abstract: Amorphous oxide semiconductors are promising new materials for various optoelectronic applications. In this study, improved electrical and optical properties upon thermal and microwave processing of mixed-oxide semiconductors are reported. First, arsenic-doped silicon was used as a model system to understand susceptor-assisted microwave annealing. Mixed oxide semiconductor films of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) were deposited by room-temperature RF sputtering on flexible polymer substrates. Thermal annealing in different environments - air, vacuum and oxygen was done. Electrical and optical characterization was carried out before and after annealing. The degree of reversal in the degradation in electrical properties of the thin films upon annealing in oxygen was assessed by subjecting samples to subsequent vacuum anneals. To further increase the conductivity of the IGZO films, Ag layers of various thicknesses were embedded between two IGZO layers. Optical performance of the multilayer structures was improved by susceptor-assisted microwave annealing and furnace-annealing in oxygen environment without compromising on their electrical conductivity. The post-processing of the films in different environments was used to develop an understanding of mechanisms of carrier generation, transport and optical absorption. This study establishes IGZO as a viable transparent conductor, which can be deposited at room-temperature and processed by thermal and microwave annealing to improve electrical and optical performance for applications in flexible electronics and optoelectronics. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the present work, we performed a study of the structural, electrical and optical properties of the compound LaCr1-xAlxO3 (x = 0.0, 0.05, 0.5, 0.95 and 1.0) produced by the combustion method. The structural analyzes were performed by X-ray diffraction (XRD) and Rietveld refinement, the electrical measurements using impedance spectroscopy and IV measurements, and optical measurements using UV-Vis spectroscopy. The results of XRD allied to the Rietveld method of refinement indicate that the samples with x = 0.0 and 0.05, have an orthorhombic structure belonging to the space group Pnma (62), and for x = 0.5, 0.95 and 1.0, a rhombohedral structure belonging to the space group R-3c (167), thus taking place a structural transition in the material. The impedance spectroscopy measurements associated to the IV curves show that the samples with higher concentration of Al present higher resistance, and the samples with lower concentration of Al present less resistance. We observe that for high frequencies a decrease of dielectric constant with frequency occurs. In addition, the appearance of only a semicircle establishes the presence of non-Debye type relaxation, where an equivalent circuit composed of two resistors (R1 and R2) and a constant phase element (CPE) were used. By means of the absorption measurements in the ultraviolet to visible region (UV-Vis), we estimated the optical gap of the samples, through the tauc equation, which vary between 3.27 - 3.43 eV. Still, we observed that the increase in Al concentration favors the increase in transmittance in the material. / No presente trabalho, realizamos um estudo das propriedades estruturais, elétricas e ópticas do composto LaCr1-xAlxO3 (x=0,0; 0,05; 0,5; 0,95 e 1,0) produzido pelo método da combustão. As análises estruturais foram realizadas por meio de difração de raios-X (DRX) e refinamento Rietveld, as elétricas por meio de espectroscopia de impedância e medidas IV, e ópticas por meio de espectroscopia de UV-Vis. Os resultados de DRX aliados ao método de refinamento Rietveld indicam que as amostras com x = 0,0 e 0,05, apresentam uma estrutura ortorrômbica pertencente ao grupo espacial Pnma (62), e para x = 0,5; 0,95 e 1,0, uma estrutura romboédrica pertencente ao grupo espacial R-3c (167), ocorrendo assim uma transição estrutural no material. As medidas de espectroscopia de impedância associadas às curvas IV mostram que as amostras com maior concentração de Al apresentam maior resistência, e as amostras com menor concentração de Al apresentam menor resistência. Observamos que para altas frequências ocorre uma diminuição da constante dielétrica com a frequência. Além disso, o aparecimento de apenas um semicírculo estabelece a presença do relaxamento do tipo não-Debye, onde foi utilizado um circuito equivalente composto por duas resistências (R1 e R2), e um elemento de fase constante (CPE). Através das medidas de absorção na região do ultravioleta ao visível (UV-Vis) estimamos o gap óptico das amostras, através da equação de tauc, os quais variam entre 3,27 - 3,43 eV. Além disso, observamos que o aumento da concentração de Al favorece o aumento da transmitância no material. / São Cristóvão, SE

A key to solar cells with lower environmental impact is higher efficiency and reduced material usages. Bifacial solar cells may have a higher efficiency as light can enter from two directions and tandem solar cells may use a larger part of the incoming solar spectrum, increasing the efficiency. However, both these applications require transparent and conducting contacts. This thesis aimed to investigate how suitable the transparent conductive oxides aluminum doped zinc oxide (AZO) and indium doped tin oxide (ITO) are as contacts in bifacial CIGS cells or CIGS/Silicon tandem cells. The contacts must remain stable when CIGS is deposited on top of it, meaning that they have to endure first 500°C and then 600°C in combination with copper, indium, gallium and selenium vapours. A thin layer of AZO topped with ITO and pure ITO films of different thicknesses were deposited by RF- and DC-sputtering, varying the oxygen flow. Opto-electrical characterization showed that the transparency in the infrared was balanced against high conductivity due to a shift in the plasmon peak's position. No great difference was seen between pure ITO samples and AZO/ITO samples, so only the first where further processed. The ITO films were annealed to 500°C in the CIGS deposition chamber, exposed to selenium vapour. The films' sheet resistances dropped drastically, which was mainly attributed to activation of tin donors. ITO produced with low oxygen flows also appeared more crystalline according to x-ray diffraction measurements. Photon absorption in the ITO was used to estimate the current loss in bifacial and tandem applications and graphs with current loss and sheet resistance can be used to select an ITO deposition process. Commercial ITO was exposed to 100s of the CIGS deposition process but only during selenium and gallium vapour. A layer of gallium selenide could be identified on the surface, but the ITO appeared to remain stable. Sodium fluoride pre deposition treatment lowered the samples absorption for all wavelengths compared to non-treated samples.

O óxido de zinco é um material semicondutor que apresenta alta transparência óptica no espectro visível, alta energia de ligação de éxcitons e piezoeletricidade. Por suas propriedades, ele é utilizado na área de sensores, eletrodos transparentes e dispositivos optoeletrônicos. No entanto, sua utilização ainda é limitada pela dificuldade de obtenção de condutividade tipo p, cujo principal dopante é o nitrogênio, devido à assimetria de dopagem ocasionada por defeitos intrínsecos do material, dopagem em valências diferentes das esperadas e formação de níveis de aceitadores profundos na banda proibida. A aplicação em dispositivos piezoelétricos também exige alta resistividade e ótimas propriedades cristalinas. Muitos processos de deposição estabelecidos hoje ainda utilizam altas temperaturas, o que impede sua deposição sobre superfícies ou substratos sensíveis a altas temperaturas. O objetivo deste trabalho é desenvolver técnicas de deposição de filmes de ZnO, principalmente em baixas temperaturas ( 100°C), pelo método de magnetron sputtering de rádio frequência, para avaliar a influência dos gases de processo nas características estruturais, estequiométricas, elétricas e ópticas dos filmes. Para isso, foram obtidos filmes utilizando pressão total de argônio, e pressões parciais de argônio e oxigênio e argônio e nitrogênio, utilizando alvo cerâmico de óxido de zinco ou alvo metálico de zinco. Para alvo de ZnO, filmes com condutividade tipo n foram obtidos em ambiente de argônio, em condições que geraram deficiências de oxigênio. Filmes altamente resistivos foram obtidos com a utilização de pressão parcial de oxigênio no gás de processo, em condições que resultaram em filmes estequiométricos, inclusive com condutividade tipo p. Condutividade tipo p mais alta foi observada, apenas por ponta quente, para uma amostra obtida em argônio logo após a utilização de nitrogênio na câmara de processo, que provavelmente sofreu influência da dopagem não intencional do cobre, que foi identificado como um contaminante do processo devido à estrutura da câmara. Para alvo de Zn, observou-se a formação de nitreto de zinco, que demonstrou alta capacidade de oxidação em ambiente atmosférico, e portanto, transforma-se naturalmente ao longo do tempo ou por processos de oxidação térmica em ZnO dopado com nitrogênio. Filmes de ZnO produzidos a partir de nitreto de zinco foram os únicos dos testados que apresentaram fotoluminescência característica do ZnO, mesmo para processos onde não houve aquecimento intencional. / Zinc oxide is a multifunctional semiconductor, which presents high optical transparency in the visible range, high exciton binding energy and piezoelectricity. Due to its properties, ZnO is used in several areas, such as sensors, transparent electrodes and optoelectronics. However, its usage is still limited by the lack of p-type conductivity, which is very difficult to achieve because of intrinsic material defects, unwanted valence states of doping elements and formation of deep acceptor levels. Piezoelectric devices also demand high electrical resistivity and excellent crystallographic properties. Many current deposition processes still apply high temperatures, preventing material deposition onto temperature sensitive substrates and surfaces. The main goal of this investigation is to develop low temperature ( 100°C) deposition techniques by radio frequency magnetron sputtering, to evaluate the influence of process gases in structural, stoichiometric, electrical and optical properties. Thin films were obtained using either pure argon, argon and oxygen or argon and nitrogen partial pressures, by sputtering ceramic ZnO or metallic Zn targets. For ZnO target, n-type conductivity was achieved in argon environment, by creating oxygen deficient films. High resistivity was observed by using oxygen partial pressure, resulting in stoichiometric material and changing carrier type from electrons to holes. Higher p-type conductivity was observed, only by Seebeck measurement, for a nonintentionally heavily doped sample, as there was copper originating from the deposition chamber. For Zn target, zinc nitride formation was observed, showing high capability of transforming itself into nitrogen-doped ZnO by air exposure or thermal annealing. ZnO films produced from zinc nitride were the only ones that exhibited photoluminescence, even when there was no intentional heating involved.

O óxido de zinco é um material semicondutor que apresenta alta transparência óptica no espectro visível, alta energia de ligação de éxcitons e piezoeletricidade. Por suas propriedades, ele é utilizado na área de sensores, eletrodos transparentes e dispositivos optoeletrônicos. No entanto, sua utilização ainda é limitada pela dificuldade de obtenção de condutividade tipo p, cujo principal dopante é o nitrogênio, devido à assimetria de dopagem ocasionada por defeitos intrínsecos do material, dopagem em valências diferentes das esperadas e formação de níveis de aceitadores profundos na banda proibida. A aplicação em dispositivos piezoelétricos também exige alta resistividade e ótimas propriedades cristalinas. Muitos processos de deposição estabelecidos hoje ainda utilizam altas temperaturas, o que impede sua deposição sobre superfícies ou substratos sensíveis a altas temperaturas. O objetivo deste trabalho é desenvolver técnicas de deposição de filmes de ZnO, principalmente em baixas temperaturas ( 100°C), pelo método de magnetron sputtering de rádio frequência, para avaliar a influência dos gases de processo nas características estruturais, estequiométricas, elétricas e ópticas dos filmes. Para isso, foram obtidos filmes utilizando pressão total de argônio, e pressões parciais de argônio e oxigênio e argônio e nitrogênio, utilizando alvo cerâmico de óxido de zinco ou alvo metálico de zinco. Para alvo de ZnO, filmes com condutividade tipo n foram obtidos em ambiente de argônio, em condições que geraram deficiências de oxigênio. Filmes altamente resistivos foram obtidos com a utilização de pressão parcial de oxigênio no gás de processo, em condições que resultaram em filmes estequiométricos, inclusive com condutividade tipo p. Condutividade tipo p mais alta foi observada, apenas por ponta quente, para uma amostra obtida em argônio logo após a utilização de nitrogênio na câmara de processo, que provavelmente sofreu influência da dopagem não intencional do cobre, que foi identificado como um contaminante do processo devido à estrutura da câmara. Para alvo de Zn, observou-se a formação de nitreto de zinco, que demonstrou alta capacidade de oxidação em ambiente atmosférico, e portanto, transforma-se naturalmente ao longo do tempo ou por processos de oxidação térmica em ZnO dopado com nitrogênio. Filmes de ZnO produzidos a partir de nitreto de zinco foram os únicos dos testados que apresentaram fotoluminescência característica do ZnO, mesmo para processos onde não houve aquecimento intencional. / Zinc oxide is a multifunctional semiconductor, which presents high optical transparency in the visible range, high exciton binding energy and piezoelectricity. Due to its properties, ZnO is used in several areas, such as sensors, transparent electrodes and optoelectronics. However, its usage is still limited by the lack of p-type conductivity, which is very difficult to achieve because of intrinsic material defects, unwanted valence states of doping elements and formation of deep acceptor levels. Piezoelectric devices also demand high electrical resistivity and excellent crystallographic properties. Many current deposition processes still apply high temperatures, preventing material deposition onto temperature sensitive substrates and surfaces. The main goal of this investigation is to develop low temperature ( 100°C) deposition techniques by radio frequency magnetron sputtering, to evaluate the influence of process gases in structural, stoichiometric, electrical and optical properties. Thin films were obtained using either pure argon, argon and oxygen or argon and nitrogen partial pressures, by sputtering ceramic ZnO or metallic Zn targets. For ZnO target, n-type conductivity was achieved in argon environment, by creating oxygen deficient films. High resistivity was observed by using oxygen partial pressure, resulting in stoichiometric material and changing carrier type from electrons to holes. Higher p-type conductivity was observed, only by Seebeck measurement, for a nonintentionally heavily doped sample, as there was copper originating from the deposition chamber. For Zn target, zinc nitride formation was observed, showing high capability of transforming itself into nitrogen-doped ZnO by air exposure or thermal annealing. ZnO films produced from zinc nitride were the only ones that exhibited photoluminescence, even when there was no intentional heating involved.

Abstract The uniformity of conductive materials is an important property in thin film electronic applications such as solar cells and light emitting diodes (LED). Such uniformity variations are often very small, invisible or below the surface of the film and thus are difficult to detect even when using high-resolution characterization devices. Thus, surface measurement instruments such as profilometer, atomic force microscope, or scanning electron microscope can all encounter remarkable challenges. The uniformity of films can also be analyzed by conductivity measurements. However, they do not provide the precise spatial uniformity information of a large area sample. To be able to investigate systematically the defects of conductive thin films an appropriate sample preparation method was constructed. In addition, a synchronized heating and IR-imaging based system (called synchronized thermography = ST) was developed to overcome the limitations of existing characterization methods. ST performance was tested and analyzed by measuring the single and multi-layer structures. In this work, Indium Tin Oxide (ITO) and poly(3,4-ethylenedioxy-thiopene):poly(styrene-sulfonate) (PEDOT: PSS) were used as examples of conductive thin films. Obtained results show that ST is capable of localizing even small defects from thin film structures based on a single IR-image. In order to make automatic identification of the defect locations and the sizes of the defects, a data processing algorithm was implemented. The performed experiments have proven ST capable of determining the conductivity of the films and the critical bending curvature of ITO. Based on thin film multi-layer PEDOT:PSS measurements, the results suggest use of the ST-method is also suitable for thickness measurements. ST with automatic data processing is a simple method to localize small defects in large-area thin film structures. This approach opens up new possibilities in measuring industrial scale manufacturing processes. / Tiivistelmä Johtavien materiaalien tasalaatuisuus on tärkeä ominaisuus ohutkalvoelektroniikan sovelluksissa kuten aurinkokennoissa ja valoa emittoivissa diodeissa (LED). Tasalaatuisuuserot ovat usein erittäin pieniä, näkymättömiä tai ne sijaitsevat pinnan alla, joten niiden havaitseminen on vaikeaa jopa korkean resoluution karakterisointivälineillä. Niinpä pintaa mittaavat laitteet kuten profilometri, atomivoimamikroskooppi ja skannaava elektronimikroskooppi kohtaavat merkittäviä haasteita. Pinnan tasalaatuisuutta voidaan analysoida myös johtavuusmittauksilla. Ne eivät kuitenkaan anna täsmällistä spatiaalista informaatiota suurista näytteistä. Johtavien ohutkalvojen rikkoutumien systemaattista tutkimista varten kehitettiin oma näytteiden käsittelymenetelmä. Lisäksi kehitettiin synkronoituun lämmitykseen ja infrapunakuvantamiseen perustuva mittaussysteemi (menetelmän nimi: synkronoitu termografia = ST), jolla pyritään ratkaisemaan nykyisten menetelmien rajoitukset. ST-menetelmää testattiin ja analysoitiin mittaamalla yksi- ja monikerroksisten kalvojen rakenteita. Indiumtinaoksidia (ITO) ja poly(3,4-etyleenidioksi-tiofeeni):poly(styreeni-sulfonaatti):a (PEDOT: PSS) käytettiin esimerkkeinä johtavista kalvoista. Tulokset osoittavat, että ST kykenee paikallistamaan pienetkin virheet ohutkalvorakenteista jopa yhden infrapunakuvan perusteella. Automaattisen tiedonkäsittelyn algoritmi implementoitiin identifioimaan virheiden paikkariippuvuuksia ja kokoja. Tehdyt kokeet osoittavat, että ST-menetelmä soveltuu kalvojen johtavuuden ja ITO:n kriittisen taivutussäteen määrittämiseen. Monikerroksisiin PEDOT:PSS rakennemittauksiin perustuen ST-menetelmä näyttäisi soveltuvan myös ohutkalvojen paksuuksien määrittämiseen. ST-menetelmä yhdistettynä automaattiseen mittaustiedon prosessointiin on yksinkertainen menetelmä paikallistamaan pieniä virheitä suuripinta-alaisilla näytteillä. Tämä lähestymistapa avaa uusia mittausmahdollisuuksia teollisuuden tuotantoprosesseihin.

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Die vorliegende Dissertation befasst sich mit dem RF- überlagerten DC-Sputtern von Indiumzinnoxid und aluminiumdotierten Zinkoxid. Bei dem dafür entwickelten synchron gepulsten RF/DC-Verfahren werden die zu untersuchenden Materialien gleichzeitig mit Hilfe eines RF- und eines PulsDC-Generators gesputtert. Ein wesentliches Resultat der Untersuchungen ist, dass durch RF- überlagertes DCSputtern Schichten abgeschieden werden können, die im Vergleich zum DC- bzw. PulsDC-Sputtern geringere spezifische Widerstände aufweisen. Dies ist auf eine Verringerung von Defekten in den abgeschiedenen Schichten zurückzuführen. Es konnte anhand der Untersuchungen gezeigt werden, dass fur die Abscheidung von Indiumzinnoxid und aluminiumdotiertem Zinkoxid die Substrattemperatur beim RF überlagerten DC-Sputtern gegenüber dem DC-Sputtern um bis zu 100°C verringert werden kann.

Das Verhalten der elektronischen Eigenschaften von gespaltenen, aus der Schmelze gezüchteten In2O3-(111) Kristallen wurde bei Deposition von Edelmetallen, In und Sn mittels winkelaufgelöster Photoelektronen-Spektroskopie untersucht. Die Stöchiometrie, strukturelle Qualität und Kristall-Orientierung, die Oberflächenmorphologie und die Elektronenkonzentration wurden jeweils mittels energiedispersiver Röntgenspektroskopie, Laue-Beugung, Raster Tunnel-Mikroskopie (STM) und Hall-Effekt untersucht. Die Ähnlichkeit der fundamentalen und Oberflächen-Bandlücken kann auf das fast flache Verhalten der Bänder auf der gespaltenen Oberfläche der Kristalle zurückgeführt werden. Die Grenzflächen von Ag und Au/In2O3 zeigen Schottky-Verhalten, während ein ohmscher in Cu, In und Sn /In2O3-Kontakten beobachtet wurde. Aufgrund der Übereinstimmung zwischen optischen und Oberflächen-Bandlücken, der Bildung eines Gleichrichterkontaktes und des Auftretens der Oberflächenphotospannung auf der frischen Kristalloberfläche kann gefolgert werden, dass SEAL nicht eine intrinsische Eigenschaft der gespaltenen Oberfläche der untersuchten Kristalle ist. Des Weiteren wurden bei dicker Au- und Cu-Beschichtung von In2O3 bei Raumtemperatur Shockley-artige Oberflächenzustände beobachtet. Zusätzlich wurde die erste Phase des Wachstums von Cu und In auf In2O3 von der Ausbildung eines 2-dimensionalen Elektrongases (2DEG) begleitet, welches bei dickeren Schichten verschwand, die von dem auf reinen Oberflächen von dünnen In2O3- Filmen gemessenen 2DEG verschieden sind. Nach Messung der Austrittarbeit von In2O3 und den jeweils untersuchten Metallen in situ und unter Verwendung der Schottky-Mott-Regel trat außer bei Ag/In2O3 eine deutliche Abweichung auf. Die experimentellen Ergebnisse stimmen auch mit fortgeschrittenen Theorien, die auf dem Elektronegativitätskonzept und MIGS–Modellen basieren, nicht überein. / The behavior of the electronic properties of as-cleaved melt-grown In2O3 (111) single crystals was studied upon noble metals, In and Sn deposition using angle-resolved photoemission spectroscopy. The stoichiometry, structural quality and crystal orientation, surface morphology, and the electron concentration were examined by energy dispersive X-ray spectroscopy, Laue diffraction, scanning tunneling microscopy (STM), and Hall-effect measurement, respectively. The similarity of the measured-fundamental and surface-band gaps reveals the nearly flat behavior of the bands at the as-cleaved surface of the crystals. Ag and Au/In2O3 interfaces show Schottky behavior, while an ohmic one was observed in Cu, In, and Sn/In2O3 contacts. From agreement of the bulk and surface band gaps, rectifying contact formation as well as the occurrence of photovoltage effect at the pristine surface of the crystals, it can be deduced that SEAL is not an intrinsic property of the as-cleaved surface of the studied crystals. Moreover, for thick Au and Cu overlayer regime at room temperature, Shockley-like surface states were observed. Additionally, the initial stage of Cu and In growth on In2O3 was accompanied by the formation of a two dimensional electron gas (2DEG) fading away for higher coverages which are not associated with the earlier-detected 2DEG at the surface of In2O3 thin films. The application of the Schottky-Mott rule, using in situ-measured work functions of In2O3 and the metals, showed a strong disagreement for all the interfaces except for Ag/In2O3. The experimental data also disagree with more advanced theories based on the electronegativity concept and metal-induced gap states models.