Fabrication et caractérisation de nanocristaux de silicium encapsulés dans des matrices siliciées amorphes : rôle des interfaces et de la matrice sur les propriétés structurales, optiques et électriques

En raison de leurs propriétés nouvelles, les matériaux composites à base de nanocristaux de silicium (nc-Si) contenus dans des matrices siliciées amorphes suscitent un intérêt grandissant pour les nombreuses applications envisagées dans les domaines de l'électronique et du photovoltaïque. La fabrication de ces nanostructures est parfaitement compatible avec les technologies existantes. Toutefois, afin d'être intégrés avec succès dans ces dispositifs, les nc-Si et leur environnement doivent avoir des propriétés maitrisées. Dans ce contexte, le travail de thèse a consisté en l'élaboration et la caractérisation de couches de carbure et nitrure de silicium contenant des nc-Si. Ces deux matrices ont retenu notre attention en raison de leur gap intermédiaire entre la silice et le silicium qui permettrait d'obtenir des propriétés améliorées pour les composants électriques. Deux techniques de fabrication ont été étudiées : la nucléation/croissance de nc-Si sur des couches minces a-SiCx par dépôt chimique en phase vapeur à basse pression (LPCVD), et le dépôt par CVD assisté par plasma pulsé (PPECVD) d'alliages a-SiNx riches en Si, suivi d'un recuit à haute température. Lors de l'interprétation des résultats, une attention particulière a été portée aux effets de surface/interface et au rôle de la matrice sur les propriétés mesurées. Après avoir étudié et maitrisé les conditions de dépôt d'alliages a-SiCx:H par PECVD, nous montrons que la nucléation/croissance de nc-Si sur une surface a-Si0,8C0,2 par LPCVD est favorisée en raison de la concentration en Si élevée de la matrice. Des densités surfaciques de nc-Si supérieures à 1012 cm-2 ont ainsi été atteintes, même pour des temps de dépôt courts ou des débits de silane faibles. Ces premiers résultats indiquent la faisabilité de ce type de structure. Une étude approfondie sur le couple nc-Si/nitrure de silicium a ensuite été menée. Les propriétés structurales, optiques et électriques de couches de nitrure contenant des nc-Si ont été caractérisées à partir d'un large éventail de techniques. Après avoir estimé la taille des nc-Si par spectroscopie Raman, la déconvolution des spectres XPS nous a permis d'expliquer les processus de formation des nc-Si lors du recuit et de proposer un modèle pour décrire la structure des interfaces nc-Si/a-Si3N4. Les propriétés optiques des nc-Si ont ensuite été déterminées par ellipsométrie spectroscopique et spectrophotométrie UV-Vis. L'élargissement du gap, le lissage des constantes diélectriques et l'augmentation du coefficient d'absorption aux faibles énergies avec la diminution de la taille des particules suggèrent un effet de confinement quantique au sein des nc-Si. Des mesures de photoluminescence résolue en temps nous ont permis de conclure que l'utilisation d'une matrice de nitrure est peu appropriée à l'étude de l'émission optique des nc-Si en raison des nombreux défauts radiatifs et non radiatifs présents dans la matrice et aux interfaces. Enfin, les mécanismes de transport des porteurs de charge à travers la couche nanocomposite ont été étudiés à partir de mesures courant-tension. En raison de son caractère percolé, la couche se comporte de façon analogue à une couche de Si polycristallin avec une faible concentration de liaisons pendantes du Si. Un effet de photoconduction attribué aux nc-Si est observé, ce qui offre des perspectives de travail intéressantesDue to their specific properties, silicon nanocrystals (Si-nc) embedded in dielectric matrix have recently attracted much interest for their use in silicon-based devices. The fabrication of these nanostructures is fully compatible with the existing technologies. However, in order to develop efficient devices, the properties of the Si-nc and their host matrix have to be strictly controlled. In this work, Si-nc embedded in silicon carbide or silicon nitride matrix have been fabricated and characterized to provide a better understanding of the structural, optical and electrical properties. These two matrices received our attention because of their intermediate gap between silicon and silicon dioxide which is expected to give improved properties for electrical components. Two synthesis techniques have been used: the nucleation/growth of Si-nc on a-Si0,8C0,2 thin films by low pressure chemical vapor deposition (LPCVD), and the deposition by pulsed plasma enhanced chemical vapor deposition (PPECVD) of Si-rich a-SiNx alloys followed by high temperature annealing. During the results interpretation, a particular attention was paid to the surface/interface effects as well as the influence of the matrix. After analyzing and controlling the deposition parameters of a-SiCx:H alloys by PECVD, we showed that the nucleation/growth of Si-nc on a-Si0,8C0,2 surface by LPCVD is appropriate because of the high Si content in the carbide matrix. We obtained Si-nc densities higher than 1012 cm-2, even for low growth time or SiH4 flow rates. These results show the feasibility of such structure. A detailed study of the Si-nc/silicon nitride couple was then realized using a large range of diagnostics. First, it was shown that the size of Si-nc can be estimated by Raman spectroscopy. We also explained the process of Si-nc formation during annealing and suggested a model for the structure of Si-nc/a-Si3N4 interfaces from the deconvolution of the XPS spectra. Then, the optical properties of Si-nc were determined by spectroscopic ellipsometry and UV-Vis spectroscopy. The increase of the gap, broadening and weakening of the dielectric constants, and increase of the absorption coefficient at low energy suggest a confinement effect in the Si-nc. Time-resolved photoluminescence measurements indicated that the use of a nitride matrix would not be appropriate to the study of Si-nc optical emission, due to the large number of radiative and non-radiative defects in the matrix and at the interfaces. Finally, charge carriers transport mechanisms through the nanocomposite layer were determined through current-voltage measurements. Because the percolation threshold is reached, the film embedding Si-nc behaves as polycristalline Si with a low amount of Si dangling bonds. A photoconduction effect is observed which gives interesting works in sigh

Radiation Hardness of Perovskite Solar Cells Based on Aluminum‐Doped Zinc Oxide Electrode Under Proton Irradiation

Due to their high specific power and potential to save both weight and stow volume, perovskite solar cells have gained increasing interest to be used for space applications. However, before they can be deployed into space, their resistance to ionizing radiations such as high‐energy protons must be demonstrated. In this report, we investigate the effect of 150 keV protons on the performance of perovskite solar cells based on aluminium‐doped zinc oxide (AZO) transparent conducting oxide (TCO). Record power conversion efficiency of 15% and 13.6% were obtained for cells based on AZO under AM1.5G and AM0 illumination, respectively. We demonstrate that perovskite solar cells can withstand proton irradiation up to 1013 protons.cm−2 without significant loss in efficiency. At this irradiation dose, Si or GaAs solar cells would be completely or severely degraded when exposed to 150 keV protons. From 1014 protons.cm−2, a decrease in short‐circuit current of the perovskite cells is observed, which is consistent with interfacial degradation due to deterioration of the Spiro‐OMeTAD HTL during proton irradiation. Using a combination of non‐destructive characterization techniques, results suggest that the structural and optical properties of perovskite remain intact up to high fluence levels. Although shallow trap states are induced by proton irradiation in perovskite bulk at low fluence levels, they can release charges efficiently and are not detrimental to the cell's performance. This work highlights the potential of perovskite solar cells based on AZO TCO to be used for space applications and give a deeper understanding of interfacial degradation due to proton irradiation

Characterization of stability of benchmark organic photovoltaic films after proton and electron bombardments

Organic solar cells have attractive potential for space applications as they have very high specific power (power generated per weight) and ultra-high flexibility (to reduce stowed volume). However, one critical issue is whether they are stable under the harsh space environment, particularly their stability under high energy, high flux, electron and proton bombardment. In this paper, the stability of benchmark organic photovoltaic layers under proton bombardment (150 keV with a fluence of 1 × 1012/cm2) and electron bombardment (1 MeV with a fluence of 1 × 1013/cm2) under vacuum is investigated. Raman spectroscopy, photoluminescence spectroscopy, and optical reflectance spectroscopy are applied to study their chemical/structural, photo-chemical/morphological, and optical stability after the bombardments. The results show that all the benchmark organic photovoltaic films are stable under the radiation, implying that organic solar cells could be feasible for space applications

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation

<p>Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C₇₁ butyric acid methyl ester (BTR:PC₇₁BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV–vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation – rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra.</p

Proton Radiation Hardness of Perovskite Solar Cells Utilizing a Mesoporous Carbon Electrode

Funder: Airbus Endeavr WalesFunder: Alexander von Humboldt FoundationWhen designing spacefaring vehicles and orbital instrumentation, the onboard systems such as microelectronics and solar cells require shielding to protect them from degradation brought on by collisions with high‐energy particles. Perovskite solar cells (PSCs) have been shown to be much more radiation stable than Si and GaAs devices, while also providing the ability to be fabricated on flexible substrates. However, even PSCs have their limits, with higher fluences being a cause of degradation. Herein, a novel solution utilizing a screen‐printed, mesoporous carbon electrode to act bi‐functionally as an encapsulate and the electrode is presented. It is demonstrated that the carbon electrode PSCs can withstand proton irradiation up to 1 × 1015 protons cm−2 at 150 KeV with negligible losses (<0.07%) in power conversion efficiency. The 12 μm thick electrode acts as efficient shielding for the perovskite embedded in the mesoporous TiO2. Through Raman and photoluminescence spectroscopy, results suggest that the structural properties of the perovskite and carbon remain intact. Simulations of the device structure show that superior radiation protection comes in conjunction with good device performance. This work highlights the potential of using a carbon electrode for future space electronics which is not limited to only solar cells

Microstructural and optical characterization of silicon nitride alloy thin films aiming at an optimization of the matrix properties for tandem cells

International audienc

Microstructural and optical characterization of silicon nitride alloy thin films aiming at an optimization of the matrix properties for tandem cells

International audienc

Microstructural and optical characterization of silicon nitride alloy thin films aiming at an optimization of the matrix properties for tandem cells

International audienc

Elaboration par PPECVD de couches minces de SiNx contenant des nanocristaux de silicium : estimation de la taille et de la dispersion en taille des cristallites par spectroscopie Raman

National audienc

Caractérisation par spectroscopie Raman de nanocristaux de silicium encapsulés dans des couches minces de SiNx

National audienc