Photodetectors are essential in optoelectronics as they allow the conversion of optical signals into electrical outputs. Silicon, germanium and III-V semiconductors currently dominate the photodetector market. In this dissertation I exploit the potential of layered materials to demonstrate a class of photodetectors able to challenge existing technological issues. I first demonstrate a fabrication method for high-mobility, chemical-vapour-deposited graphene devices which could help to increase the responsivity in graphene-based photodetectors. I then show three examples of graphene-based Schottky photodetectors working at the telecommunication wavelength $\lambda$=1550nm, two for free-space illumination and one for on-chip applications. These are able to achieve responsivities up to 1A/W with relatively-low operation voltage (-3V), similar to those achieved with germanium. I then target the mid-infrared range ($\lambda\sim$10$\mu$m), where emission from objects at room temperature has a peak. I show graphene-based pyroelectric bolometers with temperature coefficient of resistance up to 900\%/K, two orders of magnitude higher compared to current solutions based on thin oxide membranes. I present flexible photodetectors working in the visible range ($\lambda$=642nm) with gate-tunable graphene/MoS$_2$ heterostructures and show responsivity up to 45A/W, 82\% transparency, and low voltage operation (-1V). The responsivity is two orders of magnitude higher compared to semiconducting flexible membranes. Graphene/MoS$_2$ photodetectors can be bent without loss in performance down to a bending radius of 1.4cm. I finally report on the investigation of superconducting properties of layered materials with the target of realizing ultra-sensitive superconducting photodetectors. Unconventional superconductivity is induced in graphene by proximity with a cuprate superconductor. I used gating to turn semiconducting, few-layer MoS$_2$ into a superconductor, which allowed us to unveil the presence of a multi-valley transport in the superconducting state. Electrical properties of the layered superconductor NbSe$_2$ are then studied. I then used NbSe$_2$ ultrathin flakes to realize superconducting photodetectors at $\lambda$=1550nm, reaching a sensitivity down to few thousand photons.

Due to the combination of their electronic, optical and mechanical properties, graphene and other layered materials (GRMs) have great potential for applications such as flexible optoelectronics and energy storage. Given that GRMs can be dispersed in solvents, solution processing is a particularly interesting approach that allows large volume production with tailored properties according to the targeted applications. \par In this dissertation I investigate liquid phase exfoliation and formulation of GRMs-based inks for flexible (opto) electronics, energy and photocatalysis. First I develop a protocol for the characterization of graphene inks, based on the statistical analysis of their Raman spectra. Such a tool is essential because of the scattering of characteristics in liquid-phase exfoliated material. I then report two novel processing techniques. The first consists on the exfoliation of graphene in organic solvents by the means of $\alpha$-functionalized alkanes as stabilising agents, which allows yield by weight ($Y_W$) of $\sim 100\%$. The second is based on exfoliation of graphite by microfluidization, where the material is stabilised in aqueous solution, with concentrations up to 100g/L. Such inks are successfully deposited by blade coating, leading to films of conductivity $\sim$ 2$\cdot$10$^4$ S/m at 25$\mu$m. I then investigate the use of graphene inks in optoelectronics and energy applications: First, I investigate inkjet printed graphene as hole injection layer (HTL). The cells with graphene HTL show high long-term stability, retaining 85$\%$ of the initial fill factor after 900 hrs in damp heat conditions. I then demonstrate flexible displays with graphene-SWNTs as pixel electrode. A 4x4 inch$^2$ demonstrator is realised integrating the ink into 12,700 pixels. I investigate graphene/MoO$_3$ electrode for supercapacitors with a specific capacitance of 342 F/cm$^3$. The electrode shows high cyclic stability, preserving $\sim$96$\%$ of the initial capacitance after 10,000 cycles. I finally report the production of TiO$_2$/exfoliated graphite as efficient photocatalytic composite able to degrade $\sim$100$\%$ more model pollutant with respect to TiO$_2$.

The generation of electron-hole pairs in materials has great importance. In direct bandgap semiconductor materials, the mechanism of radiative recombination of electron-hole pairs leads to the emission of photons, which is the basis of Light Emitting Diodes (LEDs). The excitation of electron-hole pairs by absorption of photons is the active process in photodiodes, solar cells, and other semiconductor photodetector devices. In optoelectronic devices such as optical switches which are based on transmission and reflection of the photons, electron-hole pairs excitation is a key for the device performance. Diodes and transistors are also great discoveries in electronics which rely on the generation and recombination of electron-hole pairs at p-n junctions. In three-dimensional topological insulators (3D TIs) materials nanostructures excitation of electron-hole pairs can be utilized for the quantum memory, quantum information and quantum teleportation. In two-dimensional (2D) layered materials like graphene, MoS2, MoSe2, WS2 and WSe2 generation and recombination of electron hole pairs is main process at p-n junctions, infrared detectors and sensors. This PhD thesis is concerned with the physics of different types of electron-hole pairs in various materials, such as wide-bandgap semiconductors, 3D topological insulators, and plasmonic excitations in metallic nanostructures. The materials of interest are wide bandgap semiconductors such as TiO2 , 3D TIs such as Pb1-xSnxTe and the 2D layered materials such as MoS2 and MoO3. We study the electronic and optical properties in bulk and nanostructures and find applications in the area of semiclassical and quantum information processing. One of the interesting applications we focus in this thesis is shift in surface plasmon resonance due to reduction in index of refraction of surrounding dielectric environment which in turns shifts the wavelength of surface plasmon resonance up to 125 nm for carrier density of 10^22/cm^3. Employing this effect, we present a model of a light controlled plasmon switching using a hybrid metal-dielectric heterostructures. In 3D TIs nanostructures, the time reversible spin partners in the valence and conduction band can be coupled by a left and a right handed circular polarization of the light. Such coupling of light with electron-hole pair polarization provides an unique opportunity to utilize 3D TIs in quantum information processing and spintronics devices. We present a model of a 3D TI quantum dot made of spherical core-bulk heterostructure. When a 3D TI QD is embedded inside a cavity, the single-photon Faraday rotation provides the possibility to implement optically mediated quantum teleportation and quantum information processing with 3D TI QDs, where the qubit is defined by either an electron-hole pair, a single electron spin, or a single hole spin in a 3D TI QD. Due to excellent transport properties in single and multiple layers of 2D layered materials, several efforts have demonstrated the possibility to engineer electronic and optoelectronic devices based on MoS2. In this thesis, we focus on theoretical and experimental study of electrical property and photoluminescence tuning, both in a single-layer of MoS2.We present theoretical analysis of experimental results from the point of view of stability of MoO3 defects in MoS2 single layer and bandstructures calculation. In experiment, the electrical property of a single layer of MoS2 can be tuned from semiconducting to insulating regime via controlled exposure to oxygen plasma. The quenching of photoluminescence of a single sheet of MoS2 has also been observed upon exposure to oxygen plasmas. We calculate the direct to indirect band gap transitions by going from MoS2 single sheet to MoO3 single sheet during the plasma exposure, which is due to the formation of MoO3 rich defect domains inside a MoS2 sheet.

The characteristic polarization response of a ferroelectric material to an applied electric field enables a binary state device in the form of a thin film ferroelectric capacitor that can be used to store digital information. In a high density memory the capacitor is placed on the top of a poly-silicon plug which is connected to the drain of a transistor. Such a configuration poses constraints on the processing conditions of the ferroelectric capacitor in addition to the already existing reliability issues of a ferroelectric capacitor. The current research is an attempt to integrate the ferroelectric capacitor directly into a high density memory structure. Pb_1.1Zr_0.53Ti_0.47O₃ (PZT) and SrBi₂Ta₂O₉ (SBT) are two most promising materials for ferroelectric memory applications. PZT has excellent ferroelectric properties with wide operating temperature range. However, PZT exhibits a considerable loss of switchable polarization with cumulative switching cycles. This phenomenon is known as fatigue and is one of the critical problems affecting the life time of ferroelectric memories. In this research, Ir based electrodes are shown to improve fatigue characteristics of PZT based capacitors not only by enhancing a homogenous growth of perovskite phase of PZT but also by lowering the entrapment of oxygen vacancies at the interface. These Ir electrodes also acted as diffusion barriers for silicon, oxygen and lead. Additionally, Ir electrodes were found to be chemically stable at the processing temperatures of PZT capacitors. These features of Ir based electrodes could help in realization of a practical PZT based high density non volatile random access memories. SBT is an another promising ferroelectric material for ferroelectric memory applications. While SBT has a fatigue free nature, it has a very high processing temperature (>800 °C). Such a high processing temperature limits the choice of electrodes that could be used to integrate the ferroelectric capacitor into the high density memory structure. In this research, an attempt is made to lower the processing temperature and suitable electrodes are chosen accordingly, to enable the integration of SBT based capacitors into high density memories. Lowering the processing temperature was obtained by growing a-b oriented SBT crystallites rather than c-axis oriented crystallites. Additionally, reliability (degradation) and yield of SBT thin film capacitors was found to be correlated to the amount of segregated bismuth oxide in the films. Elimination of secondary phase bismuth oxide was found to result in dramatic improvement in the reproducibility of SBT thin films with a processing temperature close to 750 °C. PtRh based electrodes were found to be quite suitable for integrating SBT capacitors into high density memory structures. These electrodes could withstand a processing temperature of 750 °C while preventing the interdiffusion of silicon, oxygen and bismuth. A solid solution of SBT and Bi₃TiNbO₉ (BTN) is made which reduced the processing temperature of the capacitor material from 750 °C to 650 °C while retaining the excellent fatigue and retention characteristics of SBT. / Ph. D.

The investigation into the syntheses and the intercalations of LDHs is the focus of the work described in this thesis. An introduction to Layered Double Hydroxide (LDH) materials with an emphasis on the possible host lattices and to their applications is given in <strong>Chapter 1</strong>. The application of LDHs in cement including; history of cement, cement production process, and cement hydration is detailed. The synthesis of the Ga-doped Ca₂Al(OH)₆Cl•nH₂O LDHs (Ca₂Ga_xAl_(1–x)-Cl; where 0 < x < 1) via the co-precipitation method is reported in <strong>Chapter 2</strong>. The effect of doping Ga³⁺ on a parameter of Ca₂Ga_xAl_(1–x)-Cl was determined by using Vegard’s law and the correlation between a parameter and x value was derived. The intercalation of organic anions including; sodium styrene sulfonate, sodium butene dicarboxylate, sodium fumarate and ammonium poly(styrene sulfonate), in Ca₂Ga-Cl structure is described. The intercalation of lignosulfonate, naphthalene sulfonate and polycarboxylate into Ca₂Al(OH)₆NO₃·6H₂O (Ca₂Al-NO₃) is detailed in <strong>Chapter 3</strong>. The release behaviour for the LDHs and the kinetic modelling of the release are reported. The effects of these LDHs on cement hydration studied by using the in situ X-ray diffraction and the ultrasound shear-wave reflection are discussed. In <strong>Chapter 4</strong>, the synthesis of Ca₂Al(OH)₆NO₃·nH₂O via a non-ionic surfactant reverse microemulsion is reported. The effects of the amount and the solubility [Hydrophile-Lipophile Balance (HLB)] of non-ionic surfactant on the morphology and the size distribution of the LDHs are discussed. Two new nitrite intercalated Ca₂Al-LDHs [Ca₂Al(OH)₆NO₂·nH₂O] synthesised via both the co-precipitation and the reverse micro-emulsion method are detailed in <strong>Chapter 5</strong>. The hydration of Portland cement samples with additive nitrate- and nitrite-intercalated Ca₂Al-LDH made using co-precipitation is discussed. The synthesis of dispersed, uniform nanoplatelet [Ca₂Al(OH)₆DDS]•H₂O LDHs is reported in <strong>Chapter 6</strong>. The effects of the amount of the surfactant on the morphology and size distribution of the LDHs are described. The experimental procedures and characterising techniques employed in this study are listed in <strong>Chapter 7</strong>. Additional data are provided in the <strong>Appendices</strong>.

The ability to form multiple component heterostructures of two-dimensional materials promises to provide access to hybrid materials with tunable properties different from those of the bulk materials or two-dimensional constituents. By taking advantage of the unique properties of different constituents, numerous applications are possible for which none of the individual components are viable. The synthesis of multiple component heterostructures, however, is nontrivial, relying on either the cleaving and stacking of bulk materials in a “scotch tape” type technique or finding coincidentally favorable growth conditions which allow layers to be grown epitaxially on each other in any order. In addition, alloying of miscible materials occurs when the modulation wavelength is small. These synthetic challenges have limited the ability of scientists to fully utilize the potential of multiple component heterostructures. An alternative synthetic route to multiple component heterostructures may be found through expansion of the modulated elemental reactant technique which allows access to metastable products, known as ferecrystals, which are otherwise inaccessible. This work focuses on the expansion of the modulated elemental reactants technique for the formation of ferecrystals containing multiple constituents. As a starting point, the synthesis of the first alloy ferecrystals (SnSe)1.16-1.09([NbxMo1-x]Se2) will be discussed. The structural and electrical characterization of these compounds will then be used to determine the intermixing of the first three component ferecrystal heterojunction ([SnSe]1+δ)([{MoxNb1-x}Se2]1+γ)([SnSe]1+δ)({NbyMo1-y}Se2). Then, by synthesizing ([SnSe]1+δ)m([{MoxNb1-x}Se2]1+γ)1([SnSe]1+δ)m({NbxMo1-x}Se2)1 (m = 0 - 4) compounds with increasing thicknesses of SnSe, the interdiffusion of miscible constituents in ferecrystals will be studied. In addition, by comparison of the ([SnSe]1+δ)m ([{MoxNb1-x}Se2]1+γ)1([SnSe]1+δ)m({NbxMo1-x}Se2)1 (m = 0 - 4) compounds to the ([SnSe]1+δ)m(NbSe2)1 (m = 1 - 8) compounds the electronic interactions of the MoSe2 and NbSe2 layers will be determined. Finally, the effects of different alloying strategies and the interdiffusion of miscible constituents will be further examined by the synthesis of ordered ([SnSe]1.15)1([TaxV1-x]Se2)1([SnSe]1.15)1([VyTa1-y]Se2)1 and ([SnSe]1+δ) ([TaxV1-x]Se2) compounds with the effect of isoelectric doping on the charge density wave transition in (SnSe)1.15(VSe2) also being explored. This work contains previously published and unpublished co-authored material.

No description available.

Os calcogenetos têm atraído atenção devido à variedade de propriedades físicas e químicas que exibem, apontando para sua utilização em muitas aplicações tecnológicas, incluindo a possibilidade de se obter novos materiais bidimensionais. Os calcogenetos quaternários A2MIIMIV3Q8, onde A = K, Cs; MII = Mg, Zn, Cd, Hg; MIV = Ge, Sn; Q = S, Se, Te, possuem uma grande variabilidade de band gaps e portanto eles podem ser estudados para engenharia de band gap através de mudanças na composição química. Além disso, dois tipos de estruturas cristalinas são observados nessa família, um formado por empilhamento de camadas, e outro definido por uma rede tridimensional fechada. Assim, é importante entender os fatores que afetam a estabilidade de estruturas em camadas desses compostos complexos. Nesse trabalho, os materiais A2MIIMIV3Q8 são estudados com cálculos de teoria do funcional da densidade, usando funcionais de troca e correlação semi-local e híbrido, e correções de van der Waals. Os parâmetros de rede variam com a composição conforme o esperado com base no raio atômico. A redução do número atômico de um dos componentes, principalmente Q, aumenta a energia de coesão, devido à intensificação das interações iônicas. Os resultados de energia de ligação entre camadas demonstram a importância das interações de van der Waals, e os valores são similares aos reportados na literatura para vários materiais. Seguindo a tendência de funcionais semi-locais, os band gaps são subestimados, mas cálculos com o funcional híbrido fornecem valores mais apropriados. Os resultados mostram a diversidade de band gaps e uma correlação aproximadamente linear entre band gap e volume da célula unitária. O band gap é principalmente afetado pela mudança do calcogênio, em que o aumento do número atômico diminui o band gap, devido ao aumento da energia dos estados p de Q. As análises dos coeficientes de absorção óptica e elementos de matriz de transição mostram que não existe diferença significativa entre band gap fundamental e óptico nesses materiais. O estudo de estabilidade relativa das estruturas em 9 compostos, com diferentes A e Q, mostra que os raios atômicos têm um importante papel. A estrutura sem formação de camadas é favorecida comparada com as estruturas em camadas apenas na região de raios intermediários, o que é explicado com base na diminuição das tensões na estrutura e em interações coulombianas entre íons da rede. / Chalcogenides have attracted attention due to the variety of physical and chemical properties which they display, pointing to their use in many technological applications, including the possibility to obtain new bidimensional materials. The quaternary chalcogenides A2MIIMIV3Q8, where A = K, Cs; MII = Mg, Zn, Cd, Hg; MIV = Ge, Sn; Q = S, Se, Te, have a large variability of band gaps and therefore they can be studied for band gap engineering through changes in the chemical composition. Futhermore, two types of crystal structure are observed in this family, one formed by the stacking of layers, and the other defined by a closed three dimensional framework. Thus, it is important to understand the factors that affect the stability of layered structures of these complex compounds. Here, the materials A2MIIMIV3Q8 are studied with density functional theory calculations, using semi-local and hybrid exchange-correlation functionals, and van der Waals corrections. Lattice parameters vary with composition according to expected based on the atomic radius. The reduction of the atomic number of one of the components, mainly Q, increases the cohesive energy, due to the intensification of the ionic interactions. The results of interlayer binding energies demonstrate the importance of van der Waals interactions, and the values are simillar to those reported in the literature for several materials. Following the trend of semi-local functionals, band gaps are underestimated, but hybrid functional calculations provide more accurate values. The results show the diversity of band gaps and an approximate linear correlation between band gap and unit cell volume. The band gap is mainly affected by changing the chalcogen, in which the increase of the atomic number decreases the band gap, due to the increase in the energy of Q p states. The analysis of optical absorption coefficients and transition matrix elements show that there is no significative difference between fundamental and optical band gap in these materials. The study of relative stability of the structures in 9 compounds, with different A and Q, shows that the atomic radii have an important role. The structure without layer formation is favored compared with the layered structures only in the region of intermediate radii, which is explained based on the reduction of strain in the structure and coulomb interactions between ions in the framework.

Os argilominerais são empregados na área farmacêutica e cosmética tanto como excipientes quanto ingredientes ativos. Esses compostos inorgânicos são inertes quimicamente, apresentam estruturas definidas e alta estabilidade térmica, o que contribui para o uso nessas áreas. Atualmente a indústria farmacêutica busca modificações no sistema de entrega de drogas (melhorias no tempo, local e taxa de liberação), objetivando um aumento na estabilidade das drogas e a prevenção e diminuição de efeitos colaterais. Nesse sentido, surge a necessidade de desenvolver novas formulações farmacêuticas, novos métodos de preparação e novos materiais. Considerando o fato dos argilominerais incorporarem espécies diversas entre suas lamelas, é interessante explorar a possibilidade de uso dessas matrizes inorgânicas como carregadores de espécies bioativas. O principal objetivo do presente trabalho foi preparar e caracterizar argilas de uso farmacêutico e/ou cosmético intercaladas com espécies que apresentam potencial terapêutico. Para tanto, usou-se duas argilas esmectitas naturais do tipo montmorilonita (Cloisita Sódica e Veegum HS) e uma esmectita sintética do tipo hectorita (Laponita RD). Os aminoácidos L-lisina, L-arginina e L-ornitina, e o dipeptídeo L-carnosina foram imobilizados em argilas catiônicas, por meio de reação de troca iônica. Na preparação dos materiais híbridos, alguns parâmetros experimentais foram avaliados: concentração hidrogeniônica (pH) da suspensão de reação, proporção argila/aminoácido e tempo de reação. As argilas precursoras e os materiais híbridos obtidos foram caracterizados por difratometria de raios X, espectroscopia vibracional na região do infravermelho e Raman, análise termogravimétrica acoplada à espectrometria de massas e análise química de carbono. Os valores de distância interlamelar (d(001)) dos materiais sugerem que a cadeia carbônica das espécies orgânicas se orienta paralelamente em relação às lamelas de baixa densidade de carga dos argilominerais. Nos espectros vibracionais na região do infravermelho há predominância das bandas características da estrutura inorgânica, mas as bandas entre 1800 e 1400 cm-1 relativas aos grupos funcionais do aminoácido permitem inferir sobre o seu grau de protonação no material híbrido. A acidez de Brönsted gerada pela polarização das moléculas de água associadas à argila foi observada para as montmorilonitas empregadas neste estudo. Amostras preparadas em suspensões nas quais o valor do pH era maior que o valor da primeira constante ácida (pKa1) dos aminoácidos apresentam bandas atribuídas ao estiramento C=O de grupo carboxilato protonado. Os espectros Raman foram obtidos apenas para a argila sintética, uma vez que as naturais apresentam luminescência. O espectro Raman da L-carnosina imobilizada em Laponita indica a presença preponderante da espécie zwitteriônica; o deslocamento das bandas atribuídas aos grupos amida e carboxílico do dipeptídeo para região de menor energia sugere a formação de ligações de hidrogênio com os grupos silanol da Laponita. Os resultados de análise termogravimétrica acoplada à espectrometria de massas dos materiais híbridos são distintos daqueles observados para os aminoácidos livres. A temperatura de início de decomposição das espécies orgânicas não é praticamente modificada após imobilização nas argilas, mas os processos térmicos se estendem até regiões de maior temperatura, evidenciando a influência da estrutura inorgânica sobre a decomposição térmica dos aminoácidos. Através dos dados de quantidade de carbono e de água nas amostras, calculou-se a concentração de aminoácidos nos materiais híbridos (massa de aminoácido / 100 gramas de material). As maiores concentrações de aminoácido (entre seis e oito por cento) foram observadas para as amostras de Cloisita e Veegum HS, isoladas em condições nas quais predomina a interação eletrostática entre as lamelas e os aminoácidos com carga positiva. Nas condições experimentais empregadas neste trabalho não foi observada a saturação das argilas com os aminoácidos, ou seja, as cargas das lamelas não foram totalmente neutralizadas pelos íons orgânicos. / Clay minerals are used as excipients or active ingredients in the pharmaceutical and cosmetic fields. These inorganic compounds are chemically inert, have defined structures and high thermal stability, which make them useful for these areas. Currently the pharmaceutical industry seeks modifications in the drug delivery systems (improvements in the time, place and rate of release), aiming an increase in the stability of the drugs and also the prevention and reduction of side effects. In this way, it is a need to develop new pharmaceutical formulations, new preparation methods and new materials. Considering the fact that clay minerals incorporate various species between their layers, it is interesting to explore the possibility of using these inorganic matrices as carriers of bioactive species. The main aim of this work was to prepare and characterize clays of pharmaceutical and/or cosmetic usage intercalated with species of therapeutic potential. Two natural smectite clays of montmorillonite type (Sodium Cloisite and Veegum HS) and one synthetic smectite of hectorite type (Laponita RD) were employed. The amino acids L-lysine, L-arginine and L-ornithine, and the L-carnosine dipeptide were immobilized on cationic clays by ion exchange reaction. Some experimental parameters were evaluated in the preparation of hybrid materials: hydrogen ion concentration (pH) of reaction suspension, clay/amino acid proportion and reaction time. Pristine clays and hybrid materials were characterized by X-ray diffraction, infrared and Raman vibrational spectroscopies, thermogravimetric analyses coupled to mass spectrometry and chemical analysis of carbon. The materials values of interlayer distance (d(001)) suggest that the carbon chain of the organic species is oriented parallel to the layers of clay minerals. The infrared vibrational spectra are dominated by the inorganic structure bands; however the bands between 1800 and 1400 cm-1 related to the functional groups of the amino acid allow to infer about the protonation degree in the hybrid material. The Brönsted acidity generated by the polarization of water molecules associated with the clay was observed for montmorillonite samples used in this study. Materials prepared in suspensions in which the pH value was greater than the value of the first acid constant (pKa1) show bands assigned to the C=O stretching of protonated carboxylate group. Raman spectra were obtained only for the synthetic clay, since the natural ones luminesce. Raman spectrum of L-carnosine immobilized on Laponita indicates the presence of mostly zwitterionic species; the displacement of bands assigned to amide and carboxylic groups of the dipeptide to the lower energy region suggests the formation of hydrogen bonds with the Laponita silanol groups. The results of thermogravimetric analyses coupled to mass spectrometry of hybrid materials are different from those observed for the free amino acids. The onset temperature of the organic species decomposition is practically unmodified after the immobilization on clays, but thermal processes are postponed up to higher temperature, revealing the inorganic structure influence on the amino acids thermal decomposition. Data on the carbon and water amounts in the samples were used to calculate the concentration of amino acids in the hybrid materials (mass of amino acid / 100 grams of material). The highest concentrations of amino acid (between six and eight percent) was observed for Cloisite and Veegum HS samples, isolated under conditions in which the electrostatic interaction between the layers and the positively charged amino acids are predominant. Under the experimental conditions employed in this study no saturation of clay with amino acids was observed, i.e. the layer charges were not completely neutralized by the organic ions.

Os calcogenetos têm atraído atenção devido à variedade de propriedades físicas e químicas que exibem, apontando para sua utilização em muitas aplicações tecnológicas, incluindo a possibilidade de se obter novos materiais bidimensionais. Os calcogenetos quaternários A2MIIMIV3Q8, onde A = K, Cs; MII = Mg, Zn, Cd, Hg; MIV = Ge, Sn; Q = S, Se, Te, possuem uma grande variabilidade de band gaps e portanto eles podem ser estudados para engenharia de band gap através de mudanças na composição química. Além disso, dois tipos de estruturas cristalinas são observados nessa família, um formado por empilhamento de camadas, e outro definido por uma rede tridimensional fechada. Assim, é importante entender os fatores que afetam a estabilidade de estruturas em camadas desses compostos complexos. Nesse trabalho, os materiais A2MIIMIV3Q8 são estudados com cálculos de teoria do funcional da densidade, usando funcionais de troca e correlação semi-local e híbrido, e correções de van der Waals. Os parâmetros de rede variam com a composição conforme o esperado com base no raio atômico. A redução do número atômico de um dos componentes, principalmente Q, aumenta a energia de coesão, devido à intensificação das interações iônicas. Os resultados de energia de ligação entre camadas demonstram a importância das interações de van der Waals, e os valores são similares aos reportados na literatura para vários materiais. Seguindo a tendência de funcionais semi-locais, os band gaps são subestimados, mas cálculos com o funcional híbrido fornecem valores mais apropriados. Os resultados mostram a diversidade de band gaps e uma correlação aproximadamente linear entre band gap e volume da célula unitária. O band gap é principalmente afetado pela mudança do calcogênio, em que o aumento do número atômico diminui o band gap, devido ao aumento da energia dos estados p de Q. As análises dos coeficientes de absorção óptica e elementos de matriz de transição mostram que não existe diferença significativa entre band gap fundamental e óptico nesses materiais. O estudo de estabilidade relativa das estruturas em 9 compostos, com diferentes A e Q, mostra que os raios atômicos têm um importante papel. A estrutura sem formação de camadas é favorecida comparada com as estruturas em camadas apenas na região de raios intermediários, o que é explicado com base na diminuição das tensões na estrutura e em interações coulombianas entre íons da rede. / Chalcogenides have attracted attention due to the variety of physical and chemical properties which they display, pointing to their use in many technological applications, including the possibility to obtain new bidimensional materials. The quaternary chalcogenides A2MIIMIV3Q8, where A = K, Cs; MII = Mg, Zn, Cd, Hg; MIV = Ge, Sn; Q = S, Se, Te, have a large variability of band gaps and therefore they can be studied for band gap engineering through changes in the chemical composition. Futhermore, two types of crystal structure are observed in this family, one formed by the stacking of layers, and the other defined by a closed three dimensional framework. Thus, it is important to understand the factors that affect the stability of layered structures of these complex compounds. Here, the materials A2MIIMIV3Q8 are studied with density functional theory calculations, using semi-local and hybrid exchange-correlation functionals, and van der Waals corrections. Lattice parameters vary with composition according to expected based on the atomic radius. The reduction of the atomic number of one of the components, mainly Q, increases the cohesive energy, due to the intensification of the ionic interactions. The results of interlayer binding energies demonstrate the importance of van der Waals interactions, and the values are simillar to those reported in the literature for several materials. Following the trend of semi-local functionals, band gaps are underestimated, but hybrid functional calculations provide more accurate values. The results show the diversity of band gaps and an approximate linear correlation between band gap and unit cell volume. The band gap is mainly affected by changing the chalcogen, in which the increase of the atomic number decreases the band gap, due to the increase in the energy of Q p states. The analysis of optical absorption coefficients and transition matrix elements show that there is no significative difference between fundamental and optical band gap in these materials. The study of relative stability of the structures in 9 compounds, with different A and Q, shows that the atomic radii have an important role. The structure without layer formation is favored compared with the layered structures only in the region of intermediate radii, which is explained based on the reduction of strain in the structure and coulomb interactions between ions in the framework.