919 resultados para Spectrométrie UV-visible


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Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

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Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.

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Optical absorption and emission spectral studies of various phthalocyanine molecules, viz., LaPc, NdPc, SmPc, EuPc, CuPc and ZnPc in a polymer matrix of cyano acrylate are reported for the first time. All the absorption spectra show an intense B band (Soret) in the UV region followed by a weaker Q band in the visible region. The positions of the Q and B bands are found to have dependence on the metallic substitution. Values of the important spectral parameters, viz., molar extinction coefficient (ϵ), oscillator strength (f), radiative transition rate and decay time of the excited singlet state are also presented and compared with other solid matrices. The recorded fluorescence spectrum shows two broad emission bands in the case of NdPc, whereas for ZnPc only a very weak band is observed. The absence of emission bands for the other metallated phthalocyanines is attributed to increased spin orbit interaction and intersystem crossing.

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Optical absorption studies of phthalocyanines (Pc-s) in borate glass matrix have been reported for the first time. Measurements have been done corresponding to photon energies between 1.1 and 6.2 eV for free base, manganese, iron, nickel, molybdenum, cobalt and copper phthalocyanines. Several new discrete transitions are observed in the UV–vis region of the spectra in addition to a strong continuum component of absorption in the IR region. Values of some of the important optical constants viz. absorption coefficient (α), molar extinction coefficient (ε), absorption cross-section (σa), band width (Δλ), electric dipole strength (q2) and oscillator strength (f) for the relevant electronic transitions are also presented. All the data reported for Pc-s in the new matrix have been compared with those corresponding to solution, vapor and thin film media.

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In this article, we present the spectral and nonlinear optical properties of ZnOCu nanocomposites prepared by colloidal chemical synthesis. The emission consisted of two peaks. The 385-nm ultraviolet (UV) peak is attributed to ZnO and the 550-nm visible peak is attributed to Cu nanocolloids. Obvious enhancement of UV and visible emission of the samples is observed and the strongest UV emission of a typical ZnOCu nanocomposite is over three times stronger than that of pure ZnO. Cu acts as a sensitizer and the enhancement of UV emission are caused by excitons formed at the interface between Cu and ZnO. As the volume fraction of Cu increases beyond a particular value, the intensity of the UV peak decreases while the intensity of the visible peak increases, and the strongest visible emission of a typical ZnOCu nanocomposite is over ten times stronger than that of pure Cu. The emission mechanism is discussed. Nonlinear optical response of these samples is studied using nanosecond laser pulses from a tunable laser in the wavelength range of 450650 nm, which includes the surface plasmon absorption (SPA) band. The nonlinear response is wavelength dependent and switching from reverse saturable absorption (RSA) to saturable absorption (SA) has been observed for Cu nanocolloids as the excitation wavelength changes from the low absorption window region to higher absorption regime near the SPA band. However, ZnO colloids and ZnOCu nanocomposites exhibit induced absorption at this wavelength. Such a changeover in the sign of the nonlinearity of ZnOCu nanocomposites, with respect to Cu nanocolloids, is related to the interplay of plasmon band bleach and optical limiting mechanisms. The SA again changes back to RSA when we move over to the infrared region. The ZnOCu nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The nonlinear refractive index and the nonlinear absorption increases with increasing Cu volume fraction at 532 nm. The observed nonlinear absorption is explained through two-photon absorption followed by weak free-carrier absorption and interband absorption mechanisms. This study is important in identifying the spectral range and composition over which the nonlinear material acts as a RSA-based optical limiter. ZnOCu is a potential nanocomposite material for the light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

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Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

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In this article we present size dependent spectroscopic observations of nanocolloids of ZnO. ZnO is reported to show two emission bands, an ultraviolet (UV) emission band and another in the green region. Apart from the known band gap 380 nm and impurity 530 nm emissions, we have found some peculiar features in the fluorescence spectra that are consistent with the nanoparticle size distribution. Results show that additional emissions at 420 and 490 nm are developed with particle size. The origin of the visible band emission is discussed. The mechanism of the luminescence suggests that UV luminescence of ZnO colloid is related to the transition from conduction band edge to valence band, and visible luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies and by the transition from conduction band to deep acceptor level due to impurities and defect states. A correlation analysis between the particle size and spectroscopic observations is also discussed.

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Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

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The effect of lasers of three wavelengths in the visible region - 476, 488 and 514 nm on mitotic and meiotic cell divisions, growth, yield and activity of specific enzymes were studied in two taxonomically diverse plant species — A/lium cepa L. and Vicia faba. The effect of laser exposures was compared with the effect of two physical mutagens (Gamma and Ultraviolet radiations) and two chemical mutagens (Ethyl Methane Sulphonate and Hydroxyl amine). The study indicated that lasers could be mutagenic causing aberration in the mitotic and meiotic cell divisions while also producing changes in the growth and yield of the plants. Lasers of higher wavelengths 488 and 514 nm caused aberrations in the early stages of mitotic cell division whereas lasers of lower wavelengths (476 nm) caused more aberrations in the later stages of mitotic cell division. Laser exposure of 488 nm wavelength at power density 400 mW induced higher mitotic and meiotic aberrations and also induced higher pollen sterility than lasers of 476 and 514 nm. The frequency of mitotic aberrations induced by lasers was lesser than that caused by y-irradiation but comparable to that induced by EMS and HA. Lasers cause mutations in higher frequencies than UV. Lasers had a stimulatory effect on growth and yield in both plant species. This stimulatory effect of lasers on germination could not however be correlated to the activity of amylase and protease, the key enzymes in seed gennination. Enzymes such as peroxidase and catalase, involved in scavenging of free oxygen radicals often produced by irradiation, did not show increased activity in laser irradiated samples. Further studies are required for elucidating the exact mechanisms by which lasers cause mutations

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Relatively oxygen-free mesoporous cubic ZnS particles were synthesised via a facile solvo-hydrothermal route using a water–acetonitrile combination. Boosted UV emission at 349 nm is observed from the ZnS prepared by the solvo-hydrothermal route. The increased intensity of this UV emission is attributed to activation of whispering gallery modes of almost elliptical microstructures made of porous nanostructures.

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A comparison between the charge transport properties in low molecular amorphous thin films of spiro-linked compound and their corresponding parent compound has been demonstrated. The field-effect transistor method is used for extracting physical parameters such as field-effect mobility of charge carriers, ON/OFF ratios, and stability. In addition, phototransistors have been fabricated and demonstrated for the first time by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. The active materials used in this study can be divided into three classes, namely Spiro-linked compounds (symmetrically spiro-linked compounds), the corresponding parent-compounds, and photosensitive spiro-linked compounds (asymmetrically spiro-linked com-pounds). Some of symmetrically spiro-linked compounds used in this study were 2,2',7,7'-Tetrakis-(di-phenylamino)-9,9'-spirobifluorene (Spiro-TAD),2,2',7,7'-Tetrakis-(N,N'-di-p-methylphenylamino)-9,9'-spirobifluorene (Spiro-TTB), 2,2',7,7'-Tetra-(m-tolyl-phenylamino)-9,9'-spirobifluorene (Spiro-TPD), and 2,2Ž,7,7Ž-Tetra-(N-phenyl-1-naphtylamine)-9,9Ž-spirobifluorene (Spiro alpha-NPB). Related parent compounds of the symmetrically spiro-linked compound used in this study were N,N,N',N'-Tetraphenylbenzidine (TAD), N,N,N',N'-Tetrakis(4-methylphenyl)benzidine (TTB), N,N'-Bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), and N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (alpha-NPB). The photosensitive asymmetrically spiro-linked compounds used in this study were 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(biphenyl-4-yl)-9,9'-spirobifluorene (Spiro-DPSP), and 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(spirobifluorene-2-yl)-9,9'-spirobifluorene (Spiro-DPSP^2). It was found that the field-effect mobilities of charge carriers in thin films of symmetrically spiro-linked compounds and their corresponding parent compounds are in the same order of magnitude (~10^-5 cm^2/Vs). However, the thin films of the parent compounds were easily crystallized after the samples have been exposed in ambient atmosphere and at room temperature for three days. In contrast, the thin films and the transistor characteristics of symmetrically spiro-linked compound did not change significantly after the samples have been stored in ambient atmosphere and at room temperature for several months. Furthermore, temperature dependence of the mobility was analyzed in two models, namely the Arrhenius model and the Gaussian Disorder model. The Arrhenius model tends to give a high value of the prefactor mobility. However, it is difficult to distinguish whether the temperature behaviors of the material under consideration follows the Arrhenius model or the Gaussian Disorder model due to the narrow accessible range of the temperatures. For the first time, phototransistors have been fabricated and demonstrated by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. Intramolecular charge transfer between a bis(diphenylamino)biphenyl unit and a sexiphenyl unit leads to an increase in charge carrier density, providing the amplification effect. The operational responsivity of better than 1 A/W can be obtained for ultraviolet light at 370 nm, making the device interesting for sensor applications. This result offers a new potential application of organic thin film phototransistors as low-light level and low-cost visible blind ultraviolet photodetectors.

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Das Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung von donor-funktionalisierten Spiro-Perylencarboximiden, welche für den Einsatz in optoelektronischen Bauelementen wie z.B. organischen Phototransistoren, Feldeffekttransistoren oder Solarzellen vorgesehen sind. Die donorfunktionalisierten Spiro-Perylencarboximide stellen kovalent gebundene Donor-Akzeptor-Verbindungen dar, die unter geeigneter Belichtung einen ladungsgetrennten Zustand bilden können. Die Verbindungen wurden aus unterschiedlichen Spiroamin- und Perylenanhydrid-Edukten synthetisiert, die im Baukastenprinzip zu den entsprechenden Zielverbindungen umgesetzt wurden. Mittels unterschiedlicher Charakterisierungsmethoden (z.B. DSC, TGA, CV, Absorptions- und Fluoreszenzmessungen) wurden die Eigenschaften der neuartigen Zielverbindungen untersucht. Im Rahmen der Arbeit wurden vier neue Spiroamin-Edukte erstmalig synthetisiert und charakterisiert. Sie wurden durch Reduktion aus den bisher noch nicht beschriebenen Nitroverbindungen bzw. mittels Pd-katalysierter Kreuzkupplung (Hartwig-Buchwald-Reaktion) aus einer halogenierten Spiroverbindung erhalten. Als Perylenanhydrid-Edukt wurde erstmals eine perfluorierte Perylenanhydrid-Imid-Verbindung hergestellt. Aus den Spiroamin- und Perylenanhydrid-Edukten wurden insgesamt neun neue, donorfunktionalisierte Spiro-Perylencarboximide synthetisiert. Zusätzlich wurden sechs neuartige Spiro-Perylencarboximide ohne Diphenylamin-Donor hergestellt, die als Vergleichsverbindungen dienten. Die donorfunktionalisierten Spiro-Perylencarboximide besitzen eine Absorption im UV- und sichtbaren Spektralbereich, wobei hohe Extinktionskoeffizienten erreicht werden. Die Verbindungen zeigen in verdünnter Lösung (sowohl in polaren als auch in unpolaren Lösungsmitteln) eine Fluoreszenzquantenausbeute unter 1 %, was auf einen effizienten Ladungstransfer zurückzuführen ist. Alle donorfunktionalisierten Spiro-Perylencarboximide zeigen in den CV-Messungen reversibles Verhalten. Mittels CV-Messungen und optischer Methode konnten die HOMO- und LUMO-Lagen der jeweiligen Molekülhälften berechnet und das Fluoreszenzverhalten der Verbindungen erklärt werden. Ebenso konnten die Auswirkungen von unterschiedlichen Substituenten auf die jeweiligen HOMO-/LUMO-Lagen näher untersucht werden. Die durchgeführten DSC- und TGA-Untersuchungen zeigen hohe morphologische und thermische Stabilität der Verbindungen, wobei Glasübergangstemperaturen > 211 °C, Schmelztemperaturen > 388 °C und Zersetzungstemperaturen > 453 °C gemessen wurden. Diese Werte sind höher als die bisher in der Literatur für ähnliche spiroverknüpfte Verbindungen berichteten. Als besonders interessant haben sich die unsymmetrischen donorfunktionalisierten Spiro-Perylencarboximide herausgestellt. Sie zeigen hohe Löslichkeit in gängigen Lösungsmitteln, sind bis zu einer Molmasse < 1227 g/mol aufdampfbar und bilden stabile, amorphe Schichten.

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Im Rahmen dieser Arbeit wurde eine Syntheseroute zu einem neuartigen heteroanalogen Spirobifluoren auf Basis von Thiophen entwickelt und optimiert. Der neue Spirokern konnte durch Anbringung von Elektronendonor- bzw. Elektronenakzeptorgruppen funktionalisiert werden. Die erhaltenen Funktionsmaterialien wurden spektroskopisch (Ultraviolet-Visible, Fluoreszenz), thermoanalytisch (Thermogravimetrische Analyse, Differential Thermo Analysis, Differential Scanning Calorimetry), elektrochemisch (Cyclovoltammetrie) sowie teilweise mittels Feldeffekttransistor charaktrisiert.Zur Totalsynthese des neuen auf Thiophen basierenden Spirokerns 4,4´-Spirobi[cyclopenta[2,1-b:3,4-b´]dithiophen] (SCPDT) wurde eine Syntheseroute entworfen, die ausgehend von Thiophen keine weiteren aufwändigen Precursormoleküle voraussetzt. Durch die Anbringung von stabilisierenden Endgruppen war es möglich neuartige Funktionsmaterialien mit niedrigem HOMO-LUMO-Gap herzustellen. Die phenyl- bzw. biphenylsubstituierten Spirocyclopentadithiophene 4P-SCPDT und 4BP-SCPDT sind im Vergleich zu den analogen, auf Spirobifluoren basierenden Verbindungen (Spiroquaterthiophen und Spirosexiphenyl) deutlich leichter oxidier- und reduzierbar. Das erniedrigte HOMO-LUMO-Gap ist auch im Absorptions- und Fluoreszenzspektrum durch die im Vergleich zu den spirobifluorenanalogen Molekülen bathochrome bzw. bathofluore Verschiebung deutlich erkennbar. Sehr gut sind die Ergebnisse der Feldeffekttransistor- und Phototransistor-Messungen an aufgedampfem 4P-SCPDT. So lässt sich eine Lochbeweglichkeit von 2*10^-4 cm2/Vs ermitteln. Dies ist die höchste Lochbeweglichkeit, die bei Spiromolekülen im amorphen Film mit einem bottom-contact FET gemessen wurde, wobei die Grenzfläche zwischen Elektrode und Halbleiter noch nicht optimiert wurde. Selbst nach zehnmonatiger Lagerung unter Atmosphärenbedingungen bei Raumtemperatur konnten nahezu die gleichen Werte gemessen werden. Dieses Ergebnis unterstreicht die morphologische Stabilität des amorphen Filmes. Unter Bestrahlung mit UV-Licht zeigt sich ein ausgeprägter photovoltaischer Effekt. Das überrascht, da 4P-SCPDT kein typisches Donor-Akzeptor-Molekül ist. Das gemessene Ansprechvermögen (Verhältnis des elektrischen Output zum optischen Input) ist höher als das von polykristallinem Kupfer-Phthalocyanin (CuPc), konjugierten Polymeren oder anderen Spiromolekülen. Um die Lochleitungs- bzw. Elektronenleitungseigenschaften zu optimieren wurden desweiteren noch Diphenylaminophenyl-, Diphenylaminothiophenyl-, Perfluorhexylthiophenyl und Tricyanovinyl-Endgruppen an den den SCPDT-Kern angebracht und die erhaltenen Funktionsmaterialien charakterisiert.

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Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.

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In this thesis, optical gain measurement setup based on variable stripe length method is designed, implemented and improved. The setup is characterized using inorganic and organic samples. The optical gain of spiro-quaterphenyl is calculated and compared with measurements from the setup. Films with various thicknesses of spiro-quaterphenyl, methoxy-spiro-quaterphenyl and phenoxy-spiro-quaterphenyl are deposited by a vacuum vapor deposition technique forming asymmetric slab waveguides. The optical properties, laser emission threshold, optical gain and loss coefficient for these films are measured. Additionally, the photodegradation during pumping process is investigated.