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We report on a growth study of MgO films deposited on Al2O3(0001) substrates by magnetron sputtering. The films exhibited a preferred rocksalt MgO(111) orientation. Surprisingly, depending on the O2 gas flow ratio, a structure of graphiticlike wurtzite MgO(0001) has been revealed. The observed Mg-O perpendicular bond length reduction is accompanied by an atomically flat surface morphology for the development of MgO(111) films; the transition to the bulk rocksalt structure occurs in the 3-6 nm coverage range. Previously, relaxation of the electrostatic instability of MgO(111) films accompanied by an in-plane lattice increase has been suggested theoretically [Phys. Rev. Lett. 98, 205701 (2007)]. Here, relying on ab initio calculations, we infer that Mg vacancies facilitate the lattice match with the substrate. This mechanism suggests methods to engineer oxide heterostructures.

The scaling up of the Hot Wire Chemical Vapor Deposition (HW-CVD) technique to large deposition area can be done using a catalytic net of equal spaced parallel filaments. The large area deposition limit is defined as the limit whenever a further increment of the catalytic net area does not affect the properties of the deposited film. This is the case when a dense catalytic net is spread on a surface considerably larger than that of the film substrate. To study this limit, a system able to hold a net of twelve wires covering a surface of about 20 cm × 20 cm was used to deposit amorphous (a-Si:H) and microcrystalline (μ c-Si:H) silicon over a substrate of 10 cm × 10 cm placed at a filament-substrate distance ranging from 1 to 2 cm. The uniformity of the film thickness d and optical constants, n (x, λ) and α (x, ħω), was studied via transmission measurements. The thin film uniformity as a function of the filament-substrate distance was studied. The experimental thickness profile was compared with the theoretical result obtained solving the diffusion equations. The optimization of the filament-substrate distance allowed obtaining films with inhomogeneities lower than ±2.5% and deposition rates higher than 1 nm/s and 4.5 nm/s for (μ c-Si:H) and (a-Si:H), respectively. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

A transparent and conducting ZnO:Er:Yb thin film with upconversion properties has been achieved after being annealed with continuous laser radiation just before the ablation point of the material. This work demonstrates that the laser energy preserves the conductivity of the film and at the same time creates an adequate surrounding for Er and Yb to produce visible upconversion at 660, 560, 520, and 480 nm under 980 nm laser excitation. The relation between the structural, electrical and upconversion properties is discussed. It is observed that the laser energy melts part of the material, which recrystallizes creating rare earth oxides and two different wurtzite structures, one with substitutional rare earths and oxygen vacancies (responsible for the conductivity) and the other without substitutional rare earth ions (responsible for the upconversion emission). (C) 2017 Elsevier B.V. All rights reserved.

Aluminium induced texturing (AIT) method has been used to texture glass substrates to enhance photon absorption in microcrystalline thin film Si solar cells. In this process, a thin Al film is deposited on a glass substrate and a non-uniform redox reaction between the glass and the Al film occurs when they are annealed at high temperature. After etching the reaction products, the resultant glass surface presents a uniform and rough morphology. In this work, three different textures (sigma(rms) similar to 85, similar to 95, similar to 125 nm) have been achieved by tuning the dc sputtering power and over them and over smooth glass, pin micro crystalline silicon solar cells have been fabricated. The cells deposited over the textured substrates showed an efficiency improvement in comparison to the cells deposited over the smooth glass. The best result was given for the glass texture (sigma(rms)similar to 125 nm that led to an average efficiency 2.1% higher than that given by the cell deposited on smooth glass. (C) 2015 Elsevier B.V. All rights reserved.

[eng] The objective of this work was to study two different light management approaches to enhance the efficiency of thin film Si solar cells and these were the manipulation of the light path (light trapping) and changing the incoming photon energy (upconversion). In the first approach the light path was manipulated by creating either periodic or random textured interfaces. Periodic patterns were created at the front AZO by means of direct laser ablation. Amongst all the patterns assessed, the best result was achieved with a linear pattern of 10 lam of pitch and 360 nm of groove depth, that yielded to an Rs of 11 SI/sq and a haze of 12.7% at 600 nm. However structures in the sub-micrometer range cannot be created because the minimum period is limited by the laser spot. By means of the Aluminum Induced Texturing method (AIT) random textures were performed on glass substrates. In this method, a thin Al film is deposited onto a glass substrate and a redox reaction between the Al and the SiO2 of the glass is induced by high temperature annealing. The reaction products are wet-etched and the result is a uniform and rough glass surface. The process parameters were varied in order to control the resultant glass roughness and it was found that the most critical was the Al deposition method. By using evaporation smooth U-shaped craters morphology and roughness up to 90 nm were created, whereas the sputtered films resulted in rough and porous textures with roughness until 145 nm. AZO grown over the U-shape crater morphology led to a double texture with haze values above 10% at 600 nm, transparency above 84%, and Rs-7 SI/sq whereas AZO over very rough glass resulted in a cauliflower-like surface with haze values >32% at 600 nm, Rs around 9.5 SI/sq and transmittance of 74%. A-Si:H solar cells were deposited on different AIT textures and an improvement of the short circuit current, as well as a reduction of the device reflectivity was achieved in all cases in comparison to the cells deposited on smooth glass textures. The second approach was to create a transparent and conducting upconverter to be used on top of the rear reflector of a thin film Si solar cell. For that purpose, ZnO was doped with Er and Yb ions and was post-annealed under different treatments. The unique spectral properties of rare earth (RE) elements due to their electronic configuration occur as a result of their intra 4f-4f shell transitions. In the case of Er, its excitation takes places at 1500 nm and 980 nm and the upconverted photons are emitted within the Si absorption range. Moreover, codoping with Yb can enhance the Er visible emission because they cooperate together due to the matching of their energy levels for k=980 nm. As deposited ZnO doped with rare earths (RE) was found to be transparent and conducting but not luminescent. RE ions need to be surrounded by 6 oxygen in a distorted octahedron to be optically active and REs replacing zinc in the ZnO lattice do not present this symmetry; hence, a post deposition treatment is needed. When the films were post-annealed in air, visible upconversion (UC) was seen at 660 nm under 980 nm laser excitation, however, the films become almost insulating. When the films were annealed in vacuum, lower UC luminescence was achieved, and the resistivity increased 1 order of magnitude. By using CW laser radiation, the electrical properties were maintained and high UC was observed. UC came from clusters of RE06 as well as from RE203 inside or outside the matrix. When annealing in air, in vacuum or by laser radiation, oxygen from the atmosphere bound to the RE to form RE oxides and/or RE06 complexes but just laser annealing was able to preserve the conductivity while producing optically active centers., [cat] L'objectiu d'aquesta tesi és la millora de l'eficiència de les cèl•lules solars de silici en capa prima mitjançant l'estudi de nous mètodes per a l'aprofitament de la llum solar al dispositiu. El primer mètode consisteix en texturar el substrat de vidre per dispersar la llum incident i així incrementar l'absorció en la capa activa. El mètode emprat es la texturització induïda per alumini (AIT); que es basa en una reacció de reducció no uniforme entre el vidre i una capa prima d'alumini gràcies a un tractament tèrmic. Posteriorment els productes de la reacció s'eliminen mitjançant una solució basada en àcid i el resultat és un vidre transparent i texturat. S'ha fet un estudi de la rugositat en funció dels paràmetres del procés i s'ha aconseguit obtenir rugositats controlades i uniformes en superfícies de fins a 10x 10 cm2. Diferents textures s'han provat en cèl.lules solars de silici amorf i s'ha demostrat l'eficàcia d'aquestes en la millora del corrent respecte a les mateixes cèl•lules dipositades sobre vidre pla. El segon mètode estudiat és el fenomen de l'up-conversion que consisteix en la conversió de fotons de baixa energia (EEg) que podran ser absorbits en la zona activa; així doncs s'ha intentat fer una capa conductora, transparent i amb propietats d'up-conversion per utilitzar com a contacte per a cèl• lules solars. Per aquest propòsit s'han estudiat capes conductores i transparents d'òxid de zinc dopat amb erbi i iterbi dipositades per polvorització catòdica sobre vidre. Com que les terres rares han d'estar envoltades d'oxigen per actuar com a centres òptics actius, i en les capes de ZnO:Er:Yb no es dóna aquesta configuració, les capes s'han hagut de sotmetre a diferents tractaments tèrmics, com escalfament en aire, en buit o escalfament amb làser. Escalfant en aire o en buit s'aconsegueix obtenir up-conversion però la conductivitat disminueix notablement, en canvi, escalfant amb radiació làser es possible de mantenir les propietats elèctriques i a més, activar òpticament les terres rares.

Texturing of glass substrate instead of using conventional naturally textured transparent conducting oxidesis a good alternative to enhance light absorption in thin film silicon solar cells. In this work, we present textured glass substrates with two extremely different roughness values (rms =56 nm and rms =146 nm), achieved through the aluminium induced texturing method. Al-doped ZnO front contacts were deposited over both these textured glasses by sputtering resulting in a double texture based on U-shape craters for the softer roughness, and a cauliflower-like textured surface for the higher roughness one. The morphology, structure, optical and electrical properties of the ZnO:Al layers deposited over these textured glasses are described and the suitability of these textured substrates for thin film Si solar cells (c-Si p type/ a-Si p-i-n) is also presented. Refereed/Peer-reviewed

Aluminium induced texturing (AIT) method has been used to texture glass substrates in order to enhance the photon absorption in thin film solar cells. The resultant glass roughness has been analyzed by varying the AIT process parameters and it has been found that the deposition method of Al is a decisive factor in tuning the texture. Two types of textures, a soft (texture E) and a rough texture (texture S), were achieved from the thermally evaporated and sputtered Al layers through AIT process. Aluminium-doped zinc oxide (AZO) layers of different thickness were deposited over both textures and over smooth glass. Haze values above 30% were obtained for texture S + AZO and above 10% for texture E + AZO. The resultant morphologies were free from sharp edges or deep valleys and the transparency and the resistivity values were also good enough to be used as front contact for thin film solar cells. In order to demonstrate the light absorption enhancement in a solar cell device, 200 nm of a-Si:H followed by 300 nm of Ag were grown over the textured and smooth substrates with AZO, and an optical absorption enhancement of 35% for texture E and 53% for texture S was obtained in comparison to the smooth substrate. Refereed/Peer-reviewed

The optical reflection losses at the transparent conducting oxide/a-Si p-layer interface in superstrate thin film silicon solar cells can be reduced by introducing a TCO having intermediate refractive index value. Nb doped TiO2 (NTO) with refractive index 2.5 to 2.8 in the visible wavelength range was used to form a graded index structure at the TCO/p-layer interface. The optimum thickness of the NTO layer to reduce the reflection losses was found to be around 30 nm. Thin layers of NTO show high optical transmission above 80%, a band gap of 3.62 eV and a resistivity of 2×10-3 Ω·cm. NTO layers of 20, 30 and 40 nm have been deposited over flat FTO and Asahi U substrates, and amorphous silicon thin film solar cells were fabricated over this graded TCO stack. The cells over the flat FTO showed an increase in Voc values when intermediate NTO layer was used. An increase in Jsc value was also observed for cells with NTO over Asahi U substrate. Refereed/Peer-reviewed

[eng] The objective of the present work is to provide a better understanding of magnetron sputtered transparent conducting oxides based on ZnO in order to use them as electrodes in thin film silicon solar cells at the Grup d'Energia Solar of the Universitat de Barcelona. This thesis presents the properties of magnetron sputtered aluminium and gallium doped ZnO as well as the properties of multi-compound materials deposited by the co-sputtering of zinc oxide and indium tin oxide. The application of ZnO based transparent conducting oxides to the back reflector of pin amorphous solar cells is also discussed. A set of aluminium doped zinc oxide layers were deposited under different substrate temperature and discharge power. The structural, electrical and optical properties were characterised and discussed. The higher substrate temperatures and discharge powers used during deposition led to highly transparent layers in the visible range with lower resistivities. The polycrystalline layers were oriented with the c-axis perpendicular to the substrate surface and the crystalline quality of the layers improved at higher temperatures and powers. A remarkable increase in mobility was found for temperatures above 300°C and the carrier concentration also rose with temperature reaching 3.71x1020 cm-3 at 420°C. The most remarkable feature found at higher deposition power was the increase in deposition rate (from 0.9 to 9 nm/min). By means of a high temperature (650°C) annealing process under a capping layer of silicon or alumina, the mobility of aluminium doped zinc oxide layers was considerably raised achieving 68.5 cm2V-1s-1. This process led also to more transparent layers in the near infrared as well as in the ultraviolet part of the spectrum. Gallium doped zinc oxide films were deposited in order to investigate the suitability of gallium as a dopant in zinc oxide layers. Highly transparent layers with higher carrier concentrations but lower mobilities compared to aluminium doped zinc oxide were obtained. The dependence of the layer properties on the pressure, doping concentration, substrate temperature and oxygen volume concentration during deposition were studied in order to find the adequate layer to be applied as electrode in thin film solar cells. 4 wt.% Ga2O3 doping concentration was found to be optimal for the production of highly conductive ZnO:Ga layers with a high band gap energy. The incorporation of oxygen gas during the sputter deposition led to more transparent layers at wavelengths longer than 1100 nm, but was found to be detrimental for the electrical properties of the studied layers. By means of co-sputtering, a set of multi-compound layers formed by Zn-In-Sn-O were deposited and carefully characterised. The resulting layers were studied as a function of the Zn content ratio, which varied between 17.1 to 67.3%. The layers were amorphous in nature but presented embedded nanometric crystals. The incorporation of Zn cations into an indium tin oxide matrix favoured the transmittance but did not modify the mobility. The carrier concentration was found to decrease resulting in an increase in resistivity. The electronic band structure was investigated by means of photoelectron spectroscopy. The measurements showed that, with an increase in Zn concentration, the oxygen vacancy concentration of the surface increased resulting in a degenerately n-doped surface layer. The work function of the material was determined by low intensity X-ray photoelectron spectroscopy and the values varied between 4.7 and 4.3 eV with the variation of Zn content. The final experiments were focussed on the application of ZnO layers in the back reflectors of pin amorphous silicon solar cells. Trials were performed onto pin structures deposited at T-Solar Global SA and the Universitat de Barcelona. The cells deposited at T-Solar were long exposed to air before a back reflector could be deposited and evidence for the formation of a thin silicon oxide layer at the interface was obtained. The oxide layer was removed using acid etching in dilute HF, but an analysis by X-ray photoelectron spectroscopy showed that the cleaning step resulted in an important amount of carbon contamination on the surface. Both, the silicon oxide and the carbon layer led to devices with S-shaped J-V curves. Later, the n-type interface was protected by a thin ZnO:Al layer at T-Solar to avoid oxidation during transportation. However, the existence of this thin ZnO:Al protective layer determined the growth of the subsequently deposited layers. Thus, the deposition of ZnO layers under different conditions led to similar results. Finally, different back reflectors were tried over the solar cells fabricated at UB. Aluminium and gallium doped zinc oxide layers were deposited on amorphous silicon pin structures, and a clear improvement in performance with respect to devices with only a metal layer as back reflector was observed. Similar performances were observed when Ga doped ZnO or Al doped ZnO was used in the back reflector. It showed that both gallium and aluminium were suitable dopants for the ZnO to be applied in the back reflector., [cat] L'objectiu d'aquest treball rau en l'estudi i optimització dels òxids conductors transparents basats en l'òxid de zinc. Aquests materials, que s'han dipositat mitjançant polvorització catòdica magnetró, es van estudiar amb la finalitat d'emprar-los com elèctrodes en cèl•lules solars de silici en capa prima al Grup d'Energia Solar de la Universitat de Barcelona. En aquesta tesi es presenten les propietats de l'òxid de zinc dopat amb alumini o amb gal•li, així com les propietats de multi-compostos dipositats a partir de la co-polvorització catòdica d'òxid de zinc i d'òxid d'indi dopat amb estany. També es discuteix l'aplicació d'òxids conductors transparents basats en l'òxid de zinc al reflector posterior de cèl•lules solars de silici amorf amb estructura tipus pin. S’ha trobat que l’òxid de zinc dopat amb alumini, a altes temperatures de substrat i altes potències, presenta una elevada transmitància òptica i una baixa resistivitat. La mobilitat de les capes augmentà considerablement fins assolir 68.5 cm2V-1s-1 mitjançant l'aplicació de tractaments tèrmics a alta temperatura previ dipòsit d'una capa protectora de silici amorf o d'alúmina. Pel cas de l'òxid de zinc dopat amb gal•li s'han obtingut una sèrie de capes altament transparents i amb concentracions de portadors superiors, però amb mobilitats inferiors que les de capes dopades amb alumini. Mitjançant co-polvorització d’òxid de zinc i òxid d’indi dopat amb estany s’han obtingut capes amorfes del multi-compost Zn-In-Sn-O amb un contingut de zinc que varia entre el 17.1 i el 67.3%. La incorporació del zinc a l'òxid d'indi dopat amb estany afavoreix l'increment de la transmitància, sense que la mobilitat de les capes es vegi afectada. En canvi, la concentració de portadors disminueix amb la incorporació de Zn. Comparant l'ús del gal•li i de l'alumini com a dopants de l'òxid de zinc del reflector posterior de cèl•lules de silici amorf tipus pin, s'ha observat una gran similitud en el comportament dels dispositius. Això ens ha portat a la conclusió que ambdós materials són adients per ser emprats com a reflectors posteriors.

Texturing of glass substrate is an interesting alternative to enhance light trapping in thin silicon solar cells instead of using conventional naturally textured transparent conducting oxides. In this work, aluminium induced texturing method is used to obtain borofloat glass substrates with σrms values in the range 70 – 90 nm. Al-doped ZnO is deposited by sputtering onto textured glass to provide the front contact for thin film silicon solar cells. Morphology and optical properties of the textured glass substrates, as well as morphology, optical and electrical properties of the ZnO:Al layers deposited on them are described. The application of these textured substrates to a-Si solar cells is also presented. The use of this approach leads to devices with short-circuit currents similar to those obtained with optimized commercial TCO substrates. Refereed/Peer-reviewed

Tese de mestrado, Engenharia Física, Universidade de Lisboa, Faculdade de Ciências, 2009 Submitted by Teresa Boa (tdboa@fc.ul.pt) on 2011-11-23T16:01:27Z No. of bitstreams: 1 ulfc096088_tm_Silvia_Barros.pdf: 2241218 bytes, checksum: 4730789bc48b159a62197479de109507 (MD5) Made available in DSpace on 2011-11-23T16:01:39Z (GMT). No. of bitstreams: 1 ulfc096088_tm_Silvia_Barros.pdf: 2241218 bytes, checksum: 4730789bc48b159a62197479de109507 (MD5) Previous issue date: 2009