979 resultados para Charge-carrier mobility
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Diese Studie verfolgt das Konzept der "Oligomer-Ansatz", die von Müllen angesprochen wurde et.al. vor etwa 10 Jahren. Der Schwerpunkt dieser Arbeit war die Synthese, Charakterisierung und Anwendung von halbleitenden konjugierten heteroacenes für organische Elektronik.rnZur weiteren Entwicklung der Familie von schwefelhaltigen Pentacene, zwei Moleküle (Benzo [1,2 - b :4,5-b '] bis [b] benzodithiophene und dithieno-[2,3-d: 2', 3'-d ']-benzo-[1,2-b :4,5-b'] dithiophene)rnfacilely wurden synthetisiert und charakterisiert durch eine Kombination verschiedener Methoden. Die beiden neue Moleküle weisen hervorragende ökologische Stabilität und angewendet OFETs Geräte als p-Kanal-Material. Die Vorversuche gaben Ladungsträgerbeweglichkeiten von 0,1 cm2 V-1 s-1 undrn1,6 cm2 V-1 s-1 bzw. aus den beiden Molekülen.rnAusgelöst durch die Frage "je länger desto besser?", Eine Reihe von neuen heteroheptacenes wurden synthetisiert und intensiv im Hinblick auf ihre feste Struktur, Selbst-assenbly auf der studierte Oberfläche, opto-elektro-Eigenschaften und Eigenschaften des Orbits Grenze. Einer derrnheteroheptacene Moleküle wurden als die aktiven Kanäle in OFET Geräten angewendet. Jedoch in Trotz der mehr verlängert Konjugationslänge die Geräte auf der Basis zeigten heptacenes viel schlimmer Ladungsträgerbeweglichkeiten als die heteropentacenes. Viele Faktoren können Festlegung der endgültigen Leistung der Produkte und der chemischen Struktur ist nur einer von ihnen.rnIn dieser Hinsicht scheint es, dass es auch sinnvoll, den Einfluss der Heteroatome Studie und Alkylsubstitution auf der soliden und elektronischen Strukturen. Daher mehr heteroheptacenes wurden synthetisiert. Abwechslungsreiches in der Anzahl und Art der heteroatomare Brücke,rndiese Oligoazene ausgestellt dramatisch anders feste Struktur und opto-elektronischernEigenschaften. Darüber hinaus wurde eine kombinierte DFT Berechnung der Molekülorbitale dieser heptacenes darauf hingewiesen, dass die Einführung von Stickstoff Brücken wird die π-Orbitale zu destabilisieren, während stabilisieren den Schwefel Brücken sowohl HOMO und LUMO Energien. Dies ist wichtig, wenn man will hoch π verlängert Oligoazene synthetisieren und dabei eine angemessene Stabilität.
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One of the most diffused electronic device is the field effect transistor (FET), contained in number of billions in each electronic device. Organic optoelectronics is an emerging field that exploits the unique properties of conjugated organic materials to develop new applications that require a combination of performance, low cost and processability. Organic single crystals are the material with best performances and purity among the variety of different form of organic semiconductors. This thesis is focused on electrical and optical characterization of Rubrene single crystal bulk and thin films. Rubrene bulk is well known but for the first time we studied thin films. The first Current-voltage characterization has been performed for the first time on three Rubrene thin films with three different thickness to extract the charge carriers mobility and to assess its crystalline structure. As results we see that mobility increase with thickness. Field effect transistor based on Rubrene thin films on $SiO_2$ have been characterize by current-voltage (I-V) analyses (at several temperatures) and reveals a hopping conduction. Hopping behavior probably is due to the lattice mismatch with the substrate or intrinsic defectivity of the thin films. To understand effects of contact resistance we tested thin films with the Transmission Line Method (TLM) method. The TLM method revealeds that contact resistance is negligible but evidenced a Schottky behavior in a limited but well determined range of T. To avoid this effect we carried out annealing treatment after the electrode evaporation iswe performed a compete I-V characterization as a function of in temperature to extract the electronic density of states (DOS) distribution through the Space Charge Limited Current (SCLC) method. The results show a DOS with an exponential trenddistribution, as expected. The measured mobility of thin films is about 0.1cm^2/Vs and it increases with the film thickness. Further studies are necessary to investigate the reason and improve performances. From photocurrent spectrum we calculated an Eg of about 2.2eV and both thin films and bulk have a good crystal order. Further measurement are necessary to solve some open problems
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Im Rahmen dieser Arbeit wurden neuartige funktionale Nanographene synthetisiert und hinsichtlich ihrer strukturellen und elektronischen Eigenschaften charakterisiert. Basierend auf dem Strukturmotiv des Graphens konnten anellierte polyzyklische aromatische Kohlenwasserstoffe (PAKs) mit unterschiedlichen Seitenverhältnissen strukturdefiniert erhalten und gezielt in der Peripherie funktionalisiert werden. Basierend auf dem Synthesekonzept einer „Vorplanarisierung“ konnten Nanographen-Scheiben mit einem Durchmesser von bis zu 3 nm in hoher Reinheit erhalten werden. Durch die Entwicklung von Polyphenylen-Vorläufern mit einem gewinkelten Rückgrat konnten erstmals defektfreie und lösliche Nanographen-Streifen (GNRs) mit Breiten von 1,0 - 2,1 nm und Längen von über 40 nm synthetisiert werden.rnrnAm Hexa-peri-hexabenzocoronen (HBC) war es möglich, durch die Einführung kurzer linearer Alkylreste in der Peripherie den inter- und intrakolumnaren Abstand nach Selbstorganisation zu reduzieren. In Mischungen mit Perylentetracarboxydiimid (PDI) als Akzeptor konnte durch eine erhöhte Dichte und eine verbesserte Ladungsträgermobilität eine relative Steigerung der Effizienz von Donor-Akzeptor-Heteroübergangs-Solarzellen um 9 % erreicht werden. Eine kovalente Verknüpfung von HBC und PDI erlaubte hier die vollständige Kontrolle der supramolekularen Organisation, des Phasenverhaltens sowie des Abstandes zwischen Donor und Akzeptor.rnrnBasierend auf den im Rahmen dieser Arbeit entwickelten Synthesekonzepten, eröffnen sich nun zahlreiche Möglichkeiten zur Entwicklung weiterer Nanographene, die entsprechend der gewünschten Anwendung funktionalisiert werden können und ein besseres Verständnis der Eigenschaften graphenartiger Materialien erlauben werden.
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Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.
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In dieser Arbeit werden die Dynamiken angeregter Zustände in Donor-Akzeptorsystemen für Energieumwandlungsprozesse mit ultraschneller zeitaufgelöster optischer Spektroskopie behandelt. Der Hauptteil dieser Arbeit legt den Fokus auf die Erforschung der Photophysik organischer Solarzellen, deren aktive Schichten aus diketopyrrolopyrrole (DPP) basierten Polymeren mit kleiner Bandlücke als Elektronendonatoren und Fullerenen als Elektronenakzeptoren bestehen. rnEin zweiter Teil widmet sich der Erforschung von künstlichen primären Photosynthesereaktionszentren, basierend auf Porphyrinen, Quinonen und Ferrocenen, die jeweils als Lichtsammeleinheit, Elektronenakzeptor beziehungsweise als Elektronendonatoren eingesetzt werden, um langlebige ladungsgetrennte Zustände zu erzeugen.rnrnZeitaufgelöste Photolumineszenzspektroskopie und transiente Absorptionsspektroskopie haben gezeigt, dass Singulettexzitonenlebenszeiten in den Polymeren PTDPP-TT und PFDPP-TT Polymeren kurz sind (< 20 ps) und dass in Mischungen der Polymere mit PC71BM geminale Rekombination von gebundenen Ladungstransferzuständen ein Hauptverlustkanal ist. Zudem wurde in beiden Systemen schnelle nichtgeminale Rekombination freier Ladungen zu Triplettzuständen auf dem Polymer beobachtet. Für das Donor-Akzeptor System PDPP5T:PC71BM wurde nachgewiesen, dass die Zugabe eines Lösungsmittels mit hohem Siedepunkt, und zwar ortho-Dichlorbenzol, die Morphologie der aktiven Schicht stark beeinflusst und die Solarzelleneffizienz verbessert. Der Grund hierfür ist, dass die Donator- und Akzeptormaterialien besser durchmischt sind und sich Perkolationswege zu den Elektroden ausgebildet haben, was zu einer verbesserten Ladungsträgergeneration und Extraktion führt. Schnelle Bildung des Triplettzustands wurde in beiden PDPP5T:PC71BM Systemen beobachtet, da der Triplettzustand des Polymers über Laungstransferzustände mit Triplettcharakter populiert werden kann. "Multivariate curve resolution" (MCR) Analyse hat eine starke Intensitätsabhängigkeit gezeigt, was auf nichtgeminale Ladungsträgerrekombination in den Triplettzustand hinweist.rnrnIn den künstlichen primären Photosynthesereaktionszentren hat transiente Absorptionsspektroskopie bestätigt, dass photoinduzierter Ladungstransfer in Quinon-Porphyrin (Q-P) und Porphyrin-Ferrocen (P-Fc) Diaden sowie in Quinon-Porphyrin-Ferrocen (Q-P-Fc) Triaden effizient ist. Es wurde jedoch auch gezeigt, dass in den P-Fc unf Q-P-Fc Systemen die ladungsgetrennten Zustände in den Triplettzustand der jeweiligen Porphyrine rekombinieren. Der ladungsgetrennte Zustand konnte in der Q-P Diade durch Zugabe einer Lewissäure signifikant stabilisiert werden.
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One-dimensional nanostructures initiated new aspects to the materials applications due to their superior properties compared to the bulk materials. Properties of nanostructures have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these nanomaterials has not been widely investigated. Therefore, it is necessary to perform in-situ study on the physical and structural properties of nanomaterials to understand their relation. In this work, we will use a unique instrument to perform real time atomic force microscopy (AFM) and scanning tunneling microscopy (STM) of nanomaterials inside a transmission electron microscopy (TEM) system. This AFM/STM-TEM system is used to investigate the mechanical, electrical, and electrochemical properties of boron nitride nanotubes (BNNTs) and Silicon nanorods (SiNRs). BNNTs are one of the subjects of this PhD research due to their comparable, and in some cases superior, properties compared to carbon nanotubes. Therefore, to further develop their applications, it is required to investigate these characteristics in atomic level. In this research, the mechanical properties of multi-walled BNNTs were first studied. Several tests were designed to study and characterize their real-time deformation behavior to the applied force. Observations revealed that BNNTs possess highly flexible structures under applied force. Detailed studies were then conducted to understand the bending mechanism of the BNNTs. Formations of reversible ripples were observed and described in terms of thermodynamic energy of the system. Fracture failure of BNNTs were initiated at the outermost walls and characterized to be brittle. Second, the electrical properties of individual BNNTs were studied. Results showed that the bandgap and electronic properties of BNNTs can be engineered by means of applied strain. It was found that the conductivity, electron concentration and carrier mobility of BNNTs can be tuned as a function of applied stress. Although, BNNTs are considered to be candidate for field emission applications, observations revealed that their properties degrade upon cycles of emissions. Results showed that due to the high emission current density, the temperature of the sample was increased and reached to the decomposition temperature at which the B-N bonds start to break. In addition to BNNTs, we have also performed in-situ study on the electrochemical properties of silicon nanorods (SiNRs). Specifically, lithiation and delithiation of SiNRs were studied by our STM-TEM system. Our observations showed the direct formation of Li22Si5 phases as a result of lithium intercalation. Radial expansion of the anode materials were observed and characterized in terms of size-scale. Later, the formation and growth of the lithium fibers on the surface of the anode materials were observed and studied. Results revealed the formation of lithium islands inside the ionic liquid electrolyte which then grew as Li dendrite toward the cathode material.
Processing and characterization of PbSnTe-based thermoelectric materials made by mechanical alloying
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The research reported in this dissertation investigates the processes required to mechanically alloy Pb1-xSnxTe and AgSbTe2 and a method of combining these two end compounds to result in (y)(AgSbTe2)–(1 - y)(Pb1-xSnxTe) thermoelectric materials for power generation applications. In general, traditional melt processing of these alloys has employed high purity materials that are subjected to time and energy intensive processes that result in highly functional material that is not easily reproducible. This research reports the development of mechanical alloying processes using commercially available 99.9% pure elemental powders in order to provide a basis for the economical production of highly functional thermoelectric materials. Though there have been reports of high and low ZT materials fabricated by both melt alloying and mechanical alloying, the processing-structure-properties-performance relationship connecting how the material is made to its resulting functionality is poorly understood. This is particularly true for mechanically alloyed material, motivating an effort to investigate bulk material within the (y)(AgSbTe2)–(1 - y)(Pb1-xSnx- Te) system using the mechanical alloying method. This research adds to the body of knowledge concerning the way in which mechanical alloying can be used to efficiently produce high ZT thermoelectric materials. The processes required to mechanically alloy elemental powders to form Pb1-xSnxTe and AgSbTe2 and to subsequently consolidate the alloyed powder is described. The composition, phases present in the alloy, volume percent, size and spacing of the phases are reported. The room temperature electronic transport properties of electrical conductivity, carrier concentration and carrier mobility are reported for each alloy and the effect of the presence of any secondary phase on the electronic transport properties is described. An mechanical mixing approach for incorporating the end compounds to result in (y)(AgSbTe2)–(1-y)(Pb1-xSnxTe) is described and when 5 vol.% AgSbTe2 was incorporated was found to form a solid solution with the Pb1-xSnxTe phase. An initial attempt to change the carrier concentration of the Pb1-xSnxTe phase was made by adding excess Te and found that the carrier density of the alloys in this work are not sensitive to excess Te. It has been demonstrated using the processing techniques reported in this research that this material system, when appropriately doped, has the potential to perform as highly functional thermoelectric material.
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Commercially available LaBr3:5% Ce3+ scintillators show with photomultiplier tube readout about 2.7% energy resolution for the detection of 662 keV γ-rays. Here we will show that by co-doping LaBr3:Ce3+ with Sr2+ or Ca2+ the resolution is improved to 2.0%. Such an improvement is attributed to a strong reduction of the scintillation light losses that are due to radiationless recombination of free electrons and holes during the earliest stages (1–10 ps) inside the high free charge carrier density parts of the ionization track.
Improvement of LaBr3:5%Ce scintillation properties by Li+, Na+, Mg2+, Ca2+, Sr2+, and Ba2+ co-doping
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This paper reports on the effects of Li+, Na+, Mg2+, Ca2+, Sr2+, and Ba2+ co-doping on the scintillation properties of LaBr3:5%Ce3+. Pulse-height spectra of various gamma and X-ray sources with energies from 8 keV to 1.33 MeV were measured from which the values of light yield and energy resolution were derived. Sr2+ and Ca2+ co-doped crystals showed excellent energy resolution as compared to standard LaBr3:Ce. The proportionality of the scintillation response to gamma and X-rays of Ca2+, Sr2+, and Ba2+ co-doped samples also considerably improves. The effects of the co-dopants on emission spectra, decay time, and temperature stability of the light yield were studied. Multiple thermoluminescence glow peaks, decrease of the light yield at temperatures below 295 K, and additional long scintillation decay components were observed and related to charge carrier traps appearing in LaBr3:Ce3+ with Ca2+, Sr2+, and Ba2+ co-doping.
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The scintillation and luminescence properties of pure CsBa2I5 and CsBa2I5 doped with 0.5% Eu and 5% Eu were studied between 78 K and 600 K. Single crystals were grown by the vertical Bridgman method from the melt. CsBa2I5:5% Eu showed a light yield of 80,000 photons/MeV, an energy resolution of 2.3% for the 662 key full absorption peak, and an excellent proportional response. Two broad emission bands centered at 400 nm and 600 nm were observed in the radioluminescence spectrum of pure CsBa2I5. The Eu2+ 5d-4f emission band was observed at 430 nm. The radiative lifetime of the Eu2+ excited state was determined as 350 ns. With increasing temperature and Eu concentration the Eu2+ emission shifts to longer wavelengths and its decay time lengthens as a result of self-absorption of the Eu2+ emission. Multiple thermoluminescence glow peaks and a sharp decrease of the light yield at temperatures below 200 K were observed and related to the presence of the charge carrier traps in CsBa2I5:Eu.
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Deep geological storage of radioactive waste foresees cementitious materials as reinforcement of tunnels and as backfill. Bentonite is proposed to enclose spent fuel canisters and as drift seals. Sand/bentonite (s/b) is foreseen as backfill material of access galleries or as drift seals. The emplacement of cementitious material next to clay material generates an enormous chemical gradient in pore-water composition that drives diffusive solute transport. Laboratory studies and reactive transport modeling predicted significant mineral alteration at and near interfaces, mainly resulting in a decrease of porosity in bentonite. The goal of this thesis was to characterize and quantify the cement/bentonite interactions both spatially and temporally in laboratory experiments. A newly developed mobile X-ray transparent core infiltration device was used to perform X-ray computed tomography (CT) scans without interruption of running experiments. CT scans allowed tracking the evolution of the reaction plume and changes in core volume/diameter/density during the experiments. In total 4 core infiltration experiments were carried out for this study with the compacted and saturated cores consisting of MX-80 bentonite and sand/MX-80 bentonite mixture (s/b; 65/35%). Two different high-pH cementitious pore-fluids were infiltrated: a young (early) ordinary Portland cement pore-fluid (APWOPC; K+–Na+–OH-; pH 13.4; ionic strength 0.28 mol/kg) and a young ‘low-pH’ ESDRED shotcrete pore-fluid (APWESDRED; Ca2+–Na+–K+–formate; pH 11.4; ionic strength 0.11 mol/kg). The experiments lasted between 1 and 2 years. In both bentonite experiments, the hydraulic conductivity was strongly reduced after switching to high-pH fluids, changing eventually from an advective to a diffusion-dominated transport regime. The reduction was mainly induced by mineral precipitation and possibly partly also by high ionic strength pore-fluids. Both bentonite cores showed a volume reduction and a resulting transient flow in which pore-water was squeezed out during high-pH infiltration. The outflow chemistry was characterized by a high ionic strength, while chloride in the initial pore water got replaced as main anionic charge carrier by sulfate, originating from gypsum dissolution. The chemistry of the high-pH fluids got strongly buffered by the bentonite, consuming hydroxide and in case of APWESDRED also formate. Hydroxide got consumed by mineral reactions (saponite and possibly talc and brucite precipitation), while formate being affected by bacterial degradation. Post-mortem analysis showed reaction zones near the inlet of the bentonite core, characterized by calcium and magnesium enrichment, consisting predominately of calcite and saponite, respectively. Silica got enriched in the outflow, indicating dissolution of silicate-minerals, identified as preferentially cristobalite. In s/b, infiltration of APWOPC reduced the hydraulic conductivity strongly, while APWESDRED infiltration had no effect. The reduction was mainly induced by mineral precipitation and probably partly also by high ionic strength pore-fluids. Not clear is why the observed mineral precipitates in the APWESDRED experiment had no effect on the fluid flow. Both s/b cores showed a volume expansion along with decreasing ionic strengths of the outflow, due to mineral reactions or in case of APWESDRED infiltration also mediated by microbiological activity, consuming hydroxide and formate, respectively. The chemistry of the high-pH fluids got strongly buffered by the s/b. In the case of APWESDRED infiltration, formate reached the outflow only for a short time, followed by enrichment in acetate, indicating most likely biological activity. This was in agreement to post-mortem analysis of the core, observing black spots on the inflow surface, while the sample had a rotten-egg smell indicative of some sulfate reduction. Post-mortem analysis showed further in both cores a Ca-enrichment in the first 10 mm of the core due to calcite precipitation. Mg-enrichment was only observed in the APWOPC experiment, originating from newly formed saponite. Silica got enriched in the outflow of both experiments, indicating dissolution of silicate-minerals, identified in the OPC experiment as cristobalite. The experiments attested an effective buffering capacity for bentonite and s/b, a progressing coupled hydraulic-chemical sealing process and also the preservation of the physical integrity of the interface region in this setup with a total pressure boundary condition on the core sample. No complete pore-clogging was observed but the hydraulic conductivity got rather strongly reduced in 3 experiments, explained by clogging of the intergranular porosity (macroporosity). Such a drop in hydraulic conductivity may impact the saturation time of the buffer in a nuclear waste repository, although the processes and geometry will be more complex in repository situation.
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There has been significant research in the study of in-plane charge-carrier transport in graphene in order to understand and exploit its unique electrical properties; however, the vertical graphene–semiconductor system also presents opportunities for unique devices. In this letter, we investigate the epitaxial graphene/p-type 4H-SiC system to better understand this vertical heterojunction. The I–V behavior does not demonstrate thermionic emission properties that are indicative of a Schottky barrier but rather demonstrates characteristics of a semiconductor heterojunction. This is confirmed by the fitting of the temperature-dependent I–V curves to classical heterojunction equations and the observation of band-edge electroluminescence in SiC.
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In the work, the results of an investigation of GaInP/GaInAs/Ge MJ SCs intended for converting concentrated solar radiation, when operating at low temperatures (down to -190 degrees C) are presented. A kink of the cell I-V characteristic has been observed in the region close to V-oc starting from -20 degrees C at operation under concentrated sunlight. The causes for its occurrence have been analyzed and the reasons for formation of a built-in potential barrier for majority charge carriers at the n-GaInP/n-Ge isotype hetero-interface are discussed. The effect of charge carrier transport in n-GaInP/n-p Ge heterostructures on MJ SC output characteristics at low temperatures has been studied including EL technique.
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Materials with high electrical conductivity and optical transparency are needed for future flat panel display, solar energy, and other opto-electronic technologies. InxCd1-xO films having a simple cubic microstructure have been grown on amorphous glass substrates by a straightforward chemical vapor deposition process. The x = 0.05 film conductivity of 17,000 S/cm, carrier mobility of 70 cm2/Vs, and visible region optical transparency window considerably exceed the corresponding parameters for commercial indium-tin oxide. Ab initio electronic structure calculations reveal small conduction electron effective masses, a dramatic shift of the CdO band gap with doping, and a conduction band hybridization gap caused by extensive Cd 5s + In 5s mixing.
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Recovery of cell volume in response to osmotic stress is mediated in part by increases in the Cl- permeability of the plasma membrane. These studies evaluate the hypothesis that ATP release and autocrine stimulation of purinergic (P2) receptors couple increases in cell volume to opening of Cl- channels. In HTC rat hepatoma cells, swelling induced by hypotonic exposure increased membrane Cl- current density to 44.8 +/- 7.1 pA/pF at -80 mV. Both the rate of volume recovery and the increase in Cl- permeability were inhibited in the presence of the ATP hydrolase apyrase (3 units/ml) or by exposure to the P2 receptor blockers suramin and Reactive Blue 2 (10-100 microM). Cell swelling also stimulated release of ATP. Hypotonic exposure increased the concentration of ATP in the effluent of perfused cells by 170 +/- 36 nM in the presence of a nucleotidase inhibitor (P < 0.01). In whole-cell recordings with ATP as the charge carrier, cell swelling increased membrane current density approximately 30-fold to 16.5 +/- 10.4 pA/pF. These findings indicate that increases in cell volume lead to efflux of ATP through opening of a conductive pathway consistent with a channel, and that extracellular ATP is required for recovery from swelling. ATP may function as an autocrine factor that couples increases in cell volume to opening of Cl- channels through stimulation of P2 receptors.