Abstract
Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a ‘soft’ and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Huang, H. et al. Colloidal lead halide perovskite nanocrystals: synthesis, optical properties and applications. NPG Asia Mater. 8, e328 (2016).
Weidman, M. C., Goodman, A. J. & Tisdale, W. A. Colloidal halide perovskite nanoplatelets: an exciting new class of semiconductor nanomaterials. Chem. Mater. 29, 5019–5030 (2017).
Kovalenko, M. V., Protesescu, L. & Bodnarchuk, M. I. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science 358, 745–750 (2017).
Murray, C. B., Norris, D. J. & Bawendi, M. G. Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites. J. Am. Chem. Soc. 115, 8706–8715 (1993).
Saparov, B. & Mitzi, D. B. Organic–inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).
Li, W. et al. Chemically diverse and multifunctional hybrid organic–inorganic perovskites. Nat. Rev. Mater. 2, 16099 (2017).
Srivastava, V. et al. Understanding and curing structural defects in colloidal gaas nanocrystals. Nano Lett. 17, 2094–2101 (2017).
Schmidt, L. C. et al. Nontemplate synthesis of CH3NH3PbBr3 perovskite nanoparticles. J. Am. Chem. Soc. 136, 850–853 (2014).
Protesescu, L. et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 15, 3692–3696 (2015).
Huang, H. et al. Growth mechanism of strongly emitting CH3NH3PbBr3 perovskite nanocrystals with a tunable bandgap. Nat. Commun. 8, 996 (2017).
Sichert, J. A. et al. Quantum size effect in organometal halide perovskite nanoplatelets. Nano Lett. 15, 6521–6527 (2015).
Bekenstein, Y., Koscher, B. A., Eaton, S. W., Yang, P. & Alivisatos, A. P. Highly luminescent colloidal nanoplates of perovskite cesium lead halide and their oriented assemblies. J. Am. Chem. Soc. 137, 16008–16011 (2015).
Akkerman, Q. A. et al. Solution synthesis approach to colloidal cesium lead halide perovskite nanoplatelets with monolayer-level thickness control. J. Am. Chem. Soc. 138, 1010–1016 (2016).
Tong, Y. et al. Highly luminescent cesium lead halide perovskite nanocrystals with tunable composition and thickness by ultrasonication. Angew. Chem. Int. Ed. 55, 13887–13892 (2016).
Zhu, Z.-Y. et al. Solvent-Free mechanosynthesis of composition-tunable cesium lead halide perovskite quantum dots. J. Phys. Chem. Lett. 8, 1610–1614 (2017).
Pan, Q. et al. Microwave-assisted synthesis of high-quality all-inorganic CsPbX3 (X = Cl, Br, I) perovskite nanocrystals and the application in light emitting diode. J. Mater. Chem. C 5, 10947–10954 (2017).
Chen, S. et al. Exploring the stability of novel wide bandgap perovskites by a robot based high throughput approach. Adv. Energy Mater. 1701543 (2017).
Lignos, I. et al. Synthesis of cesium lead halide perovskite nanocrystals in a droplet-based microfluidic platform: fast parametric space mapping. Nano Lett. 16, 1869–1877 (2016).
Dirin, D. N. et al. Harnessing defect-tolerance at the nanoscale: highly luminescent lead halide perovskite nanocrystals in mesoporous silica matrixes. Nano Lett. 16, 5866–5874 (2016).
Malgras, V. et al. Observation of quantum confinement in monodisperse methylammonium lead halide perovskite nanocrystals embedded in mesoporous silica. J. Am. Chem. Soc. 138, 13874–13881 (2016).
Huang, H. et al. Lead halide perovskite nanocrystals in the research spotlight: stability and defect-tolerance. ACS Energy Lett. 2, 2071–2083 (2017).
Brandt, R. E., Stevanović, V., Ginley, D. S. & Buonassisi, T. Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites. MRS Commun. 5, 265–275 (2015).
Kang, J. & Wang, L.-W. High defect tolerance in lead halide perovskite CsPbBr3. J. Phys. Chem. Lett. 8, 489–493 (2017).
Koscher, B. A., Swabeck, J. K., Bronstein, N. D. & Alivisatos, A. P. Essentially trap-free cspbbr3 colloidal nanocrystals by postsynthetic thiocyanate surface treatment. J. Am. Chem. Soc. 139, 6566–6569 (2017).
Liu, F. et al. Highly luminescent phase-stable CsPbI3 perovskite quantum dots achieving near 100% absolute photoluminescence quantum yield. ACS Nano 11, 10373–10383 (2017).
Zhu, H. et al. Screening in crystalline liquids protects energetic carriers in hybrid perovskites. Science 353, 1409–1413 (2016).
Bakulin, A. A. et al. Real-time observation of organic cation reorientation in methylammonium lead iodide perovskites. J. Phys. Chem. Lett. 6, 3663–3669 (2015).
Walsh, A. & Zunger, A. Instilling defect tolerance in new compounds. Nat. Mater. 16, 964–967 (2017).
Boles, M. A., Ling, D., Hyeon, T. & Talapin, D. V. The surface science of nanocrystals. Nat. Mater. 15, 141–153 (2016).
De Roo, J. et al. Highly dynamic ligand binding and light absorption coefficient of cesium lead bromide perovskite nanocrystals. ACS Nano 10, 2071–2081 (2016).
Trots, D. M. & Myagkota, S. V. High-temperature structural evolution of caesium and rubidium triiodoplumbates. J. Phys. Chem. Solids 69, 2520–2526 (2008).
Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52, 9019–9038 (2013).
Swarnkar, A. et al. Quantum dot–induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics. Science 354, 92–95 (2016).
Protesescu, L. et al. Dismantling the “red wall” of colloidal perovskites: highly luminescent formamidinium and formamidinium–cesium lead iodide nanocrystals. ACS Nano 11, 3119–3134 (2017).
Wang, C., Chesman, A. S. R. & Jasieniak, J. J. Stabilizing the cubic perovskite phase of CsPbI3 nanocrystals by using an alkyl phosphinic acid. Chem. Commun. 53, 232–235 (2017).
Beal, R. E. et al. Cesium lead halide perovskites with improved stability for tandem solar cells. J. Phys. Chem. Lett. 7, 746–751 (2016).
Akkerman, Q. A., Meggiolaro, D., Dang, Z., De Angelis, F. & Manna, L. Fluorescent alloy CsPbxMn1–xI3 perovskite nanocrystals with high structural and optical stability. ACS Energy Lett. 2, 2183–2186 (2017).
Zou, S. et al. Stabilizing cesium lead halide perovskite lattice through Mn(II) substitution for air-stable light-emitting diodes. J. Am. Chem. Soc. 139, 11443–11450 (2017).
Hu, Y. et al. Bismuth incorporation stabilized α-CsPbI3 for fully inorganic perovskite solar cells. ACS Energy Lett. 2, 2219–2227 (2017).
Ai, B. et al. Precipitation and optical properties of CsPbBr3 quantum dots in phosphate glasses. J. Am. Ceram. Soc. 99, 2875–2877 (2016).
Liu, S., Luo, Y., He, M., Liang, X. & Xiang, W. Novel CsPbI3 QDs glass with chemical stability and optical properties. J. Eur. Ceram. Soc. 38, 1998–2004 (2017).
Ai, B. et al. Low temperature photoluminescence properties of CsPbBr3 quantum dots embedded in glasses. Phys. Chem. Chem. Phys. 19, 17349–17355 (2017).
Di, X. et al. Use of long-term stable CsPbBr3 perovskite quantum dots in phospho-silicate glass for highly efficient white LEDs. Chem. Commun. 53, 11068–11071 (2017).
Nedelcu, G. et al. Fast anion-exchange in highly luminescent nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). Nano Lett. 15, 5635–5640 (2015).
Akkerman, Q. A. et al. Tuning the optical properties of cesium lead halide perovskite nanocrystals by anion exchange reactions. J. Am. Chem. Soc. 137, 10276–10281 (2015).
Akkerman, Q. A. et al. Nearly monodisperse insulator Cs4PbX6 (X = Cl, Br, I) nanocrystals, their mixed halide compositions, and their transformation into CsPbX3 nanocrystals. Nano Lett. 17, 1924–1930 (2017).
van der Stam, W. et al. Highly emissive divalent-ion-doped colloidal CsPb1–xMxBr3 perovskite nanocrystals through cation exchange. J. Am. Chem. Soc. 139, 4087–4097 (2017).
Barker, A. J. et al. Defect-assisted photoinduced halide segregation in mixed-halide perovskite thin films. ACS Energy Lett. 2, 1416–1424 (2017).
De Trizio, L. & Manna, L. Forging colloidal nanostructures via cation exchange reactions. Chem. Rev. 116, 10852–10887 (2016).
Liu, W. et al. Mn2+-doped lead halide perovskite nanocrystals with dual-color emission controlled by halide content. J. Am. Chem. Soc. 138, 14954–14961 (2016).
Guria, A. K., Dutta, S. K., Adhikari, S. D. & Pradhan, N. Doping Mn2+ in lead halide perovskite nanocrystals: successes and challenges. ACS Energy Lett. 2, 1014–1021 (2017).
Palazon, F. et al. Changing the dimensionality of cesium lead bromide nanocrystals by reversible postsynthesis transformations with amines. Chem. Mater. 29, 4167–4171 (2017).
Wu, L. et al. From nonluminescent Cs4PbX6 (X = Cl, Br, I) nanocrystals to highly luminescent CsPbX3 nanocrystals: water-triggered transformation through a CsX-stripping mechanism. Nano Lett. 17, 5799–5804 (2017).
Liu, Z. et al. Ligand mediated transformation of cesium lead bromide perovskite nanocrystals to lead depleted Cs4PbBr6 nanocrystals. J. Am. Chem. Soc. 139, 5309–5312 (2017).
Eperon, G. E. et al. Perovskite-perovskite tandem photovoltaics with optimized band gaps. Science 354, 861–865 (2016).
Saliba, M. et al. Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance. Science 354, 206–209 (2016).
Kovalenko, M. V. et al. Prospects of nanoscience with nanocrystals. ACS Nano 9, 1012–1057 (2015).
Zhang, H. et al. Embedding perovskite nanocrystals into a polymer matrix for tunable luminescence probes in cell imaging. Adv. Funct. Mater. 27, 1604382 (2017).
Quan, L. N. et al. Highly emissive green perovskite nanocrystals in a solid state crystalline matrix. Adv. Mater. 27, 1605945 (2017).
Guhrenz, C. et al. Solid-state anion exchange reactions for color tuning of CsPbX3 perovskite nanocrystals. Chem. Mater. 28, 9033–9040 (2016).
Li, J. et al. 50-fold eqe improvement up to 6.27% of solution-processed all-inorganic perovskite CsPbBr3 QLEDs via surface ligand density control. Adv. Mater. 29, 1603885 (2017).
Chiba, T. et al. High-efficiency perovskite quantum-dot light-emitting devices by effective washing process and interfacial energy level alignment. ACS Appl. Mater. Interfaces 9, 18054–18060 (2017).
Zhang, X. et al. Bright perovskite nanocrystal films for efficient light-emitting devices. J. Phys. Chem. Lett. 7, 4602–4610 (2016).
Deng, W. et al. Organometal halide perovskite quantum dot light-emitting diodes. Adv. Funct. Mater. 26, 4797–4802 (2016).
Akkerman, Q. A. et al. Strongly emissive perovskite nanocrystal inks for high-voltage solar cells. Nat. Energy 2, 16194 (2016).
Engler, R. E., MacDougall, L. S., Xu, J. B. & Willis, J. Supplemental Statement on Life Cycle Assessment (QD Vision, 2015); http://go.nature.com/2ERm8Fs
Babayigit, A., Ethirajan, A., Muller, M. & Conings, B. Toxicity of organometal halide perovskite solar cells. Nat. Mater. 15, 247–251 (2016).
Zhou, C. et al. Low-dimensional organic tin bromide perovskites and their photoinduced structural transformation. Angew. Chem. Int. Edit. 56, 9018–9022 (2017).
Giustino, F. & Snaith, H. J. Toward lead-free perovskite solar cells. ACS Energy Lett. 1, 1233–1240 (2016).
McCall, K. M., Stoumpos, C. C., Kostina, S. S., Kanatzidis, M. G. & Wessels, T. C. Strong electron–phonon coupling and self-trapped excitons in the defect halide perovskites A3M2I9 (a = Cs, Rb; M = Bi, Sb). Chem. Mater. 29, 4129–4145 (2017).
Slavney, A. H., Hu, T., Lindenberg, A. M. & Karunadasa, H. I. A Bismuth-halide double perovskite with long carrier recombination lifetime for photovoltaic applications. J. Am. Chem. Soc. 138, 2138–2141 (2016).
Volonakis, G. et al. Lead-free halide double perovskites via heterovalent substitution of noble metals. J. Phys. Chem. Lett. 7, 1254–1259 (2016).
Raino, G. et al. Single cesium lead halide perovskite nanocrystals at low temperature: fast single-photon emission, reduced blinking, and exciton fine structure. ACS Nano 10, 2485–2490 (2016).
Becker, M. A. et al. Bright triplet excitons in lead halide perovskites. Nature 553, 189–193 (2018).
Efros, A. L. & Nesbitt, D. J. Origin and control of blinking in quantum dots. Nat. Nanotech. 11, 661–671 (2016).
Aharonovich, I., Englund, D. & Toth, M. Solid-state single-photon emitters. Nat. Photon. 10, 631–641 (2016).
Fu, M. et al. Neutral and charged exciton fine structure in single lead halide perovskite nanocrystals revealed by magneto-optical spectroscopy. Nano Lett. 17, 2895–2901 (2017).
Isarov, M. et al. Rashba effect in a single colloidal CsPbBr3 perovskite nanocrystal detected by magneto-optical measurements. Nano Lett. 17, 5020–5026 (2017).
Yin, C. et al. Bright-exciton fine-structure splittings in single perovskite nanocrystals. Phys. Rev. Lett. 119, 026401 (2017).
Nirmal, M. et al. Observation of the "dark exciton" in CdSe quantum dots. Phys. Rev. Lett. 75, 3728–3731 (1995).
Tighineanu, P. et al. Single-photon superradiance from a quantum dot. Phys. Rev. Lett. 116, 163604 (2016).
Park, Y.-S., Guo, S., Makarov, N. S. & Klimov, V. I. Room temperature single-photon emission from individual perovskite quantum dots. ACS Nano 9, 10386–10393 (2015).
Hu, F. et al. Slow Auger recombination of charged excitons in nonblinking perovskite nanocrystals without spectral diffusion. Nano Lett. 16, 6425–6430 (2016).
Utzat, H. et al. Probing linewidths and biexciton quantum yields of single cesium lead halide nanocrystals in solution. Nano Lett. 17, 6838–6846 (2017).
Mizuochi, N. et al. Electrically driven single-photon source at room temperature in diamond. Nat. Photon. 6, 299–303 (2012).
Nothaft, M. et al. Electrically driven photon antibunching from a single molecule at room temperature. Nat. Commun. 3, 628 (2012).
Bertolotti, F. et al. Coherent nanotwins and dynamic disorder in cesium lead halide perovskite nanocrystals. ACS Nano 11, 3819–3831 (2017).
Saidaminov, M. I. et al. Pure Cs4PbBr6: highly luminescent zero-dimensional perovskite solids. ACS Energy Lett. 1, 840–845 (2016).
Nikl, M. et al. Photoluminescence of Cs4PbBr6 crystals and thin films. Chem. Phys. Lett. 306, 280–284 (1999).
Mitzi, D. B. Synthesis, crystal structure, and optical and thermal properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb). Chem. Mater. 8, 791–800 (1996).
Blancon, J.-C. et al. Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites. Science 355, 1288–1292 (2017).
Bhaumik, S. et al. Highly stable, luminescent core-shell type methylammonium-octylammonium lead bromide layered perovskite nanoparticles. Chem. Commun. 52, 7118–7121 (2016).
Chen, W. et al. Giant five-photon absorption from multidimensional core-shell halide perovskite colloidal nanocrystals. Nat. Commun. 8, 15198 (2017).
Liu, F. et al. Highly luminescent phase-stable CsPbI3 perovskite quantum dots achieving near 100% absolute photoluminescence quantum yield. ACS Nano 11, 10373–10383 (2017).
Gross, E. F. & Kapliansky, A. A. A spectroscopic study of absorption and luminescence of cuprous chloride, introduced into a crystal of rock salt. Opt. Spektrosk. 2, 204–209 (1957).
Berry, C. R. Structture and opticcal absorption of AgI microcrystals. Phys. Rev. B 161, 848–851 (1967).
Ekimov, A. I. & Onushchenko, A. A. Quantum size effects in 3-dimensional microscopic semiconductor crystals. J. Exp. Theor. Phys. Lett. 34, 345–349 (1981).
Efros, A. L. Interband absorption of light in a semiconductor sphere. Sov. Phys. Semicond. 16, 772–775 (1982).
Wells, H. L. Über die Cäsium- und Kalium-Bleihalogenide. Z. Anorg. Allg. Chem. 3, 195–210 (1893).
Moller, C. K. A phase transition in caesium plumbochloride. Nature 180, 981–982 (1957).
Moller, C. K. Crystal structure and photoconductivity of caesium plumbohalides. Nature 182, 1436–1436 (1958).
Mizusaki, J., Arai, K. & Fueki, K. Ionic-conduction of the perovskite-type halides. Solid State Ion. 11, 203–211 (1983).
Radhakrishna, S. Polarised luminescence from lead centers in cesium halides. J. Lumin. 12, 409–411 (1976).
Nikl, M. et al. Optical-properties of the Pb2+ based aggregated phase in a CsCl host crystal – quantum-confinement effects. Phys. Rev. B 51, 5192–5199 (1995).
Nikl, M. et al. Quantum size effect in the excitonic luminescence of CsPbX3-like quantum dots in CsX (X = Cl, Br) single crystal host. J. Lumin. 72, 377–379 (1997).
Aceves, R. et al. Spectroscopy of CsPbBr3 quantum dots in CsBr:Pb crystals. J. Lumin. 93, 27–41 (2001).
Kondo, S., Sakai, T., Tanaka, H. & Saito, T. Amorphization-induced strong localization of electronic states in CsPbBr3 and CsPbCl3 studied by optical absorption measurements. Phys. Rev. B 58, 11401–11407 (1998).
Kondo, S. et al. High intensity photoluminescence of microcrystalline CsPbBr3 films: evidence for enhanced stimulated emission at room temperature. Curr. Appl. Phys. 7, 1–5 (2007).
Kondo, S., Saito, T., Asada, H. & Nakagawa, H. Stimulated emission from microcrystalline CsPbBr3 films: edge emission versus surface emission. Mater. Sci. Eng. B 137, 156–161 (2007).
Weber, D. CH3NH3PbX3, ein Pb (II)-System mit Kubischer Perowskitstruktur. Z. Naturforsch. B 33, 1443–1445 (1978).
Papavassiliou, G. C. et al. Nanocrystalline/microcrystalline materials based on lead-halide units. J. Mater. Chem. 22, 8271–8280 (2012).
Papavassiliou, G. C., Pagona, G., Mousdis, G. A. & Karousis, N. Enhanced phosphorescence from nanocrystalline/microcrystalline materials based on (CH3NH3)(1-naphthylmethyl ammonium)2Pb2Cl7 and similar compounds. Chem. Phys. Lett. 570, 80–84 (2013).
Aygüler, M. F. et al. Light-emitting electrochemical cells based on hybrid lead halide perovskite nanoparticles. J. Phys. Chem. C 119, 12047–12054 (2015).
Weidman, M. C., Seitz, M., Stranks, S. D. & Tisdale, W. A. Highly tunable colloidal perovskite nanoplatelets through variable cation, metal, and halide composition. ACS Nano 10, 7830–7839 (2016).
Protesescu, L. et al. Monodisperse formamidinium lead bromide nanocrystals with bright and stable green photoluminescence. J. Am. Chem. Soc. 138, 14202–14205 (2016).
Acknowledgements
Q.A.A and L.M. thank the European Union’s Seventh Framework Programme (grant agreement no. 614897, ERC Consolidator Grant ‘TRANS-NANO’) for funding. M.V.K. is grateful for financial support by the European Research Council under the European Union’s Seventh Framework Programme (grant agreement no. 306733, ERC Starting Grant ‘NANOSOLID’). We thank N. Stadie for reading the manuscript.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Akkerman, Q.A., Rainò, G., Kovalenko, M.V. et al. Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals. Nature Mater 17, 394–405 (2018). https://doi.org/10.1038/s41563-018-0018-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-018-0018-4
This article is cited by
-
Manipulating solvent fluidic dynamics for large-area perovskite film-formation and white light-emitting diodes
Nature Communications (2024)
-
Electron-donating functional groups strengthen ligand-induced chiral imprinting on CsPbBr3 quantum dots
Scientific Reports (2024)
-
Designer phospholipid capping ligands for soft metal halide nanocrystals
Nature (2024)
-
Multipeak emission Eu3+-doped perovskite quantum dots in molecular sieve
Applied Physics A (2024)
-
Coupling to octahedral tilts in halide perovskite nanocrystals induces phonon-mediated attractive interactions between excitons
Nature Physics (2024)