A rapid thermal processing (RTP) reactor for the preparation of graded CuIn1-xGaxSe2-ySy (CIGSeS) thin-film solar cells has been designed, assembled and is being used at the Photovoltaic Materials Laboratory of the Florida Solar Energy Center. CIGSeS films having the optimum composition, morphology, and semiconducting properties were prepared using RTP. Initially films having various Cu/(In+Ga) ratios were prepared. In the next step selenium incorporation in these films was optimized, followed by sulfur incorporation in the surface to increase the bandgap at the surface. The compositional gradient of sulfur was fine-tuned so as to increase the conversion efficiency. Materials properties of these films were characterized by optical microscopy, SEM, AFM, EDS, XRD, GIXRD, AES, and EPMA. The completed cells were extensively studied by electrical characterization. Current-voltage (I-V), external and internal quantum efficiency (EQE and IQE), capacitance-voltage (C-V), and light beam induced current (LBIC) analysis were carried out. Current Density (J)-Voltage (V) curves were obtained at different temperatures. The temperature dependence of the open circuit voltage and fill factor has been estimated. The bandgap value calculated from the intercept of the linear extrapolation was ~1.1-1.2 eV. Capacitance-voltage analysis gave a carrier density of ~4.0 x 1015 cm-3. Semiconductor properties analysis of CuIn1-xGaxSe2-ySy (CIGSeS) thin-film solar cells has been carried out. The values of various PV parameters determined using this analysis were as follows: shunt resistance (Rp) of ~510 Ohms-cm2 under illumination and ~1300 Ohms-cm2 in dark, series resistance (Rs) of ~0.8 Ohms-cm2 under illumination and ~1.7 Ohms-cm2 in dark, diode quality factor (A) of 1.87, and reverse saturation current density (Jo) of 1.5 x 10-7A cm-2. The efficiency of 12.78% obtained during this research is the highest efficiency obtained by any University or National Lab for copper chalcopyrite solar cells prepared by RTP. CIGS2 cells have a better match to the solar spectrum due to their comparatively higher band-gap as compared to CIGS cells. However, they are presently limited to efficiencies below 13% which is considerably lower than that of CIGS cells of 19.9%. One of the reasons for this lower efficiency is the conduction band offset between the CIGS2 absorber layer and the CdS heterojunction partner layer. The band offset value between CIGS2 and CdS was estimated by a combination of ultraviolet photoelectron spectroscopy (UPS) and Inverse Photoemission Spectroscopy (IPES) to be -0.45 eV, i.e. a cliff is present between these two layers, enhancing the recombination at the junction, this limits the efficiency of CIGS2 wide-gap chalcopyrite solar cells.

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High deposition rates on large areas are industrial needs for mass production of microcrystalline silicon (μc-Si:H) solar cells. This doctoral work aims at exploring the usefulness of Matrix Distributed Electron Cyclotron Resonance (MDECR) plasmas to process the intrinsic layer of μc-Si:H p-i-n solar cells at high rates. With the high dissociation of silane achieved in MDECR plasmas, deposition rates as high as 6nm/s and 2.8nm/s have been demonstrated in our lab for amorphous and microcrystalline silicon respectively, without hydrogen dilution. This technique is also promising because it can be easily scaled up on large areas, just by extending the matrix of elementary microwave applicators. This subject was a unique opportunity to cover the whole chain of this field of research : A new MDECR reactor has been specially designed and assembled during this project. Its maintenance and its improvement have been important technical challenges : for example, the addition of a load-lock enabled us to lower the oxygen concentration in our films by a factor of 10. The impact of the deposition parameters (e.g. the ion energy, the substrate temperature, different gas mixtures, the microwave power) has been explored in extensive parametric studies in order to optimize the material quality. Great efforts have been invested in the characterization of the films. Our strategy has been to develop a wide range of diagnostics (ellipsometry, Raman spectroscopy, SIMS, FTIR, XRD, electrical characterizations etc.). Finally, p-i-n cells have been processed with the selected interesting materials. The successive successful improvements in the material quality (e.g. diffusion lengths of holes parallel to the substrate as high as 250 nm) did unfortunately not result in high efficiency solar cells. Their limited performance is in particular due to a very poor response in the red part of the spectrum resulting in low current densities. Consequently, the potential sources of limitation of the reactor, the material and the device have been studied : e.g. the presence of “cracks” prone to post-oxidation in the highly crystallized materials and the risk of deterioration of the ZnO substrate or of the p-doped layer by a too high process temperature or by hydrogen diffusing from the plasma.

Compared to wafer based solar cells, thin film solar cells greatly reduce material cost and thermal budget due to low temperature process. Monolithically manufacturing allows large area fabrication and continuous processing. In this work, several photovoltaic thin films have been developed by rf-PECVD including a-Si:H and μc-Si, both intrinsic and doped on Corning 4 inch glass substrate at low temperature. The conductivity of n type and p type μc-Si at 180ºC was 17S/cm and 7.1E-2S/cm, respectively. B dopants either in a-Si:H or μc-Si films require higher plasma power to get active doping. The B2H6-to-SiH4 flow ratio for p type μc-Si lies from 0.01 to 0.025. Chamber conditions have critical effect on film quality. Repeatable and superior results require a well-established cleaning passivation procedure. Moreover, μc-Si films have been deposited from pure silane on glass substrate by modified rf-ICP-CVD. The deposition rate has been dramatically increased to 5Å/s due to little H2 dilution with crystalline fraction was around 69%, and 6.2Å/s with crystalline fraction 45%. Microstructure started to form at 150ºC with a thin incubation layer on the glass substrate, and became fully dense conical conglomerates around 300nm where conductivity and crystallinity saturated. Additionally, a-SiGe:H films have been developed by modified rf-ICP-CVD. The optical band gaps have been varied from 1.25 to 1.63eV by changing SiH4-to-GeH4 ratio. Also high temperature resulted in low bandgap. Cross-section TEM showed some microcrystllites appeared near interface region. Heterojunction solar cells on p type c-Si wafer have been fabricated using films developed in this thesis. Interference fringes in EQE disappeared on either textured substrate or cells with lift-off contacts. Maximum EQE was 87% around 700nm. I-V curves have also been studied where the interesting kink suggests a counter-diode has formed between emitter region and contacts.

Compared to wafer based solar cells, thin film solar cells greatly reduce material cost and thermal budget due to low temperature process. Monolithically manufacturing allows large area fabrication and continuous processing. In this work, several photovoltaic thin films have been developed by rf-PECVD including a-Si:H and μc-Si, both intrinsic and doped on Corning 4 inch glass substrate at low temperature. The conductivity of n type and p type μc-Si at 180ºC was 17S/cm and 7.1E-2S/cm, respectively. B dopants either in a-Si:H or μc-Si films require higher plasma power to get active doping. The B2H6-to-SiH4 flow ratio for p type μc-Si lies from 0.01 to 0.025. Chamber conditions have critical effect on film quality. Repeatable and superior results require a well-established cleaning passivation procedure. Moreover, μc-Si films have been deposited from pure silane on glass substrate by modified rf-ICP-CVD. The deposition rate has been dramatically increased to 5Å/s due to little H2 dilution with crystalline fraction was around 69%, and 6.2Å/s with crystalline fraction 45%. Microstructure started to form at 150ºC with a thin incubation layer on the glass substrate, and became fully dense conical conglomerates around 300nm where conductivity and crystallinity saturated. Additionally, a-SiGe:H films have been developed by modified rf-ICP-CVD. The optical band gaps have been varied from 1.25 to 1.63eV by changing SiH4-to-GeH4 ratio. Also high temperature resulted in low bandgap. Cross-section TEM showed some microcrystllites appeared near interface region. Heterojunction solar cells on p type c-Si wafer have been fabricated using films developed in this thesis. Interference fringes in EQE disappeared on either textured substrate or cells with lift-off contacts. Maximum EQE was 87% around 700nm. I-V curves have also been studied where the interesting kink suggests a counter-diode has formed between emitter region and contacts.

Thin film cadmium telluride (CdTe) technology is the most important competitor for silicon (Si) based solar cells. Pulsed direct current (DC) magnetron sputtering is a new technique has been developed for thin film CdTe deposition. This technique is industrially scalable and provides uniform coating. It is also possible to deposit thin films at low substrate temperatures. A series of experiments are presented for the optimisation of the cadmium chloride (CdCl2) activation process. Thin film CdTe solar cells require CdCl2 activation process to improve conversion efficiencies. The role of this activation process is to increase the grain size by recrystallisation and to remove stacking faults. Compaan and Bohn [1] used the radio-frequency (RF) sputtering technique for CdTe solar cell deposition and they observed small blisters on CdTe layer surface. They reported that blistering occurred after the CdCl2 treatment during the annealing process. Moreover, void formation was observed in the CdTe layer after the CdCl2 activation process. Voids at the cadmium sulphide (CdS)/CdTe junction caused delamination hence quality of the junction is poor. This issue has been known for more than two decades but the mechanisms of the blister formation have not been understood. One reason may be the stress formation during CdTe solar cells deposition or during the CdCl2 treatment. Therefore, the stress analysis was performed to remove the defects observed after the CdCl2 treatment. This was followed by the rapid thermal annealing to isolate the CdCl2 effect by simply annealing. Small bubbles observed in the CdTe layer which is the first step of the blister formation. Using high resolution transmission electron microscopy (HR-TEM), it has been discovered that argon (Ar) working gas trapped during the deposition process diffuses in the lattice which merge and form the bubbles during the annealing process and grow agglomeration mainly at interfaces and grain boundaries (GBs). Blister and void formation were observed in the CdTe devices after the CdCl2 treatment. Therefore, krypton (Kr), neon (Ne) gases were used as the magnetron working gas during the deposition of CdTe layer. The results presented in this thesis indicated that blister and void formation were still existing with the use of Kr an Ne. Xe, which has a higher atomic mass than Kr, Ne, Ar, Cd and Te, was used as the magnetron working gas and it resulted in surface blister and void free devices.

To cope with energy requirements the utilization of renewable energies, particularly the Sun supplies the biggest and abundant energy source in Earth. Photo-voltaic and solar cell are the well advance and burning technology and a field of hot research. Majority of research centers and universities are working in this field. 1G, 2G, 3G and next generation of photo-voltaic cells have been developed and still to improve its efficiency and to decrease it 0.2 $/W cost. Our work mainly based on the theoretical and physical analysis of thin-film Photovoltaic devices. We will explore different software used for the analysis of PV cells, and will analyse different simulation related to solar cells like open circuit voltage VOC, Short circuit current JSC, Fill Factor FF (%) and external Quantum efficiency (%) for thin film solar cell including CIGS, CIS, CGS, CdTe, SnS/CdS/ZnO etc. To have different analysis for different combination and different replacement for materials used in the solar cell fabrication. To cope with the PV cost and environmental hazards we have to find alternate solutions. / Ullah, H. (2015). Simulation studies of photovoltaic thin film devices [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/48800

This thesis investigates the possibility of enhancing the efficiency of thin film solar cells by including periodic material nonhomogeneities in combination with periodically corrugated back reflectors. Two different types of solar cell are investigated; p-i-n junctions solar cells made from alloys of hydrogenated amorphous silicon (a-Si:H) (containing either carbon or germanium), and Schottky barrier junction solar cells made from alloys of indium gallium nitride (InξGa1-ξN). Material nonhomogeneities are produced by varying the fractions of the constituent elements of the alloys. For example, by varying the content of carbon or germanium in the a-Si:H alloys, semiconductors with bandgaps ranging from 1:3 eV to 1:95 eV can be produced. Changing the bandgap alters both the optical and electrical properties of the material so this necessitates the use of coupled optical and electrical models. To date, the majority of solar cell simulations either prioritise the electrical portion of the simulation or they prioritise the optical portion of the simulation. In this thesis, a coupled optoelectronic model, developed using COMSOL Multiphysics®, was used to simulate solar cells: a two-dimensional finite-element optical model, which solved Maxwell's equations throughout the solar cells, was used to calculate the absorption of incident sunlight; and a finite-element electrical drift-diffusion transport model, either one- or two-dimensional depending on the symmetries of the problem, was used to calculate the steady state current densities throughout the solar cells under external voltage biases. It is shown that a periodically corrugated back reflector made from silver can increase efficiency of an a-Si:H alloy single p-i-n junction solar cell by 9:9% compared to a baseline design, while for a triple junction the improvement is a relatively meagre 1:8%. It is subsequently shown that the efficiency of these single p-i-n junction solar cells with a back reflector can be further increased by the inclusion of material nonhomogeneities, and that increasing the nonhomogeneity progressively increases efficiency, especially in thicker solar cells. In the case of InξGa1-ξN Schottky barrier junction solar cells, the gains are shown to be even greater. An overall increase in efficiency of up to 26:8% over a baseline design is reported.

A deeper understanding of Cu(In,Ga)Se2 (CIGS) solar cells is important for the further improvement of these devices. This thesis is focused on the use of electrical modelling as a tool for pursuing this aim. Finished devices and individual layers are characterized and the acquired data are used as input in the simulations. Band gap gradients are accounted for when modelling the devices. The thesis is divided into two main parts. One part that treats the influence of cadmium free buffer layers, mainly atomic layer deposited (Zn,Mg)O, on devices and another part in which the result of CIGS absorber layer modifications is studied. Recombination analysis indicates that interface recombination is limitting the open circuit voltage (Voc) in cells with ZnO buffer layers. This recombination path becomes less important when magnesium is introduced into the ZnO giving a positive conduction band offset (CBO) towards the CIGS absorber layer. Light induced persistent photoconductivity (PPC) is demonstrated in (Zn,Mg)O thin films. Device modelling shows that the measured PPC, coupled with a high density of acceptors in the buffer-absorber interface region, can explain light induced metastable efficiency improvement in CIGS solar cells with (Zn,Mg)O buffer layers. It is shown that a thin indium rich layer closest to the buffer does not give any significant impact on the performance of devices dominated by recombination in the CIGS layer. In our cells with CdS buffer the diffusion length in the CIGS layer is the main limitting factor. A thinner CIGS layer improves Voc by reducing recombination. However, for thin enough absorber layers Voc deteriorates due to recombination at the back contact. Interface recombination is a problem in thin devices with Zn(O,S) buffer layers. This recombination path is overshadowed in cells of standard thickness by recombination in the CIGS bulk. Thin cells with Zn(O,S) buffer layers have a higher efficiency than CdS cells with the same absorber thickness.

Solar irradiation is a vast and plentiful source of energy. The use of photovoltaic (PV) devices to convert solar energy directly to electrical energy is an elegant way of sustainable power generation which can be distributed or in large PV plants based on the need. Solar cells are the small building blocks of photovoltaics and when connected together they form PV modules. Thin film solar cells require significantly less energy and raw materials to be produced, as compared to the dominant Si wafer technologies. CIGS thin film solar cells are considered to be the most promising thin film alternative due to its proven high efficiency. Most thin film PV modules utilise monolithic integration, whereby thin film patterning steps are included between film deposition steps, to create interconnection of individual cells within the layered structure. The state of the art is that CIGS thin film modules are made using one laser patterning step (P1) and two mechanical patterning steps (P2 and P3). Here we present work which successfully demonstrates the replacement of mechanical patterning by laser patterning methods. The use of laser ablation promises such advantages as increased active cell area and reduced maintenance and downtime required for regular replacement of mechanical tools. The laser tool can also be used to transform CIGS into a conducting compound along a patterned line. We have shown that this process can be performed after all semiconductor layers are deposited using a technique we call laser micro-welding. By performing patterning at the end of the process flow P2 and P3 patterning could be performed simultaneously. Such solutions will further reduce manufacturing times and may offer increased control of semiconductor interfaces. While showing promising performance on par with reference processes there are still open questions of importance for these novel techniques, particularly that of long term stability. Thin film modules are inherently sensitive to moisture and require reliable encapsulation. Before the techniques introduced here can be seen industrially they must have achieved proven stability. In this work we present a proof of existence of stable micro-welded interconnections. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 731