Optimization of the plasmonic properties of titanium nitride films sputtered at room temperature through microstructure and thickness control.

A current approach to depositing highly plasmonic titanium nitride films using the magnetron sputtering technique assumes that the process is performed at temperatures high enough to ensure the atoms have sufficient diffusivities to form dense and highly crystalline films. In this work, we demonstrate that the plasmonic properties of TiN films can be efficiently tuned even without intentional substrate heating by influencing the details of the deposition process and entailed films' stoichiometry and microstructure. We also discuss the dependence of the deposition time/films' thickness on the optical properties, which is another degree of freedom in controlling the optical response of the refractory metal nitride films. The proposed strategy allows for robust and cost-effective production of large-scale substrates with good plasmonic properties in a CMOS technology-compatible process that can be further processed, e.g., structurized. All reported films are characterized by the maximal values of the plasmonic Figure of Merit (FoM = - ε1/ε2) ranging from 0.8 to 2.6, and the sample with the best plasmonic properties is characterized by FoM at 700 nm and 1550 nm that is equal 2.1 in both cases. These are outstanding results, considering the films' polycrystallinity and deposition at room temperature onto a non-matched substrate.

Ultrafast optical properties of stoichiometric and non-stoichiometric refractory metal nitrides TiNx, ZrNx, and HfNx.

Refractory metal nitrides have recently gained attention in various fields of modern photonics due to their cheap and robust production technology, silicon-technology compatibility, high thermal and mechanical resistance, and competitive optical characteristics in comparison to typical plasmonic materials like gold and silver. In this work, we demonstrate that by varying the stoichiometry of sputtered nitride films, both static and ultrafast optical responses of refractory metal nitrides can efficiently be controlled. We further prove that the spectral changes in ultrafast transient response are directly related to the position of the epsilon-near-zero region. At the same time, the analysis of the temporal dynamics allows us to identify three time components: the "fast" femtosecond one, the "moderate" picosecond one, and the "slow" at the nanosecond time scale. We also find out that the non-stoichiometry does not significantly decrease the recovery time of the reflectance value. Our results show the strong electron-phonon coupling and reveal the importance of both the electron and lattice temperature-induced changes in the permittivity near the ENZ region and the thermal origin of the long tail in the transient optical response of refractory nitrides.

Titanium Nitride as a Plasmonic Material from Near-Ultraviolet to Very-Long-Wavelength Infrared Range.

Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 µm. The films' composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.

Study of Structural and Optoelectronic Properties of Thin Films Made of a Few Layered WS2 Flakes.

We report a surfactant-free exfoliation method of WS2 flakes combined with a vacuum filtration method to fabricate thin (<50 nm) WS2 films, that can be transferred on any arbitrary substrate. Films are composed of thin (<4 nm) single flakes, forming a large size uniform film, verified by AFM and SEM. Using statistical phonons investigation, we demonstrate structural quality and uniformity of the film sample and we provide first-order temperature coefficient χ, which shows linear dependence over 300-450 K temperature range. Electrical measurements show film sheet resistance RS = 48 MΩ/Υ and also reveal two energy band gaps related to the intrinsic architecture of the thin film. Finally, we show that optical transmission/absorption is rich above the bandgap exhibiting several excitonic resonances, and nearly feature-less below the bandgap.

Study of optical properties of graphene flakes and its derivatives in aqueous solutions.

In this work, we study optical spectroscopy of graphene flakes and its derivatives such as graphene oxide and reduced graphene oxide in the same surfactant-free aqueous solution. We show that transmittance (T) and absorbance (A) spectra of different graphene suspension is nearly feature-less as a function of wavelength (λ) in the VIS-NIR range (350-1000 nm) except graphene oxide solution and the smallest graphene flakes, and they change linearly with concentration. The optical absorption coefficient (at 660 nm) of pure graphene solution seems to be flake-size dependent, changing from ∼730 mL·mg-1m-1 (for ∼25 µm flake size) to ∼4400 mL·mg-1m-1 (for ∼2 µm flake size), and it is several times higher than in the case of graphene oxide, which also varies with type and level of doping/defects (checked by FTIR and statistical Raman spectroscopy). Finally, we show wavelength-dependent evolution of optical absorption coefficient in the VIS-NIR range, which is roughly mimicking the A(λ) function but is strongly material-dependent. Our study could be useful for application of graphene solution in optofluidic devices, functional inks or printed flexible optoelectronics.

Thermal properties of thin films made from MoS2 nanoflakes and probed via statistical optothermal Raman method.

A deep understanding of the thermal properties of 2D materials is crucial to their implementation in electronic and optoelectronic devices. In this study, we investigated the macroscopic in-plane thermal conductivity (κ) and thermal interface conductance (g) of large-area (mm2) thin film made from MoS2 nanoflakes via liquid exfoliation and deposited on Si/SiO2 substrate. We found κ and g to be 1.5 W/mK and 0.23 MW/m2K, respectively. These values are much lower than those of single flakes. This difference shows the effects of interconnections between individual flakes on macroscopic thin film parameters. The properties of a Gaussian laser beam and statistical optothermal Raman mapping were used to obtain sample parameters and significantly improve measurement accuracy. This work demonstrates how to address crucial stability issues in light-sensitive materials and can be used to understand heat management in MoS2 and other 2D flake-based thin films.

Graphene-based plastic absorber for total sub-terahertz radiation shielding.

Increasing the requirements on telecommunications systems such as the need for higher data rates and connectivity via the Internet of things results in continuously increasing amounts of electromagnetic radiation in ever-higher telecommunications bands (up to terahertz). This can generate unwanted electromagnetic radiation that can affect the operation of electronic devices and human health. Here, we demonstrate that nonconductive and lightweight, graphene-based composites can shield more than 99.99% of the electromagnetic energy in the sub-THz range mainly via absorption. This contrasts with state-of-the-art electromagnetic radiation shielding materials that simply redirect the energy of the radiation from a protected area via conduction-based reflection mechanisms. This shifts the problem of electromagnetic pollution from one place to another. We have demonstrated that the proposed composites can be fabricated by industrial compatible methods and are characterized by specific shielding efficiency values that exceed 30 dB cm3 g-1, which is more than those for typical metals used today. Therefore these materials might help to solve the problem of electromagnetic environmental pollution.

Temperature dependence of phonon properties in CVD MoS2 nanostructures - a statistical approach.

In this paper, we report the results of Raman measurements on various molybdenum disulfide (MoS2) nanostructures grown by the chemical vapor deposition (CVD) method on a typical Si/SiO2 substrate. The phonon properties investigated include the positions, widths, and intensities of the E2g and A1g modes and the derivative of the mode positions with respect to the temperature in the 300-460 K range. Our results give new insight into changes in phonon energies in response to different disturbances and show that changes induced by the temperature are similar to the changes induced by stress, making these two factors hardly resolvable in the hωA1g-hωE2g coordinate system. We prove that all our samples are weakly coupled to the substrate; thus, the presented results almost purely illustrate the effect of the temperature and thickness. The much stronger coupling to the substrate, however, can explain the high variation in the data reported in the literature. The statistical approach applied makes our results highly reliable and allows proper uncertainty assessment of the obtained results, which is helpful when comparing our results to the results reported by other authors.

CNT-based saturable absorbers with scalable modulation depth for Thulium-doped fiber lasers operating at 1.9 µm.

In this work, we demonstrate a comprehensive study on the nonlinear parameters of carbon nanotube (CNT) saturable absorbers (SA) as a function of the nanotube film thickness. We have fabricated a set of four saturable absorbers with different CNT thickness, ranging from 50 to 200 nm. The CNTs were fabricated via a vacuum filtration technique and deposited on fiber connector end facets. Each SA was characterized in terms of nonlinear transmittance (i.e. optical modulation depth) and tested in a Thulium-doped fiber laser. We show, that increasing the thickness of the CNT layer significantly increases the modulation depth (up to 17.3% with 200 nm thick layer), which strongly influences the central wavelength of the laser, but moderately affects the pulse duration. It means, that choosing the SA with defined CNT thickness might be an efficient method for wavelength-tuning of the laser, without degrading the pulse duration. In our setup, the best performance in terms of bandwidth and pulse duration (8.5 nm and 501 fs, respectively) were obtained with 100 nm thick CNT layer. This is also, to our knowledge, the first demonstration of a fully polarization-maintaining mode-locked Tm-doped laser based on CNT saturable absorber.

Charge Blinking Statistics of Semiconductor Nanocrystals Revealed by Carbon Nanotube Single Charge Sensors.

We demonstrate the relation between the optical blinking of colloidal semiconductor nanocrystals (NCs) and their electrical charge blinking for which we provide the first experimental observation of power-law statistics. To show this, we harness the performance of CdSe/ZnS NCs coupled with carbon nanotube field-effect transistors (CNTFETs), which act as single charge-sensitive electrometers with submillisecond time resolution, at room temperature. A random telegraph signal (RTS) associated with the NC single-trap charging is observed and exhibits power-law temporal statistics (τ(-α), with α in the range of ∼1-3), and a Lorentzian current noise power spectrum with a well-defined 1/f(2) corner. The spectroscopic analysis of the NC-CNTFET devices is consistent with the charging of NC defect states with a charging energy of Ec ≥ 200 meV. These results pave the way for a deeper understanding of the physics and technology of nanocrystal-based optoelectronic devices.

High accuracy determination of the thermal properties of supported 2D materials.

We present a novel approach for the simultaneous determination of the thermal conductivity κ and the total interface conductance g of supported 2D materials by the enhanced opto-thermal method. We harness the property of the Gaussian laser beam that acts as a heat source, whose size can easily and precisely be controlled. The experimental data for multi-layer graphene and MoS2 flakes are supplemented using numerical simulations of the heat distribution in the Si/SiO2/2D material system. The procedure of κ and g extraction is tested in a statistical approach, demonstrating the high accuracy and repeatability of our method.

Temperature-dependent thermal properties of supported MoS2 monolayers.

Thermal properties can substantially affect the operation of various electronics and optoelectronics devices based on two-dimensional materials. In this work, we describe our investigation of temperature-dependent thermal conductivity and interfacial thermal conductance of molybdenum disulfide monolayers supported on SiO2/Si substrates, using Raman spectroscopy. We observed that the calculated thermal conductivity (κ) and interfacial thermal conductance (g) decreased with increasing temperature from 62.2 W m(-1) K(-1) and 1.94 MW m(-2) K(-1) at 300 K to 7.45 W m(-1) K(-1) and 1.25 MW m(-2) K(-1) at 450 K, respectively.

Temperature-dependent nonlinear phonon shifts in a supported MoS2 monolayer.

We report Raman spectra measurements on a MoS(2) monolayer supported on SiO(2) as a function of temperature. Unlike in previous studies, the positions of the two main Raman modes, E(2g)(1) and A(1g) exhibited nonlinear temperature dependence. Temperature dependence of phonon shifts and widths is explained by optical phonon decay process into two acoustic phonons. On the basis of Raman measurements, local temperature change under laser heating power at different global temperatures is derived. Obtained results contribute to our understanding of the thermal properties of two-dimensional atomic crystals and can help to solve the problem of heat dissipation, which is crucial for use in the next generation of nanoelectronic devices.

Laser heating control with polarized light in isolated multiwalled carbon nanotubes.

We propose a novel method of laser heating control only through change in polarization of the incident light, keeping its power density constant. The idea combines an antenna effect found in isolated multiwalled carbon nanotubes and the possibility of their heating by light illumination. To observe this we used the Raman spectroscopy technique, where the heating manifests itself in a pronounced downshift of the Raman G and 2D lines as a function of the polarization angle. Our method can be useful in field electron emission devices or in selective nanotubes heating and destruction. It can also be extended to other one dimensional nano-objects, if only certain conditions are fulfilled.