La realización de esta tesis doctoral permitió confirmar la combinación exitosa de la configuración de láseres guiados y las propiedades espectroscópicas de los dobles tungstatos de potasio y tierra rara para ser usados en la fabricación de dispositivos de óptica integrada. Mediante crecimiento epitaxial en fase líquida (LPE) de capas monocristalinas de KY1-x-yGdxLuy(WO4)2 activadas con Er3+ y Tm3+ se fabricaron guías de onda planas. Usando la composición KY0.58Gd0.22Lu0.17Tm0.03(WO4)2 se demostró por primera vez un láser guiado en los regímenes continuo y pulsado (Q-switch) con emisión a 1.84 m. Combinando técnicas de fotolitografía UV, Ar-ion milling y LPE, se fabricaron guías de onda acanaladas de dos tipos: superficiales y soterradas. Mediante esta novedosa combinación, se demostró por primera vez un láser guiado de Tm3+ con emisión a 1.84 m sin la necesidad de añadir espejos a la guía acanalada soterrada. / The successful combination of the advantages of the waveguide laser geometry and the spectroscopic properties of monoclinic double tungstates was confirmed in this work by the realization of planar and channel waveguide lasers activated with Tm3+. Planar waveguides activated with Er3+ and Tm3+ were fabricated by Liquid Phase Epitaxial growth (LPE) of KY1-x-yGdxLuy(WO4)2 single crystalline layers over KY (WO4)2 substrates. CW and Q-switch laser operation at 1.84 m were, for the first time, demonstrated using the lattice matched composition KY0.58Gd0.22Lu0.17Tm0.03(WO4)2 . Surface channel waveguides were fabricated by structuring the surface of the Er3+ and Tm3+-doped planar waveguides by means of standard UV-photolithography and Ar-ion milling. Buried channel waveguides were fabricated by a novel combination of LPE of the activated layers after structuring of the surface of the KY (WO4)2 substrates by Ar-ion milling. Mirrorles waveguide laser in CW regime was demonstrated using these buried channel waveguides.

Neste trabalho, foram realizadas sínteses dos tungstatos duplos NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) e LiLa(WO4)2 (LLW) puros e simplesmente dopados com os íons Nd3+ e Yb3+; comparando-se dois métodos de obteção: o de reação no estado sólido e o sol-gel modificado (Pechini). Verificou-se que o envelhecimento do reagente La2O3 (adsorção de umidade ambiente) é um fator determinante na formação dos materiais desejados. Ambos os métodos testados são análogos para obtenção desses materiais se a proporção estequiométrica dos reagentes for a correta. Um estudo empírico foi realizado para crescimento, a partir da fusão, de fibras cristalinas, através do método de micro-pulling-down (µ-PD) (nos modos de aquecimento resistivo e indutivo), de NLW, NGW e LLW puros e simplesmente dopados com os íons Nd3+ e Yb3+. Neste estudo observou-se a evaporação do líquido durante o processo, o efeito da variação das taxas de puxamento e a interação do líquido com o material do cadinho e com a interface de cristalização. Foram obtidas fibras monocristalinas para todos os compostos. Amostras destas fibras foram caracterizadas por difratometria de raios-X (DRX) para verificação da fase formada, por microscopia ótica (MO) e eletrônica de varredura (MEV) para caracterização do diâmetro das fibras, espectrometria por dispersão em energia (EDS/EDX) para determinação da concentração dos dopantes; e também espectroscopia ótica de absorção no VIS-IR para determinação da incorporação do dopante na forma trivalente. / At the present work, the pure and Nd,Yb-doped alkali rare earth double tungstates NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) and LiLa(WO4)2 (LLW) were synthesized. Two synthesis methods were evaluated: the solid state reaction method and the modified sol-gel method (Pechini). Both of them are similar for the synthesis of these materials if stoichiometric proportion of reagents is used. It was verified that the moisture adsorption from air by the reagent La2O3 is a problem in the formation of the studied compounds. An empirical study of growth from the melt of single-crystalline fibers was achieved through the micro-pulling-down (µ-PD) method (in the heating inductive and resistive modes) of pure and Nd,Yb-doped NLW, NGW and LLW. It was observed in this study the liquid evaporation during the process, the effect of different pulling rates, the liquid interaction with the crucible material and the crystallization interface. Single-crystalline fibers were achieved for all compounds studied. Samples were characterized through X-ray powder diffraction (XRD) for phases identification, optical (OM) and scanning electronic microscopy (SEM) for fiber diameter visualization, energy dispersion scattering (EDS/EDX) for determining dopants concentration and also optical absorption spectroscopy in the VIS-IR for determining dopants incorporation in the trivalent state.

Neste trabalho, foram realizadas sínteses dos tungstatos duplos NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) e LiLa(WO4)2 (LLW) puros e simplesmente dopados com os íons Nd3+ e Yb3+; comparando-se dois métodos de obteção: o de reação no estado sólido e o sol-gel modificado (Pechini). Verificou-se que o envelhecimento do reagente La2O3 (adsorção de umidade ambiente) é um fator determinante na formação dos materiais desejados. Ambos os métodos testados são análogos para obtenção desses materiais se a proporção estequiométrica dos reagentes for a correta. Um estudo empírico foi realizado para crescimento, a partir da fusão, de fibras cristalinas, através do método de micro-pulling-down (µ-PD) (nos modos de aquecimento resistivo e indutivo), de NLW, NGW e LLW puros e simplesmente dopados com os íons Nd3+ e Yb3+. Neste estudo observou-se a evaporação do líquido durante o processo, o efeito da variação das taxas de puxamento e a interação do líquido com o material do cadinho e com a interface de cristalização. Foram obtidas fibras monocristalinas para todos os compostos. Amostras destas fibras foram caracterizadas por difratometria de raios-X (DRX) para verificação da fase formada, por microscopia ótica (MO) e eletrônica de varredura (MEV) para caracterização do diâmetro das fibras, espectrometria por dispersão em energia (EDS/EDX) para determinação da concentração dos dopantes; e também espectroscopia ótica de absorção no VIS-IR para determinação da incorporação do dopante na forma trivalente. / At the present work, the pure and Nd,Yb-doped alkali rare earth double tungstates NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) and LiLa(WO4)2 (LLW) were synthesized. Two synthesis methods were evaluated: the solid state reaction method and the modified sol-gel method (Pechini). Both of them are similar for the synthesis of these materials if stoichiometric proportion of reagents is used. It was verified that the moisture adsorption from air by the reagent La2O3 is a problem in the formation of the studied compounds. An empirical study of growth from the melt of single-crystalline fibers was achieved through the micro-pulling-down (µ-PD) method (in the heating inductive and resistive modes) of pure and Nd,Yb-doped NLW, NGW and LLW. It was observed in this study the liquid evaporation during the process, the effect of different pulling rates, the liquid interaction with the crucible material and the crystallization interface. Single-crystalline fibers were achieved for all compounds studied. Samples were characterized through X-ray powder diffraction (XRD) for phases identification, optical (OM) and scanning electronic microscopy (SEM) for fiber diameter visualization, energy dispersion scattering (EDS/EDX) for determining dopants concentration and also optical absorption spectroscopy in the VIS-IR for determining dopants incorporation in the trivalent state.

Material and structure engineering are increasingly employed in active optical media,in this context defined as media capable of providing laser or/and optical parametric gain. For laser materials, the main aim of the engineering is to tailor the absorption and emission cross sections in order to optimise the laser performance. At the same time, the engineering also results in a collateral modification of the material’s nonlinear response. In the first part of this work, the nonlinear index of refraction is characterised for two crystallographic forms of laser-ion doped and undoped double-tungstate crystals. These laser crystals have broad gain bandwidths, in particular when doped with Yb3+. As shown in this work, the crystals also have large Kerr nonlinearities, where the values vary significantly for different chemical compositions of the crystals. The combination of a broad gain bandwidthand a high Kerr nonlinearity makes the laser-ion doped double tungstates excellent candidates to employ for the generation of ultrashort laser pulses by Kerr-lens modelocking. The second part of the work relates to the applications of engineered second-order nonlinear media, which here in particular are periodically-poled KTiOPO4 crystals. Periodic structure engineering of second-order nonlinear crystals on a submicrometre scale opens up for the realisation of novel nonlinear devices. By the use of quasi-phase matching in these structures, it is possible to efficiently downconvert a pump wave into two counterpropagating parametric waves, which leads to a device called a mirrorless optical parametric oscillator. The nonlinear response in these engineered submicrometre structures is such that the parametric wave that propagates in the opposite direction of the pump automatically has a narrow bandwidth, whereas the parametric wave that propagates with the pump essentially is a frequency-shifted replica of the pump wave. The unusual spectral properties andthe tunabilities of mirrorless optical parametric oscillators are investigated. / QC 20120330

Estudou-se neste trabalho a preparação de LiLa(WO4)2:TR3+ (LLW:TR) nas formas de fibras monocristalinas (micro-pulling-down) e de microcristais pó cerâmico (método dos precursores poliméricos). No que se refere às fibras: a taxa de puxamento no crescimento de LiLa(1-x)Eux(WO4)2 para 0≤x≤1 é influenciada pela diferença de raio iônico do Li e das TR; a estrutura tetragonal da scheelita descreve as composições 0≤x≤1; a incorporação do Eu gera distorções na estrutura sem reduzir a simetria local do íon; uma queda de luminescência para x>0,20 é observada; e as estruturas para 0≤x≤1 foram modeladas através de simulação atomística com bastante precisão. No que se refere aos microcristais: o efeito do controle de pH na preparação de LLW:Nd 1,0 mol% foi avaliado; obteve-se aglomerados de morfologia irregular e com tamanhos médios entre 22-48 μm, cujo aumento é maior em função da temperatura do que do tempo de calcinação. No que se refere à construção experimental do diagrama de fases do sistema xLi2W2O7-(1-x)La2W2O9: confirmou-se que o LLW (formado numa região de homogeneidade de 0,48≤x≤0,55) se decompõe peritéticamente a 1000°C; a dopagem por TR influencia sua fusão; dados do crescimento, de DTA e de DRX de fibras de LLW, crescidas com composições baseadas neste diagrama, corroboram o mesmo. O processo de obtenção de fibras foi otimizado, com um excesso mínimo de 1,5 mol% de Li2W2O7. / In this work, the preparation and characterization of LiLa(WO4)2:RE3+ (LLW:RE) microcrystals as single crystal fibers (micro-pulling-down technique) and as powder (polymerizable complex method) was studied. Concerning the fibers: the pulling rate for LiLa(1-x)Eux(WO4)2 (0≤x≤1) is influenced by the difference between the constituents ionic radii; the tetragonal scheelite-like structure describes all compositions; the Eu incorporation distorts the LLW lattice without reducing the dopant local symmetry; a luminescence quenching for x>0.20 was observed; and the structure modelling for 0≤x≤1 by atomistic simulation was carried out with good precision. Concerning the powder microcrystals: the pH control effect on the preparation of Nd:LLW 1,0 mol% was evaluated; they presented irregular morphology and agglomerates with average sizes of 22-48 μm with higher increase for the calcination temperature than for the time. Concerning the experimental construction of the phase diagram of the system xLi2W2O7-(1-x)La2W2O9: it was confirmed that the LLW (formed in the a homogeneity region of 0.48≤x≤0.55) decomposes peritectically at 1000°C; RE-doping influences the LLW melting; growth, DTA and XRD data of LLW fibers (grown from the compositions based on this diagram) confirmed it. The process of fiber obtaining was optimized with a minimum excess of 1.5 mol% of Li2W2O7.

Estudou-se neste trabalho a preparação de LiLa(WO4)2:TR3+ (LLW:TR) nas formas de fibras monocristalinas (micro-pulling-down) e de microcristais pó cerâmico (método dos precursores poliméricos). No que se refere às fibras: a taxa de puxamento no crescimento de LiLa(1-x)Eux(WO4)2 para 0≤x≤1 é influenciada pela diferença de raio iônico do Li e das TR; a estrutura tetragonal da scheelita descreve as composições 0≤x≤1; a incorporação do Eu gera distorções na estrutura sem reduzir a simetria local do íon; uma queda de luminescência para x>0,20 é observada; e as estruturas para 0≤x≤1 foram modeladas através de simulação atomística com bastante precisão. No que se refere aos microcristais: o efeito do controle de pH na preparação de LLW:Nd 1,0 mol% foi avaliado; obteve-se aglomerados de morfologia irregular e com tamanhos médios entre 22-48 μm, cujo aumento é maior em função da temperatura do que do tempo de calcinação. No que se refere à construção experimental do diagrama de fases do sistema xLi2W2O7-(1-x)La2W2O9: confirmou-se que o LLW (formado numa região de homogeneidade de 0,48≤x≤0,55) se decompõe peritéticamente a 1000°C; a dopagem por TR influencia sua fusão; dados do crescimento, de DTA e de DRX de fibras de LLW, crescidas com composições baseadas neste diagrama, corroboram o mesmo. O processo de obtenção de fibras foi otimizado, com um excesso mínimo de 1,5 mol% de Li2W2O7. / In this work, the preparation and characterization of LiLa(WO4)2:RE3+ (LLW:RE) microcrystals as single crystal fibers (micro-pulling-down technique) and as powder (polymerizable complex method) was studied. Concerning the fibers: the pulling rate for LiLa(1-x)Eux(WO4)2 (0≤x≤1) is influenced by the difference between the constituents ionic radii; the tetragonal scheelite-like structure describes all compositions; the Eu incorporation distorts the LLW lattice without reducing the dopant local symmetry; a luminescence quenching for x>0.20 was observed; and the structure modelling for 0≤x≤1 by atomistic simulation was carried out with good precision. Concerning the powder microcrystals: the pH control effect on the preparation of Nd:LLW 1,0 mol% was evaluated; they presented irregular morphology and agglomerates with average sizes of 22-48 μm with higher increase for the calcination temperature than for the time. Concerning the experimental construction of the phase diagram of the system xLi2W2O7-(1-x)La2W2O9: it was confirmed that the LLW (formed in the a homogeneity region of 0.48≤x≤0.55) decomposes peritectically at 1000°C; RE-doping influences the LLW melting; growth, DTA and XRD data of LLW fibers (grown from the compositions based on this diagram) confirmed it. The process of fiber obtaining was optimized with a minimum excess of 1.5 mol% of Li2W2O7.

Laseres de estado sólido que operan en la región espectral de seguridad ocular alrededor de los 2 micrómetros (2µm) son de elevado interés en la actualidad debido a su potencial aplicación en los campos de la medicina, teledetección remota y como fuentes de bombeo en osciladores ópticos paramétricos (OPOs) para conversión en el infrarrojo medio. La transición láser en las 2 µm es posible en los iones de tulio (Tm) ligeramente por debajo de las 2 µm y en iones de holmio (Ho) ligeramente por encima de las 2 µm. La generación láser en iones de Tm es relativamente simple con la utilización de láseres de diodo como fuentes de bombeo, sin embargo, los láseres basados en Ho se han conseguido tradicionalmente en el pasado mediante el codopaje con Tm o mediante bombeo directo del nivel emisor del Ho. Recientemente, diodos láser que operan a 1.9 µm han aparecido en el mercado con buena eficiencia y con alto potencial para el escalado en potencia de los láseres de Ho. Los láseres de Ho son más apropiados que los láseres de Tm especialmente para aplicaciones médicas por dos razones: La longitud de onda láser ligeramente por encima de las 2 µm, donde el agua (mayor componente del cuerpo humano) presenta una ligera menor absorción que la típica longitud de onda láser del Tm, hace que el láser penetre más en el tejido humano. La segunda razón es que los láseres de Ho pueden operar en régimen pulsado generando mayores energías por pulso que los láseres de Tm debido al mayor tiempo de vida del nivel emisor 5I7 y las aplicaciones médicas requieren por lo general régimen pulsado para evitar daño térmico del tejido. Numerosos óxidos y fluoruros cristalinos han demostrado ser adecuadas matrices para Ho, sin embargo, poca atención se ha puesto en los dobles tungstatos cristalinos de fase monoclínica, de fórmula química KRE(WO4)2, brevemente KREW, donde RE = Y, Gd y Lu conocidos por ser matrices láser muy eficientes para la generación láser a potencias intermedias. Estos cristales anisotrópicos presentan una elevada sección eficaz de absorción y emisión cuando son dopados con iones lantánidos y especialmente para ciertas polarizaciones. Considerando el potencial del Ho y las buenas propiedades de KREW, nuestro trabajo se centra en la investigación de las prestaciones láser en cristales de KREW dopados con Ho utilitzando tanto Tm o Yb como iones sensibilizadores y utilizando fuentes de bombeo emitiendo a 1.9 µm que permiten la excitación directa del nivel emisor. En esta tesis, presentamos los resultados basados en el crecimiento cristalino de monocristales de Ho:KREW, codopajes (Ho,Tm) y (Ho,Yb):KLuW a diferentes concentraciones de Ho, su caracterización en términos de estructura, composición y espectroscopia y finalmente la generación láser alrededor de 2.1 µm. / Eye-safe solid-state lasers that operate in the 2µm spectral range are the subject of interest in the present years because of their potential applications in the field of remote sensing, medicine and as a pump source for Optical Parametric Oscillators (OPOs). Laser transitions around 2 µm are possible in the trivalent lanthanide ions Tm3+ (Tm) (slightly below 2 µm) and Ho3+ (Ho) (slightly above 2 µm). Laser generation in Tm ions is easily achieved with comfortable diode pump sources, however, Ho lasers have usually been achieved in the past either by co-doping the active medium with Tm or by direct pumping of the Ho ions with Tm lasers. Recently, relatively cheap diodes emitting around 1.9 µm are in the market to realize Ho lasers with great potential for power scaling. Ho lasers are more suitable than Tm lasers especially for medical applications because of two reasons: The laser wavelength is slightly above 2µm, where water (main component of human tissue) shows slightly less absorption than the typical wavelength of Tm leading to a deeper penetration in human tissue. The second reason is that Ho lasers can operate in pulsed regime delivering higher energies than Tm lasers due to the longer lifetime of the emitting level 5I7 and medical applications are required to be generally in pulsed regime to avoid thermal damage of human tissue. Many oxide and fluoride crystals were shown to be suitable host for Ho, however little attention was paid to the monoclinic potassium rare earth double tungstate crystal, shortly KRE(WO4)2 or KREW, where RE= Y, Gd, Lu known to be very efficient rare earth solid state hosts for generating intermediate power levels. These anisotropic crystals exhibit very high absorption and emission cross sections when doped with lanthanide ions and especially for selected polarizations. Considering the potentialities of Ho and good properties of KREW, our work focuses in the investigation of the laser performances of a Ho doped KREW either by using Tm or Yb as sensitizers and by using in-band pump sources emitting around 1.9 µm, where the development of compact solid state infrared laser emitting at 2.1 µm for intermediate power levels is followed. Here, in this thesis, we present the results based on growth of single doped Ho:KREW, co-doped (Ho,Tm) and (Ho,Yb):KLuW crystals of several doping concentrations, their characterisation in terms of structure, composition and spectroscopy and finally dedicated for the laser generation around 2.1 µm from these materials, which was highly successful.