The response of a graphene-based humidity sensor is considered as a function of film structures. Analysis of the resistance changes due to water molecule adsorption on the graphene or multi-layer graphene (MLG) surface is performed for films with different structures and resistivities from hundreds of ohms/sq to hundreds of kilo-ohms/sq. The results revealed possible increase, decrease and non-monotonous behavior of resistance with changes in film structure. Adsorption of water molecules at grain boundary defects is assumed to lead to an increase in film resistivity due to the donor property of water and the p-type conductivity of graphene. Another type of conductive center with a higher capture cross-section is realized in the case of water molecule adsorption at edge defects in MLG films (the formation of conductive chains with ionic conductivity). If these chains form a continuous network the film resistivity decreases. The result of the competition between the opposite effects of the conductivity compensation and formation of the water-based conductive chains depends on the film structure and determines the response of humidity sensors. Sensor sensitivity is found to increase when only one type of defect determines water adsorption (edge defects or grain boundary defects).
A comparison of the structure and sensitivity of humidity sensors prepared from graphene (G)-PEDOT: PSS (poly (3,4-ethylenedioxythiophene)) composite material on flexible and solid substrates is performed. Upon an increase in humidity, the G: PEDOT: PSS composite films ensure a response (a linear increase in resistance versus humidity) up to 220% without restrictions typical of sensors fabricated from PEDOT: PSS. It was found that the response of the examined sensors depends not only on the composition of the layer and on its thickness but, also, on the substrate used. The capability of flexible substrates to absorb the liquid component of the ink used to print the sensors markedly alters the structure of the film, making it more porous; as a result, the response to moisture increases. However, in the case of using paper, a hysteresis of resistance occurs during an increase or decrease of humidity; that hysteresis is associated with the capability of such substrates to absorb moisture and transfer it to the sensing layer of the sensor. A study of the properties of G: PEDOT: PSS films and test device structures under deformation showed that when the G: PEDOT: PSS films or structures are bent to a bending radius of 3 mm (1.5% strain), the properties of those films and structures remain unchanged. This result makes the composite humidity sensors based on G: PEDOT: PSS films promising devices for use in flexible and printed electronics.
The present study of deep level transient spectroscopy (DLTS) is focused on a comparison of the trap states in two types of Ge nanocrystallites (NCs)-insulator composites. The investigated systems were the dielectric matrices Al2O3 and SiO2 in which the Ge NCs were embedded. We have found couples of traps with related values of activation energies in both the Ge:Al2O3 and the Ge:SiO2 films. In the films with a relatively low Ge content (where only small NCs sized 3–5 nm could have been detected by means of Raman spectroscopy), we observed traps with an energy level ∼50 meV in the Ge:Al2O3 films and 120 and 50 meV in the Ge:SiO2 films. In both systems, we found that the electron traps have a small carrier capture cross-section (10−21–10−23 cm2). We have identified the levels of the traps to be the quantum confinement levels in the small Ge NCs. For samples of higher Ge contents, where the NC size reaches about 20 nm and where an appreciable portion of the dielectric matrix consists of amorphous Ge (α-Ge), we found traps with an energy of 0.22–0.24 eV in the Ge:Al2O3, and 0.26–0.27 eV in the Ge:SiO2 samples. We suggest that this peak in the charge DLTS (Q-DLTS) spectra is associated with a trap at the Ge-NC/α-Ge interface. We have also identified the energy position of a defect level in the Ge:Al2O3 layers, which lies 0.46–0.49 eV below the conduction-band edge of the Si substrate.
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