Rapid thermal annealing was used to produce n⁺-surface layers in tin- and selenium-implanted GaAs. Hall effect and differential Van der Pauw measurements were performed and peak electron carrier concentrations of about 9 x 10¹⁸ cm⁻³ with corresponding sheet resistivities as low as 28 Ω/□, were achieved for high-dose, room-temperature Sn and Se implants. To realise this, development of new encapsulants and improvements to existing annealing methods were made. A novel method of depositing evaporated AIN for protecting the GaAs surface has been developed. This consists of the evaporation of Al in the presence of pure ammonia gas or an aqueous NH3/N5 gas mixture. The evaporated AlN layers were characterised using RBS and RHEED techniques and found to consist mainly of Al, N and 0 (as contaminant). These layers were used to successfully encapsulate GaAs at temperatures of up to 1100°C which is well above 950°C, the characteristic maximum useful temperature achieved using the existing CVD Si₃N₄. A double-layer encapsulant, consisting of ≈ 300 Å CVD Si₃N₄ plus 600 Å evaporated AlN was also developed and found to withstand even higher temperatures (≈1150°C) and to provide more reliable and reproducible results than either AlN or Si₃N₄ when used singly.

This thesis reports a study of certain aspects of ion beam mixing in amorphous silicon. The amorphous silicon films are deposited by RF sputter deposition technique, and heavy metal markers of gold and tantalum are used to section these films. Mixing in the amorphous silicon films is brought about by energetic argon ions of various energies (100 keV to 300 keV) and an estimate of mixing is made by observing the shift and broadening in the marker profile using Rutherford backscattering spectrometry. Mixing versus depth as a function of the angle of incidence is investigated experimentally, by implanting at ten different angles (0° to 85°), films, with the marker at various depths. A comparison of the experimental results is made with the Wilson and Webb model, the average diffusion model, and a computer simulation code TRIM-Cascade. All the comparisons show evidence of radiation enhanced diffusion in the experiment. The presence of radiation enhanced diffusion is confirmed when a double marker technique is employed to determine the effect of sputtering, contraction and swelling, in an amorphous silicon film, due to mass transport under argon ion irradiation, both at room temperature and at LN2 temperature. Finally, as an application of the ion beam mixing process, silicide formation at the interface of a Ni-Si and an Fe-Si system is considered. The need to form useful silicides is evident from the recent developments in VLSI technology where transition metal silicides have been explored for interconnect metallization, gate metallization and low resistivity contacts. In the research work presented here, it is found that both the Ni-Si and Fe-Si systems show cascade type of mixing but silicide formation is more evident in the Ni-Si system.

Orientador: Carlos Frederico de Oliveira Graeff / Banca: Monica Alonso Cotta / Banca: Fenelon Martinho Lima Pontes / Resumo: A síntese DMSO foi proposta a cerca de seis anos e o resultado mais importante foi o fato da melanina obtida ser solúvel em DMSO o que permitiu a produção de filmes finos de alta qualidade. Para tal fim, a L-Dopa foi utilizada como reagente principal, em sínteses onde se variou: a concentração de perióxido de benzoíla e a concentração de água no DMSO. A síntese em água foi realizada para fins de comparação. A síntese em DMSO apresentou-se mais lenta em comparação a síntese de melanina em água através dos resultados obtidos pela técnica UV-Vis. O peróxiso de benzoíla tem influência significativa na síntese, agindo diretamente na oxidação do DMSO e na oxidação da L-Dopa. Teste de solubilidade com diferentes solventes foi realizado nas amostras de H2O-melanina, DMSO-melanina recém sintetizada e DMSO-melanina envelhecida com tempo de estocagem de quatro anos. Os solventes utilizados foram; água, DMSO, DMF, THF, acetonitrila e acetato de etila. Os resultados mostraram a insolubilidade da H2O-melanina e da DMSO-melanina envelhecida em todos os solventes e somente a solubilidade da DMSO-melanina recém sintetizada no solvente DMSO foi observada. Indicando novamente que as amostras possuem estruturas diferentes e que a DMSO-melanina sofre alterações estruturais quando exposta no ar. Nos espectros da FTIR, grupos sulfonados só foram observados na DMSO-melanina recém sintetizada, que desapareceram nas amostras envelhecidas, e que não estão presentes na H2O-melanina. Ou seja, os grupos sulfonados responsáveis pela solubilidade da DMSO-melanina com o passar do tempo sofrem degradação e saem da estrutura da DMSO-melanina, explicando assim a insolubilidade da amostra de DMSO-melanina envelhecida. O mesmo foi observado para os espectros de 13C RMN. Para entender esse processo de degradação utilizamos o NaOH2 cuja a ação é a retirada dos grupos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Synthesis in DMSO was proposed about six year and the most important result was the fact that it is soluble in DMSO which allowed the production of thin films of high quality. To this end, the L-Dopa was used as primary reagent in primary reagent in syntheses where varied: the concentration of benzoyl peroxide and water concentration in DMSO. The synthesis was carried out in water for comparison purposes. The synthesis presented in DMSO is slower than the synthesis of melanin in water for analysis of the results obtained with the technique of UV-vis. When we analyzed the effect of the concentration of benzoyl peroxide in the synthesis, we found that the concentration of 0.5 moles of benzoyl peroxide gave summary more efficient to malanin in DMSO. Benzoyl peroxide has significant influence on the synthesis, acting directly on the oxidation of DMSO and the oxidation of L-Dopa. Solubility test was carried out with different solvents in the samples of H2O-melanin, DMSO-melanin newly synthesized and old DMSO-melanin with storage time of four years. The solvents used were: water, DMSO, DMF, THF, acetonitrile and ethyl acetate. The results showed the insolubility of H2O-melanin and old DMSO-metanin in all solvents and only the solubility of newly synthesized DMSO-melanin in the solvent DMSO was observed. Indicating again that the samples have different structures and that the DMSO-melanin undergoes structural changes when exposed to air. In FTIR, sulphonated groups were only observed in DMSO-melanin newly synthesized, which disappeared in the old samples, which are not present in the H2O-melanin. That is, the sulfonated groups responsible for the solubility in DMSO-melanin suffer degradation over the time and leave the structure of DMSO-melanin, thus explaining the insolubility of old DMSO-melanin. A chemical model was proposed, using tools... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-01-19Bitstream added on 2014-06-13T20:53:34Z : No. of bitstreams: 1 moralesmorales_o_me_ilha.pdf: 672260 bytes, checksum: 722e9d33ee2b26bf51fb6c4b9a1ef435 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho, o objeto de estudo foi células Solares CdS/CdTe. Estas células usam o filme de sulfeto de cádmio (CdS) como semicondutor do tipo n e o filme de telureto de cádmio (CdTe) como semicondutor do tipo p. O recorde mundial, alcançado no laboratório, para estas células é 16,5% de eficiência. Nos Laboratórios do Departamento de Física e Química de Unesp - Ilha Solteira, este trabalho é pioneiro na fabricação de Células Solares de CdS/CdTe. Para realizar este trabalho foi necessário melhorar o sistema de deposição por spray de SnO2:F já existente, acondicionar o sistema de banho químico para deposição do filme de CdS e implementar o sistema de sublimação para depositar a camada de CdTe. Todos estes sistemas de deposição de filmes finos foram implementados no laboratório do Grupo de Desenvolvimento e Aplicação de Materiais (GDAM). A fabricação da Célula Solar CdS/CdTe consistiu na deposição sequencial sobre vidro de a) Eletrodo condutor transparente utilizando óxido de estanho dopado com Flúor (SnO2:F) pelo método de spray, com controle automático de jato; b) deposição de sulfeto de Cádmio (CdS) pelo método de banho Químico (CBD); c) deposição de Telureto de Cádmio (CdTe) pela técnica de sublimação no espaço fechado (CSS) e d) deposição do contato metálico traseiro de prata por colocação de camada liquida e posteriormente a melhora deste contato com grafite-prata. A estrutura final destas células foi: Vidro/SnO2:F/CdS/CdTe/contato. A caracterização estrutural e óptica das camadas destas células foi realizada pelas técnicas de DRX e UV-vis; os parâmetros elétricos das células foram determinados pela construção da curva I-V. A camada CdTe da célula solar foi tratada termicamente com dicloreto de cádmio (CdCl2) para comparar a sua eficiência com outra célula que não foi tratada... / The object of this work was the study solar Cells CdS/CdTe. These cells use a cadmium sulfide film as an n-type semiconductor and a cadmium telluride film as a p- type semiconductor The world record for maximum efficiency achieved in laboratory for these cells is 16.5%. In laboratories of Departament of Physics and Chemistry of Unesp-Ilha Solteira, this work is a pioneer in the manufacture of CdS/CdTe Solar Cell. To carry out this work it was necessary to improve the existing system of Spray deposition of SnO2: F, conditioning of the system for chemical bath deposition of CdS film and manufacture the sublimation system to deposit the CdTe layer. All of these systems for the deposition of thin films were developed in the laboratory. The manufacture of CdS/CdTe solar cell consisted of sequential deposition on glass of a) transparent conductive tin oxide doped with fluorine (SnO 2:F) using automatic control system of the spray; b) deposition of cadmium sulfide (CdS) for method (CBD); c) deposition of cadmium telluride for technique in closed space sublimation (CSS) and d) the rear metallic contact of silver was deposited by placing the liquid layer and subsequent improvement of contact with graphite-silver. The final structure of cell used in this work was: glass/SnO2:F/CdS/CdTe/contact. The CdTe solar cell layer was heat treated with cadmium dichloride (CdCl2) to compare its efficiency with another cell that was not treated with cadmium dichloride. Then we investigated the performance of only putting back metal contact layer of silver of silver and silver-graphite layer, the latter was giving better results, achieving an efficiency is a well more than 5%

Master of Science / Biochemistry and Molecular Biophysics Interdepartmental Program / Erika Rae Geisbrecht / The E3 ubiquitin ligase TRIM32 is a member of tripartite motif (TRIM) family of proteins involved in various processes including differentiation, cell growth, muscle regeneration and cancer. TRIM32 is conserved between vertebrates (humans, mouse) and invertebrates (Drosophila). The N-terminus of this protein is characterized by a RING domain, B-box domain, and Coiled-Coil region, while the C-terminus contains six NHL repeats. In humans, mutations that cluster in the NHL domains of TRIM32 result in the muscle disorders Limb-Girdle Muscular Dystrophy type 2H (LGMD2H) and Sarcotubular Myopathy (STM). Mutations in the B-box region cause Bardet-Biedl Syndrome (BBS), a clinically separate disorder that affects multiple parts of the body. A comprehensive genetic analysis in vertebrate models is complicated by the ubiquitous expression of TRIM32 and neurogenic defects in TRIM32-/- mutant mice that are independent of the muscle pathology associated with LGMD2H. The model organism Drosophila melanogaster possesses a TRIM32 [dTRIM32/Thin (Tn)/Abba] homolog highly expressed in muscle tissue. We previously showed that dTRIM32 is localized to Z-disk of the sarcomere and is required for myofibril stability. Muscles form correctly in Drosophila tn mutants, but exhibit a degenerative muscle phenotype once contraction ensues. Mutant or RNAi knockdown larvae are also defective in locomotion, which mimics clinical features associated with loss of TRIM32 in LGMD2H patients. It is predicted that mutations in the NHL domain either affect protein structure or are involved in protein-protein interactions. However, the molecular mechanism by which these mutations affect the interaction properties of dTRIM32 is not understood. Biochemical pulldown assays using the bait fusion protein GST-dTRIM32-NHL identified numerous dTRIM32 binding proteins in larval muscle tissue. Many key glycolytic enzymes were present in the dTRIM32 pulldowns and not in control experiments. Glycolytic genes are expressed in the developing Drosophila musculature and are required for myoblast fusion. Strikingly, many glycolytic proteins are also found at the Z-disk, consistent with dTRIM32 localization. Our biochemical and genetic studies provide evidence that there is direct interaction between dTRIM32 and glycolytic proteins (Aldolase and PGLYM). dTRIM32 also regulates glycolytic enzyme levels and protein localization at their sites of action. These data together suggest a role for dTRIM32 in coordinating glycolytic enzyme function, possibly for localized ATP production or to maintain muscle mass via glycolytic intermediates.

Made available in DSpace on 2014-06-11T19:30:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-10Bitstream added on 2014-06-13T19:00:06Z : No. of bitstreams: 1 goncalves_tm_me_bauru.pdf: 1834288 bytes, checksum: 9d41cc9f6ebce4061033368ea92fec9c (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Filmes finos de carbono amorfo hidrogenado contendo silício e dopados com flúor foram produzudos pelos métodos de Deposição de Vapor Químico Assistido e Plasma (PECVD) e Deposição e Implantação Iônica por Imersão em Plasma (PIIID). Para PECVD foi utilizada uma pressão total de gases/vapor de 100 mTorr e inicialmente, 100W de potência de excitação. A proporção dos gases foi estudada, mantendo a concentração do hexametildisiloxano (HMDSO) em 75% e variando a proporção do argônio (Ar) e do hexafluoreto de enxofre (SF6). As porcentagens de flúor utilizadas na alimentação do plasma variaram em 0,6,9 e 12,5%. Visando maior concentração atômica de flúor na estrutura dos filmes, determinou-se a proporção de gases/vapor mais apropriada (75% HMDSO, 19% Ar e 6% SF6), e posteriormente, foi realizado um novo estudo da potência de excitação. Variando a potência entre 40 e 70 W, 50 W foi considerada como sendo a melhor condição de excitação para a descarga luminosa, considerando os efeitos causados pela corrosão relacionada ao flúor e a incorporação do elemento. Um estudo sobre as mesmas proporções foi realizada pela técnica de PIIID, com uma pressão total de 50 mTorr, potência de 50 W e pulsos negativos com magnitude de 800 V. Para este método o filme produzido com 12,5% de SF6 foi escolhido como sendo a melhor opção, tendo em vista que apresentou a maior quantidade atômica de flúor em sua estrutura. Posteriormente, a intensidade dos pulsos aplicados foi variada entre 544 e 14801 V, onde verificou-se que o aumento da intensidade dos pulsos resulta na diminuição da incorporação de flúor / Hydrogenated amorphous carbon films containing silicon and doped with fluorine were produced by two methods: Plasma Enhanced Chemical Vapor Deposition (PECVD) and Deposition (PIIID). For PECVD a total pressure of 100 mTorr was used at a excitation power of 100 W. The gas/vapor proportion was studied, keeping 75% hexamethyldisiloxane and varying the argon (Ar) and sulfur hexafluoride (SF6) ratio. The following proportions of SF6) ratio. The following proportions of SF6 were examined: 0, 6, 9 and 12.5%. Aiming for the highest atomic concentration of fluorine in film structure the best condition (75% HMDSO, 19% Ar and 6% SF6) was determined and a new study of the influence of the radiofrequency power. Considering the corrosion effects gernerated by fluorine in the plasma, variation of the applied power between 40 and 70 W, allowed the selection of 50 W as the best conditions. A study employing the same proportior PIIID was performed using 50 mTorr of total pressure, an applied power of 50 W and a pulse bias of 800 V. Considering the results of the chemical characterizations, films were produced with 12.5% of SF6 in the plasma feed. Subsequently, bias voltage was varied between 544 and 1480 V, where it was observed that the increasing the pulse bias decreased the fluorine concentration in film structure

Made available in DSpace on 2014-06-11T19:30:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-29Bitstream added on 2014-06-13T19:39:42Z : No. of bitstreams: 1 silva_vdl_me_bauru.pdf: 1285191 bytes, checksum: cca22db63612f5a769cb9b3084296342 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo principal deste trabalho é elucidar quais são os mecanismos de transporte de portadores de carga presentes na interface entre SnO2 e o contato metálico, pois tal conhecimento é fundamental para a aplicação na eletrônica. Além disso, é objetivo aqui também, estudar características de transporte em SnO2 dopado com alguns íons terras-raras. As amostras de SnO2 dopadas em Eu3+ e Ce3+ utilizadas nesta pesquisa foram sintetizadas a partir do método sol-gel e os filmes finos depositados pela técnica dip-coating. Os contatos estudados foram feitos a partir dos metais In, Sn e Al, depositados via evaporação resistiva. Medidas de resistência em função da temperatura nas amostras dopadas com Eu indicaram uma variação significativa da resistividade, de até 10 vezes, quando alterado o metal do contato. Isto se deve a diferença entre a função de trabalho de cada metal, que consequentemente acarreta em variação da barreira de potencial na junção metal-semicondutor. Pela característica das curvas de corrente medida em função da tensão aplicada, observou-se que os dois mecanismos de condução elétrica dominantes na interface são a emisssão termiônica, quando em baixas temperaturas e tensões de menor intensidade, e o tunelamento através da barreira, quando em temperaturas mais altas e tensões de maior intensidade. Com base nesses resultados e na aplicação do método proposto por Rhoderick estimou-se os valores da altura da barreira de potencial na junção metal-semicondutor, em 132 meV, 162 meV e 187 meV para os metais In, Al, Sn, respectivamente. Além disso, o tratamento térmico realizado nas amostras promoveu, de modo geral, a diminuição da resistividade do dispositivo devido, provavelmente, ao estreitamento da barreira de potencial e consequente aumento da... / The main goal of this work is the verification of electrical transport mechanisms of charge carriers at the interface between SnO2 and the metallic contact, because this knowledge is fundamental for electronic applications. Besides, another goal here is to investigate transport characteristics of rare-earth doped SnO2 samples doped with Eu3+ and Ce3+ used in this research were made from the sol-gel method and the thin films were deposited via dip-coating technique. The analyzed contacts were deposited from metals In, Sn and Al, via resistive evaporation technique. Resistance as function of temperature measurements applied to Eu-doped samples indicates a significant resistivity, up to 10 times, when the contact metal is varied. This is due to the differences in the work function of each metal, leading to variation in the potential barrier at interface of the metal-semiconductor junction. The characteristics of the current-voltage curves yield two dominant electrical mechanisms at the interface: thermo-ionic emission, for low temperatures and higher applied bias, and quantum tunneling through the barrier, when the temperature is higher and so is the applied bias magnitude. Based on these results and the application of the method proposed by Rhoderick, the potential barrier height of metal-semiconductor junction values were evaluated, yielding 132 meV, 162 meV and 187 meV for the metals In, Al and Sn, respectively. Besides, generally speaking, thermal annealing promotes the resistivity decrease, probably due to the potential barrier narrowing, increasing the tunneling probability. The variation of Ce3+ concentration, from 0,1% also leads to variation in the device resistivity, but this is not related to the potential at the junction interface, instead it is related with other bulk factors, as the charge... (Complete abstract click electronic access below)

Glow discharge sputtering has been used for many years to produce thin films but its commercial applications are severely limited by low deposit ion rates. The DC planar magnetron, developed a decade ago, allows much higher deposition rates and its commercial use has expanded rapidly. Non-reactive magnetron sputtering of metallic thin films is well understood and utilized. However when a reactive gas is introduced the process becomes harder to control and can switch between two stable modes. Often films are produced simply by using one of these stable modes even though this does not lead to optimum film properties or high deposition rates. This work gives a model of reactive magnetron sputtering and verifies experimentally its predictions. A 0.5 m long magnetron was designed and built specifically to allow reactive sputtering onto A4 rigid substrates. This magnetron has a variable magnetic field distribution which allows plasma bombardment of the substrate during film growth. This was shown to activate reactions at the substrate. The target lifetime was extended in our design by broadening the erosion zone and increasing the target thickness. The reactive sputtering process was shown to be inherently unstable and a control system was designed to maintain the magnetron in an unstable state. Light emission by the plasma at metal line emission wavelengths changes across the instability and so with this control signal a feedback system was built. The accuracy of control was shown experimentally and theoretically to depend on the delay time between measurement, action and effect. In practice this delay was limited by the time constant of the gas distribution manifold. The time constant of such manifolds was measured and calculated. Using our controller high quality films were produced at high rates in normally unstable deposition systems. Conducting indium oxide was produced at 6 nm/s with a resistivity of 6 x 10-6 ohm. metres onto A4 glass sheets. Tin oxide was produced at increased rates onto 2.5 m by 3 m substrates.

The effect of the configuration of the confining magnetic field on the operating characteristics of a planar magnetron has been observed. In particular, the heat load and charged particle bombardment of the substrate were measured. A circular planar magnetron was constructed with a magnetic field which could be controlled by the adjustment of the current flowing through coils placed around the circumference and with a separate supply feeding a coil around the centre pole. This allowed the magnetic field configuration to be unbalanced and caused the negative glow plasma to be incident on the substrate. It was found that the "unbalanced" electrically-controlled model could give six times the heat load to a substrate in comparison with a balanced permanent magnet structure. Such a load resulted from the bombardment of the substrate with the plasma (revealed by the measurement of the I-V characteristics), and gave a 30 volt negative bias as well as saturated electron and ion currents of around 90 and 1 mA respectively (a magnetron operating current: 0.8A). The heat load was lkWm⁻². This compared to a 1 volt positive bias with current of 1.4 and 0.5 mA for the balanced case. This bombardment was used as a neutralised ion beam to enhance film growth during sputtering. The effect of the magnetic field configuration has been observed on the operating characteristics of a planar magnetron. In particular, the deposition rate, the currents to a probe and heat load, as a function of the outer pole solenoid current, were measured. The deposition rate/input power was constant at 19 mÅ/s/W, independent of the outer pole solenoid current. In the region from 20 to 40 A of the outer pole solenoid current, the configuration of the magnetic field seemed to be concentric and the electrons were confined by it. But from 40 to 80 A, the magnetic field became dispersed outwards along the direction to the magnetron and the electrons followed it. Consequently, following bombardment of the surface by electrons and neutralising ions, the currents to a probe and the heat load, gave a behaviour. The effect of the pressure has been observed on probe current, floating potential and heat load. With the pressure increasing, they decreased. It seems that the mean free path of particles becomes shorter and then scattering of them increases. The influence of the magnetic field strength on the plasma, created at the rear of a substrate, has been observed. In particular, the floating potential and the charged particle bombardment of the substrate were measured. Permanent magnets at the rear of the substrate, outside of the chamber, could make the configuration of the magnetic field change and control the floating potential from -3 to -59 V. At the same time, they influenced the current-voltage characteristics of a probe and made it change following the direction of the field. Ti0₂ is a very important thin film material in optics because the refractive index is high and it can also satisfy the requirements of a hard, dense and chemically stable coating. In our study, the effect of the floating potential, and the resulting ion beam bombardment on the properties of Ti0₂ thin films deposited by reactive planar magnetron sputtering, has been observed. In reactive magnetron sputtering of Ti0₂, as the partial pressure of oxygen is increased, reaction products form on the target (it is poisoned) which lead to an unstable situation with the cathode switching from metal to oxide uncontrollably. More sophisticated control techniques are required in order to get a stoichiometric Ti0₂, film. The oxygen flow was controlled by observation of the light emission of the Ti spectral line. This was measured using a band pass filter and a photomultiplier. It maintained the oxygen flow by regulating a piezovalve. The optical emission controller gave a complete range of Ti to oxygen ratios. As a result, we obtained samples with a high refractive index of 2.52 at 633 nm and a high deposition rate of 4 Å/s. The properties measured were the refractive index, the surface composition and morphology, and the crystallinity. The relationship between the refractive index and the proportions of 'anatase' and 'rutile' crystal structures of the Ti0₂ films was especially considered and the dependence on the floating potential was assessed. Also, Al₂0₃, Cuo, ZnO have been sputtered and the effect of pressure instability assessed. Their properties were measured.

Pregnanediol (5B Pregnane- 3⋉- 20⋉- dial) is the chief urinary metabolite of progesterone, and as such is important in that variations in its concentration reflect variations in progesterone secretion. Estimations of pregnanediol concentration are therefore of considerable interest to the obstetrician and gynaecologist. Pregnanediol was first identified in the urine of pregnant women in 1929 by Marrian. Nearly ten years later Venning developed a method by which the glucuronic acid ester of pregnanediol could be extracted from the urine and its concentration gravimetrically determined. Numerous variations of the Venning theme were published in the next few years, each being claimed by its authors to be an improvement on the original. Most of these involved the estimation of the conjugated form, and it was a while before the advantage of estimating the hydrolysed aglycone was realized. Hydrolysis, when it was practised, resolved itself into two methods - namely, hydrolysis by heating the urine with a mineral acid, and enzymic hydrolysis by incubation with beta-glucuronidase. Acid hydrolysis, while producing a less clean hydrolysate, is more rapid and convenient than enzyme hydrolysis, and is used in the Klapper method which is presently the most widely used method in clinical studies. Klapper employs a double chromategraphic column separation of pregnanediol followed by colorimetric evaluation. Variations of Klapper's method have also appeared and not a few investigators have published comparisons of the various methods. Klapper himself compared his method to certain other methods and concluded that his was definitely superior. Of the accuracy of the Klapper method there is no doubt. Subsequent methods have proved more sensitive, but in terms of practicability Klapper's is the method of choice. As was pointed out with some complacency, "practicability is most satisfactory, one technician readily performing some twenty determinations in one week." In contrast to the flood of criticisms, comparisons, variations, claims and counter-claims which accompanied the publication of the abovementioned methods, the thin layer chromatographic method perfected by Waldi attracted very little attention. It is very much more rapid than all other existing techniques, is very sensitive, specific and of acceptable accuracy. In an attempt to ensure its usefulness for clinical and medical research laboratories, the Waldi method has been marketed in 'kit' form. It is intended primarily as a diagnostic aid in establishing pregnancy, and as such it might have enjoyed considerable application had it not been for the advent of the immunological method of pregnancy diagnosis which is very much more rapid. Nevertheless, the Waldi method, used purely as a means of assessing the pregnanediol content of the urine is extremely useful, and it is the purpose of this investigation to establish this usefulness, especially with respect to routine clinical investigations. The validity of some diagnoses which are based on pregnanediol assay results, is also investigated. As it is impossible to explain the significance or usefulness of a pregnanediol assay without first explaining the functions of progesterone, some time and space must be expended in a brief description, firstly, of the role played by progesterone in the phenomenon of the menstrual cycle, and secondly, of its vital importance in pregnancy. It must be realized that progesterone is only one of the many hormones involved in these events, but, in order to limit the introduction of extraneous detail, no mention is made of the other hormonal participants except when necessary for the understanding of the whole. It may be mentioned here that much of the evidence that was used for the elucidation of the functions and origins of progesterone, was derived from studies of its metabolite, pregnanediol.