A sensor for monitoring the volume of nutrient in a solid substrate-based growth media by using electrochemical admittance spectroscopy

A sensor was fashioned to monitor the volume of nutrient in a solid substrate-based growth media by using electrochemical admittance spectroscopy. Several experimental parameters were investigated (i.e. The use of two- or three-electrode cells, the superficial area of the electrode, the amount of nutrient solution added to the growth media, and the influence of varying the dc and ac potential) to assess how these variables affect the admittance of the system. A linear correlation was observed between the maximum of the imaginary admittance and the volume of nutrient present. The response factor was 2.8 x 10(-5) S cm(-2) ml(-1) and the limit of detection (LOD) was 0.54 ml. The humidity of the growth media does not change the response of the nutrient toward the monitoring measurements. These results demonstrate that the volume of nutrient in this solid substrate-based growth media can be assessed using a ceramic sensor to measure the imaginary admittance. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Phenomenological model for the interpretation of impedance/admittance spectroscopy results in polymer light-emitting electrochemical cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of Alkali Ions in Enhancing the Nonlinearity of ZnO-Bi2O3-Co3O4 Varistor Ceramics

Zinc oxide ceramic varistors with simplified compositions of ZnO+Bi2O3+Co3O4+M(2)O (M=K or Na) show nonlinearity coefficients (alpha) of 40-75. The electron paramagnetic resonance spectra and optical reflectance spectra show that there is a direct interdependence between the oxidation state of transition metals and the alkali ions. The X-ray photoelectron spectra indicate that the alkali ions preserve a higher oxidation state of cobalt, Co(III), in the grain boundary regions than in the grain interiors having more Co(II). Admittance spectroscopy shows that, while the nature of traps remains unaltered, the trap density increases with the concentration of alkali ions near the interface. The observed defect states are associated with the grain bulk than with the grain boundary interfaces, as indicated by the isothermal capacitance transient signals

The effect of aluminosilicate on the delayed onset of upturn voltages of zinc oxide varistor ceramics

The effect of aluminosilicate (Al2SiO5) on the upturn characteristics of ZnO varistor ceramics has been investigated. Addition of Al2SiO5 shifts the point of upturn above 10(4) A cm(-2). The extended nonlinearity in the high current density region is better correlatable to the presence of higher density of trap stales and changing pattern of trap depths at the grain boundary interface as much as the grain interior conductivity. Microstructure studies show the formation and involvement of a liquid phase during sintering. The secondary phases, predominantly are antimony spinel, Zn7Sb2O12, zinc silicate, Zn2SiO4 and magnesium aluminium silicate. MgAl2Si3O10. Energy dispersive X-ray analyses (EDAX) show that Al and Si are distributed more in the grain boundaries and within the secondary phases than in the grain interiors. Capacitance-voltage analyses and dielectric dispersion studies indicate the presence of negative capacitance and associated resonance, indicative of the oscillatory charge redistribution involving increased trapping at the interface states. The admittance spectroscopy data show that the type of trap slates remains unaltered whereas the addition of Al2SiO5 increases the density of low energy traps. (C) 1997 Published by Elsevier Science S.A.

Células solares de Cu2ZnSnS4 por sulfurização de camadas metálicas

As energias renováveis têm estado em destaque desde o fi nal do século XX. São vários os motivos para que isto esteja a acontecer. As previsões apontam para problemas de depleção das reservas de combustíveis fósseis, nomeadamente o petróleo e gás natural, durante o presente século. O carvão, ainda abundante, apresenta problemas ambientais signi cativos. Os perigos associados à energia nuclear estão fazer com que os governos de vários países repensem as suas políticas energéticas . Todas estas tecnologias têm fortes impactos ambientais. Considerando o conjunto das energias renováveis, a energia solar fotovoltaica tem ainda um peso menor no panorama da produção energética actual. A explicação para este facto deve-se ao custo, ainda elevado, dos sistemas fotovoltaicos. Várias iniciativas governamentais estão em curso, a SET for 2020 (UE) e a Sunshot (EUA), para o desenvolvimento de tecnologias que façam frente a este problema. A fatia de mercado que a tecnologia de filmes fi nos representa ainda é pequena, mas tem vindo a aumentar nos últimos anos. As vantagens relativamente à tecnologia tradicional baseada em Si são várias, como por ex. os custos energéticos e materiais para a fabricação das células. Esta dissertação apresenta um processo de fabricação de células solares em fi lmes finos usando como camada absorvente um novo composto semicondutor, o Cu2ZnSnS4, que apresenta como grande argumento, relativamente aos seus predecessores, o facto de ser constituído por elementos abundantes e de toxicidade reduzidas. Foi realizado um estudo sobre as condições termodinâmicas de crescimento deste composto, bem como a sua caracterização e das células solares finais. Este trabalho inclui um estudo dos compostos ternários, CuxSnSx+1 e compostos binários SnxSy, justi cado pelo facto de surgirem como fases secundárias no crescimento do Cu2ZnSnS4. Em seguida são descritos resumidamente os vários capítulos que constituem esta tese. No capítulo 1 é abordada de forma resumida a motivação e o enquadramento da tecnologia no panorama energético global. A estrutura da célula solar adoptada neste trabalho é também descrita. O capítulo 2 é reservado para uma descrição mais detalhada do composto Cu2ZnSnS4, nomeadamente as propriedades estruturais e opto-electrónicas. Estas últimas são usadas para explicar as composições não estequiométricas aplicadas no crescimento deste composto. São também descritas as várias técnicas de crescimento apresentadas na literatura. A última secção deste capítulo apresenta os resultados da caracterização publicados pelos vários grupos que estudam este composto. O método que foi implementado para crescer a camada absorvente, bem como os efeitos que a variação dos vários parâmetros têm neste processo são abordados no capítulo 3. Neste é também incluída uma descrição detalhada dos equipamentos usados na caraterização da camada absorvente e das células solares finais. As fases calcogêneas binária e ternárias são estudadas no capítulo 4. É apresentada uma descrição do método de crescimento, quer para as fases do tipo CuxSnSx+1, quer para as fases do tipo SnxSy e a sua caracterização básica, nomeadamente a sua composição e as propriedades estruturais, ópticas e eléctricas. No caso dos compostos binários são também apresentados os resultados de uma célula solar. No capítulo 5 são reportados os resultados da caracterização dos fi lmes de Cu2ZnSnS4. Técnicas como a dispersão Raman, a fotoluminescência, a efi ciência quântica externa e a espectroscopia de admitância são usadas para analisar as propriedades quer da camada absorvente quer da célula solar. No capítulo 6 é apresentada uma conclusão geral do trabalho desenvolvido e são referidas sugestões para melhorar e complementar os estudos feitos.

Determining carrier mobility with a metal–insulator–semiconductor structure

The electron and hole mobility of nickel-bis(dithiolene) (NiDT) are determined in a metal– insulator–semiconductor (MIS)structure using admittance spectroscopy. The relaxation times found in the admittance spectra are attributed to the diffusion time of carriers to reach the insulator interface and via Einstein’s relation this yields the mobility values. In this way, an electron mobility of 1:9 104 cm2=Vs and a hole mobility of 3:9 106 cm2=Vs were found. It is argued that the low mobility is caused by an amphoteric mid-gap trap level. The activation energy for electrons and holes from these traps is found to be 0.46 eV and 0.40 eV, respectively.

Electrical relaxation in proton conductor composites based on (NH4)H2PO4/TiO2

We report on electrical relaxation measurements of (1-x)NH4H2PO4-xTiO(2) (x = 0.1) composites by admittance spectroscopy, in the 40-Hz-5-MHz frequency range and at temperatures between 303 and 563 K. Simultaneous thermal and electrical measurements on the composites identify a stable crystalline phase between 373 and 463 K. The real part of the conductivity, sigma', shows a power-law frequency dependence below 523 K, which is well described by Jonscher's expression sigma' = sigma(0)(1 + (omega/omega(p))(n)), where sigma(0) is the dc conductivity, omega(p)/2 pi = f(p) is a characteristic relaxation frequency, and n is a fractional exponent between 0 and 1. Both sigma(0) and f(p) are thermally activated with nearly the same activation energy in the II region, indicating that the dispersive conductivity originates from the migration of protons. However, activation energies decrease from 0.55 to 0.35 eV and n increases toward 1.0, as the concentration of TiO2 nanoparticles increases, thus, enhancing cooperative correlation among moving ions. The highest dc conductivity is obtained for the composite x = 0.05 concentration, with values above room temperature about three orders of magnitude higher than that of crystalline NH4H2PO4 (ADP), reaching values on the order of 0.1 (Omega cm)(-1) above 543 K.

Lanthanum-lithium-sodium double chromates as ionic conductors

Lanthanum-lithium-sodium double chromates Li1-xNaxLa(CrO4)2 were prepared and analysed by means of admittance spectroscopy. Their a.c. conductivity parameters are correlated with structural details of high and low temperature forms of pure lanthanum-lithium double chromates. Lithium compounds show the lowest conductivity values and the highest activation energy for ion motion, while the sample Li0.5Na0.5La(CrO4)2 exhibits the highest conductivity 10-5 S cm-1 and the lowest activation energy 0.58 eV.

Experimental verification of intermediate band formation on titanium-implanted silicon

Intermediate band formation on silicon layers for solar cell applications was achieved by titanium implantation and laser annealing. A two-layer heterogeneous system, formed by the implanted layer and by the un-implanted substrate, was formed. In this work, we present for the first time electrical characterization results which show that recombination is suppressed when the Ti concentration is high enough to overcome the Mott limit, in agreement with the intermediate band theory. Clear differences have been observed between samples implanted with doses under or over the Mott limit. Samples implanted under the Mott limit have capacitance values much lower than the un-implanted ones as corresponds to a highly doped semiconductor Schottky junction. However, when the Mott limit is surpassed, the samples have much higher capacitance, revealing that the intermediate band is formed. The capacitance increasing is due to the big amount of charge trapped at the intermediate band, even at low temperatures. Ti deep levels have been measured by admittance spectroscopy. These deep levels are located at energies which vary from 0.20 to 0.28?eV below the conduction band for implantation doses in the range 1013-1014 at./cm2. For doses over the Mott limit, the implanted atoms become nonrecombinant. Capacitance voltage transient technique measurements prove that the fabricated devices consist of two-layers, in which the implanted layer and the substrate behave as an n+/n junction.

Electrical investigation of p-type 4H-SiC heavily doped by ion implantation

In the last decades, an increasing interest in the research field of wide bandgap semiconductors was observed, mostly due to the progressive approaching of silicon-based devices to their theoretical limits. 4H-SiC is an example among these, and is a mature compound for applications. The main advantages offered 4H-SiC in comparison with silicon are an higher breakdown field, an higher thermal conductivity, a higher operating temperature, very high hardness and melting point, biocompatibility, but also low switching losses in high frequencies applications and lower on-resistances in unipolar devices. Then, 4H-SiC power devices offer great performance improvement; moreover, they can work in hostile environments where silicon power devices cannot function. Ion implantation technology is a key process in the fabrication of almost all kinds of SiC devices, owing to the advantage of a spatially selective doping. This work is dedicated to the electrical investigation of several differently-processed 4H-SiC ion- implanted samples, mainly through Hall effect and space charge spectroscopy experiments. It was also developed the automatic control (Labview) of several experiments. In the work, the effectiveness of high temperature post-implant thermal treatments (up to 2000°C) were studied and compared considering: (i) different methods, (ii) different temperatures and (iii) different duration of the annealing process. Preliminary p + /n and Schottky junctions were also investigated as simple test devices. 1) Heavy doping by ion implantation of single off-axis 4H-SiC layers The electrical investigation is one of the most important characterization of ion-implanted samples, which must be submitted to mandatory post-implant thermal treatment in order to both (i) recover the lattice after ion bombardment, and (ii) address the implanted impurities into lattice sites so that they can effectively act as dopants. Electrical investigation can give fundamental information on the efficiency of the electrical impurity activation. To understand the results of the research it should be noted that: (a) To realize good ohmic contacts it is necessary to obtain spatially defined highly doped regions, which must have conductivity as low as possible. (b) It has been shown that the electrical activation efficiency and the electrical conductivity increase with the annealing temperature increasing. (c) To maximize the layer conductivity, temperatures around 1700°C are generally used and implantation density high till to 10 21 cm -3 . In this work, an original approach, different from (c), is explored by the using very high annealing temperature, around 2000°C, on samples of Al + -implant concentration of the order of 10 20 cm -3 . Several Al + -implanted 4H-SiC samples, resulting of p-type conductivity, were investigated, with a nominal density varying in the range of about 1-5∙10 20 cm -3 and subjected to two different high temperature thermal treatments. One annealing method uses a radiofrequency heated furnace till to 1950°C (Conventional Annealing, CA), the other exploits a microwave field, providing a fast heating rate up to 2000°C (Micro-Wave Annealing, MWA). In this contest, mainly ion implanted p-type samples were investigated, both off-axis and on-axis <0001> semi-insulating 4H-SiC. Concerning p-type off-axis samples, a high electrical activation of implanted Al (50-70%) and a compensation ratio below 10% were estimated. In the work, the main sample processing parameters have been varied, as the implant temperature, CA annealing duration, and heating/cooling rates, and the best values assessed. MWA method leads to higher hole density and lower mobility than CA in equivalent ion implanted layers, resulting in lower resistivity, probably related to the 50°C higher annealing temperature. An optimal duration of the CA treatment was estimated in about 12-13 minutes. A RT resistivity on the lowest reported in literature for this kind of samples, has been obtained. 2) Low resistivity data: variable range hopping Notwithstanding the heavy p-type doping levels, the carrier density remained less than the critical one required for a semiconductor to metal transition. However, the high carrier densities obtained was enough to trigger a low temperature impurity band (IB) conduction. In the heaviest doped samples, such a conduction mechanism persists till to RT, without significantly prejudice the mobility values. This feature can have an interesting technological fall, because it guarantee a nearly temperature- independent carrier density, it being not affected by freeze-out effects. The usual transport mechanism occurring in the IB conduction is the nearest neighbor hopping: such a regime is effectively consistent with the resistivity temperature behavior of the lowest doped samples. In the heavier doped samples, however, a trend of the resistivity data compatible with a variable range hopping (VRH) conduction has been pointed out, here highlighted for the first time in p-type 4H-SiC. Even more: in the heaviest doped samples, and in particular, in those annealed by MWA, the temperature dependence of the resistivity data is consistent with a reduced dimensionality (2D) of the VRH conduction. In these samples, TEM investigation pointed out faulted dislocation loops in the basal plane, whose average spacing along the c-axis is comparable with the optimal length of the hops in the VRH transport. This result suggested the assignment of such a peculiar behavior to a kind of spatial confinement into a plane of the carrier hops. 3) Test device the p + -n junction In the last part of the work, the electrical properties of 4H-SiC diodes were also studied. In this case, a heavy Al + ion implantation was realized on n-type epilayers, according to the technological process applied for final devices. Good rectification properties was shown from these preliminary devices in their current-voltage characteristics. Admittance spectroscopy and deep level transient spectroscopy measurements showed the presence of electrically active defects other than the dopants ones, induced in the active region of the diodes by ion implantation. A critical comparison with the literature of these defects was performed. Preliminary to such an investigation, it was assessed the experimental set up for the admittance spectroscopy and current-voltage investigation and the automatic control of these measurements.

Determination of deep and shallow levels in conjugated polymers by electrical methods

Conjugated organic semiconductors have been submitted to various electrical measurement techniques in order to reveal information about shallow levels and deep traps in the forbidden gap. The materials consisted of poly[2-methoxy, 5 ethyl (2' hexyloxy) paraphenylenevinylene] (MEH-PPV), poly(3-methylthiophene) (PMeT), and alpha-sexithienyl (alpha T6) and the employed techniques were IV, CV, admittance spectroscopy, TSC, capacitance and current transients. (C) 1999 Elsevier Science B.V. All rights reserved.

Electrical study of impurity states in conjugated polymers

Schottky diodes resulting from an intimate contact of aluminum on electro-deposited poly(3-methylthiopene), PMeT, have been studied by admittance spectroscopy, capacitance-voltage and current-voltage measurements, and optically-induced current transients. The loss-tangents show the existence of interface states that can be removed by vacuum annealing, also visible in the transients. Furthermore, the CV curves don't substantiate the idea of movement of the dopant ions.

Electrical characterization of semiconducting polymers

Schottky diodes resulting from an intimate contact of aluminum on electrodeposited poly(3-methylthiopene) were studied by admittance spectroscopy, capacitance-voltage measurements and voltaic and optically-induced current and capacitance transients. The loss tangents show the existence of interface states that can be removed by vacuum annealing. Furthermore, the C-V curves contradict the idea of movement of the dopant ions.

Minority-carrier effects in poly-phenylenevinylene as studied by electrical characterization

Electrical measurements have been performed on poly[2-methoxy, 5 ethyl (2' hexyloxy) paraphenylenevinylene] in a pn junction with silicon. These included current-voltage measurements, capacitance-voltage measurements, capacitance-transient spectroscopy, and admittance spectroscopy. The measurements show evidence for large minority-carrier injection into the polymer possibly enabled by interface states for which evidence is also found. The shallow acceptor level depth (0.12 eV) and four deep trap level activation energies (0.30 and 1.0 eV majority-carrier type; 0.48 and 1.3 eV minority-carrier type) are found. Another trap that is visible at room temperature has point-defect nature. (C) 2001 American Institute of Physics.

Determination of deep and shallow levels in conjugated polymers by electrical methods

Conjugated organic semiconductors have been submitted to various electrical measurement techniques in order to reveal information about shallow levels and deep traps in the forbidden gap. The materials consisted of poly[2-methoxy, 5 ethyl (2' hexyloxy) paraphenylenevinylene] (MEH-PPV), poly(3-methylthiophene) (PMeT), and alpha-sexithienyl (alpha T6) and the employed techniques were IV, CV, admittance spectroscopy, TSC, capacitance and current transients. (C) 1999 Elsevier Science B.V. All rights reserved.