Capacitance spectroscopy in hydrogenated amorphous silicon Schottky diodes and high efficiency silicon heterojunction solar cells.

Les travaux développés dans cette thèse sont dédiés à l étude des propriétés électroniques de diodes Schottky de silicium amorphe hydrogéné (a-Si:H) et d'hétérojonctions entre silicium amorphe hydrogéné et silicium cristallin, a-Si:H/c-Si au moyen de spectroscopies de capacité de jonctions.Lors de la fabrication des cellules solaires à haut rendement plusieurs paramètres d une hétérojonction a-Si:H/c-Si doivent être considérés. Premièrement, la densité d états dans le gap du a-Si:H est d une grande importance car il s agit de défauts qui favorisent le piégeage et la recombinaison de porteurs. Deuxièmement, la détermination des désaccords des bandes entre la couche amorphe et la couche cristalline est indispensable puisque ceux-ci contrôlent le transport à travers la jonction et déterminent la courbure des bandes dans c-Si, ce qui va notamment influencer la recombinaison des porteurs sous lumière, donc la tension de circuit ouvert des cellules. Cette thèse a pour but d étudier la spectroscopie de capacité comme technique d'analyse de paramètres clés pour les dispositifs à hétérojonctions de silicium : la densité d états dans le a-Si:H et les désaccords des bandes entre a-Si:H et c-Si.La première partie est dédiée à l étude de la capacité de diodes Schottky. Nous nous concentrons sur un traitement simplifié de la capacité en fonction de la température et de la fréquence reposant sur une expression analytique obtenue par une résolution approchée de l'équation de Poisson. Ce traitement permet en principe d extraire la densité d états au niveau de Fermi dans le a-Si:H et la fréquence de saut des électrons depuis un état localisé au niveau de Fermi vers la bande de conduction. En appliquant ce traitement simplifié à la capacité calculée sans approximation à l'aide de deux logiciels de simulation numérique, nous montrons que sa fiabilité et sa validité dépendent fortement de la distribution des états localisés dans la bande interdite du a-Si:H et de la position du niveau de Fermi. Puis nous abordons l étude de la capacité des hétérojonctions entre a-Si:H de type p et c-Si de type n, et nous mettons particulièrement en avant l existence d'une couche d inversion forte à l interface dans le c-Si, formant un gaz bidimensionnel de trous. Dans une première partie, nous présentons une étude par simulation numérique de la dépendance de la capacité en fonction de la température, pour laquelle un ou deux échelons peuvent être mis en évidence à basse température. Leur analyse montre qu un des ces échelons est attribué à l activation de la réponse de la charge dans le a-Si:H, alors que l autre, présentant une énergie d'activation plus grande, est lié à la modulation de la concentration des trous dans la couche d inversion forte, lorsque celle-ci existe. On présente ensuite une discussion de résultats expérimentaux. Le régime quasi-statique de la capacité fait ainsi l objet d une discussion. Nous mettons en relief le fait que l approximation de la zone de déplétion ne permet pas de reproduire cette augmentation de la capacité en fonction de la température. Du fait de l existence de la couche d inversion forte, la chute de potentiel dans la zone de déplétion du c-Si est plus faible que la valeur déterminée par le calcul attribuant toute la chute de potentiel à la zone de déplétion. Par conséquent, cette approximation conduit à sous-estimer la capacité ainsi que son augmentation avec la température. Nous présentons alors un calcul analytique complet qui tient compte à la fois de la distribution particulière du potentiel dans le a-Si:H, et des trous dans le c-Si dont la contribution à la concentration totale de charges n'est pas négligeable dans la couche d inversion forte. Le calcul analytique complet permet de bien reproduire les résultats expérimentaux de capacité en fonction de la température; ceci confirme la présence de la couche d inversion forte dans les échantillons étudiés.In this thesis, research on a-Si:H Schottky diodes and a-Si:H/c-Si heterojunctions is presented with the focus on the capacitance spectroscopy and information on electronic properties that can be derived from this technique. Last years a-Si:H/c-Si heterojunctions (HJ) have received growing attention as an approach which combines wafer and thin film technologies due to their low material consumption and low temperature processing. HJ solar cells benefit from lower fabrication temperatures thus reduced costs, possibilities of large-scale deposition, better temperature coefficient and lower silicon consumption. The most recent record efficiency belongs to Panasonic with 24.7% for a cell of 100 cm was obtained. The aim of this thesis is to provide a critical study of the capacitance spectroscopy as a technique that can provide information on both subjects: DOS in a-Si:H and band offset values in a-Si:H/c-Si heterojunctions.The first part of the manuscript is devoted to capacitance spectroscopy in a-Si:H Schottky diodes. The interest is concentrated on the simplified treatment of the temperature and frequency dependence of the capacitance that allows one to extract the density of states at the Fermi level in a-Si:H. We focus on the study of the reliability and validity of this approach applied to a-Si:H Schottky barriers with various magnitudes and shapes of the DOS. Several structures representing n-type and undoped hydrogenated amorphous silicon Schottky diodes are modeled with the help of numerical simulation softwares. We show that the reliability of the studied treatment drastically depends on the approximations used to obtain the explicit analytical expression of the capacitance in such an amorphous semiconductor.In the second part of the chapter, we study the possibility of fitting experimental capacitance data by numerical calculations with the input a-Si:H parameters obtained from other experimental techniques. We conclude that the simplified treatment of the experimentally obtained capacitance data together with numerical modeling can be a valuable tool to assess some important parameters of the material if one considers the results of numerical modeling and performs some adjustments. The second part is dedicated to capacitance spectroscopy of a-Si:H/c-Si heterojunctions with special emphasis on the influence of a strong inversion layer in c-Si at the interface. Firstly, we focus on the study of the frequency dependent low temperature range of capacitance-temperature dependencies of a-Si:H/c-Si heterojunctions. The theoretical analysis of the capacitance steps in calculated capacitance-temperature dependencies is presented by means of numerical modeling. It is shown that two steps can occur in the low temperature range, one being attributed to the activation of the response of the gap states in a-Si:H to the small signal modulation, the other one being related to the response of holes in the strong inversion layer in c-Si at the interface. The experimental behavior of C-T curves is discussed. The quasi-static regime of the capacitance is studied as well. We show that the depletion approximation fails to reproduce the experimental data obtained for (p) a-Si:H/(n) c-Si heterojunctions. Due to the existence of the strong inversion layer, the depletion approximation overestimates the potential drop in the depleted region in crystalline silicon and thus underestimates the capacitance and its increase with temperature. A complete analytical calculation of the heterojunction capacitance taking into account the hole inversion layer is developed. It is shown that within the complete analytical approach the inversion layer brings significant changes to the capacitance for large values of the valence band offset. The experimentally obtained C-T curves show a good agreement with the complete analytical calculation and the presence of the inversion layer in the studied samples is thus confirmed.PARIS11-SCD-Bib. électronique (914719901) / SudocSudocFranceF

Development, characterization and modeling of interfaces for high efficiency silicon heterojunction solar cells

L interface entre le silicium amorphe (a-Si:H) et le silicium cristallin (c-Si) est un constituent clés de cellules solaires à haut rendement reposant sur des procédés à basse température. Trois propriétés de l interface déterminent le rendement des cellules solaires à hétérojonction de silicium: les décalages de bandes entre a-Si:H et c-Si, les défauts d interface et la courbure de bande dans c-Si. Ces trois aspects sont traités dans ces travaux de thèse.Dans un premier un temps, un calcul analytique de la courbure de bande dans c-Si est développé. Il repose sur l approximation d une densité d état (DE) constante dans la bande interdite de a-Si:H. L influence des principaux paramètres de la structure sur la courbure de bande est étudiée : décalage de bande, densité d état dans a-Si:H, défaut d interface, etc. La présence d un effet de confinement quantique est discutée. Grâce à une comparaison entre ces calculs et des mesures de conductance planaire en fonction de la température sur des structures (p)a-Si:H/(n)c-Si et (n)a-Si:H/(p)c-Si, les décalages de bande de valence et de conduction ont pu être estimés à 0.36 eV et 0.15 eV respectivement. En outre, il est montré que le décalage de la bande de valence est indépendant de la température, alors que le décalage de la bande de conduction suit les évolutions des bandes interdites de c-Si et a-Si:H. Ces mesures tendent à prouver que le branch point dans a-Si:H est indépendant du dopage.Ensuite, les calculs analytiques sont approfondis pour prendre en compte différents aspects de la structure complète incorporée dans les cellules : contact avec un oxyde transparent conducteur, présence d une couche de a-Si:H non-dopée à l interface. A l aide de simulations numériques et à la lumière de mesures de conductance planaire conjuguées à des mesures de la qualité de passivation de l interface, des pistes pour optimiser les cellules à hétérojonction sont commentées. En particulier, il est montré qu un optimum doit être trouvé entre une bonne passivation et une courbure de bande suffisante. Ceci peut être accompli par un réglage fin des propriétés de la couche tampon (épaisseur, dopage), du contact (travail de sortie élevé) et de l émetteur (p)a-Si:H (densité de défauts et épaisseur). En particulier, un émetteur avec une DE importante conduit paradoxalement à de meilleures performances.Enfin, un nouveau type d interface a été développé. La surface de c-Si a été oxydée volontairement dans de l eau pure dé-ionisée à 80 C avant le dépôt de (p)a-Si:H afin d obtenir une structure (p)a-Si:H/SiO2/(n)c-Si. A l aide d un modèle de courant par effet tunnel implémenté dans le logiciel de simulation numérique AFORS-HET, l effet d une couche à grande bande interdite (comme c est le cas pour SiO2) sur les performances de cellules est étudié : le facteur de forme et le courant de court-circuit sont extrêmement réduits. En revanche, une couche de SiO2 n a que peu d impact sur les propriétés optiques de la structure. Expérimentalement, les échantillons réalisés montrent une qualité de passivation à mi-chemin entre le cas sans couche tampon et le cas avec (i)a-Si:H : ceci est expliqué par la présence d une charge fixe négative dans l oxyde. La courbure de bande dans c-Si est moins affectée par la présence d une couche d oxyde que d une couche de (i)a-Si:H. Les cellules solaires réalisées démontrent que le concept a le potentiel d aboutir à de hauts rendements : sur des structures non-optimisées, une tension de court-circuit supérieure à 650 mV a été démontrée, alors que l oxyde ne semble pas limiter le transport de charge.The interface between amorphous silicon (a-Si:H) and crystalline silicon (c-Si) is the building block of high efficiency solar cells based on low temperature fabrication processes. Three properties of the interface determine the performance of silicon heterojunction solar cells: band offsets between a-Si:H and c-Si, interface defects and band bending in c-Si. These three points are addressed in this thesis.First, an analytical model for the calculation of the band bending in c-Si is developed. It assumes a constant density of states (DOS) in the a-Si:H band gap. The influence of most parameters of the structure on the band bending is studied: band offsets, DOS in a-Si:H, interface defects, etc. The presence of quantum confinement at the interface is discussed. Analytical calculations and temperature dependent planar conductance measurements are compared such that the band offsets on both (p)a-Si:H/(n)c-Si and (n)a-Si:H/(p)c-Si can be estimated: the valence band offset amounts 0.36 eV while the conduction band offset is 0.15 eV. In addition, it is shown that the valence band offset is independent of temperature whereas the conduction band offset follows the evolutions of c-Si and a-Si:H band gaps with temperature. A discussion of these results in the frame of the branch point theory for band line-up leads to the conclusion that the branch point in a-Si:H is independent of the doping.Then, analytical calculations are developed further to take into account the real solar cell structure where the a-Si:H/c-Si structure is in contact with a transparent conductive oxide and an undoped buffer layer is present at the interface. Measurements of the planar conductance and of the interface passivation quality are interpreted in the light of analytical calculations and numerical simulations to open a way towards a method for the optimization of silicon heterojunction solar cells. It is particularly shown that a trade-off has to be found between a good passivation quality and a significant band bending. This can be realized by tuning the buffer layer properties (thickness, doping), the TCO-contact (high work function) and the emitter (defect density and thickness). Interestingly, an emitter with a high DOS leads to better cell performances.Finally, a new type of interface has been developed, that was not applied to heterojunction solar cells so far. The c-Si surface has been oxidized in deionized water at 80 C before the (p)a-Si:H emitter deposition such that (p)a-Si:H/SiO2/(n)c-Si structures were obtained. A tunneling current model has been developed, implemented in the 1D numerical device simulator AFORS-HET and used to study the effect of a wide band gap interfacial layer (as it is the case for SiO2) on cell performance: the fill-factor and the short-circuit current are dramatically reduced for thick and high barriers. However, a SiO2 layer has only little impact on optical properties. Fabricated samples show a passivation quality halfway between samples with no buffer layer and with an (i)a-Si:H buffer layer: this is explained by the presence of a negative fixed charge in the oxide. The band bending in (n)c-Si is higher with an oxide layer than with an (i)a-Si:H buffer layer. Solar cells demonstrate that this new concept has the potential to achieve high power conversion efficiencies: for non-optimized structures, an open-circuit voltage higher than 650 mV has been demonstrated, while the oxide does not seem to create a barrier to charge transport.PARIS11-SCD-Bib. électronique (914719901) / SudocSudocFranceF

Growth Route Toward III-V Multispectral Solar Cells on Silicon

To date, high efficiency multijunction solar cells have been developed on Ge or GaAs substrates for space applications, and terrestrial applications are hampered by high fabrication costs. In order to reduce this cost, we propose a breakthrough technique of III-V compound heteroepitaxy on Si substrates without generation of defects critical to PV applications. With this technique we expect to achieve perfect integration of heterogeneous Ga1-xInxAs micro-crystals on Si substrates. In this paper, we show that this is the case for x=0. GaAs crystals were grown by Epitaxial Lateral Overgrowth on Si (100) wafers covered with a thin SiO2 nanostructured layer. The cristallographic structure of these crystals is analysed by MEB and TEM imaging. Micro-Raman and Micro-Photomuminescence spectra of GaAs crystals grown with different conditions are compared with those of a reference GaAs wafer in order to have more insight on eventual local strains and their cristallinity. This work aims at developping building blocks to further develop a GaAs/Si tandem demonstrator with a potential conversion efficiency of 29.6% under AM1.5G spectrum without concentration, as inferred from our realistic modeling. This paper shows that Epitaxial Lateral Overgrowth has a very interesting potential to develop multijunction solar cells on silicon approaching the today 30.3% world record of a GaInP/GaAs tandem cell under the same illumination conditions, but on a costlier substrate than silicon.Comment: Preprint of the 28th EUPVSEC proceedings, September 2013, Paris, France. (5 pages

Geometrical optimization and electrical performance comparison of thin-film tandem structures based on pm-Si:H and µc-Si:H using computer simulation

International audienceThis article investigates the optimal efficiency of a photovoltaic system based on a silicon thin film tandem cell using polymorphous and microcrystalline silicon for the top and bottom elementary cells, respectively. Two ways of connecting the cells are studied and compared: (1) a classical structure in which the two cells are electrically and optically coupled; and (2) a new structure for which the "current-matching" constraint is released by the electrical decoupling of the two cells. For that purpose, we used a computer simulation to perform geometrical optimization of the studied structures as well as their electrical performance evaluation. The simulation results show that the second structure is more interesting in terms of efficiency

Characterization of silicon heterojunctions for solar cells

Conductive-probe atomic force microscopy (CP-AFM) measurements reveal the existence of a conductive channel at the interface between p-type hydrogenated amorphous silicon (a-Si:H) and n-type crystalline silicon (c-Si) as well as at the interface between n-type a-Si:H and p-type c-Si. This is in good agreement with planar conductance measurements that show a large interface conductance. It is demonstrated that these features are related to the existence of a strong inversion layer of holes at the c-Si surface of (p) a-Si:H/(n) c-Si structures, and to a strong inversion layer of electrons at the c-Si surface of (n) a-Si:H/(p) c-Si heterojunctions. These are intimately related to the band offsets, which allows us to determine these parameters with good precision

Epitaxy and characterization of InP/InGaAs tandem solar cells grown by MOVPE on InP and Si substrates

The integration of III-V multi-junction solar cells on Si substrates is currently one of the most promising possibilities to combine high photovoltaic performance with a reduction of the manufacturing costs. In this work, we propose a prospective study for the realization of an InP/InGaAs tandem solar cell lattice-matched to InP on a commercially available Si template by direct MOVPE growth. The InP top cell and the InGaAs bottom cell were firstly separately grown and optimized using InP substrates, which exhibited conversion efficiencies of 13.5% and 11.4%, respectively. The two devices were then combined in a tandem device by introducing an intermediate InP/AlInAs lattice-matched tunnel junction, showing an efficiency of 18.4%. As an intermediate step towards the realization of the tandem device on Si, the InP and InGaAs single junction solar cells were grown on top of a commercial InP/GaP/Si template. This transitional stage enabled to isolate and evaluate the effects of the growth of III-V on Si on the photovoltaic performance through the comparison with the aforementioned devices on InP. Each cell was electrically characterized by external quantum efficiency and dark and illuminated current-voltage under solar simulator. The material quality was also analyzed by means of X-ray diffraction, Atomic-Force Microscopy, Transmission Electron and Scanning Electron Microscopy. The III-V on Si devices showed efficiencies of 3.6% and 2.0% for the InP and InGaAs solar cells, respectively

Conductive-probe atomic force microscopy characterization of silicon nanowire

The electrical conduction properties of lateral and vertical silicon nanowires (SiNWs) were investigated using a conductive-probe atomic force microscopy (AFM). Horizontal SiNWs, which were synthesized by the in-plane solid-liquid-solid technique, are randomly deployed into an undoped hydrogenated amorphous silicon layer. Local current mapping shows that the wires have internal microstructures. The local current-voltage measurements on these horizontal wires reveal a power law behavior indicating several transport regimes based on space-charge limited conduction which can be assisted by traps in the high-bias regime (> 1 V). Vertical phosphorus-doped SiNWs were grown by chemical vapor deposition using a gold catalyst-driving vapor-liquid-solid process on higly n-type silicon substrates. The effect of phosphorus doping on the local contact resistance between the AFM tip and the SiNW was put in evidence, and the SiNWs resistivity was estimated

The Completed SDSS-IV extended Baryon Oscillation Spectroscopic Survey: Large-scale structure catalogues for cosmological analysis

We present large-scale structure catalogues from the completed extended Baryon Oscillation Spectroscopic Survey (eBOSS). Derived from Sloan Digital Sky Survey (SDSS) IV Data Release 16 (DR16), these catalogues provide the data samples, corrected for observational systematics, and random positions sampling the survey selection function. Combined, they allow large-scale clustering measurements suitable for testing cosmological models. We describe the methods used to create these catalogues for the eBOSS DR16 Luminous Red Galaxy (LRG) and Quasar samples. The quasar catalogue contains 343 708 redshifts with 0.8 1000 km s−1). For quasars, these rates are 95 and 2 per cent (with Δz > 3000 km s−1). We apply corrections for trends between the number densities of our samples and the properties of the imaging and spectroscopic data. For example, the quasar catalogue obtains a χ2/DoF = 776/10 for a null test against imaging depth before corrections and a χ2/DoF= 6/8 after. The catalogues, combined with careful consideration of the details of their construction found here-in, allow companion papers to present cosmological results with negligible impact from observational systematic uncertainties

Measurement of inclusive π0\pi^{0} production in hadronic Z0Z^{0} decays

An analysis is presented of inclusive \pi^0 production in Z^0 decays measured with the DELPHI detector. At low energies, \pi^0 decays are reconstructed by \linebreak using pairs of converted photons and combinations of converted photons and photons reconstructed in the barrel electromagnetic calorimeter (HPC). At high energies (up to x_p = 2 \cdot p_{\pi}/\sqrt{s} = 0.75) the excellent granularity of the HPC is exploited to search for two-photon substructures in single showers. The inclusive differential cross section is measured as a function of energy for {q\overline q} and {b \bar b} events. The number of \pi^0's per hadronic Z^0 event is N(\pi^0)/ Z_{had}^0 = 9.2 \pm 0.2 \mbox{(stat)} \pm 1.0 \mbox{(syst)} and for {b \bar b}~events the number of \pi^0's is {\mathrm N(\pi^0)/ b \overline b} = 10.1 \pm 0.4 \mbox{(stat)} \pm 1.1 \mbox{(syst)} . The ratio of the number of \pi^0's in b \overline b events to hadronic Z^0 events is less affected by the systematic errors and is found to be 1.09 \pm 0.05 \pm 0.01. The measured \pi^0 cross sections are compared with the predictions of different parton shower models. For hadronic events, the peak position in the \mathrm \xi_p = \ln(1/x_p) distribution is \xi_p^{\star} = 3.90^{+0.24}_{-0.14}. The average number of \pi^0's from the decay of primary \mathrm B hadrons is found to be {\mathrm N} (B \rightarrow \pi^0 \, X)/\mbox{B hadron} = 2.78 \pm 0.15 \mbox{(stat)} \pm 0.60 \mbox{(syst)}