999 resultados para structural holes
The effects of strength of ties, structural holes, and the non-redundance of ties on team innovation
Resumo:
Tutkimuksessa arvioidaan millaisia kyvykkyyksiä toimijoiltavaaditaan, jotta voidaan edistää verkostoja palvelevan innovaatiopolitiikan toteutumista ja toteuttaa käytäntölähtöistä innovaatiotoimintaa. Empiirinen osa tarkastelee Päijät-Hämeen toimijoiden asenneympäristöä ja toimimisen valmiuksia käytäntölähtöisen innovaatiotoiminnan tarpeisiin sopivaksi. Osaaminen kerääntyy yliopistopaikkakunnille ulkoisten suurtuotannon etujen mukaisesti. Ne alueet, joilla ei ole yliopistoa joutuvat luomaan muunlaista innovaatiokyvykkyyttä saavuttaakseen kilpailuetua. Siksi Päijät-Hämeen visiona on tulla johtavaksi käytäntölähtöisen innovaatiotoiminnan alueeksi hyvien toimintamallien ja tehokkaiden tiedonsiirtomekanismien avulla. Tämä vaatii alueen toimijoilta mm. korkeaa absorptiivista kapasiteettia ja heikkoja linkkejä alueen ulkopuolelle. Työn empiirinen osa koostuu 12:sta puolistrukturoidusta haastattelusta sekä kyselytutkimuksesta. Tiedonluonti ja -siirto alueelle nähtiin pääasiassa tutkimusmaailman tehtävänä, mutta varianssianalyysin perusteella tutkimusmaailma ei itse nähnyt olevansa siinä asemassa. Yhteisen kielen puuttuminen tutkimus- ja käytännön työelämän väliltä nähtiin puutteena.
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Appearance of trust in regional, co-operative networks In our times, the value of social networks has been widely acknowledged. One can say that it is important for private persons to get networked, whilst it is even a must for companies and organizations in business life. This doctor's thesis examines three co-operative regional networks. Networks are located in Western Uusimaa (Länsi-Uusimaa) region in southernmost Finland, and they had both public organizations and private companies as participants (later called ‘players’). Initially, all of them were co-financed from public funds, and two of them are still operational while writing this. The main target of these networks has been to act as learning networks. The learning network stands for an ensemble of research and development units and workplaces constituting a common forum for learning. The main focus in this study has been on qualitative and structural characteristics of the networks, and how they are relating with intrinsic trust. In addition to the development of trust, it has been studied, at what level organizational learning within the networks takes place, and lastly, what kind of factors facilitate the development of social capital. The theoretical framework for the study is built on analysing trust and social capital. It is a 'mission impossible' to find single definitions for such major concepts. In this study, from the research questions' point of view it has been more relevant to concentrate on the aspects of networking and the relationships between the participating organizations. The total view in this study is very network-centric, and therefore those theories which have similar point of view have been prioritized. Such is the theory about structural holes by Ronald S. Burt (1992). It has been widely applied; especially his views on constraints affecting players in networks. The purpose of this study has not been to create new theories or to analyse and compare thoroughly the existing theoretical trends. Instead, the existing theories have provided the study with conceptual tools, which have been utilized for supporting the empirical results. The aim has been to create an explanatory case study consisting relevant discussion on the relationship between the network characteristics and the appearance of trust. The conceptual categorization for confidence vs. trust created by Niklas Luhmann (1979) is another important theoretical building block. In most cases, co-operation in networks is initiated by people already trusting in each other and willing to work together. However, personal trust is not sufficient in the long run to sustain the co-operation within the network: more abstract systemic trust described by Luhmann must also emerge. In the networks with different structures and at different development phases, these forms of trust appear at different levels. In this study, Luhmann’s systemic trust as a term has been replaced by the concept of 'trust in network as a system'. Structural characteristics of a network (density, centrality, structural holes etc.) have been selected to explain the creation of social capital and trust. The ability to adapt new information is essential for the development of social capital. Qualitative analysis for development phase has been used, and the Learning Network Maturity Test by Leenamaija Otala (2000) and her work have been applied. Thus, the qualitative characteristics and the structural characteristics of the networks are utilized together, when the creation of social capital and appearance of trust are assessed. Social Network Analysis, questionnaires and interviews have been the research methods. Quantitative and qualitative data have been combined. There is a similarity in viewpoints to research data with Extensive Case Study method, in which different cases are searched by exploring various cases and comparing certain common features between them and generic models. Development of trust, social capital and organizational learning has been explained in the study by comparing the networks in hand. Being a case study, it doesn't have targets to provide with general results and findings like conventional surveys. However, in this work phenomena and mechanisms related to them are interpreted from the empirical data. Key finding of this study is that the networks with high structural equality and clear target setting enable building trust to the network as a system. When systemic trust is present, e.g. changes in personnel involved in the co-operation won't hinder the network from remaining operational. On the other hand, if the players are not well motivated to co-operate, if the network is extremely centralized structurally, or if the network has players holding very much more beneficial position compared to the others, systemic trust won't develop: trust tends to remain at the personal level, and is directed to some players only. Such networks won't generate results and benefits to its players, and most probably they won’t live very long. In other words, learning networks cannot solely be based on willingness to learn, but also on willingness to co-operate.
Resumo:
Julkisen sektorin itsensä synnyttämien innovaatioiden ja innovoinnin näkökulma on verrattain tuore innovaatiotutkimuksen tutkimuskohde. Vielä uudempaa lähestymistapaa edustaa käyttäjälähtöinen ja käyttäjää osallistava palveluinnovaatiotutkimus julkisella sektorilla. Käyttäjälähtöisen ja käyttäjää osallistavan palveluinnovoinnin lähestymistavan toteuttamisesta ollaan kiinnostuneita, mutta tieteelliseen tutkimukseen perustuva tieto lähestymistavasta on vielä kohtuullisen niukkaa. Tämän käyttäjälähtöiseen palvelujen innovointiin keskittyvän väitöskirjatutkimuksen päätavoitteena on mikrotasolla tunnistaa ja ryhmitellä käyttäjää osallistavan palveluinnovoinnin lähestymistavan toteuttamisen haasteita julkisella sektorilla. Väitöskirjatutkimuksen alatavoitteena on tutkimuksesta saatavan tiedon avulla muodostaa kysymyslista tukemaan lähestymistavan käyttöönottamista ja toteuttamista julkisen sektorin palveluorganisaatioissa ja -verkostoissa. Julkisen palvelusektorin ohella väitöskirjan tutkimustuloksia voivat soveltuvin osin hyödyntää myös yksityisen ja kolmannen sektorin palveluorganisaatiot ja -verkostot sekä käyttäjälähtöisen innovaatiopolitiikan suunnitteluun ja sen jalkauttamiseen osallistuvat tahot. Haasteita lähestytään tutkimuksessa käyttäjälähtöisen ja käyttäjää osallistavan palveluinnovoinnin lähestymistavan piirteiden kautta ja haasteita tarkastellaan kehittäjäviranomaisten (ryhmätaso) näkökulmasta. Kuntasektori on valittu tutkimukseen edustamaan julkista sektoria. Lähestymistavan piirteiksi tutkimuksessa määritellään käyttäjänäkökulman ohjaava rooli organisaation innovaatiotoiminnan strategisella tasolla ja palvelujen uudistamisprosessien tasoilla, avoimuus (erityisesti käyttäjärajapinta) ja tulkinnallisuus innovaatioprosessien varhaisessa vaiheessa sekä laaja-alainen käsitys innovaatioiden lähteistä käyttäjänäkökulmaa muodostettaessa. Tutkimuksen kohteena on hyvinvointipalveluinnovaatioprosessien varhainen vaihe, jolloin keskeisessä asemassa on uusien ideoiden sekä uuden tiedon ja ymmärryksen hankinta hyödynnettäväksi innovaatioprosessien seuraavissa vaiheissa. Tutkimuksessa rajaudutaan käyttäjälähtöisen palveluinnovoinnin muotoon, jossa käyttäjät intentionaalisesti ja konkreettisesti osallistetaan kehittäjäviranomaisjohtoisiin palveluinnovaatioprosesseihin. Käyttäjiksi tutkimuksessa ymmärretään palvelun loppukäyttäjät palvelujen ”ulkoisina hyödyntäjinä” ja yli sektorialisten palveluprosessien henkilöstö palvelujen ”sisäisinä hyödyntäjinä”. Hyvinvointipalveluista tutkimuksessa ovat edustettuina sosiaali- ja terveyspalvelut sekä ikäihmisten palvelukeskusten tarjoamat palvelut. Kuntasektorin innovaatiotoiminnan kenttä ymmärretään tutkimuksessa verkostomaisena kokonaisuutena, joka ylittää kuntien hallinnolliset rajat. Artikkeliväitöskirjana toteutetun väitöskirjatutkimuksen metodologia perustuu usean tapauksen tapaustutkimukseen (multiple case-studies) ja kvalitatiiviseen tutkimusotteeseen. Työn empiirinen osuus koostuu viidestä artikkelina julkaistusta osatutkimuksesta. Osatutkimuksissa käytetään tapaustutkimuksen eri variaatioita, ja tutkimusaineistot on kerätty kolmesta eri perustutkimusympäristöstä. Osatutkimuksien tapaukset on valittu palvelun käyttäjien ”äänen jatkumon” (the voice of the customer) eri kohdista. Käyttäjän ääntä käytetään tutkimuksessa metodisena ratkaisuna ja metaforana. Lisäksi käyttäjän ääni ymmärretään tutkimuksessa paremminkin kollektiivisena ja laajemmista palvelujen kehittämisnäkökulmista kertovana tekijänä kuin yksittäisten palvelun käyttäjien tarpeista ja toiveista kertovana metaforana. Käyttäjää osallistavan palveluinnovoinnin lähestymistavan toteuttamisen haasteiksi julkisella sektorilla tutkimuksessa tunnistetaan viisi haastetta. Tiivistetysti haasteena on 1. palvelujen käyttäjien subjektiuteen perustuva käyttäjälähtöisyys palvelujen uudistamisessa 2. tunnistaa palvelun käyttäjät innovaatiotoiminnan voimavarana ja rohkaistua heidän osallistamiseensa 3. sitoutuminen yhteistoiminnallisuuteen käyttäjä- ja muita rajapintoja ylittävissä palvelujen uudistamisprosesseissa ja innovaatiohakuisuus työskentelyssä 4. oivaltaa palvelutoivelistoja ja asiakaspalautteita laajempia kehittämisnäkökulmia 5. synnyttää luottamukseen perustuva hyvä kierre palvelun käyttäjien ja kehittäjien välille. Tutkimustuloksena syntyneet haasteet paikannetaan tutkimuksessa käyttäjän äänen jatkumolle erilaisin painotuksin. Lisäksi tutkimustulosten pohjalta tehdään kolme keskeistä johtopäätöstä. Ensinnäkin palvelun kehittäjätahon sekä palvelun loppukäyttäjien ja palvelujen sisäisten hyödyntäjien väliltä on tunnistettavissa innovaatiopotentiaalia sisältäviä rakenteellisia aukkoja. Toiseksi kehittäjäviranomaistahon valmius ja halu laajentaa tiedonmuodostustaan palvelujen uudistamisessa palvelun käyttäjien kanssa yhteisöllisen tiedonmuodostuksen suuntaan on puutteellinen. Kolmanneksi palvelujen kehittäjätaho ei ole sisäistänyt riittävässä määrin käyttäjää osallistavan palveluinnovoinnin lähestymistavan metodologisia perusajatuksia. Tutkimuksessa tunnistetut viisi haastetta osoittavat, että käyttäjää osallistavan palveluinnovoinnin lähestymistavan käyttöönotto hyvinvointipalveluorganisaation tai -verkoston palvelujen innovoinnin lähestymistavaksi ei ole mekaaninen toimenpide. Lähestymistavan käyttöönottoa tukeva kysymyslista perustuu tutkimuksessa tunnistettuihin haasteisiin. Kysymyslista on laadittu siten, että kysymykset liittyvät laajasti julkisten palveluorganisaatioiden ja -verkostojen innovaatiokulttuuriin. Kaksiosaisen kysymyslistan ensimmäisen osan kysymykset käsittelevät innovointia ohjaavia mentaalisia malleja. Ensimmäisessä osassa esitetään esimerkiksi seuraava kysymys: ”Millaista käsitystäpalvelun käyttäjistä (kuntalaisista) sekä käyttäjien ja kehittäjien (viranomaisten) välisestä suhteesta ilmennämme palvelujen innovoinnissa; onko palvelujen käyttäjä (kuntalainen) kohde, jolle kehitetään palveluja, vai onko hän jopa välttämätön kehittämiskumppani?”. Kysymyslistan toisen osan kysymykset liittyvät innovaatiokäytänteisiin ja valmiuksiin. Esimerkkinä voidaan mainita seuraava kaksiosainen kysymys: ”Tukevatko innovaatiokäytänteemme käyttäjärajapinnan ylittäviä innovaatioprosesseja ja sitoudummeko avoimin mielin työskentelyyn palvelun käyttäjien, potentiaalisten käyttäjien tai ei-käyttäjien kanssa? Mitä hyötyjä koemme yhteistoiminnallisuudesta koituvan meille ja käyttäjille sekä innovaation laatuominaisuuksiin?”. Mitä tulee tutkimuksen otsikon alkuosaan ”kuulla vai kuunnella”, vastaus on, että pääpaino on sanalla ”kuulla”. Pohdintaluvussa tuodaan myös esille tarve – tai ainakin kriittisen tarkastelun tarve – käyttäjälähtöisen ja käyttäjää osallistavan palveluinnovoinnin käsitteen ja sen luonteen sekä tavoitteiden määrittelemiselle julkisen sektorin ominaispiirteistä käsin vastapainona alkuperältään yksityisen sektorin liiketoimintakontekstista lähtöisin oleville määrittelyille.
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Il confronto in corso tra gli esperti di management sanitario sui dipartimenti ospedalieri, la crescente attenzione sui modelli di organizzazione a rete e le indagini sui servizi sanitari condotte con strumenti di analisi dei network hanno rappresentato la base su cui sviluppare il disegno dello studio. La prospettiva relazionale e le tecniche di social network analysis (Sna) sono state impiegate in un indagine empirica effettuata presso tre Dipartimenti Ospedalieri dell’Azienda USL di Bologna per osservare la struttura delle relazioni che intercorrono nell’ambito dei dipartimenti, tra le unità operative e tra i clinici, al fine di assicurare il quotidiano svolgersi dei processi clinico assistenziali dei pazienti. L’indagine si è posta tre obiettivi. Il primo è quello di confrontare la rete delle relazioni “reali” che intercorrono tra unità operative e tra clinici con le relazioni “progettate” attraverso l’afferenza delle unità operative nei dipartimenti e dei singoli clinici nelle unità operative. In sostanza si tratta di confrontare, con intenti esclusivamente conoscitivi, la struttura organizzativa formale – istituzionale con quella “informale”, che emerge dalle relazioni giornaliere tra i professionisti. In secondo luogo si intende comprendere se e come i fattori di natura attributiva che caratterizzano i singoli rispondenti, (es. età, sesso, laurea, anni di permanenza in azienda, ecc.) incidano sulla natura e sull’intensità delle relazioni e delle collaborazioni intrattenute con i colleghi all’interno dell’azienda. L’analisi ha un intento “esplicativo”, in quanto si cerca di indagare come le similitudini nelle caratteristiche individuali possano o meno incidere sull’intensità degli scambi e quindi delle collaborazioni tra professionisti. Il terzo obiettivo è volto a comprendere se e come i fattori attributivi e/o relazionali siamo in grado di spiegare l’attitudine mostrata dai singoli professionisti rispetto l’adozione di un approccio alla pratica clinica ispirato all’Evidence based medicine. Lo scopo è quello di verificare se la disponibilità / orientamento ad operare in una prospettiva evidence based sia più legata ad elementi e caratteristiche personali piuttosto che all’influenza esercitata da coloro con i quali si entra in contatto per motivi lavorativi. La relativa semplicità della fase di indagine ha indotto ad arricchire i contenuti e gli obiettivi originari del lavoro allo scopo di correlare indicatori relazionali e attributivi con indicatori di “performance”, in particolare di efficienza e appropriatezza. Le relazioni sono state rilevate attraverso un questionario sociometrico inserito in uno spazio web accessibile dalla rete ospedaliera e compilato online da parte dei medici. Il questionario è stato organizzato in tre sezioni: la prima per la raccolta di informazioni anagrafiche e dati attributivi dei clinici; la seconda volta a raccogliere i dati relazionali, funzionali e di consulenza, verso le equipe di professionisti (unità operative) e verso i singoli colleghi clinici; la terza sezione è dedicata alla raccolta di informazioni sull’utilizzo delle evidenze scientifiche a supporto della propria pratica clinica (consultazione di riviste, banche dati, rapporti di HTA, etc,) e sulla effettiva possibilità di accesso a tali strumenti. L’azienda ha fornito i dati di struttura e la base dati degli indicatori di attività delle UO arruolate nello studio. La compliance complessiva per i tre dipartimenti è stata pari a circa il 92% (302 rispondenti su un campione di 329 medici.). Non si sono rilevate differenze significative sulla compliance per i tre dipartimenti considerati. L’elaborazione dei dati è stata effettuata mediante specifici software per l’analisi delle reti sociali, UCINET 6 per il calcolo degli indicatori relazionali (centralità, densità, structural holes etc.), e Pajek per l’analisi grafica dei network. L’ultima fase è stata realizzata con l’ausilio del software statistico STATA vers. 10. L’analisi dei risultati è distinta in due 2 fasi principali. In primis è stato descritto il network di relazioni professionali rilevate, sono stai calcolati i relativi indicatori di centralità relazionale e verificato il grado di sovrapposizione tra struttura formale dei dipartimenti in studio con le relazioni informali che si stabiliscono tra di essi nell’ambito clinico. Successivamente è stato analizzato l’impatto che le relazioni esercitano sulla propensione da parte dei singoli medici a utilizzare nuove evidenze scientifiche I primi risultati emersi dallo studio forniscono interessanti evidenze, con particolare riguardo al dato di un discreto grado di “sovrapposizione” tra struttura formale e informale delle unità organizzative in studio e a correlazioni significative tra fattori relazionali e attitudine dei medici verso l’utilizzo dell’approccio EBM. Altre evidenze, in specie la correlazione tra “centralità” degli attori organizzativi e alcuni indicatori di performance /appropriatezza, meritano ulteriori approfondimenti e una definitiva validazione. In conclusione lo studio dimostra che la prospettiva relazionale e la Sna consentono di porre in evidenza caratteristiche dei dipartimenti, dei suoi attori e delle loro reti di reciproche relazioni, in grado di favorire la comprensione di alcune dinamiche ricercate proprio attraverso l’organizzazione dipartimentale e quindi di specifico interesse per il management, i clinici e quanti altri impegnati nella gestione e nello sviluppo di questo modello di organizzazione dell’ospedale.
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In the last decades, the increasing significance of “projectivization” (Lundin & Steinthórsson, 2003) has stimulated considerable interest in project-based organizations as new economic actors able to introduce a new logic of organizing work and weakening boundaries in favour of networks of collaborations. In these contexts, work is often delegated to project teams. Deciding whom to put on a project team is one of the biggest challenges faced by a project manager; in particular which characteristics rely on to compose and match effective teams. We address this issue, focusing on the individual flexibility (Raudsepp, 1990), as team composition variable that affects project team performance. Thus, the research question investigated is: Is it better to compose project teams with flexible team members or not flexible project team members to achieve higher levels of project performance? The temporary nature of PBOs involves that after achieving the purpose for which team members are enrolled, they are disbanded but their relationships remain, allowing them to be involved in future projects (Starkey, Barnatt & Tempest, 2000). Pre-existing relationships together with the current relationships create a network of relationships that yields some implications for project teams as well as for team members. We address this issue, exploring the following research question: To what extent is the individual flexibility influenced by the network structure? The conceptual framework is used to articulate the research questions investigated with respect to the Television drama serials production. Their project-team organizing combined with their capacity to dissolve and recreate over time make it an interesting field to develop. We contribute to the organizational literature, providing a clear operationalization of individual flexibility construct and its role on affecting project performance. Second, we contribute to the organizational network literature addressing the effects yielded by the network structure-structural holes and network closure- on the individual flexibility.
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Policy brokers and policy entrepreneurs are assumed to have a decisive impact on policy outcomes. Their access to social and political resources is contingent on their influence on other agents. In social network analysis (SNA), entrepreneurs are often closely associated with brokers, because both are agents presumed to benefit from bridging structural holes; for example, gaining advantage through occupying a strategic position in relational space. Our aim here is twofold. First, to conceptually and operationally differentiate policy brokers from policy entrepreneurs premised on assumptions in the policy-process literature; and second, via SNA, to use the output of core algorithms in a cross-sectional analysis of political brokerage and political entrepreneurship. We attempt to simplify the use of graph algebra in answering questions relevant to policy analysis by placing each algorithm within its theoretical context. In the methodology employed, we first identify actors and graph their relations of influence within a specific policy event; then we select the most central actors; and compare their rank in a series of statistics that capture different aspects of their network advantage. We examine betweenness centrality, positive and negative Bonacich power, Burt’s effective size and constraint and honest brokerage as paradigmatic. We employ two case studies to demonstrate the advantages and limitations of each algorithm for differentiating between brokers and entrepreneurs: one on Swiss climate policy and one on EU competition and transport policy.
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Numerous structural features occur in the Leg 128 cores from the Japan Sea. They include (1) gravity-induced structures such as slump folds, (2) dewatering structures comprising several sets of veins, and (3) larger faults and veins developed in the volcanic basement of the Yamato Basin as well as in the sedimentary rocks of the Oki Ridge and Kita-Yamato Trough. Gravity-induced structures, mainly slumps and associated faults, suggest the existence of paleoslopes and the dominance of gravitational tectonics during the early and middle Miocene, at the Pliocene/Pleistocene boundary, and during the Quaternary. Several types of mud-filled veins having various shapes were observed. These are especially abundant in the middle Miocene siliceous claystones and porcellanites from the Kita-Yamato Trough. They have been interpreted as dewatering conduits that formed preferentially in highly porous, water-saturated diatomaceous muds on a slope, because of episodic loss of sediment strength, collapse of the sediment framework, and consequent fluid migration. The central part of the vein serves once as a fluid conduit, whereas the transition between conduit-controlled and intergranular flow occurs at the branching extremities, with concentration of fines. The likely trigger responsible for the strength loss is seismic activity. Development of these veins, spatially and chronologically linked to small normal microfaults, implies an extensional regime having layer-parallel extension and a local bedding-parallel shear couple, probably the result of gravitational gliding. The brittle fractures found in Yamato Basin basement Hole 794D cores comprise joints, faults, and veins filled with chlorite-saponite, saponite, and calcite. They suggest a likely transpressive to transtensional regime around the early Miocene/ middle Miocene boundary, with a north-northeast-south-southwest compression alternating with a west-northwest-eastsoutheast extension. The faults from Site 799 cores on the Yamato Rise exhibit a prominent early Miocene-middle Miocene extensional environment, a late Miocene-early Pliocene phase of normal and strike-slip faulting, and a final phase that began during the latest Pliocene. Site 798, on the Oki Ridge, reveals faults that recorded a consistent extensional tectonic regime from Pliocene to the Holocene. These data support the pull-apart kinematic model for early Miocene-middle Miocene time, as regarding the stress regime deduced from the Yamato Basin basement fractures. The recent compression known in the eastern margin of the Japan Sea was not documented by compressive structures at any site. The late Miocene-early Pliocene faulting phase corresponds to a major and general reorganization of the stress distribution in the arc area. Evidence for rapid and main subsidence and synsedimentary extension of the Yamato Basin and Yamato Rise areas between 20 and 15 Ma, and the concomitant rotation of southwest Japan, raise the question of links between this opening and the Shimanto Belt collision in southwest Japan, between the arc and the Philippine Sea Plate.
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Non-periodic structural variation has been found in the high T-c cuprates, YBa2Cu3O7-x and Hg0.67Pb0.33Ba2Ca2Cu3O8+delta, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high T-c cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high T-c cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.
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The remarkable difference between the nuclear quadrupole frequencies v_Q of Cu(1) and Cu(2) in YBa_2Cu_3O_6 and YBa_2Cu_3O_7 is analyzed. We calculate the ionic contribution to the electric field gradients and estimate, by using experimental results for Cu_2O and La_2CuO_4, the contribution of the d valence electrons. Thus, we determine v_Q1, v_Q2, and the asymmetry parameter η for YBa_2Cu_3O_6 and YBa_2Cu_3O_7. The number of holes in dthe Cu-O planes and chains is found to be important for the different behavior of v_Q1 and v_Q2.
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Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.
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Lead molybdate (PbMoO4) crystals were synthesized by the co-precipitation method at room temperature and then processed in a conventional hydrothermal (CH) system at low temperature (70 °C for different times). These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, micro-Raman (MR) and Fourier transformed infrared (FT-IR) spectroscopies. Field emission scanning electron microscopy images were employed to observe the shape and monitor the crystal growth process. The optical properties were investigated by ultraviolet-visible (UV-Vis) absorption and photoluminescence (PL) measurements. XRD patterns and MR spectra indicate that these crystals have a scheelite-type tetragonal structure. Rietveld refinement data possibilities the evaluation of distortions in the tetrahedral [MoO 4] clusters. MR and FT-IR spectra exhibited a high mode ν1(Ag) ascribed to symmetric stretching vibrations as well as a large absorption band with two modes ν3(Eu and Au) related to anti-symmetric stretching vibrations in [MoO 4] clusters. Growth mechanisms were proposed to explain the stages involved for the formation of octahedron-like PbMoO4 crystals. UV-Vis absorption spectra indicate a reduction in optical band gap with an increase in the CH processing time. PL properties of PbMoO4 crystals have been elucidated using a model based on distortions of tetrahedral [MoO4] clusters due to medium-range intrinsic defects and intermediary energy levels (deep and shallow holes) within the band gap. © 2012 Elsevier Ltd. All rights reserved.
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Highly charged vesicles of the saturated anionic lipid dimyristoyl phosphatidylglycerol (DMPG) in low ionic strength medium exhibit a very peculiar thermo-structural behavior. Along a wide gel-fluid transition region, DMPG dispersions display several anomalous characteristics, like low turbidity, high electrical conductivity and viscosity. Here, static and dynamic light scattering (SLS and DLS) were used to characterize DMPG vesicles at different temperatures. Similar experiments were performed with the largely studied zwitterionic lipid dimyristoyl phosphatidylcholine (DMPC). SLS and DLS data yielded similar dimensions for DMPC vesicles at all studied temperatures. However, for DMPG, along the gel-fluid transition region, SLS indicated a threefold increase in the vesicle radius of gyration, whereas the hydrodynamic radius, as obtained from DLS, increased 30% only. Despite the anomalous increase in the radius of gyration, DMPG lipid vesicles maintain isotropy, since no light depolarization was detected. Hence, SLS data are interpreted regarding the presence of isotropic vesicles within the DMPG anomalous transition, but highly perforated vesicles, with large holes. DLS/SLS discrepancy along the DMPG transition region is discussed in terms of the interpretation of the Einstein-Stokes relation for porous vesicles. Therefore, SLS data are shown to be much more appropriate for measuring porous vesicle dimensions than the vesicle diffusion coefficient. The underlying nanoscopic process which leads to the opening of pores in charged DMPG bilayer is very intriguing and deserves further investigation. One could envisage biotechnological applications, with vesicles being produced to enlarge and perforate in a chosen temperature and/or pH value. (C) 2012 Elsevier Ireland Ltd. All rights reserved.