondroudis, K.; Kagan, C. R. Organic-Inorganic Electronics. IBM J. Res. Dev. 2001, 45, 29−45. (25) Manser, J. S.; Christians, J. A.; Kamat, P. V. Intriguing Optoelectronic Properties of Metal Halide Perovskites. Chem. Rev. 2016, 116, 12956−13008. (26) Odenthal, P.; Talmadge, W.; Gundlach, N.; Wang, R.; Zhang, C.; Sun, D.; Yu, Z.-G.; Vardeny, Z. V.; Li, Y. S. Spin-Polarized Exciton Quantum Beating in Hybrid Organic−Inorganic Perovskites. Nat. Phys. 2017, 13, 894−899. (27) Long, G.; Jiang, C.; Sabatini, R.; Yang, Z.; Wei, M.; Quan, L. N.; Liang, Q.; Rasmita, A.; Askerka, M.; Walters, G.; et al. Spin Control in Reduced-Dimensional Chiral Perovskites. Nat. Photonics 2018, 12, 528−533. (28) Kepenekian, M.; Even, J. Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spin3035
DOI: 10.1021/acs.chemrev.8b00800 Chem. Rev. 2019, 119, 3033−3035
