Hybrid perovskites are currently one of the most active fields of research owing to their enormous potential for photovoltaics. The performance of 3D hybrid organic–inorganic perovskite solar cells has increased at an incredible rate, reaching power conversion efficiencies comparable to those of many established technologies. However, the commercial application of 3D hybrid perovskites is inhibited by their poor stability. Relative to 3D hybrid perovskites, low-dimensional — that is, 2D — hybrid perovskites have demonstrated higher moisture stability, offering new approaches to stabilizing perovskite-based photovoltaic devices. Furthermore, 2D hybrid perovskites have versatile structures, enabling the fine-tuning of their optoelectronic properties through compositional engineering. In this Review, we discuss the state of the art in 2D perovskites, providing an overview of structural and materials engineering aspects and optical and photophysical properties. Moreover, we discuss recent developments along with the main limitations of 3D perovskites and assess the advantages of 2D perovskites over their 3D parent structures in terms of stability. Finally, we review recent achievements in combining 3D and 2D perovskites as an approach to simultaneously boost device efficiency and stability, paving the way for mixed-dimensional perovskite solar cells for commercial applications.
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Green, M. A. & Ho-Baillie, A. Perovskite solar cells: the birth of a new era in photovoltaics. ACS Energy Lett. 2, 822–830 (2017).
Grätzel, M. The rise of highly efficient and stable perovskite solar cells. Acc. Chem. Res. 50, 487–491 (2017).
Correa-Baena, J.-P. et al. Promises and challenges of perovskite solar cells. Science 358, 739–744 (2017).
Snaith, H. J. Perovskites: the emergence of a new era for low-cost, high-efficiency solar cells. J. Phys. Chem. Lett. 4, 3623–3630 (2013).
Kieslich, G., Sun, S. & Cheetham, A. K. Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog. Chem. Sci. 5, 4712–4715 (2014).
Stranks, S. D. & Snaith, H. J. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat. Nanotechnol. 10, 391–402 (2015).
D’Innocenzo, V. et al. Excitons versus free charges in organo-lead tri-halide perovskites. Nat. Commun. 5, 3586 (2014).
Grancini, G. et al. One-year stable perovskite solar cells by 2D/3D interface engineering. Nat. Commun. 8, 15684 (2017).
Wang, D., Wright, M., Elumalai, N. K. & Uddin, A. Stability of perovskite solar cells. Sol. Energy Mater. Sol. Cells 147, 255–275 (2016).
Slavney, A. H. et al. Chemical approaches to addressing the instability and toxicity of lead–halide perovskite absorbers. Inorg. Chem. 56, 46–55 (2017).
Berhe, T. A. et al. Organometal halide perovskite solar cells: degradation and stability. Energy Environ. Sci. 9, 323–356 (2016).
You, J. et al. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers. Nat. Nanotechnol. 11, 75–81 (2016).
Bella, F. et al. Improving efficiency and stability of perovskite solar cells with photocurable fluoropolymers. Science 354, 203–206 (2016).
Li, X. et al. Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides. Nat. Chem. 7, 703–711 (2015).
Smith, I. C., Hoke, E. T., Solis-Ibarra, D., McGehee, M. D. & Karunadasa, H. I. A layered hybrid perovskite solar-cell absorber with enhanced moisture stability. Angew. Chem. Int. Ed. 53, 11232–11235 (2014).
Tsai, H. et al. High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 536, 312–316 (2016).
Cao, D. H., Stoumpos, C. C., Farha, O. K., Hupp, J. T. & Kanatzidis, M. G. 2D homologous perovskites as light-absorbing materials for solar cell applications. J. Am. Chem. Soc. 137, 7843–7850 (2015).
Stoumpos, C. C. et al. Ruddlesden–Popper hybrid lead iodide perovskite 2D homologous semiconductors. Chem. Mater. 28, 2852–2867 (2016).
Chen, Y. et al. 2D Ruddlesden–Popper perovskites for optoelectronics. Adv. Mater. 30, 1703487 (2018).
Saparov, B. & Mitzi, D. B. Organic–inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).
Du, K. et al. Two-dimensional lead(ii) halide-based hybrid perovskites templated by acene alkylamines: crystal structures, optical properties, and piezoelectricity. Inorg. Chem. 56, 9291–9302 (2017).
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. 303, 157–164 (1999).
Mitzi, D. B. in Progress in Inorganic Chemistry Vol. 48 (ed. Karlin, K. D.) 1–121 (John Wiley & Sons, Inc., 1999).
Younts, R. et al. Efficient generation of long-lived triplet excitons in 2D hybrid perovskite. Adv. Mater. 29, 1604278 (2017).
Quan, L. N. et al. Ligand-stabilized reduced-dimensionality perovskites. J. Am. Chem. Soc. 138, 2649–2655 (2016).
Tanaka, K. et al. Image charge effect on two-dimensional excitons in an inorganic-organic quantum-well crystal. Phys. Rev. 71, 45312 (2005).
Tanaka, K. et al. Two-dimensional Wannier excitons in a layered-perovskite-type crystal (C6H13NH3)2PbI4. Solid State Commun. 122, 249–252 (2002).
Ishihara, T., Hong, X., Ding, J. & Nurmikko, A. V. Dielectric confinement effect for exciton and biexciton states in PbI4-based two-dimensional semiconductor structures. Surf. Sci. 267, 323–326 (1992).
Dohner, E. R., Jaffe, A., Bradshaw, L. R. & Karunadasa, H. I. Intrinsic white-light emission from layered hybrid perovskites. J. Am. Chem. Soc. 136, 13154–13157 (2014).
Cho, H. et al. Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science 350, 1222–1225 (2015).
Era, M., Hattori, T., Taira, T. & Tsutsui, T. Self-organized growth of PbI-based layered perovskite quantum well by dual-source vapor deposition. Chem. Mater. 9, 8–10 (1997).
Mitzi, D. B. A layered solution crystal growth technique and the crystal structure of (C6H5C2H4NH3)2PbCl4. J. Solid State Chem. 145, 694–704 (1999).
Gan, X. et al. 2D homologous organic-inorganic hybrids as light-absorbers for planer and nanorod-based perovskite solar cells. Sol. Energy Mater. Sol. Cells 162, 93–102 (2017).
Cortecchia, D. et al. Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. J. Am. Chem Soc. 139, 39–42 (2017).
Knutson, J. L., Martin, J. D. & Mitzi, D. B. Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating. Inorg. Chem. 44, 4699–4705 (2005).
Venkatesan, N. R., Labram, J. G. & Chabinyc, M. L. Charge-carrier dynamics and crystalline texture of layered Ruddlesden–Popper hybrid lead iodide perovskite thin films. ACS Energy Lett. 3, 380–386 (2018).
Misra, R. K., Cohen, B.-E., Iagher, L. & Etgar, L. Low-dimensional organic–inorganic halide perovskite: structure, properties, and applications. ChemSusChem 10, 3712–3721 (2017).
Chen, A. Z. et al. Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance. Nat. Commun. 9, 1336 (2018).
Tsai, H. et al. Design principles for electronic charge transport in solution-processed vertically stacked 2D perovskite quantum wells. Nat. Commun. 9, 2130 (2018).
Ball, J. M. & Petrozza, A. Defects in perovskite-halides and their effects in solar cells. Nat. Energy 1, 16149 (2016).
Li, W. et al. Chemically diverse and multifunctional hybrid organic–inorganic perovskites. Nat. Rev. Mater. 2, 16099 (2017).
Peng, W. et al. Ultralow self-doping in two-dimensional hybrid perovskite single crystals. Nano Lett. 17, 4759–4767 (2017).
Wu, X., Trinh, M. T. & Zhu, X.-Y. Excitonic many-body interactions in two-dimensional lead iodide perovskite quantum wells. J. Phys. Chem. 119, 14714–14721 (2015).
Trinh, M. T., Wu, X., Niesner, D. & Zhu, X.-Y. Many-body interactions in photo-excited lead iodide perovskite. J. Mater. Chem. A 3, 9285–9290 (2015).
Grancini, G. et al. Role of microstructure in the electron–hole interaction of hybrid lead halide perovskites. Nat. Photonics 9, 695–701 (2015).
Poglitsch, A. & Weber, D. Dynamic disorder in methylammoniumtrihalogenoplumbates (ii) observed by millimeter-wave spectroscopy. J. Chem. Phys. 87, 6373–6378 (1987).
Anderson, P. W. Absence of diffusion in certain random lattices. Phys. Rev. 109, 1492–1505 (1958).
Peyghambarian, N. et al. Blue shift of the exciton resonance due to exciton–exciton interactions in a multiple-quantum-well structure. Phys. Rev. Lett. 53, 2433–2436 (1984).
Hulin, D. et al. Well-size dependence of exciton blue shift in GaAs multiple-quantum-well structures. Phys. Rev. 33, 4389–4391 (1986).
Cortecchia, D. et al. Polaron self-localization in white-light emitting hybrid perovskites. J. Mater. Chem. C 5, 2771–2780 (2017).
Hu, T. et al. Mechanism for broadband white-light emission from two-dimensional (110) hybrid perovskites. J. Phys. Chem. Lett. 7, 2258–2263 (2016).
Neogi, I. et al. Broadband-emitting 2D hybrid organic–inorganic perovskite based on cyclohexane-bis(methylamonium) cation. ChemSusChem 10, 3765–3772 (2017).
Yangui, A. et al. Optical investigation of broadband white-light emission in self-assembled organic–inorganic perovskite (C6H11NH3)2PbBr4. J. Phys. Chem. 119, 23638–23647 (2015).
Ohnishi, A., Tanaka, K. & Yoshinari, T. Exciton self-trapping in two-dimensional system of (C2H5NH3)2CdCl4 single crystal. J. Phys. Soc. Jpn 68, 288–290 (1999).
Smith, D. et al. Structural origins of broadband emission from layered Pb–Br hybrid perovskites. Chem. Sci. 8, 4497–4504 (2017).
Manchon, A., Koo, H. C., Nitta, J., Frolov, S. M. & Duine, R. A. New perspectives for Rashba spin–orbit coupling. Nat. Mater. 14, 871–882 (2015).
Dresselhaus, G., Kip, A. F. & Kittel, C. Spin-orbit interaction and the effective masses of holes in germanium. Phys. Rev. 95, 568–569 (1954).
Zhai, Y. et al. Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies. Sci. Adv. 3, e1700704 (2017).
Aristidou, N. et al. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells. Nat. Commun. 8, 15218 (2017).
De Bastiani, M. et al. Ion migration and the role of preconditioning cycles in the stabilization of the J–V characteristics of inverted hybrid perovskite solar cells. Adv. Energy Mater. 6, 1501453 (2016).
Bi, E. et al. Diffusion engineering of ions and charge carriers for stable efficient perovskite solar cells. Nat. Commun. 8, 15330 (2017).
Gratia, P. et al. Intrinsic halide segregation at nanometer scale determines the high efficiency of mixed cation/mixed halide perovskite solar cells. J. Am. Chem. Soc. 138, 15821–15824 (2016).
Leijtens, T. et al. Mapping electric field-induced switchable poling and structural degradation in hybrid lead halide perovskite thin films. Adv. Energy Mater. 5, 1500962 (2015).
Nie, W. et al. Light-activated photocurrent degradation and self-healing in perovskite solar cells. Nat. Commun. 7, 11574 (2016).
Leijtens, T. et al. Overcoming ultraviolet light instability of sensitized TiO2 with meso-superstructured organometal tri-halide perovskite solar cells. Nat. Commun. 4, 2885 (2013).
Lee, S.-W. et al. UV degradation and recovery of perovskite solar cells. Sci. Rep. 6, 38150 (2016).
Hoke, E. T. et al. Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics. Chem. Sci. 6, 613–617 (2014).
Fang, H.-H. et al. Unravelling light-induced degradation of layered perovskite crystals and design of efficient encapsulation for improved photostability. Adv. Funct. Mater. 28, 1800305 (2018).
Li, Y. et al. Light-induced degradation of CH3NH3PbI3 hybrid perovskite thin film. J. Phys. Chem. C 121, 3904–3910 (2017).
Zu, F.-S. et al. Impact of white light illumination on the electronic and chemical structures of mixed halide and single crystal perovskites. Adv. Opt. Mater. 5, 1700139 (2017).
Yang, Y. & You, J. Make perovskite solar cells stable. Nature 544, 155–156 (2017).
Saliba, M. et al. Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance. Science 354, 206–209 (2016).
McMeekin, D. P. et al. A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells. Science 351, 151–155 (2016).
Zhang, Y., Grancini, G., Feng, Y., Asiri, A. M. & Nazeeruddin, M. K. Optimization of stable quasi-cubic FAxMA1−xPbI3 perovskite structure for solar cells with efficiency beyond 20%. ACS Energy Lett. 2, 802–806 (2017).
Jodlowski, A. D. et al. Large guanidinium cation mixed with methylammonium in lead iodide perovskites for 19% efficient solar cells. Nat. Energy 2, 972–979 (2017).
Soe, C. M. M. et al. New type of 2D perovskites with alternating cations in the interlayer space, (C(NH2)3)(CH3NH3)nPbnI3n+1: structure, properties, and photovoltaic performance. J. Am. Chem. Soc. 139, 16297–16309 (2017).
Guarnera, S. et al. Improving the long-term stability of perovskite solar cells with a porous Al2O3 buffer layer. J. Phys. Chem. Lett. 6, 432–437 (2015).
Domanski, K. et al. Not all that glitters is gold: metal-migration-induced degradation in perovskite solar cells. ACS Nano 10, 6306–6314 (2016).
Taek Cho, K. et al. Selective growth of layered perovskites for stable and efficient photovoltaics. Energy Environ. Sci. 11, 952–959 (2018).
Mei, A. et al. A hole-conductor–free, fully printable mesoscopic perovskite solar cell with high stability. Science 345, 295–298 (2014).
Christians, J. A. et al. Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability. Nat. Energy 3, 68–74 (2018).
Arora, N. et al. Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20%. Science 358, 768–771 (2017).
Pathak, S. K. et al. Performance and stability enhancement of dye-sensitized and perovskite solar cells by Al doping of TiO2. Adv. Funct. Mater. 24, 6046–6055 (2014).
Shin, S. S. et al. Colloidally prepared La-doped BaSnO3 electrodes for efficient, photostable perovskite solar cells. Science 356, 167–171 (2017).
Han, Y. et al. Degradation observations of encapsulated planar CH3NH3PbI3 perovskite solar cells at high temperatures and humidity. J. Mater. Chem. A 3, 8139–8147 (2015).
Xu, R.-P. et al. In situ observation of light illumination-induced degradation in organometal mixed-halide perovskite films. ACS Appl. Mater. Interfaces 10, 6737–6746 (2018).
Pedesseau, L. et al. Advances and promises of layered halide hybrid perovskite semiconductors. ACS Nano 10, 9776–9786 (2016).
Wang, Z. et al. Efficient ambient-air-stable solar cells with 2D−3D heterostructured butylammonium-caesium-formamidinium lead halide perovskites. Nat. Energy 2, 17135 (2017).
Chen, Y. et al. Tailoring organic cation of 2D air-stable organometal halide perovskites for highly efficient planar solar cells. Adv. Energy Mater. 7, 1700162 (2017).
Iagher, L. & Etgar, L. Effect of Cs on the stability and photovoltaic performance of 2D/3D perovskite-based solar cells. ACS Energy Lett. 3, 366–372 (2018).
Jiang, W. et al. A new layered nano hybrid perovskite film with enhanced resistance to moisture-induced degradation. Chem. Phys. Lett. 658, 71–75 (2016).
Yao, K., Wang, X., Li, F. & Zhou, L. Mixed perovskite based on methyl-ammonium and polymeric-ammonium for stable and reproducible solar cells. Chem. Commun. 51, 15430–15433 (2015).
Yao, K., Wang, X., Xu, Y., Li, F. & Zhou, L. Multilayered perovskite materials based on polymeric-ammonium cations for stable large-area solar cell. Chem. Mater. 28, 3131–3138 (2016).
Koh, T. M. et al. Nanostructuring mixed-dimensional perovskites: a route toward tunable, efficient photovoltaics. Adv. Mater. 28, 3653–3661 (2016).
Quan, L. N. et al. Tailoring the energy landscape in quasi-2D halide perovskites enables efficient green-light emission. Nano Lett. 17, 3701–3709 (2017).
Cohen, B.-E., Wierzbowska, M. & Etgar, L. High efficiency quasi 2D lead bromide perovskite solar cells using various barrier molecules. Sustain. Energy Fuels 1, 1935–1943 (2017).
Cohen, B.-E., Wierzbowska, M. & Etgar, L. High efficiency and high open circuit voltage in quasi 2D perovskite based solar cells. Adv. Funct. Mater. 27, 1604733 (2016).
Ma, C. et al. 2D/3D perovskite hybrids as moisture-tolerant and efficient light absorbers for solar cells. Nanoscale 8, 18309–18314 (2016).
Lin, Y. et al. Enhanced thermal stability in perovskite solar cells by assembling 2D/3D stacking structures. J. Phys. Chem. Lett. 9, 654–658 (2018).
Chen, J., Seo, J.-Y. & Park, N.-G. Simultaneous improvement of photovoltaic performance and stability by in situ formation of 2D perovskite at (FAPbI3)0.88(CsPbBr3)0.12/CuSCN interface. Adv. Energy Mater. 8, 1702714 (2018).
Cho, K. T. et al. Water-repellent low-dimensional fluorous perovskite as interfacial coating for 20% efficient solar cells. Nano Lett. 18, 5467–5474 (2018).
Chen, J., Lee, D. & Park, N.-G. Stabilizing the Ag electrode and reducing J–V hysteresis through suppression of iodide migration in perovskite solar cells. ACS Appl. Mater. Interfaces 9, 36338–36349 (2017).
Lee, D. S. et al. Passivation of grain boundaries by phenethylammonium in formamidinium-methylammonium lead halide perovskite solar cells. ACS Energy Lett. 3, 647–654 (2018).
Koh, T. M. et al. Enhancing moisture tolerance in efficient hybrid 3D/2D perovskite photovoltaics. J. Mater. Chem. A 6, 2122–2128 (2018).
Giustino, F. & Snaith, H. J. Toward lead-free perovskite solar cells. ACS Energy Lett. 1, 1233–1240 (2016).
Hao, F., Stoumpos, C. C., Cao, D. H., Chang, R. P. H. & Kanatzidis, M. G. Lead-free solid-state organic–inorganic halide perovskite solar cells. Nat. Photonics 8, 489–494 (2014).
Ran, C. et al. Bilateral interface engineering toward efficient 2D–3D bulk heterojunction tin halide lead-free perovskite solar cells. ACS Energy Lett. 3, 713–721 (2018).
Cao, D. H. et al. Thin films and solar cells based on semiconducting two-dimensional Ruddlesden–Popper (CH3(CH2)3NH3)2(CH3NH3)n−1SnnI3n+1 perovskites. ACS Energy Lett. 2, 982–990 (2017).
Mao, L. et al. Role of organic counterion in lead- and tin-based two-dimensional semiconducting iodide perovskites and application in planar solar cells. Chem. Mater. 28, 7781–7792 (2016).
Blancon, J.-C. et al. Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites. Science 355, 1288–1292 (2017).
Zheng, K. et al. Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations. J. Mater. Chem. A 6, 6244–6250 (2018).
Quintero-Bermudez, R. et al. Compositional and orientational control in metal halide perovskites of reduced dimensionality. Nat. Mater. 17, 900–907 (2018).
Liao, Y. et al. Highly oriented low-dimensional tin halide perovskites with enhanced stability and photovoltaic performance. J. Am. Chem. Soc. 139, 6693–6699 (2017).
Shang, Q. et al. Unveiling structurally engineered carrier dynamics in hybrid quasi-two-dimensional perovskite thin films toward controllable emission. J. Phys. Chem. Lett. 8, 4431–4438 (2017).
Liu, J., Leng, J., Wu, K., Zhang, J. & Jin, S. Observation of internal photoinduced electron and hole separation in hybrid two-dimensional perovskite films. J. Am. Chem. Soc. 139, 1432–1435 (2017).
Gélvez-Rueda, M. C. et al. Interconversion between free charges and bound excitons in 2D hybrid lead halide perovskites. J. Phys. Chem. C 121, 26566–26574 (2017).
Yuan, Z. et al. One-dimensional lead halide perovskites with bluish white-light emission. Nat. Commun. 8, 14051 (2017).
The authors acknowledge the Swiss National Science Foundation (SNSF) for financial support of National Research Programme 70 (project no. 407040_154056 and ‘Tailored design and in-depth understanding of perovskite solar materials using in-house developed 3D/4D nanoscale ion-beam analysis’, project no. 200020L_1729/1, CTI 25590.1PFNM-NM, Solaronix, Aubonne). G.G. acknowledges the SNSF for funding through the Ambizione Energy project HYPER (grant no. PZENP2_173641). The authors thank V. Queloz and S. Aghazada for reading the manuscript and for useful discussions.
The authors declare no competing interests.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Grancini, G., Nazeeruddin, M.K. Dimensional tailoring of hybrid perovskites for photovoltaics. Nat Rev Mater 4, 4–22 (2019). https://doi.org/10.1038/s41578-018-0065-0
Moisture tolerant solar cells by encapsulating 3D perovskite with long-chain alkylammonium cation-based 2D perovskite
Communications Materials (2021)
Communications Materials (2021)
Effect of polystyrene treatment on the efficiency and stability of fully printable mesoscopic perovskite solar cells with carbon electrode
Journal of Materials Science: Materials in Electronics (2021)
Two-dimensional materials for light emitting applications: Achievement, challenge and future perspectives
Nano Research (2021)
Controllable Two-dimensional Perovskite Crystallization via Water Additive for High-performance Solar Cells
Nanoscale Research Letters (2020)