Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: a.castellanosgomez@tudelft.nl ABSTRACT Isolation and characterization of mechanically exfoliated black phosphorus flakes with a thickness down to two single-layers is presented. A modification of the mechanical exfoliation method, which provides higher yield of atomically thin flakes than conventional mechanical exfoliation, has been developed. We present general guidelines to determine the number of layers using optical microscopy, Raman spectroscopy and transmission electron microscopy in a fast and reliable way. Moreover, we demonstrate that the exfoliated flakes are highly crystalline and that they are stable even in free-standing form through Raman spectroscopy and transmission electron microscopy measurements. A strong thickness dependence of the band structure is found by density functional theory calculations. The exciton binding energy, within an effective mass approximation, is also calculated for different number of layers. Our computational results for the optical gap are consistent with preliminary photoluminescence results on thin flakes. Finally, we study the environmental stability of black phosphorus flakes finding that the flakes are very hydrophilic and that long term exposure to air moisture etches black phosphorus away. Nonetheless, we demonstrate that the aging of the flakes is slow enough to allow fabrication of field-effect transistors with strong ambipolar behavior. Density functional theory calculations also give us insight into the water-induced changes of the structural and electronic properties of black phosphorus.

Few-layer black phosphorus, a new elemental 2D material recently isolated by mechanical exfoliation, is a high-mobility layered semiconductor with a direct bandgap that is predicted to strongly depend on the number of layers, from 0.35 eV (bulk) to 2.0 eV (single-layer). Therefore, black phosphorus is an appealing candidate for tunable photodetection from the visible to the infrared part of the spectrum. We study the photoresponse of field-effect transistors (FETs) made of few-layer black phosphorus (3 nm to 8 nm thick), as a function of excitation wavelength, power and frequency. In the dark state, the black phosphorus FETs can be tuned both in hole and electron doping regimes allowing for ambipolar operation. We measure mobilities in the order of 100 cm 2 /V s and current ON/OFF ratio larger than 10 3 . Upon illumination, the black phosphorus transistors show response to excitation wavelengths from the visible up to 940 nm and rise time of about 1 ms, demonstrating broadband and fast detection. The responsivity reaches 4.8 mA/W and it could be drastically enhanced by engineering a detector based on a PN junction. The

Two-dimensional (2D) materials have attracted a great deal of interest in recent years. This family of materials allows for the realization of versatile electronic devices and holds promise for next-generation (opto)electronics. Their electronic properties strongly depend on the number of layers, making them interesting from a fundamental standpoint. For electronic applications, semiconducting 2D materials benefit from sizable mobilities and large on/off ratios, due to the large modulation achievable via the gate field-effect. Moreover, being mechanically strong and flexible, these materials can withstand large strain (>10%) before rupture, making them interesting for strain engineering and flexible devices. Even in their single layer form, semiconducting 2D materials have demonstrated efficient light absorption, enabling large responsivity in photodetectors. Therefore, semiconducting layered 2D materials are strong candidates for optoelectronic applications, especially for photodetection. Here, we review the state-of-the-art in photodetectors based on semiconducting 2D materials, focusing on the transition metal dichalcogenides, novel van der Waals materials, black phosphorus, and heterostructures.

In conventional photovoltaic solar cells, photogenerated carriers are extracted by the built-in electric field of a semiconductor PN junction, defined by ionic dopants. In atomically thin semiconductors, the doping level can be controlled by the field effect, enabling the implementation of electrically tunable PN junctions. However, most two-dimensional (2D) semiconductors do not show ambipolar transport, which is necessary to realize PN junctions. Few-layer black phosphorus (b-P) is a recently isolated 2D semiconductor with direct bandgap, high mobility, large current on/off ratios and ambipolar operation. Here we fabricate few-layer b-P field-effect transistors with split gates and hexagonal boron nitride dielectric. We demonstrate electrostatic control of the local charge carrier type and density in the device. Illuminating a gate-defined PN junction, we observe zero-bias photocurrents and significant open-circuit voltages due to the photovoltaic effect. The small bandgap of the material allows power generation for illumination wavelengths up to 940 nm, attractive for energy harvesting in the near-infrared.

Icosahedral symmetry, which is not compatible with truly long-range order, can be found in many systems, such as liquids, glasses, atomic clusters, quasicrystals and virus-capsids. To obtain arrangements with a high degree of icosahedral order from tens of particles or more, interparticle attractive interactions are considered to be essential. Here, we report that entropy and spherical confinement suffice for the formation of icosahedral clusters consisting of up to 100,000 particles. Specifically, by using real-space measurements on nanometre- and micrometre-sized colloids, as well as computer simulations, we show that tens of thousands of hard spheres compressed under spherical confinement spontaneously crystallize into icosahedral clusters that are entropically favoured over the bulk face-centred cubic crystal structure. Our findings provide insights into the interplay between confinement and crystallization and into how these are connected to the formation of icosahedral structures.

Tungsten diselenide (WSe2), a semiconducting transition metal dichalcogenide (TMDC), shows great potential as active material in optoelectronic devices due to its ambipolarity and direct bandgap in its single-layer form. Recently, different groups have exploited the ambipolarity of WSe2 to realize electrically tunable PN junctions, demonstrating its potential for digital electronics and solar cell applications. In this Letter, we focus on the different photocurrent generation mechanisms in a double-gated WSe2 device by measuring the photocurrent (and photovoltage) as the local gate voltages are varied independently in combination with above- and below-bandgap illumination. This enables us to distinguish between two main photocurrent generation mechanisms, the photovoltaic and photothermoelectric effect. We find that the dominant mechanism depends on the defined gate configuration. In the PN and NP configurations, photocurrent is mainly generated by the photovoltaic effect and the device displays a maximum responsivity of 0.70 mA/W at 532 nm illumination and rise and fall times close to 10 ms. Photocurrent generated by the photothermoelectric effect emerges in the PP configuration and is a factor of 2 larger than the current generated by the photovoltaic effect (in PN and NP configurations). This demonstrates that the photothermoelectric effect can play a significant role in devices based on WSe2 where a region of strong optical absorption, caused by, for example, an asymmetry in flake thickness or optical absorption of the electrodes, generates a sizable thermal gradient upon illumination.

We investigate the thickness-dependent electronic structure of ultrathin SrIrO 3 and discover a transition from a semimetallic to a correlated insulating state below 4 unit cells. Low-temperature magnetoconductance measurements show that spin fluctuations in the semimetallic state are significantly enhanced while approaching the transition point. The electronic structure is further studied by scanning tunneling spectroscopy, showing that 4 unit cells SrIrO 3 is on the verge of a gap opening. Our density functional theory calculations reproduce the critical thickness of the transition and show that the opening of a gap in ultrathin SrIrO 3 is accompanied by antiferromagnetic order.

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