D. Mogilyansky

Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials.

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I1-x Brx )3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr3 films exhibited no degradation, while MAPbI3 and mixed halide MAPb(I1-x Brx )3 films decomposed yielding crystallization of inorganic PbI2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials.

Chemical disorder influence on magnetic state of optimally-doped La0.7Ca0.3MnO3

X-band electron magnetic resonance and dc/ac magnetic measurements have been employed to study the effects of chemical disorder on magnetic ordering in bulk and nanometer-sized single crystals and bulk ceramics of optimally-doped La0.7Ca0.3MnO3 manganite. The magnetic ground state of bulk samples appeared to be ferromagnetic with the lower Curie temperature and higher magnetic homogeneity in the vicinity of the ferromagnetic-paramagnetic phase transition in the crystal, as compared with those characteristics in the ceramics. The influence of technological driven “macroscopic” fluctuations of Ca-dopant level in crystal and “mesoscopic” disorder within grain boundary regions in ceramics was proposed to be responsible for these effects. Surface spin disorder together with pronounced inter-particle interactions within agglomerated nano-sample results in well defined core/shell spin configuration in La0.7Ca0.3MnO3 nano-crystals. The analysis of the electron paramagnetic resonance data enlightened the reasons f...

Size-dependent spin state and ferromagnetism in La0.8Ca0.2CoO3 nanoparticles

Magnetic and structural properties of nanocrystalline low-doped La0.8Ca0.2CoO3 cobaltites with particle size of 8, 13, 23, and 50 nm, prepared by the glycine-nitrate method, were investigated in temperature range 5–320 K, magnetic field up to 50 kOe and under hydrostatic pressure up to 10 kbar. With particle downsizing, a noticeable expansion of unit cell, with concomitant changes in the rhombohedral structure toward the cubic one was observed. It was found that the increased surface-disorder effect strongly suppresses the ferromagnetic state in La0.8Ca0.2CoO3 nanoparticles leading to a decrease, by factor of about 2, both in spontaneous magnetization, MS, and Curie temperature, TC, when particle’s size decreases from 23 to 8 nm. The effective magnetic moment μeff was found also to decrease distinctly due to the strong interdependence between Co–O–Co interactions and Co spin state. The size-induced magnetic disorder drives the La0.8Ca0.2CoO3 nanoparticles to a dominant glassy behavior for 8 nm particles. This is evidenced by the fact that the freezing temperature varies with magnetic field in a strict conformity with the de Almeida–Thouless law for spin glasses and also by the observation of characteristic slowing down in the spin dynamics. The applied pressure suppresses TC, MS, and coercive field HC, like it is observed for bulk La0.8Ca0.2CoO3. Nevertheless, in nanoparticles the pressure effect on TC is noticeably stronger, while HC diminishes with pressure much slower then in bulk material.

Ferromagnetic domain structure of La0.78Ca0.22MnO3 single crystals

The magneto-optical technique has been employed to observe spontaneous ferromagnetic domain structures in La0.78Ca0.22MnO3 single crystals. The magnetic domain topology was found to be correlated with the intrinsic twin structure of the investigated crystals. With decreasing temperature the regular network of ferromagnetic domains undergoes significant changes resulting in apparent rotation of the domain walls in the temperature range of 70–150 K. The apparent rotation of the domain walls can be understood in terms of the Jahn-Teller deformation of the orthorhombic unit cell, accompanied by additional twinning.

Magnetic properties of Sm0.1Ca0.9MnO3 nanoparticles

Magnetic properties of compacted Sm0.1Ca0.9MnO3 nanoparticles with average particle size of 25 and 60 nm have been investigated. It was found that the relative volume of the ferromagnetic phase decreases with decreasing particle size. Magnetization curves measured in field cooled and zero field cooled mode separate near the transition temperature TC and remain different even in magnetic field of 15 kOe. AC-susceptibility is strongly frequency dependent below TC, although the temperature of the maximum depends on frequency only slightly. Magnetization hysteresis loops exhibit horizontal and vertical shifts, relatively small in 60 nm and much larger in 25 nm particles, due to size-dependent exchange bias effect. The exchange bias field and the coercive field depend in a non-monotonic way on cooling magnetic field, while the asymmetry of remanence magnetization and magnetic coercivity increase monotonously with the increase of cooling field. Applied pressure enhances Curie temperature TC of nanoparticles wit...

Size-driven magnetic transitions in La1/3Ca2/3MnO3 nanoparticles

Magnetic properties of electron-doped La1/3Ca2/3MnO3 manganite nanoparticles with average particle size ranging from 12 to 42 nm, prepared by the glycine-nitrate method, have been investigated in temperature range 5–300 K and in magnetic fields up to 90 kOe. Reduction in the particle size suppresses antiferromagnetism and decreases the Neel temperature. In contrast to bulk crystals, the charge ordering does not occur in all studied nanoparticles, while a weak ferromagnetism appears above 200 K. Low temperature magnetic hysteresis loops indicate upon exchange bias effect displayed by horizontal and vertical shifts in field cooled processes. The spontaneous and remanent magnetization at low temperature shows a relatively complex variation with particle size. The size-induced structural/magnetic disorder drives the La1/3Ca2/3MnO3 nanoparticles to a pronounced glassy behavior for the smallest 12 nm particles, as evidenced by large difference between zero field cooled and field cooled magnetization, frequency ...

Irreversibility, remanence, and Griffiths phase in Sm0.1Ca0.9MnO3 nanoparticles

Magnetic properties of compacted Sm0.1Ca0.9MnO3 particles with 25 and 60 nm average sizes have been investigated. Particular attention has been paid to Griffiths-like features at temperatures above magnetic transition temperature TC and to the system glassiness at low temperatures. Griffiths-like features in inverse magnetic susceptibility of Sm0.1Ca0.9MnO3 nanoparticles have been linked to the presence of short range ferromagnetically correlated spin clusters above TC. Glassy behavior has been revealed in temperature and frequency dependence of ac-susceptibility, temperature and field dependence of thermoremanent and isothermoremanent magnetization, and time decay of the remanent magnetization. Experiments revealed the major impact of the glassy component on magnetic properties of investigated nanoparticles. The magnetic relaxation associated with glassy features was found to be much more pronounced in smaller particles, where a formation of collective state in an ensemble of phase separated nanoparticle...

Doping dependent magnetism and exchange bias in CaMn1−xWxO3 manganites

Magnetic properties of CaMn1−xWxO3 (0 ≤ x ≤ 0.1) have been investigated, and the research was focused on the exchange bias (EB) phenomenon in CaMn0.93W0.07O3. Magnetic ground state was found to be dependent on tungsten doping level and the following states were distinguished: (i) G-type antiferromagnetic (AFM) state with a weak ferromagnetic (FM) component at x = 0 and 0.04; (ii) mostly orbitally ordered C-type AFM at x = 0.07 and 0.1. For the studied manganites, spontaneous magnetization increases sharply with increasing doping level reaching M0 ≈ 9.5 emu/g at T = 10 K for x = 0.04, and then decreases rapidly reaching zero for x = 0.1. Exchange bias effect, manifested by vertical and horizontal shifts in the hysteresis loop for field cooled sample, has been observed in CaMn0.93W0.07O3. Exchange bias field, coercivity, remanence asymmetry, and magnetic coercivity depend strongly on temperature, cooling field, and maximal measuring field. Horizontal and vertical shifts of magnetization loop sharply decreas...

Magnetic dynamic properties of electron-doped La0.23Ca0.77MnO3 nanoparticles

Magnetic properties of basically antiferromagnetic La(0.23)Ca(0.77)MnO(3) particles with average sizes of 12 and 60 nm have been investigated in a wide range of magnetic fields and temperature. Particular attention has been paid to magnetization dynamics through measurements of the temperature dependence of ac-susceptibility at various frequencies, the temperature and field dependence of thermoremanent and isothermoremanent magnetization originating from nanoparticles shells, and the time decay of the remanent magnetization. Experimental results and their analysis reveal the major role in magnetic behaviour of investigated antiferromagnetic nanoparticles played by the glassy component, associated mainly with the formation of the collective state formed by ferromagnetic clusters in frustrated coordination at the surfaces of interacting antiferromagnetic nanoparticles. Magnetic behaviour of nanoparticles has been ascribed to a core-shell scenario. Magnetic transitions have been found to play an important role in determining the dynamic properties of the phase separated state of coexisting different magnetic phases.

‘Griffiths phase’ versus chemical disorder in low-doped manganites: La0.9Sr0.1MnO3 crystal revisited

Magnetic properties, electron paramagnetic and ferromagnetic resonance were studied in the vicinity and above ferromagnetic-paramagnetic (FM-PM) phase transition of the La0.9Sr0.1MnO3 crystal. It appears that complex chemical/structural disorder inherent to manganites influences strongly on both magnetic and resonance properties of this crystal. In particular, it changes the nature of a FM–PM transition to the first- or mixed-order one and induces FM clustering in their PM state. The latter effect results in coexistence of resonance signals, and non-linearity of the PM inverse magnetic susceptibility versus temperature. This model seems to be much more realistic for description of the PM state in La0.9Sr0.1MnO3 than an idealized Griffiths phase approach.