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This paper describes an investigation into the fabrication of absorber layer CuInSe2 films by co-evaporation process. And we used the stainless steel substrates to manufacture Al / ZnO:Al / ZnO /CdS / CuInSe2 / Mo / SLGTF / Stainless Steel(SS) flexible thin-film solar cell. The flexible solar cells were fabricated using soda-lime glass thin layers (SLGTL) as a diffusion barrier layer and an alkali source material deposited on various flexible substrates prior to the Mo backcontact layer deposition. Mo back contact layers were deposited by DC sputtering. The CIS absorber layers were grown by the two-stage process using a molecular beam epitaxy (MBE) apparatus. Then the CdS buffer layer was deposited by the chemical bath, RF sputter deposition of intrinsic ZnO and ZnO:Al (AZO) layer. Under the same process condition, using SLGTF as diffusion barrier layer improved open circuit voltage (Voc) 16.7% and short circuit current density (Jsc) 9.8%.

Photoreflectance (PR) is a sensitive technique to measure semiconductor properties at room temperature due to its derivative nature. The normalized

This thesis studies the effects of Na diffusion in Cu(In,Ga)Se2 (CIGS) solar cells,caused by electrical Potential Induced Degradation (PID) and how to prevent it. Thiswas done by subjecting CIGS solar cells a temperature of 850C and an electrical biasfrom the backside of the glass substrate to the Mo back contact of the CIGS cell.When the bias was negative at the back contact the Na diffused in to the CIGS(degradation) and when it was positive the ions diffused out again (recovery). TheCIGS samples were electrically characterized with IV- and EQE-measurements duringthese conditions and compositional depth profiling was used to track the Nadistribution.This study showed that during degradation Na seemed to accumulate in the interfacesbetween the different layers in the CIGS cell. The buffer and window layers arestrongly affected by Na diffusion. Zn(O,S) buffer layer showed a clear difference inrecovery behavior compared to CdS buffer layer. The introduction of an Al2O3barrier layer between the CIGS and Mo back contact increased the degradation timefrom 50 h to 160 h. During this study it was also found that in some cases the CIGSsolar cells efficiency could be improved by degrading the cells and then recoveringthem, in the best case from 13% average energy efficiency to 15% efficiency.

La connaissance approfondie sur la luminescence des dispositifs photovoltaïques (PV) en a fait un outil de caractérisation puissant qui capte l'intérêt de la recherche et des industries du PV. Dans cette thèse, nous nous concentrons sur la luminescence des cellules solaires photovoltaïques à base de Cu(In,Ga)Se2. En particulier, nous explorons et revisitons ses dépendances temporelles, spectrales et spatiales. Cela a abouti dans un premier temps à la mise au point de nouvelles méthodes de caractérisation basée sur la luminescence de cette technologie PV en particulier. Nous montrons d’abord que par l’intermédiaire d'une méthode sans contact toute optique, nous sommes en mesure de détecter et de localiser les métastabilités de cette technologie. En utilisant une approche numérique basée sur des résultats expérimentaux de photoluminescence résolue en temps (TRPL) nous avions réussi à quantifier la densité des défauts de piégeage qui sont derrière ces métastabilités. Une fois quantifiée, nous traduisons cette densité en pertes absolues de performance PV de la cellule solaire. Ensuite, en explorant la dépendance spatiale de la luminescence des cellules solaires à base de Cu(In,Ga)Se2, nous avions corrélé avec succès, ses aspects temporels et spectrales en se basant sur la microscopie confocale à balayage et l’imagerie hyperspectrale. Cela nous a permis de généraliser nos résultats précédents à l'échelle globale des cellules solaires. Cette partie de la thèse nous a aidés à mieux comprendre une des origines fondamentales derrière l’inhomogénéité spatiale de la luminescence de ce type de dispositifs photovoltaïques.La dernière partie de la thèse était essentiellement technique et exploratoire. En particulier, nous introduisons une nouvelle technique optique dans le domaine de la caractérisation des dispositifs PV. Cette technique est dédiée à l’imagerie résolue en temps du temps de vie de fluorescence (TR-FLIM). Le principe de cette technique consiste essentiellement en acquisition d'images de luminescence du dispositif PV qui sont résolues temporellement. Avec ce nouveau dispositif expérimental, nous sommes maintenant en mesure de résoudre spatialement, et en temps réel la dynamique des porteurs de charge d'une technologie photovoltaïque donnée et accéder à ses propriétés électroniques clés. Une première démonstration a été faite sur une cellule solaire à base de GaAs, et pour laquelle nous avions extrait optiquement, la longueur de diffusion, la mobilité et le temps de vie de ses porteurs. De plus, nous avions pu estimer le coefficient de diffusion du matériau et son taux de dopage. / The extensive knowledge on the luminescence of photovoltaic (PV) devices has made it a powerful characterization tool that captures the interest of both research and industrial PV communities. In this thesis, we focus on the luminescence of Cu(In,Ga)Se2-based solar PV. In particular, we explore and revisit the luminescence temporal, spectral and spatial dependencies. This resulted in the development of new luminescence-based characterization methods for this particular PV technology. We show initially that by means of an all-optical, contactless methodology, we are able to detect and localize the metastabilities of this technology. Using a numerical approach based on experimental time-resolved photoluminescence (TRPL) we managed to quantify the trapping defects that are behind these metastabilities. Once quantified, we translated it into absolute losses in the PV performance of the solar cell. By exploring the spatial dependence of the luminescence of Cu(In,Ga)Se2 solar cells, we successfully correlated its temporal and spectral aspects based on scanning confocal microscopy and hyperspectral imaging. This allowed us to generalize our previous findings at the global solar cell scale. This part of the thesis helped us better understand one of the fundamental origins behind the spatially inhomogeneous luminescence of Cu(In,Ga)Se2 PV devices. The final part of the thesis was mainly technical and exploratory. In particular, we introduced a new optical technique to the field of PV characterization. It is dedicated to time-resolved fluorescence lifetime imaging (TR-FLIM) which basically consists of acquiring time-resolved luminescence images of the PV device. With this new setup we are now able to spatially resolve, in real-time the charge carrier dynamics of a given PV technology and access its key electronic properties. A first application was made on a GaAs-based solar cell, for which we were able to optically extract the mobility, diffusion length and lifetime of its carriers. Finally, we were also able to estimate the diffusion coefficient of the material and its doping density.

The photovoltaic solar cell industry is growing rapidly, but high cost per watt is still an obstacle. Thin film solar cells, especially thin film solar cells using CIGS absorbers that have the highest proven efficiency, have the potential to reduce the cost through cheap manufacturing. Academic research concerning CIGS solar cells has so far been focused on cells with absorber layers deposited by co-evaporation, which can be used to make very high efficiency cells but is a deposition process ill suited for large scale production. In this thesis a process for depositing CIGS absorber layers by gas flow sputtering, a deposition technique enabling high rate depositions of low energy particles that is potentially easier to apply to a large scale production, has been outlined. Equipment for CIGS-deposition by gas flow sputtering has been prepared, characteristics of the process have been investigated and ultimately a series of first prototype CIGS absorber layers has been deposited as part of complete solar cells. A lot of focus in this thesis is on the practical work and problem solving around the equipment, e.g. pulsed DC power supplies and electrical connections, heating and heating control in a reactive vacuum environment, and on the basic functionality of the gas flow sputter, how process and film properties like deposition rate, thickness uniformity etc. vary with sputter conditions like pressure, gas flow etc. Following the process design the first prototype series produced crystalline CIGS absorbers of desired elemental composition and thickness but having rather small grain sizes, while the complete cells exhibited solar cell IV-characteristics but very poor efficiencies.

It is widely known that the element sodium plays a vital role in providing highefficiency CIGS solar cells and that when cells are built on sodium free substrates theyneed an alternative (a substitute) sodium source. In this study a molybdenum-sodiumcompound has been deposited, investigated and evaluated as an alternative backcontact layer containing sodium. The compound had a 5 at % sodium concentrationand it was manufactured by an Austrian company called Plansee. The aim of the studywas to create an equivalent back contact in the sense of sodium delivery, conductivityand adhesion compared to a normal molybdenum back contact on a soda lime glass. The experimental part of the study started with the construction of complete cells,which were fabricated and measured. This work took place at the ÅngströmLaboratory, Uppsala University, Sweden. The characteristics of the layer and the cellswere analyzed by current voltage measurements, quantum efficiency measurementsand secondary ion mass spectrometry analysis. Cell manufacturing involved sputtering,co evaporation and chemical deposition processes. Results show that the molybdenum-sodium compound increases the efficiency of acell built on a sodium-free substrate. Efficiencies reached 8 % for cells without sodiumin the molybdenum and these cells produced 67 % efficiency and 80 % open circuitvoltage of the reference value. Cells with sodium in the back contact layer produced90 % of the efficiency and 95% of the open circuit voltage relative to the references.The best cell with the molybdenum-sodium compound reached an efficiency of 13.3%. This implies that the new back contact layer acts as a sodium source but the cellshave 1-2 % lower efficiency than the reference cells built on soda lime glass. Othercharacteristics of the layer as conductivity and adhesion show no significant differenceto an ordinary molybdenum back contact. Measurements also indicate that the sodium is probably located inside themolybdenum grains and just a small amount is found at the boundaries and in betweenthe grains. Sodium inside the molybdenum grains is difficult to extract and thereforenot enough sodium will diffuse into the CIGS layer. The conclusions drawn from this study are that the molybdenum-sodium compoundhelps to increase the efficiency of a CIGS solar cell built on a sodium-free substrate,but it does not deliver enough sodium to constitute a substitute sodium source.

The buffer layer in Cu(In,Ga)Se2 solar cells can improve cell performance. In this work we make CdS buffer layer by chemical bath deposition (CBD) without ammonia. CBD without ammonia were sought out since ammonia is a volatile compound. Different recipes for making CdS were tested; only one of the tested recipes actually produced something that is worth further investigating. This recipe used sodium citrate, an innocuous compound instead of ammonia. The best performance was 0.15 % off from the reference.This is almost as good as the used baseline process. However the worst almost completely killed the solar cells. Cell performance dropped by more than absolute 10 %. This demonstrates that chemical bath deposition can have profound effects on the solar cell performance. When trying to improve the best cells only detrimental effects showed up. This might show that, a part in the recipe used, NaOH has detrimental effects on solar cells. Ammonia free chemical bath deposition is possible, however so far it has not produced as good results as the reference. The difference is however very small, which makes it worth further investigating with moreand better solar cell material.

Low-cost and high-efficiency are of continuous interest for the fabrication of solar cells. I-III-VI compound semiconductors Cu(In,Ga)Se2 (CIGS) are the most important absorber materials in developing thin film solar cells. The bandgap of CIGS varies from about 1.1 to 1.7 eV, which is within the maximum solar absorption region. This is very important for the optimum conversion efficiency. The extraordinarily high absorption coefficient from direct bandgap leads to thinner thickness and lower fabrication cost for its use in thin film solar cells. In this experiment, we deposit CuInGa alloy layer on Mo-coated soda-lime glass by RF sputtering and then use selenization process to form Cu(In,Ga)Se2. We study the characterization of sputtered CIG alloy layer and selenized CIGS thin film.

In this experiment, selenides are used as the precursor and CIGS thin films are synthesized through selenization. At the first stage, the precursor with the layers of In-Se/Ga-Se/Cu-Se failed to produce CIGS thin films when the temperature is going up 10¢J per minute to the target temperature during selenization and the change of the composition of the precursor, the temperature duration and the temperature of selenization is tried. Later, the reaction is successfully done when the layers are changed into In-Ga-Se/Cu-Se with the temperature going up 10¢J per minute to 550¢J, lasting for 5 minutes. With various Ga containments, I analyize the optical and electronic properties. In order to see the composition of CIGS thin films in different propotion of Cu/In+Ga and Ga/In+Ga, I use EPMA and the properties of XRD peak shift with the containment of Ga to estimate the proportion of the containment of Ga. I found the conclusions by EPMA and XRD are very similar. At 150¢J, the precursors Cu-Se, In-Se and Ga-Se are fabricated and XPS, Raman, XRD or else are used to speculate the bonding of them. In addition, using XRD and Raman to analyze In-Ga-Se/Cu-Se selenides, I found, between 150¢J and 300¢J, Cu2-xSe bonding is the main; at 350¢J, InSe bonding intensifies obviously; at 400¢J, CIGS is formed.