influence-hybrid-perovskite-fabrication-methods-on-film-formation

Influence of Hybrid Perovskite Fabrication Methods on Film Formation, Electronic Structure, and Solar Cell Performance

Hybrid organic/inorganic halide perovskites have lately been a topic of great interest in the field of solar cell applications, with the potential to ...

University of Cologne

Tail states in organic semiconductors have a significant influence on device performances by acting as traps in charge transport. We present a study of the controlled passivation of acceptor tail states in fullerene C(60) by the addition of electrons introduced by molecular n doping. Using ultralow doping, we are able to successively fill the traps with charges and examine the changes in conductivity, activation energy, mobility, and Fermi-level position. Passivation of the traps leads to an increase of the electron mobility in C(60) by more than 3 orders of magnitude, to reach 0.21 cm(2)/(V s).

Ultralow doping in organic semiconductors: evidence of trap filling.

The discovery of air-stable n-dopants for organic semiconductor materials has been hindered by the necessity of high-energy HOMOs and the air sensitivity of compounds that satisfy this requirement. One strategy for circumventing this problem is to utilize stable precursor molecules that form the active doping complex in situ during the doping process or in a postdeposition thermal- or photo-activation step. Some of us have reported on the use of 1H-benzimidazole (DMBI) and benzimidazolium (DMBI-I) salts as solution- and vacuum-processable n-type dopant precursors, respectively. It was initially suggested that DMBI dopants function as single-electron radical donors wherein the active doping species, the imidazoline radical, is generated in a postdeposition thermal annealing step. Herein we report the results of extensive mechanistic studies on DMBI-doped fullerenes, the results of which suggest a more complicated doping mechanism is operative. Specifically, a reaction between the dopant and host that begins with either hydride or hydrogen atom transfer and which ultimately leads to the formation of host radical anions is responsible for the doping effect. The results of this research will be useful for identifying applications of current organic n-doping technology and will drive the design of next-generation n-type dopants that are air stable and capable of doping low-electron-affinity host materials in organic devices.

Mechanistic study on the solution-phase n-doping of 1,3-dimethyl-2-aryl-2,3-dihydro-1H-benzoimidazole derivatives.

Structural order in organic solar cells is paramount: it reduces energetic disorder, boosts charge and exciton mobilities, and assists exciton splitting. Owing to spatial localization of electronic states, microscopic descriptions of photovoltaic processes tend to overlook the influence of structural features at the mesoscale. Long-range electrostatic interactions nevertheless probe this ordering, making local properties depend on the mesoscopic order. Using a technique developed to address spatially aperiodic excitations in thin films and in bulk, we show how inclusion of mesoscale order resolves the controversy between experimental and theoretical results for the energy-level profile and alignment in a variety of photovoltaic systems, with direct experimental validation. Optimal use of long-range ordering also rationalizes the acceptor-donor-acceptor paradigm for molecular design of donor dyes. We predict open-circuit voltages of planar heterojunction solar cells in excellent agreement with experimental data, based only on crystal structures and interfacial orientation.

Impact of mesoscale order on open-circuit voltage in organic solar cells.

The electronic structure of a large sample set of CH3 NH3 PbI3 -based perovskites is studied. Combined investigations by UV/X-ray photoelectron spectroscopy and X-ray diffraction reveal that interstitials present in the film lead to changes in the occupied density of states close to the valence band, which in turn influences the performance of solar cells. Changes in elemental composition tune the ionization energy of the perovskite film by almost 1 eV without introducing significant amounts of gap states.

Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH3 NH3 PbI3 Perovskites.

We present investigations on the interface formation between the hybrid perovskite MAPbI3 and various substrates, covering a wide range of work functions. The perovskite films are incrementally evaporated in situ while the electronic structure is evaluated using photoelectron spectroscopy. Our results show that there is an induction period in the growth of the perovskite during which volatile compounds are formed, catalyzed by the substrate. The duration of the induction period depends strongly on the nature of the substrate material, and it can take up to 20-30 nm of formal precursor deposition before the surface is passivated and the perovskite film starts forming. The stoichiometry of the 2-3 nm thin passivation layer deviates from the expected perovskite stoichiometry, being rich in decomposition products of the organic cation. During the regular growth of the perovskite, our measurements show a deviation from the commonly assumed flat band condition, i.e., dipole formation and band bending dominate the interface. Overall, the nature of the substrate not only changes the energetic alignment of the perovskite, it can introduce gap states and influence the film formation and morphology. The possible impact on device performance is discussed.

Article	Year
Ultralow doping in organic semiconductors: evidence of trap filling. Physical review letters\| PubMed ID: 23215211	2012
Mechanistic study on the solution-phase n-doping of 1,3-dimethyl-2-aryl-2,3-dihydro-1H-benzoimidazole derivatives. Journal of the American Chemical Society\| PubMed ID: 24011269	2013
Impact of mesoscale order on open-circuit voltage in organic solar cells. Nature materials\| PubMed ID: 25532071	2015
Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH3 NH3 PbI3 Perovskites. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 26604080	2016
Substrate-dependent electronic structure and film formation of MAPbI3 perovskites. Scientific reports\| PubMed ID: 28084313	2017

Selina Olthof

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