While preparing oxide layers as gas sensors by a sol-gel approach, a high-temperature annealing makes a challenge to apply in numerous applications like flexible electronics with a heavy influence on the oxide microstructure. Therefore, its replacing by UV irradiation combined with a mild heating as “photo-annealing” paves the way to develop soft protocols when designing oxide-based gas sensors bearing a fine nanocrystallinity. Herein, we consider hierarchical sol-gel derived ZnO films which were a subject of conventional annealing and photoannealing to compare their gas-sensor performance when exposed to alcohol vapors. It is found that films obtained by photoannealing have an X-ray amorphous character, in contrast to ones being thermally annealed; although, the hierarchical organization of both samples revealed by SEM is almost identical. The DFTB modeling performed for ZnO crystal exposed to alcohol molecules and water has indicated the chemiresistive effect to be enhanced with a molecular weight of analytes. These observations were validated in experiment with sol-gel ZnO layers which exhibited an alcohol response in sub-ppm concentration range down to 10 ppb. To selectively compare the impact of various alcohols, we successfully applied a linear-discriminant analysis to the vector signal of the on-chip multisensor array.

The results of studying the electronic states of the conduction band of ultrathin films of furan-phenylene co-oligomer 1,4-bis(5-phenylfuran-2-yl)benzene and the results of analyzing the interfacial potential barrier upon the formation of these films on the surfaces of (SiO2)n-Si and layer-by-layer deposited ZnO are presented. The formation of a (8–10)-nm-thick co-oligomer film was investigated by total current spectroscopy; the energy range from 5 to 20 eV above EF was analyzed. Furan-phenylene co-oligomer films on the (SiO2)n-Si surface have a domain structure with a characteristic domain size of 1 × 1 µm and surface roughness within a domain of no more than 1 nm. The films on the ZnO surface have a granular structure with a grain height of 40–50 nm.

A method for the formation of nanostractured coatings from ZnO nanorods for use in adsorption gas sensors is presented. It has been shown that ultrasonic spray pyrolysis provides the formation of local growth centers for the formation of ZnO nanorods by the low-temperature hydrothermal synthesis. The obtained ZnO nanorods with a small diameter demonstrate a high concentration of oxygen vacancies in the near-surface region of the nanorods and a high surface concentration of hydroxyl groups. An additional method is proposed for testing seed layers by resistance using a liquid probe based on an indium-gallium melt without the need to apply top contacts. The presented technique is suitable for mass production of sensor coatings. The obtained nanostructured coatings from ZnO nanorods demonstrate a high gas analytical response.

The effect of UV irradiation on sol-gel prepared ZnO films subjected to mild thermal annealing was investigated, with special attention to their structural and surface properties. Sol-gel processes, including a high-temperature annealing stage, have been adapted to the requirements of flexible electronics for in situ synthesis of semiconductor ZnO films on polymer substrates at lower temperatures due to UV irradiation. Application of UV radiation with emission peaks at 185 and 254 nm to films annealed at 180 degrees C made it possible to obtain ZnO films with Zn/O ratios of ca. 1, which cannot be achieved by heat treatment alone.

The surface topography and density of unoccupied electronic states at thermal deposition of ultrathin dibromo-bianthracene films on the ZnO surface have been studied. The electronic characteristics of unoccupied electronic states during growth of dibromo-bianthracene films to a thickness of 10 nm have been investigated by total current spectroscopy using a probe electron beam. The experimental dependences have been analyzed using theoretical calculation of the orbital energies for dibromo-bianthracene molecules by the method of density functional theory (DFT).

Приведены результаты исследования топографии поверхности и плотности незаполненных электронных состояний при термическом осаждении сверхтонких пленок дибромо-биантрацена на поверхность ZnO. Измерения электронных характеристик незаполненных электронных состояний в процессе роста пленок дибромо-биантрацена до толщины 10 нм проводили методом спектроскопии полного тока с использованием тестирующего электронного пучка. Анализ экспериментальных зависимостей проводили с использованием теоретического расчета энергий орбиталей молекул дибромо-биантрацена методом теории функционала плотности.

The results of a study of the unoccupied electronic states of ultrathin films of phenolphthalein molecules on a ZnO surface formed by atomic layer deposition technique are presented. The atomic composition of the ZnO layer was determined by X-ray photoelectron spectroscopy (XPS) and its crystallinity was characterized using X-ray diffraction. The predominance of the content of O atoms by 5-10%, compared with the content of Zn atoms, was found. The electronic characteristics of the ZnO/phenolphthalein structure were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF during thermal vacuum deposition of phenolphthalein films up to 8 nm thick. Phenolphthalein molecules contain two hydroxyl functional groups. The TCS results on the phenolphthalein films are compared with the TCS results obtained from films of molecules that represent the backbone of phenolphthalein molecules without hydroxyl groups. The TCS fine structure maxima of phenolphthalein films located in the energy range from 5 eV to 8 eV above EF can be associated with the boundaries of the p* bands of electronic states. The work function of the ZnO surface formed by the ALD method were 4.2±0.1 eV. The deposition of a phenolphthalein film led to a decrease in the work function of the surface by 0.1 eV.

The effect of an increase in the electrical conductivity of a system of zinc oxide nanorods by a factor of 105 during atomic layer deposition of a thin dielectric layer of aluminum oxide was found. It is shown that a change in the electrical conductivity of zinc oxide during atomic layer deposition of aluminum oxide on the surface is also observed for thin polycrystalline layers of zinc oxide. A study of polycrystalline layers of zinc oxide coated with aluminum oxide using ultraviolet and X-ray photoelectron spectroscopy is presented. Based on the results of photoelectron spectroscopy, two main factors for changing the electrical conductivity are proposed, which consist in the formation of a two-dimensional electron gas at the ZnO|Al2O3 interface and doping of the near-surface region of zinc oxide with aluminum atoms. Keywords: nanorods, zinc oxide, aluminum oxide, atomic layer deposition, transparent electrodes, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy.

The results of a study of the unoccupied electronic states of ultrathin films of phenolphthalein molecules on a ZnO surface formed by atomic layer deposition technique are presented. The atomic composition of the ZnO layer was determined by X-ray photoelectron spectroscopy (XPS) and its crystallinity was characterized using X-ray diffraction. The predominance of the content of O atoms by 5-10%, compared with the content of Zn atoms, was found. The electronic characteristics of the ZnO/phenolphthalein structure were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF during thermal vacuum deposition of phenolphthalein films up to 8 nm thick. Phenolphthalein molecules contain two hydroxyl functional groups. The TCS results on the phenolphthalein films are compared with the TCS results obtained from films of molecules that represent the backbone of phenolphthalein molecules without hydroxyl groups. The TCS fine structure maxima of phenolphthalein films located in the energy range from 5 eV to 8 eV above EF can be associated with the boundaries of the π* bands of electronic states. The work function of the ZnO surface formed by the ALD method were 4.2±0.1 eV. The deposition of a phenolphthalein film led to a decrease in the work function of the surface by 0.1 eV. Keywords: Phenolphthalein, ultrathin films, ZnO, atomic layer deposition, electronic properties, low-energy electron spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy.

Organic electronic devices often suffer from poor charge injection limiting their performance. Specifically, high-performance electronic devices usually need Ohmic contacts, but it is not easy to realize them in junctions of the organic semiconductor with the electrodes because of the contact problems. In this work, polarity switching in organic field-effect transistors (OFETs) that is independent of the electrode work function is demonstrated-the switching of charge injection from the p-type to ambipolar and to the n-type -via modification of the donor/acceptor character of the molecular terminal substituents. By using three thiophene-phenylene co-oligomers with the same conjugated core, similar crystal packings, but different terminal substituents (methyl, trimethylsilyl, and trifluoromethyl), the polarity switching in both thin-film and single-crystal OFETs is demonstrated. The ultraviolet photoelectron spectroscopy studies and electronic structure calculations justify a definitive role of the interface dipole stemming from the terminal groups in controlling the heights of charge injection barriers and hence in charge injection into the OFET active layer. The results obtained are expected to facilitate rational design of organic semiconductors for high -performance electronic devices.

The effect of an increase in the electrical conductivity of a system of zinc oxide nanorods by a factor of 10^5 during atomic layer deposition of a thin dielectric layer of aluminum oxide was found. It is shown that a change in the electrical conductivity of zinc oxide during atomic layer deposition of aluminum oxide on the surface is also observed for thin polycrystalline layers of zinc oxide. A study of polycrystalline layers of zinc oxide coated with aluminum oxide using ultraviolet and X-ray photoelectron spectroscopy is presented. Based on the results of photoelectron spectroscopy, two main factors for changing the electrical conductivity are proposed, which consist in the formation of a two-dimensional electron gas at the ZnO/Al2O3 interface and doping of the near-surface region of zinc oxide with aluminum atoms.

The surface properties of zinc oxide powders prepared using mechanical activation, electron beam irradiation, and vacuum annealing, as well using combinations of these types of treatments, were studied using X-ray photoelectron spectroscopy. The structure of the obtained materials was studied by an X-ray diffraction technique and by scanning electron microscopy. We found that over five hours of grinding in an attritor, the size of nanocrystals decreases from 37 to 21 nm, and microdeformations increase from 0.3% to 0.6%. It was also found that a five-hour grinding treatment promoted formation of vacancies in the zinc sublattice at the surface and diffusion of Zn2+ cations into the bulk of the material. Irradiation of commercial zinc oxide powders with an electron beam with an energy of 0.9 MeV and a dose of 1 MGy induced breaking of Zn–O bonds, diffusion of interstitial zinc ions into the bulk, and oxygen atom escape from regular positions into the gas phase. A combined treatment of five hours of grinding and electron beam irradiation promoted accumulation of interstitial zinc ions at the surface of the material. Annealing of both initial and mechanically activated ZnO powders at temperatures up to 400 °C did not lead to a significant change in the properties of the samples. Upon exceeding the 400 °C annealing temperature the X-ray photoelectron spectra show almost identical atomic composition of the two types of materials, which is related to diffusion of interstitial zinc ions from the bulk of the material to the surface.

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO substrate. This corresponds to the transfer of a negative charge from the СH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The СH3-PTTP-СH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 micrometers x 10 micrometers. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10–15 nm.

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene -CH3(CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO-substrate. This corresponds to the transfer of a negative charge from the CH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO-substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The CH3-PTTP-CH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 μmx10 μm. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10-15 nm. Keywords: thiophene-phenylene co-oligomers, biphenyl tetracarboxylic dianhydride, ultrathin films, ZnO, atomic layer deposition method, electronic properties, low-energy electron spectroscopy, interface potential barrier.

The morphology of organic semiconductor films of perylenetetracarboxylic acid dianhydride (PTCDA) and perylenetetracarboxylic acid dibenzyl-diimide (N, N`-DBPTCDI) formed by thermal vacuum deposition was studied by atomic force microscopy. It was shown that annealing of films at 420 K leads to rearrangement of their structure and crystallization. The optical absorption spectra of the films under study were used to estimate the optical band gap. The temperature dependence of the dark conductivity of PTCDA and N, N-DBPTCDI films before and after annealing (Т = 420 K) was established. The values of the activation energy of charge carrier traps are determined. The computer simulation of the density of localized states in the band gap of the films studied was carried out using the photoconductivity spectra in the constant photocurrent mode. Model photovoltaic cells based on PTCDA / СuPc and N, N-DBPTCDI / СuPc structures were formed. The kinetics of decay of the interfacial photo-voltage of the cells prepared was measured using pulsed light as an excitation source. On the basis of the performed measurements, the charge carrier mobility values in the investigated semiconductor materials were estimated.

Films of the organic semiconductors perylenetetracarboxylic acid dianhydride (PTCDA) and dibenzyl-perylenetetracarboxylic acid diimide (N,N'-DBPTCDI) are prepared by thermal sputtering in vacuum, and their surface morphology is studied by atomic force microscopy. Annealing the films at 420 K induces restructuring and crystallization. The optical band gap of the films is estimated from their absorption spectra. The temperature dependence of dark conductivity of PTCDA and N,N'-DBPTCDI films is measured before and after annealing (T = 420 K). The activation energy of charge carrier traps is determined. The density of states localized in the band gap is reconstructed from photoconductivity spectra of considered films recorded using the constant photocurrent method. Model photovoltaic cells are fabricated on the basis of PTCDA/CuPc and N,N'-DBPTCDI/CuPc structures (CuPc, copper phthalocyanine). Transient photovoltage decay curves are measured for these photovoltaic cells in the barrier photovoltage mode under pulsed illumination. The carrier mobility in the semiconducting materials under study is estimated based on these measurements.

The results of a study of the unoccupied electronic states of ultrathin films of bis-carboxyphenyl-phthalide (DCA-DPP) and bis-methylphenyl-phthalide (DM-DPP) up to 8 nm thick are presented. The studies were carried out by total current spectroscopy (TCS) technique in the energy range from 5 eV to 20 eV above EF during thermal vacuum deposition of these organic films on the surface of highly oriented pyrolytic graphite (HOPG). The energy Evac relative to EF, that is, the electronic work function of the DM-DPP films, at a film thickness of 5–8 nm was 4.3 ± 0.1 eV. The electronic work function of the DCA-DPP films was 3.7 ± 0.1 eV. The structure of the maxima of the unoccupied electronic states of DCA-DPP films and DM-DPP films in the studied energy range is determined. The properties determined of DCA-DPP and DM-DPP films are compared with the properties of films of unsubstituted diphenylphthalide (DPP). According to our analysis, –CH3 substitution of the DPP molecule practically did not affect the height of the potential barrier between the film and the HOPG surface, and –COOH substitution of the DPP molecule led to an increase in the height of the potential barrier between the film and the HOPG substrate surface by 0.5–0.6 eV. Substitution of DPP molecules with –COOH functional groups which represents formation of DCA-DPP molecules led to a shift of two peaks of the experimental total current spectra located at energies in the range from 5 eV to 8 eV above EF, by about 1 eV towards lower electron energies.

The results of a study of unoccupied electronic states and the formation of a boundary potential barrier during thermal vacuum deposition of ultrathin films of 4-quaterphenyl oligophenylene on the surface of CdS and on the surface of oxidized silicon are presented. Using X-ray photoelectron spectroscopy (XPS) it was determined, that the atomic concentrations of Cd and S were equal in the surface layer of a 75-nm-thick CdS film formed by atomic layer deposition (ALD). The electronic properties of 4-quaterphenyl films up to 8 nm thick were studied during their deposition on the surface of the CdS layer and on the surface of oxidized silicon using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. The energetic position of the main maxima of the fine structure of the total current spectra (FSTCS) of 4-quaterphenyl films was determined. The location of the maxima was reproducible when two selected substrate materials were used. A minor decrease in the work function, from 4.2 eV to 4.1 eV, was registered during the thermal deposition of 4-quaterphenyl onto the CdS surface. During the deposition of a 4-quaterphenyl film on the oxidized silicon surface, an increase in the work function from 4.2 eV to 4.5 eV was found. Possible mechanisms of the physicochemical interaction between the 4-quaterphenyl film and the surface of the investigated substrates, which lead to a difference in the observed values of the work function of the films on these substrates, are discussed.

Some results of studying the unoccupied electron states and the formation of a boundary potential barrier during the thermal vacuum deposition of ultrathin 4-quaterphenyl oligophenyl films onto the surfaces of CdS and oxidized silicon were presented. Using X-ray photoelectron spectroscopy (XPS), the atomic Cd and S concentrations were established to be the same on the surface of a 75-nm CdS layer formed by atomic layer deposition (ALD). The electron characteristics of 4-quaterpheyn films with a thickness of up to 8 nm were studied in the process of their deposition onto the surface of a formed CdS layer and the surface of oxidized silicon by total current spectroscopy (TCS) within an energy range from 5 to 20 eV above E-F. The energy positions of major maxima in the fine structure of the total current spectra (FSTCS) of 4-quaterphenyl films were established. The positions of maxima were reproducible, when the two selected materials of substrates were used. A slight decrease in the work function from 4.2 to 4.1 eV during the thermal deposition of 4-quaterpheynl onto the CdS surface was established. The work function was revealed to grow from 4.2 to 4.5 eV, when a 4-quaterphenyl film was deposited onto the surface of oxidized silicon. Some possible mechanisms of physicochemical interaction between the 4-quaterphenyl film and the surfaces of the studied substrates that lead to different work function values observed on these substrates were discussed.

The results of studying unoccupied electronic states in the energy range from 5 eV to 20 eV above the Fermi level of ultrathin films of dimethyl-substituted thiophene-phenylene co-oligomers CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) are presented. The films were deposited on two types of surface of polycrystalline Au: ex situ Au layer thermally deposited in a separate chamber, and on the in situ Au surface prepared inside the analytical chamber. The structure of the films was studied by X-ray diffraction (XRD). The formation of a superposition of the amorphous and crystalline phases with a period of 3.8 nm is discussed. Investigations of the energy positioning of the maxima of unoccupied electronic states and of the process of the formation of the potential boundary barrier were carried out by the method of total current spectroscopy (TCS). The maxima of the fine structure of the total current spectra (FSTCS) of the CH3-PTTP-CH3 film 5–7 nm thick did not differ when using different types of Au substrates and the surface of the ZnO semiconductor prepared by the atomic layer deposition (ALD) method. When the CH3-PTTP-CH3 layer was deposited both on the ex situ Au surface and on the in situ Au surface, a slight (about 0.1 eV) increase in the electronic work function was observed with an increase in the coating thickness to 5–7 nm. At such CH3-PTTP-CH3 film thicknesses, the electron work function was determined as 4.7 ± 0.1 eV for the ex situ Au substrate and 4.9 ± 0.1 eV for the in situ Au substrate. The possible influence of the processes of physicochemical interaction at the film – substrate interface on the formation of the potential boundary barrier in the structures under study is discussed.