Solid-State Physics Perspective on Hybrid Perovskite Semiconductors

Even, Jacky; Pédesseau, Laurent; Katan, Claudine; Képénékian, Mikaël; Lauret, Jean‐sébastien; Sapori, Daniel; Deleporte, Emmanuelle

doi:10.1021/acs.jpcc.5b00695

Cited by 229 publications

(283 citation statements)

References 146 publications

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“…The hybrid perovskite CH 3 NH 3 PbI 3 is well known to undergo a transition from the tetragonal to the orthorhombic structure at about 160 K. [ 12,13,17 ] Using X-ray diffraction (XRD), we confi rmed that this transition also takes place in our sample (see Figure S2, Supporting Information). At low fl uence such as 0.75 µJ cm −2 , we thus attribute the broad emission above 160 K centered at 1.60 to 1.75 eV to emission from the tetragonal crystal structure, while the broad emission centered at 1.64-1.68 eV at temperatures below 160 K is attributed to the orthorhombic phase.…”

Section: Discussionmentioning

confidence: 64%

Reversible Laser‐Induced Amplified Spontaneous Emission from Coexisting Tetragonal and Orthorhombic Phases in Hybrid Lead Halide Perovskites

Panzer

Baderschneider

Gujar

et al. 2016

Advanced Optical Materials

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and with low trap-state densities. [ 3 ] This enabled the fabrication of perovskites solar cells that convinced the solar cell community with high performances such as power conversion effi ciencies of over 20%, [ 4,5 ] while offering the possibility for low cost production, e.g., by solution-processing. [ 6 ] Meanwhile, further device applications for organic-inorganic mixed halide perovskites have been discovered. For example, in 2014, low threshold levels for amplifi ed spontaneous emission showed that mixed halide perovskites can also be used for the facile fabrication of lasers with high quality factors. [7][8][9][10] Furthermore, it is known that most halide perovskite materials can exist in different crystal structures, depending on environmental conditions such as temperature. [11][12][13] Here, we show that a coexistence of tetragonal and orthorhombic phases within apparently the same crystalline grain can be optically induced into the halide perovskite CH 3 NH 3 PbI 3 at low temperatures, leading to amplifi ed spontaneous emission (ASE) simultaneously at two distinct wavelengths. The ASE feature associated with the (high temperature) tetragonal phase can be reproducibly written, read-out, and erased at 5 K by choosing appropriateThe photoluminescence in a lead halide perovskite is measured for different temperatures (5-300 K) and excitation fl uences (21-1615 µJ cm −2 ). It is found that amplifi ed spontaneous emission (ASE) is observed for an excitation density larger than about 1 × 10 18 cm −3 for both the tetragonal phase above 163 K and the orthorhombic phase below about 163 K. The fl uence that is required to obtain this excitation density depends on temperature and phase since the nonradiative decay of excitations is temperature activated with different activation energies of 85 20 ± and 24 5 meV ± for the tetragonal and orthorhombic phase, respectively. The ASE from the tetragonal phase-usually prevailing at temperatures above about 163 K-can also be observed at 5 K, in addition to the ASE from the orthorhombic phase, when the sample is previously exposed to a fl uence exceeding 630 µJ cm −2 at a photon energy of 3.68 eV. This additional ASE can be removed by mild heating to 35 K or optically, by exposing the sample by typically a few seconds with a fl uence around 630 µJ cm −2 . The physical mechanism underlying this optically induced phase transition process is discussed. It is demonstrated that this phase change can, in principle, be used for an all-optical "write-read-erase" memory device.

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Section: Discussionmentioning

confidence: 64%

Reversible Laser‐Induced Amplified Spontaneous Emission from Coexisting Tetragonal and Orthorhombic Phases in Hybrid Lead Halide Perovskites

Panzer

Baderschneider

Gujar

et al. 2016

Advanced Optical Materials

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“…Fig 5 and Table 1 show that at 2K both µ and R * are weakly increasing functions of the material band gap. The relatively simple band structure of these materials, which have non-degenerate band edges which are relatively isotropic and have similar effective masses suggests that they can be described by a simple semi-empirical two band k.p Hamiltonian approach 35 with effective masses for the electron and hole given by where the Kane energy is 2m 0 (|P| 2 ), with P =< ψ V B |ih…”

Section: Resultsmentioning

confidence: 99%

Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors

Gałkowski

Mitioglu

Miyata

et al. 2016

Energy Environ. Sci.

661

637

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The family of organic-inorganic halide perovskite materials has generated tremendous interest in the field of photovoltaics due to their high power conversion efficiencies. There has been intensive development of cells based on the archetypal methylammonium (MA) and recently introduced formamidinium (FA) materials, however, there is still considerable controversy over their fundamental electronic properties. Two of the most important parameters are the binding energy of the exciton (R * ) and its reduced effective mass µ. Here we present extensive magneto optical studies of Cl assisted grown MAPbI 3 as well as MAPbBr 3 and the FA based materials FAPbI 3 and FAPbBr 3 . We fit the excitonic states as a hydrogenic atom in magnetic field and the Landau levels for free carriers to give R * and µ. The values of the exciton binding energy are in the range 14 -25 meV in the low temperature phase and fall considerably at higher temperatures for the tri-iodides, consistent with free carrier behaviour in all devices made from these materials. Both R * and µ increase approximately proportionally to the band gap, and the mass values, 0.09-0.117 m 0 , are consistent with a simple k.p perturbation approach to the band structure which can be generalized to predict values for the effective mass and binding energy for other members of this perovskite family of materials. Broader contextThe recent development of organic/inorganic perovskite semiconductors has had a dramatic impact on the field of thin-film solar cells leading to efficiencies of over 20% in materials such as MAPbI 3 . We have recently shown that significant factors contributing to their remarkable performance are the small excitonic reduced effective mass and the small exciton binding energy. Expanding the perovskite family to materials with a range of different band gaps is opening up the potential of this materials system for a range of different applications, including the design of tandem PV cells and other optoelectronic components such as lasers and light emitting diodes. Knowledge of basic materials parameters such as the effective masses of the charge carriers is vital to the use and design of devices using perovskites. Here we show that the effective masses remain small in this system up to band gaps as high as 2.3 eV, as found in MAPbBr 3 and the exciton binding energy in this system is also much smaller than previously reported. This suggests that sophisticated devices using large band gap perovskites can be expected to show free carrier behaviour at room temperature and will make device design significantly easier. Exchanging the organic cations (Methyammonium or Formamodimium) is also shown to have very little effect on their bandstructure, suggesting that they can be used interchangeably to enhance device performance and stability. IntroductionOrganic-inorganic hybrid materials, in particular the tri-halide perovskites, have been driving a rapid series of breakthroughs in the field of photovoltaic (PV) devices with conversion efficiencies already up t...

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“…18 Reciprocal lattice vectors K m are related to the translational periodicity of the reciprocal lattice, thus enabling a representation of the various lattice properties within the first BZ. It is, for example, useful to describe the electronic energy eigenfunctions as Bloch waves 12…”

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confidence: 99%

Pedestrian Guide to Symmetry Properties of the Reference Cubic Structure of 3D All-Inorganic and Hybrid Perovskites

Even

2015

J. Phys. Chem. Lett.

112

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Solid-State Physics Perspective on Hybrid Perovskite Semiconductors

Cited by 229 publications

References 146 publications

Reversible Laser‐Induced Amplified Spontaneous Emission from Coexisting Tetragonal and Orthorhombic Phases in Hybrid Lead Halide Perovskites

Reversible Laser‐Induced Amplified Spontaneous Emission from Coexisting Tetragonal and Orthorhombic Phases in Hybrid Lead Halide Perovskites

Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors

Pedestrian Guide to Symmetry Properties of the Reference Cubic Structure of 3D All-Inorganic and Hybrid Perovskites

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