Previous experiments have demonstrated that carbon nanoisland films (or disordered quantum-dot arrays) deposited on silicon wafers may possess the property of low-field electron emission. This paper presents our new work on comparative characterization of emitting and nonemitting thin carbon films. The experimental results acquired by Auger spectroscopy, electron energy loss spectroscopy, Anderson's technique for workfunction measurement, and secondary-emission techniques confirmed that the emitting films are discontinuous and consist of carbon in sp2-hybridization state, while their workfunction is relatively high (>4 eV). These experimental data clearly contradict the commonly accepted Fowler–Nordheim theory of field emission and suggest that the observed emission phenomenon has a different nature. A novel model is proposed as a development of the well-known hot-electron emission mechanism supplemented with nanoscale-related features of thermoelectric phenomena.

In this paper we show that the electronic properties of ultrathin tetrahedral amorphous carbon (ta-C) films are heavily dependent on their thickness. By using scanning tunnelling spectroscopy, Raman spectroscopy, and conductive atomic force microscopy, it was found that a decrease of ta-C thickness from 30 to 7 nm leads to (i) the narrowing of the band gap; (ii) appearance of shallower monoenergetic traps as well as the increase of their concentration; (iii) the increase of the equilibrium concentration of free charge carriers and their mobility; which were caused by (iv) the increase in the sp² fraction. However, beyond a certain ta-C thickness (7 nm) the electronic properties of the studied samples start to deteriorate, which is highly likely related to titanium oxide formation at the Ti/ta-C interface. The same tendency is observed for the sample with beforehand air-formed native titanium oxide at the interface. With respect to the last point, it is suggested that the ta-C layer has no uniform coverage if its thickness is small enough (less than 7 nm). The experimental results were rationalized by detailed atomistic simulations. By using the so-called “Tauc plot” we introduce the possibility of the coexistence of bulk and surface band gaps originating from the large increase in sp² bonded carbon atoms in the surface region compared to that in the bulk ta-C. The results from the simulations were found to be consistent with the experimental measurements. The previously stated variation in the electronic properties of the layers as a function of their thickness was also exhibited in the electrochemical properties of the samples. It appears that the thinner ta-C layers had more facile electron transfer kinetics as determined with a ferrocenemethanol (FcMeOH) outer sphere redox system. However, if the ta-C layer thickness was reduced too much, the films were not stable anymore.

Graphene derivatization to either engineer its physical and chemical properties or overcome the problem of the facile synthesis of nanographenes is a subject of significant attention in the nanomaterials research community. In this paper, we propose a facile and scalable method for the synthesis of thiolated graphene via a two-step liquid-phase treatment of graphene oxide (GO). Employing the core-level methods, the introduction of up to 5.1 at.% of thiols is indicated with the simultaneous rise of the C/O ratio to 16.8. The crumpling of the graphene layer upon thiolation without its perforation is pointed out by microscopic and Raman studies. The conductance of thiolated graphene is revealed to be driven by the Mott hopping mechanism with the sheet resistance values of 2.15 kΩ/sq and dependable on the environment. The preliminary results on the chemiresistive effect of these films upon exposure to ethanol vapors in the mix with dry and humid air are shown. Finally, the work function value and valence band structure of thiolated graphene are analyzed. Taken together, the developed method and findings of the morphology and physics of the thiolated graphene guide the further application of this derivative in energy storage, sensing devices, and smart materials.

The electronic structure of island carbon films on silicon, which are capable of low-voltage field electron emission (at the mean electric-field strength above several hundreds of V/mm), have been investigated. It has been shown by tunnel spectroscopy that islands of these coatings are characterized by a continuous spectrum of the allowed delocalized states near the Fermi level, i.e., they contain carbon in the sp² state. The photoconductivity of the coatings under study has been observed. Based on the current and spectral characteristics of this phenomenon, it has been shown that islands are separated from each other by tunnel barriers and from the substrate by a Schottky barrier.

Influence of fabrication technology on field electron emission properties of nanoporous carbon (NPC) was investigated. Samples of NPC derived from different carbides via chlorination at different temperatures demonstrated similar low‐field emission ability with threshold electric field 2‐3 V/μm. This property correlated with presence of nanopores with characteristic size 0.5–1.2 nm, determining high values of specific surface area (>800 m²/g) of the material. In most cases, current characteristics of emission were approximately linear in Fowler‐Nordheim coordinates (excluding a low‐current part near the emission threshold), but the plots’ slope angles were in notable disagreement with the known material morphology and electronic properties, unexplainable within the frames of the classical emission theory. We suggest that the actual emission mechanism for NPC involves generation of hot electrons at internal boundaries and that emission centers may be associated with relatively large (20–100 nm) onion‐like particles observed in many microscopic images. Such particles can serve two functions: to provide additional “internal” enhancement of the electric field and to inhibit relaxation of hot charge carriers due to the “phonon bottleneck” effect.

An ultrafast compact classical Mott detector is described. The efficiency of the polarimeter is $\epsilon \approx 6\times {10}^{-4}$ and the maximum counting rate $\sim 2000\mathrm{kcps}$ . The Mott polarimeter employs photomultipliers with scintillators as electron energy sensitive detectors with low dark noise. The photomultipliers and scintillators are placed in vacuum. With this choice of technology, it will be possible to build a classical Mott detector with a bulk size of cubic decimeter in the future.