京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19007号 / 工博第4049号 / 新制||工||1623(附属図書館) / 31958 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 赤木 和夫, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23586号 / エネ博第432号 / 新制||エネ||82(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 松田 一成, 教授 宮内 雄平 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Time-domain terahertz spectroscopy (THz-TDS) is a valuable technique for studying collective ultrafast phenomena. Several mechanisms exist for converting ultrashort optical laser pulses into coherent THz sources. Broadband THz pulses can be obtained from electron currents in air plasma, which requires combinations of different colors of light to be most effective. I report multi-color generation schemes of THz pulses that deliver coherent THz output. Experimental and theoretical work using the photocurrent model describe ways to use non-harmonic color combinations to utilize several sources of light available in a table-top laser setup. Additionally, THz-TDS is used to study a variety of ultrafast electronic phenomena. I describe measurements of THz induced conductivity in high-speed semiconductors, discussed with carrier generation and carrier mobility mechanisms.

Femtosecond pump-probe, spectroscopy was performed on ZnO thin film and a double layer structure of ZnO / BaTiO3. Using a model based on the dielectric function of ZnO obtained by spectral ellipsometry, the observed spectral features were explained. Further, the influence of the BTO layer on the charge carrier dynamis of ZnO was investigated.

InGaN based blue and near-ultraviolet light emitting diodes and laser diodes have been successfully commercialized for many applications such as general lighting, display backlighting and high density optical storage devices. Despite having a comparably high defect density, these devices are known for their efficient operation, which is attributed to localization in potential fluctuations preventing carriers from reaching the centers of nonradiative recombination. Nitride research is currently headed towards improving deep ultraviolet AlGaN and green InGaN emitters with higher Al and In molar fractions. The efficiency of these devices trails behind the blue counterparts as the carrier localization does not seem to aid in supressing nonradiative losses. In addition, the operation of ternary nitride heterostructure based devices is further complicated by the presence of large built-in electric fields. Although the problem can be ameliorated by growing structures in nonpolar or semipolar directions, the step from research to production still awaits. In this thesis, carrier dynamics and localization effects have been studied in three different nitride ternary compounds: AlGaN epitaxial layers and quantum wells with high Al content, nonpolar m-plane InGaN/GaN quantum wells and lattice matched AlInN/GaN heterostructures. The experimental methods of this work mainly consist of spectroscopy techniques such as time-resolved photoluminescence and differential transmission pump-probe measurements as well as spatial photoluminescence mapping by means of scanning near-field microscopy. The comparison of luminescence and differential transmission measurements has allowed estimating the localization depth in AlGaN quantum wells. Additionally, it has been demonstrated that the polarization degree of luminescence from m-InGaN quantum wells decreases as carriers diffuse to localization centers.What is more, dual-scale localization potential has been evidenced by near-field measurements in both AlGaN and m-InGaN. Larger scale potential fluctuation have been observed directly and the depth of nanoscopic localization has been estimated theoretically from the recorded linewidth of the near-field spectra. Lastly, efficient carrier transport has been observed through AlInN layer despite large alloy inhomogeneities evidenced by broad luminescence spectra and the huge Stokes shift. Inhomogeneous luminescence from the underlying GaN layer has been linked to the fluctuations of the built-in electric field at the AlInN/GaN interface. / <p>QC 20121101</p>

Spectrally-resolved differential reflectivity experiments on GaMnAs over a broad spectral range (1.4-2.0 eV) are presented, representing the first such measurements in a III-Mn-V diluted magnetic semiconductor. Comparison of the measured nonlinear spectra with results in GaAs and LT-GaAs, together with calculations of the pump probe signal contributions, has allowed an unambiguous identification of the relevant scattering and relaxation processes for optically-excited carriers in this material system. The measured spectra indicate a clear blue shift in the nonlinear optical response, providing support for the valence band model of ferromagnetism in III-Mn-V diluted magnetic semiconductors. / Spectrally-resolved differential reflectivity experiments on GaMnAs over a broad spectral range (1.4-2.0 eV) are presented, representing the first such measurements in a III-Mn-V diluted magnetic semiconductor. Comparison of the measured nonlinear spectra with results in GaAs and LT-GaAs, together with calculations of the pump probe signal contributions, has allowed an unambiguous identification of the relevant scattering and relaxation processes for optically-excited carriers in this material system. The measured spectra indicate a clear blue shift in the nonlinear optical response, providing support for the valence band model of ferromagnetism in III-Mn-V diluted magnetic semiconductors.

The thesis is dedicated to investigation of carrier dynamics in InN, InGaN, and GaAsBi heterostructures by using light-induced transient gratings and differential transmission techniques. The experimental studies in a wide range of excess carrier densities and temperatures revealed that trap-assisted Auger recombination is the dominant recombination mechanism in MBE-grown InN layers at room temperature. Investigation of carrier dynamics in In-rich InGaN alloys revealed that density of fast nonradiative recombination centers increases with Ga content. The correlation between excess carrier lifetime and diffusion coefficient in MOCVD-grown single InGaN layer with 13% In is governed by diffusive flow to the extended defects. Investigations of carrier lifetime and diffusivity dependence on excitation fluence indicated that both nonradiative and radiative recombination contribute to an increase of excess carrier recombination rate at high photo-excitation levels in MOCVD-grown InGaN multiple quantum wells. Transient grating measurements in MBE-grown GaAsBi layers with different Bi content revealed that Bi induced potential fluctuations determine the tenfold decrease in nonequilibrium hole mobility, if compare to GaAs. / Disertacija skirta nepusiausvirųjų krūvininkų dinamikos tyrimams InN, InGaN ir GaAsBi heterosandarose naudojant šviesa indukuotų dinaminių gardelių ir skirtuminio pralaidumo metodikas. Atlikti tyrimai plačiame nepusiausvirųjų krūvininkų tankių ir bandinio temperatūrų intervale parodė, kad krūvininkų rekombinacijos sparta MBE būdu užaugintuose InN sluoksniuose dominuojantis rekombinacijos mechanizmas kambario temperatūroje yra gaudyklių įtakota Ožė rekombinacija. Nustatyta koreliacija tarp krūvininkų gyvavimo trukmės ir difuzijos koeficiento MOCVD būdu užaugintame InGaN sluoksnyje su 13% In parodė, kad krūvininkų gyvavimo trukmę lemia difuzinė jų perneša link rekobinacijos centrų. Parodoma, kad MBE metodu užaugintuose InGaN sluoksniuose su dideliu In kiekiu (x>0,7) didėjant Ga kiekiui didėja nespindulinės rekombinacijos centrų tankis, o krūvininkų rekombinacijos sparta yra termiškai aktyvuojama. MOCVD metodu užaugintose InGaN kvantinėse sandarose dinaminių gardelių tyrimais parodoma, kad spartėjančią krūvininkų rekombinaciją didėjant sužadinimo intensyvumui lemia ne tik spindulinė rekombinacija, tačiau reikia atsižvelgti ir į nespindulinės rekombinacijos spartėjimą. Nustatyta, kad į GaAs įterpiant Bi atomus daugiau nei dešimt kartų sumažėja skylių judris dėl Bi atomų kuriamų valentinės juostos fliuktuacijų.

Disertacija skirta nepusiausvirųjų krūvininkų dinamikos tyrimams SiC, GaN bei deimantuose naudojant šviesa indukuotų dinaminių gardelių, diferencinio pralaidumo, diferencinio atspindžio bei fotoliuminescencijos metodikas. Taipogi pristatomos naujos sugerties koeficiento matavimo bei gyvavimo trukmės mikroskopijos metodikos. Tyrimai atlikti plačiame nepusiausvirųjų krūvininkų tankių ir temperatūrų intervale esant vienfotoniam bei dvifotoniam sužadinimui. Nustatytas stiprus krūvininkų difuzijos koeficiento priklausomumas nuo krūvininkų tankio ir temperatūros. Jis paaiškintas fononine sklaida, krūvininkų tarpusavio sąveikos procesais bei išsigimimu. Buvo nustatyta, kad netiesiatarpiuose SiC ir deimanto puslaidininkiuose prie mažų sužadinimų rekombinacija yra ribota taškiniais bei paviršiniais defektais, o GaN dominuoja rekombinacija ant tarpkristalitinių ribų. Taipogi pasireiškė netiesinis Ože rekombinacijos procesas, kuris prie žemų sužadinimų buvo sustiprintas kulonine sąveika bei susilpnintas prie didelių dėl elektron-fononinės sąveikos ekranavimo bei išsigimimo. Fotoliuminescencijos efektyvumas parodė, kad spindulinės rekombinacijos koeficientas GaN mažėja nuo sužadinimo, tuo tarpu SiC jis nuo žadinimo nepriklauso. Kompensuojančių defektų (aliuminio SiC ir boro deimante) koncentracijos ir aktyvacijos energijos nustatytos stebint jų sąlygotos sugerties įsisotinimą bei jų signalo relaksacijos spartos priklausomybę nuo temperatūros. / The thesis is dedicated to investigation of carrier dynamics in SiC, GaN and diamond by using light-induced transient gratings, differential transmittivity, differential reflectivity and photoluminescence techniques. Also new absorption coefficient measurement and carrier lifetime microscopy techniques are presented. The experimental studies were performed in a wide range of excess carrier densities and temperatures under single- and two- photon excitation conditions. Strong diffusion coefficient temperature and injection dependences were determined. They were explained by phonon scattering, inter-carrier interaction processes and degeneracy. It was determined, that in indirect-gap SiC and diamond semiconductors at low injections lifetime is limited by point and surface defects, while in GaN recombination on grain boundaries prevails. Also nonlinear Auger recombination coefficient was observed. It was Coulombically enhanced at low injections and screened at high ones. Photoluminescence efficiency revealed radiative recombination coefficient reduction with injection in GaN. On the other hand, in SiC radiative coefficient was injection independent. Compensating defect (aluminum in SiC and boron in diamond) concentrations and activation energies were determined from their absorption saturation and recovery rate temperature dependences.

Disertacija skirta nepusiausvirųjų krūvininkų dinamikos tyrimams InN, InGaN ir GaAsBi heterosandarose naudojant šviesa indukuotų dinaminių gardelių ir skirtuminio pralaidumo metodikas. Atlikti tyrimai plačiame nepusiausvirųjų krūvininkų tankių ir bandinio temperatūrų intervale parodė, kad krūvininkų rekombinacijos sparta MBE būdu užaugintuose InN sluoksniuose dominuojantis rekombinacijos mechanizmas kambario temperatūroje yra gaudyklių įtakota Ožė rekombinacija. Nustatyta koreliacija tarp krūvininkų gyvavimo trukmės ir difuzijos koeficiento MOCVD būdu užaugintame InGaN sluoksnyje su 13% In parodė, kad krūvininkų gyvavimo trukmę lemia difuzinė jų perneša link rekobinacijos centrų. Parodoma, kad MBE metodu užaugintuose InGaN sluoksniuose su dideliu In kiekiu (x>0,7) didėjant Ga kiekiui didėja nespindulinės rekombinacijos centrų tankis, o krūvininkų rekombinacijos sparta yra termiškai aktyvuojama. MOCVD metodu užaugintose InGaN kvantinėse sandarose dinaminių gardelių tyrimais parodoma, kad spartėjančią krūvininkų rekombinaciją didėjant sužadinimo intensyvumui lemia ne tik spindulinė rekombinacija, tačiau reikia atsižvelgti ir į nespindulinės rekombinacijos spartėjimą. Nustatyta, kad į GaAs įterpiant Bi atomus daugiau nei dešimt kartų sumažėja skylių judris dėl Bi atomų kuriamų valentinės juostos fliuktuacijų. / The thesis is dedicated to investigation of carrier dynamics in InN, InGaN, and GaAsBi heterostructures by using light-induced transient gratings and differential transmission techniques. The experimental studies in a wide range of excess carrier densities and temperatures revealed that trap-assisted Auger recombination is the dominant recombination mechanism in MBE-grown InN layers at room temperature. Investigation of carrier dynamics in In-rich InGaN alloys revealed that density of fast nonradiative recombination centers increases with Ga content. The correlation between excess carrier lifetime and diffusion coefficient in MOCVD-grown single InGaN layer with 13% In is governed by diffusive flow to the extended defects. Investigations of carrier lifetime and diffusivity dependence on excitation fluence indicated that both nonradiative and radiative recombination contribute to an increase of excess carrier recombination rate at high photo-excitation levels in MOCVD-grown InGaN multiple quantum wells. Transient grating measurements in MBE-grown GaAsBi layers with different Bi content revealed that Bi induced potential fluctuations determine the tenfold decrease in nonequilibrium hole mobility, if compare to GaAs.

Electromagnetic radiation in the frequency range between about 100 GHz and 5 THz can be used for spectroscopy and microscopy, but it is also promising for security screening and even wireless communication. In the present thesis a planar photoconducting large-area THz radiation source is presented. The device exhibits outstanding properties, in particular high THz field strength and generation efficiency and large spectral bandwidth with short THz pulse length. The THz emission is based on acceleration and deceleration of photoexcited carriers in semiconductor substrates. A metallic interdigitated structure at the surface of semi-insulating GaAs provides the electrodes of an Auston switch. In a biased structure photoexcited charge carriers are accelerated. Hence electromagnetic waves are emitted. An appropriately structured second metallization, electrically isolated from the electrodes, prevents destructive interference of the emitted waves. The structure investigated here combines several advantages of different conventional photoconducting THz sources. First, it provides high electric acceleration fields at moderate voltages owing to the small electrode separation. Second, the large active area in the mm2 range allows excitation by large optical powers of some mW. Optical excitation with near-infrared femtosecond lasers is possible with repetition rates in the GHz range. The presented results point out the excellent characteristics regarding the emitted THz field strength, average power, spectral properties, and easy handling of the interdigitated structure in comparison to various conventional emitter structures. Various modifications of the semiconductor substrate and the optimum excitation conditions were investigated. In the second part of this thesis the dynamic conductivity of GaAs/AlxGa1-xAs superlattices in an applied static electric field was investigated with time-resolved THz spectroscopy. The original goal was to explore whether the predicted effect of gain of electromagnetic radiation at THz frequencies is present in such structures. Superlattice samples were grown according to the experimental requirements, which include high specific resistance and sufficient THz transparency. The characterization of the superlattices by Fourier transform infrared spectroscopy and photoluminescence spectroscopy confirms the pronounced miniband properties of the bandstructure. Furthermore indications of Bloch oscillations were found by transport measurements. However, we could not measure a change of the dynamic conductivity when the electric field was toggled. Specific reasons for this and related experiments of other groups are discussed. / Elektromagnetische Strahlung im Frequenzbereich zwischen etwa 100 GHz und 5 THz wird für verschiedene Anwendungen wie Spektroskopie und Mikroskopie genutzt, kann aber auch für Sicherheitstechnik oder sogar Datenübertragung interessant sein. In der hier vorgestellten Forschungsarbeit wird eine großflächige fotoleitende THz-Strahlungsquelle beschrieben, die sich durch eine große THz-Feldstärke und große spektrale Bandbreite auszeichnet. Die THz-Emission basiert auf der Beschleunigung und Verzögerung fotogenerierter Ladungen in Halbleitersubstraten. Eine metallische Interdigitalstruktur auf der Oberfläche von semi-isolierendem GaAs bildet die Elektroden eines Fotoschalters. Ist an diese Struktur eine Spannung angeschlossen, werden optisch generierte Ladungsträger beschleunigt und strahlen elektromagnetische Wellen ab. Eine geeignet strukturierte und isolierte zweite Metallisierung verhindert destruktive Interferenzen der abgestrahlten Wellen. Die vorgeschlagene Struktur vereinigt dabei die Vorteile verschiedener herkömmlicher fotoleitender THz-Quellen. Einerseits ermöglicht der kleine Elektrodenabstand große elektrische Felder zur Beschleunigung fotogenerierter Ladungen schon bei moderaten Spannungen. Andererseits kann die große aktive Fläche von einigen mm2 mit großen optischen Leistungen im Bereich einiger mW angeregt werden. Die optische Anregung mit Nahinfrarot-Femtosekunden- Lasern kann mit Wiederholraten bis in den GHz-Bereich geschehen. Bedingt durch die Eigenschaften der Anregungspulse entstehen kurze spektral breite THz-Pulse. Die vorliegenden Ergebnisse verdeutlichen die hervorragenden Eigenschaften der Interdigitalstruktur im Vergleich zu verschiedenen herkömmlichen Geometrien bezüglich der Feldstärke der abgestrahlten Wellen, der mittleren Leistung und der spektralen Eigenschaften. Dabei ist die Struktur sehr einfach zu handhaben. Es wurden verschiedene Modifikationen des Substrates und die optimalen Bedingungen der optischen Anregung untersucht. Der zweite Teil dieser Arbeit behandelt die Erforschung der dynamische Leitfähigkeit von GaAs/AlxGa1-xAs-Übergittern in Abhängigkeit von einem elektrischen Feld mit Hilfe der zeitaufgelösten THz-Spektroskopie. Es sollte geklärt werden, ob der vorhergesagte Effekt der Verstärkung elektro-magnetischer Strahlung in solchen Strukturen möglich ist. Dazu wurden Übergitterproben gemäß den experimentellen Anforderungen hergestellt. Zu den Vorgaben gehört ein hoher spezifischer Widerstand und ausreichende Transparenz im THz-Bereich. Die Charakterisierung der Übergitter mit Fotolumineszenz- und Fourier-Transformations-IR-Spektroskopie bestätigte die ausgeprägten Minibandeigenschaften der Bandstruktur. Hinweise auf Bloch-Oszillationen wurden durch Ladungstransportmessungen gefunden. Dennoch war eine Änderung der dynamischen Leitfähigkeit beim Schalten des elektrischen Feldes nicht messbar. Gründe dafür und ähnliche Experimente anderer Gruppen werden diskutiert.