We report on the fabrication and properties of the semiconducting 2D (CH3(CH2)3NH3)2(CH3NH3)n–1PbnI3n+1 (n = 1, 2, 3, and 4) perovskite thin films. The band gaps of the series decrease with increasing n values, from 2.24 eV (CH3(CH2)3NH3)2PbI4 (n = 1) to 1.52 eV CH3NH3PbI3 (n = ∞). The compounds exhibit strong light absorption in the visible region, accompanied by strong photoluminescence at room temperature, rendering them promising light absorbers for photovoltaic applications. Moreover, we find that thin films of the semi-2D perovskites display an ultrahigh surface coverage as a result of the unusual film self-assembly that orients the [PbnI3n+1]− layers perpendicular to the substrates. We have successfully implemented this 2D perovskite family in solid-state solar cells, and obtained an initial power conversion efficiency of 4.02%, featuring an open-circuit voltage (Voc) of 929 mV and a short-circuit current density (Jsc) of 9.42 mA/cm2 from the n = 3 compound. This result is even more encouraging con...

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2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications

The hybrid two-dimensional (2D) halide perovskites have recently drawn significant interest because they can serve as excellent photoabsorbers in perovskite solar cells. Here we present the large scale synthesis, crystal structure, and optical characterization of the 2D (CH3(CH2)3NH3)2(CH3NH3)n−1PbnI3n+1 (n = 1, 2, 3, 4, ∞) perovskites, a family of layered compounds with tunable semiconductor characteristics. These materials consist of well-defined inorganic perovskite layers intercalated with bulky butylammonium cations that act as spacers between these fragments, adopting the crystal structure of the Ruddlesden–Popper type. We find that the perovskite thickness (n) can be synthetically controlled by adjusting the ratio between the spacer cation and the small organic cation, thus allowing the isolation of compounds in pure form and large scale. The orthorhombic crystal structures of (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 (n = 2, Cc2m; a = 8.9470(4), b = 39.347(2) A, c = 8.8589(6)), (CH3(CH2)3NH3)2(CH3NH3)2Pb3I10 (...

http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.6b00847

Ruddlesden-Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors

A new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic–inorganic (A = organic) MHPs are reviewed with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2-dimensional compounds, where rele...

Intriguing Optoelectronic Properties of Metal Halide Perovskites

Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

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Atomically thin two-dimensional organic-inorganic hybrid perovskites

There are only few semiconducting materials that have been shaping the progress of third generation photovoltaic cells as much as perovskites. Although they are deceivingly simple in structure, the archetypal AMX3-type perovskites have built-in potential for complex and surprising discoveries. Since 2009, a small and somewhat exotic class of perovskites, which are quite different from the common rock-solid oxide perovskite, have turned over a new leaf in solar cell research. Highlighted as one of the major scientific breakthroughs of the year 2013, the power conversion efficiency of the title compound hybrid organic–inorganic perovskite has now exceeded 18%, making it competitive with thin-film PV technology. In this minireview, a brief history of perovskite materials for photovoltaic applications is reported, the current state-of-the-art is distilled and the basic working mechanisms have been discussed. By analyzing the attainable photocurrent and photovoltage, realizing perovskite solar cells with 20% efficiency for a single junction, and 30% for a tandem configuration on a c-Si solar cell would be realistic.

Jun Takahashi

Papers

Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4