Bálint Náfrádi

Microengineered CH3NH3PbI3 Nanowire/Graphene Phototransistor for Low‐Intensity Light Detection at Room Temperature

The first hybrid phototransistors are reported where the performance of a network of photoactive CH3NH3PbI3 nanowires is enhanced by CVD-grown monolayer graphene. These devices show responsivities as high as ≈2.6 × 106 A W-1 in the visible range, showing potential as room-temperature single-electron detectors.

Magnetic Fullerenes inside Single-Wall Carbon Nanotubes

C(59)N magnetic fullerenes were formed inside single-wall carbon nanotubes by vacuum annealing functionalized C(59)N molecules encapsulated inside the tubes. A hindered, anisotropic rotation of C(59)N was deduced from the temperature dependence of the electron spin resonance spectra near room temperature. Shortening of the spin-lattice relaxation time T(1) of C(59)N indicates a reversible charge transfer toward the host nanotubes above approximately 350 K. Bound C(59)N-C(60) heterodimers are formed at lower temperatures when C(60) is coencapsulated with the functionalized C(59)N. In the 10-300 K range, T(1) of the heterodimer shows a relaxation dominated by the conduction electrons on the nanotubes.

Controlled growth of CH3NH3PbI3 nanowires in arrays of open nanofluidic channels

Spatial positioning of nanocrystal building blocks on a solid surface is a prerequisite for assembling individual nanoparticles into functional devices. Here, we report on the graphoepitaxial liquid-solid growth of nanowires of the photovoltaic compound CH3NH3PbI3 in open nanofluidic channels. The guided growth, visualized in real-time with a simple optical microscope, undergoes through a metastable solvatomorph formation in polar aprotic solvents. The presently discovered crystallization leads to the fabrication of mm2-sized surfaces composed of perovskite nanowires having controlled sizes, cross-sectional shapes, aspect ratios and orientation which have not been achieved thus far by other deposition methods. The automation of this general strategy paves the way towards fabrication of wafer-scale perovskite nanowire thin films well-suited for various optoelectronic devices, e.g. solar cells, lasers, light-emitting diodes and photodetectors.

A Neutral Zwitterionic Molecular Solid

We report on the acid ethylenedithiotetrathiafulvaleneamidoglycine (EDT-TTF-CO-NH-CH(2)-CO(2)H; 1; EDT-TTF=ethylenedithiotetrathiafulvalene) and the 1:1 adduct [(EDT-TTF)(·+)-CO-NH-CH(2)-(CO(2))(-)][(EDT-TTF)-CO-NH-CH(2)-(CO(2)H)]·CH(3)OH (2), a new type of hydrogen-bonded, 1:1 acid/zwitterion hybrid embrace of redox peptidics into a two-dimensional architecture, an example of a system deliberately fashioned so that oxidation of π-conjugated cores toward the radical-cation form would interfere with the activity of the appended ionizable residues in the presence of a templating base during crystal growth. First-principles calculations demonstrate that, notwithstanding preconceived ideas, a metallic state is more stable than the hole-localized alternatives for a neat 1:1 neutral acid/zwitterion hybrid. The inhomogeneous Coulomb field associated with proton-shared, interstacks O-H···O hydrogen bonds between the ionizable residues distributed on both sides of the two-dimensional π-conjugated framework leads, however, to a weak hole localization responsible for the activated but high conductivity of 1 S cm(-1). This situation is reminiscent of the role of the environment on electron transfer in tetraheme cytochrome c, in which the protonation state of a heme propionate becomes paramount, or ion-gated transport phenomena in biology. These observations open rather intriguing opportunities for the construction of electronic systems at the interface of chemistry and biology.

Continuous-wave far-infrared ESR spectrometer for high-pressure measurements

We present a newly-developed microwave probe for performing sensitive high-field/multi-frequency electron spin resonance (ESR) measurements under high hydrostatic pressures. The system consists of a BeCu-made pressure-resistant vessel, which accommodates the investigated sample and a diamond microwave coupling window. The probes interior is completely filled with a pressure-transmitting fluid. The setup operates in reflection mode and can easily be assembled with a standard oversized microwave circuitry. The probe-head withstands hydrostatic pressures up to 1.6 GPa and interfaces with our home-built quasi-optical high-field ESR facility, operating in a millimeter/submillimeter frequency range of 105-420 GHz and in magnetic fields up to 16 T. The overall performance of the probe was tested, while studying the pressure-induced changes in the spin-relaxation mechanisms of a quasi-1D conducting polymer, KC(60). The preliminary measurements revealed that the probe yields similar signal-to-noise ratio to that of commercially available low-frequency ESR spectrometers. Moreover, by observing the conduction electron spin resonance (CESR) linewidth broadening for KC(60) in an unprecedented microwave frequency range of 210-420 GHz and in the pressure range of up to 1.6 GPa, we demonstrate that a combination of high-pressure ESR probe and high-field/multi-frequency spectrometer allows us to measure the spin relaxation rates in conducting spin systems, like the quasi-1D conductor, KC(60).

Synthesis of Homogeneous Manganese-Doped Titanium Oxide Nanotubes from Titanate Precursors

We report a novel synthesis route of homogeneously manganese-doped TiO2 nanotubes in a broad concentration range. The scroll-type trititanate (H2Ti3O7) nanotubes prepared by hydrothermal synthesis were used as precursors. Mn2+ ions were introduced by an ion exchange method resulting MnxH2–xTi3O7. In a subsequent heat treatment, they were transformed into MnyTi1–yO2, where y = x/(3 + x). The state and the local environment of the Mn2+ ions in the precursor and final products were studied by the electron spin resonance (ESR) technique. It was found that the Mn2+ ions occupy two positions: the first having an almost perfect cubic symmetry while the other is in a strongly distorted octahedral site. The ratio of the two Mn2+ sites is independent of the doping level and amounts to 15:85 in MnxH2–xTi3O7 and to 5:95 in MnyTi1–yO2. SQUID magnetometry does not show long-range magnetic order in the homogeneously Mn2+-doped nanotubes.

Microwave frequency modulation in continuous-wave far-infrared ESR utilizing a quasi-optical reflection bridge

We report the development of the frequency-modulation (FM) method for measuring electron spin resonance (ESR) absorption in the 210- to 420GHz frequency range. We demonstrate that using a high-frequency ESR spectrometer without resonating microwave components enables us to overcome technical difficulties associated with the FM method due to nonlinear microwave-elements, without sacrificing spectrometer performance. FM was achieved by modulating the reference oscillator of a 13GHz Phase-Locked Dielectric Resonator Oscillator, and amplifying and frequency-multiplying the resulting millimeter-wave radiation up to 210, 315 and 420GHz. ESR spectra were obtained in reflection mode by a lock-in detection at the fundamental modulation frequency, and also at the second and third harmonic. Sensitivity of the setup was verified by conduction electron spin resonance measurement in KC60.

Optically switched magnetism in photovoltaic perovskite CH3NH3(Mn:Pb)I3.

The demand for ever-increasing density of information storage and speed of manipulation boosts an intense search for new magnetic materials and novel ways of controlling the magnetic bit. Here, we report the synthesis of a ferromagnetic photovoltaic CH3NH3(Mn:Pb)I3 material in which the photo-excited electrons rapidly melt the local magnetic order through the Ruderman–Kittel–Kasuya–Yosida interactions without heating up the spin system. Our finding offers an alternative, very simple and efficient way of optical spin control, and opens an avenue for applications in low-power, light controlling magnetic devices.

Ultrasensitive 1D field-effect phototransistors: CH3NH3PbI3 nanowire sensitized individual carbon nanotubes

Field-effect phototransistors were fabricated based on individual carbon nanotubes (CNTs) sensitized by CH3NH3PbI3 nanowires (MAPbI3NWs). These devices represent light responsivities of R = 7.7 × 10(5) A W(-1) under low-lighting conditions in the nW mm(-2) range, unprecedented among CNT-based photodetectors. At high incident power (∼1 mW mm(-2)), light soaking results in a negative photocurrent, turning the device insulating. We interpret the phenomenon as a result of efficient free photoexcited charge generation and charge transfer of photoexcited holes from the perovskite to the carbon nanotube. The charge transfer improves conductance by increasing the number of carriers, but leaves electrons behind. At high illumination intensity their random electrostatic potential quenches mobility in the nanotube.

Pressure and temperature dependence of interlayer spin diffusion and electrical conductivity in the layered organic conductors kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]X (X = Cl, Br)

A high frequency (111.2-420 GHz) electron spin resonance study of the inter-layer (perpendicular) spin diffusion as a function of pressure and temperature is presented in the conducting phases of the layered organic compounds, {\kappa}-(BEDT-TTF)2-Cu[N(CN)2]X ({\kappa}-ET2-X), X=Cl or Br. The resolved ESR lines of adjacent layers at high temperatures and high frequencies allows for the determination of the inter-layer cross spin relaxation time, Tx and the intrinsic spin relaxation time, T2 of single layers. In the bad metal phase spin diffusion is two-dimensional, i.e. spins are not hopping to adjacent layers within T2. Tx is proportional to the perpendicular resistivity at least approximately, as predicted in models where spin and charge excitations are tied together. In {\kappa}-ET2-Cl, at zero pressure Tx increases as the bad metal-insulator transition is approached. On the other hand, Tx decreases as the normal metal and superconducting phases are approached with increasing pressure and/or decreasing temperature.