We have examined effects of gas velocity and gas pressure on a deposition rate of hydrogenated amorphous silicon (a-Si:H) films and on a volume fraction of clusters in the films using a multi-hollow discharge plasma CVD method. The maximum deposition rate realized for each pressure exponentially increases with decreasing the pressure from 1.0 Torr to 0.1 Torr, whereas the volume fraction of clusters very slightly increases with increasing the deposition rate. Based on the results, we have succeeded in depositing highly stable a-Si:H films of 4.9×1015cm-3 in a stabilized defect density at a rate of 3.0nm/s using the method.

The road to achieve ultra high efficiency is through multi-junction solar cells operating at high solar concentrations, larger than 1000 suns. Critical to the success of this approach is the development of tunnel junctions (TJ) that serve as electrically low loss interconnections, yet are optically transparent, using high band gap semiconductor material systems. We have previously reported the fabrication of a TJ made of n+-InGaP/ p+-AlGaAs with a band gap about 1.9 eV using Se and C doping, respectively. This TJ structure has a peak current density of 88 A/cm2 allowing it to be implemented in a three junction cell structure at solar concentrations as high as 4000 suns (x4000). Almost all reported conversion efficiencies higher than 40% have used this tunnel junction. This very high peak current density is unexpected in a high band gap material system, which is good news for the multi junction solar community. This seems to be due to the fact that the InGaP/AlGaAs interface has a staggered band line up. We will present the effect of this band line up at the heterointerface and its effect on the width of the depletion region and the peak current density. We also compare the current result from this heterostructure junction with an artificial homojunction made of n+-AlGaAs/ p+-AlGaAs doped to the same levels as that of the heterojunction. Results from the homojunction showed that peak current density is about one half of that obtained from the heterojunction at the same doping levels. A reasonable match between experimental result and the model was obtained when a value of 150 meV was used for ΔEc, the conduction band discontinuity at the interface. Both experiment and theory predicted that at a current density of about 80 A/cm2 with only about a few tens of meV drop across the TJ. This will have a minimal effect on the overall efficiency of the tandem solar cell structure when used at high solar concentrations.

The present communication will present the results obtained at CEA/LETI in Grenoble, France, in the frame of an experimental work finalized to directly test the criticalities and chances of this technology row. By means of Closed Space Sublimation (CSS) and Chemical Bath Deposition (CBD) processes, appropriate annealing treatments and specific CdTe-contacting procedures, we reached the state-of-art of this technology with about 15% conversion efficiency under standard illumination conditions in “superstrate” cells configuration both for structures deposited on 3 mm thick low-iron containing sodalime glass (SLG) and Borosilicate glass (BSG).

We report on epitaxial growth of ZnO on polycrystalline and (112) orientated CuInS2 and CuInSe2 thin films. Step-by-step growth and investigation by photoelectron spectroscopy (PES) and low energy electron diffraction (LEED) provided information on the growth mode and the electronic structure of the ZnO-CuInS2-interface. During the initial growth no ZnO is deposited. Instead a monolayer of ZnS is formed by depletion the CuInS2 surface of excess sulfur. Thereafter, the ZnO growth starts on the ZnS buffer layer. The band alignment derived from PES shows that the ZnS buffer layer is thin enough to provide a beneficial band alignment for photovoltaic applications. CuInSe2 (112) samples showed a similar behaviour, but at the chosen deposition temperature of 450°C only ZnSe growth is detected. At lower temperatures ZnO growth on top of ZnSe is observed. XPEEM experiments show an inhomogeneous interface.

Hydrogen is commonly introduced into silicon solar cells to reduce the deleterious effects of defects and to increase cell efficiency. We have developed strategies by which hydrogen in silicon can be detected by IR spectroscopy with high sensitivity. The introduction of hydrogen into Si by the post-deposition annealing of a hydrogen-rich, SiNx coating has been investigated to determine hydrogen's concentration and penetration depth. Different hydrogenation processes were studied so that their effectiveness for the passivation of bulk defects could be compared. The best conditions investigated in our experiments yielded a hydrogen concentration near 1015 cm-3 and a diffusion depth consistent with the diffusivity of H found by Van Wieringen and Warmoltz.

The performance of polymer-based photovoltaic devices is limited by several factors like high band-gap and low charge-carrier mobility, to name a few. Thicker active-layers have high optical absorption but the transport of carriers in them is inefficient. Thus the optimal thickness of the active-layers has to be determined carefully. This conflict can be resolved using a three-dimensional (3D) microscale textured grating shaped solar cell geometry. The solar cells in this study were fabricated on photoresist gratings to give them 3D texture required for enhanced light absorption. Introduction of texturing has a significant effect on over all power conversion efficiency of the devices. Grating based solar cell having 2 micron pitch showed improved power conversion efficiency over the flat solar cell. In addition to favorable guiding of optical modes, the improvement in efficiency is accomplished by homogenous coverage of the spin-coated active layer, which is a challenging process for non-flat surfaces. Uniform thickness in this study was facilitated by the sufficiently high pitch and low height of the underlying photoresist gratings.

A systematic study on the effect of sputtering deposition parameters on material properties of Al doped ZnO (ZnO:Al) films prepared by an in-line rf magnetron sputtering and on surface morphology of the films after wet etching process was carried out. For application to silicon thin film solar cells as a front electrode, the as-deposited films were surface-textured by a dilute HCl solution to improve the light scattering properties such as haze and angle resolved distribution of scattered light on the film surfaces. The microstructure of as-deposited films is affected significantly by the working pressure and film compactness decreases with increasing working pressure from 1.5 mTorr to 10 mTorr. High quality ZnO:Al films with electrical resistivity of 4.25 × 10-4 Ω cm and optical transmittance of 80% in a visible range are obtained at low working pressure of 1.5 mTorr and substrate temperature of 100℃. Crater-like surface morphologies are observed on the textured ZnO:Al films after wet etching. The size and shape of craters are closely dependent on the microstructure and film compactness of as-deposited films. Haze values of the textured ZnO:Al films are improved in a whole wavelength of 300 – 1100 nm compared to commercial SnO2:F films (Asahi U type) and incident light on the textured films is scattered effectively with 30° angle.

Many impurity complexes in silicon such as boron-oxygen and iron-boron complexes are found to be bistable. Commonly bistable recombinative complexes in silicon are studied through carrier lifetime experiments and are analysed by use of Shockley-Read-Hall (SRH) recombination theory. SRH recombination theory is valid for stable defects with one configuration and one energy level in the band gap, however, the theory might fail upon considering the recombination centers through bistable defects, which can be in two different configurations separated by a potential barrier. This work presents a study of electrical properties of silicon with bistable impurity complexes. The analysis has been performed for statistics of free electrons and holes, their recombination rate and lifetime. The results have been compared with those obtained from the Shockley-Read-Hall recombination theory.

Since the initiation and propagation of a micro-crack in a silicon wafer introduces local variations in stress, it is critical to the understanding of wafer breakage that accurate profiling of stress be performed in the vicinity of the micro-crack. In this study, nanoindentation has been used to investigate the stress-relaxation during crack initiation and propagation in material of particular interest to the photovoltaic (PV) industry. The low load (<1 mN) capability of a Hysitron Triboindenter® was used to accurately profile the extent of plastic deformation and resulting amorphization. Measurements were made on Si samples extracted from top, middle and bottom of a (100) oriented single crystal ingot to evaluate the impact of different carbon, oxygen and metallic impurity concentrations. A gradual but significant drop in hardness from 10.2 to 6.9 GPa occurred as indents were made closer to the micro-crack and was attributed to local amorphization. Electron back scattered diffraction (EBSD) and Raman spectroscopy confirmed the amorphization, respectively, at nano- and micro-scale.

Deposition of MgHx (MgH2 + Mg) thin films is performed using RF reactive sputtering in argon-hydrogen plasma. Films are characterized using x-ray diffraction (XRD), scanning electron microscopy, optical and resistivity measurements. Formation of crystalline MgH2 is confirmed by XRD, but the formation of some metallic Mg in the films could not be avoided. Increased H/Mg ratio by deposition at high hydrogen flow or high total pressure gives films that oxidize within days or weeks. Deposition at elevated substrate temperature results in improved crystallinity and stability. Initial studies of MgHx for silicon surface passivation are presented.

Different methods for Na incorporation are known for the use of Na-free substrates like stainless steel or polyimide foil. In this work Cu(In,Ga)Se2 (CIGS) absorber layers with different amounts of Na are investigated. The CIGS samples were prepared via a roll-to-roll deposition process with ion beam assistance (Solarion) and by a multi-stage low temperature co-evaporation process (HZB). Na was either incorporated via in-situ co-evaporation of NaF (for roll-to-roll deposition) or by a Na-containing precursor (for multi-stage deposition). With increasing amounts of Na an increase of VOC is observed for both deposition tech-niques. In contrast, within the deposition parameters used, jSC decreases with increasing Na amount for co-evaporation of NaF while it seems unaffected when using a NaF precursor layer. The elemental depth profiles of the different CIGS thin films were studied via secondary ion mass spectroscopy and were found to depend strongly on the deposition technique. It seems that beneficial effects of the addition of Na are independent of the method of in-corporation, even if the distribution of Na in the CIGS layer is different due to different methods of incorporation and CIGS deposition processes.

In situ, real time spectroscopic ellipsometry (RTSE) has been used to study the growth processes and optical properties of Cu2-xSe - an important binary compound in the fabrication of high efficiency copper indium gallium diselenide (CIGS) photovoltaic devices. It was found that the high surface roughness of the Cu2-xSe layers necessitated a “graded” optical model in order to extract meaningful dielectric functions at both 550 °C and room temperature. The optical model was verified at room temperature against SEM micrographs and reflectance measurements carried out ex situ. The growth temperature dielectric functions presented in this study are expected to allow for a greater level of control and understanding of the so-called 2- and 3-stage processes for CIGS fabrication in which a Cu2-xSe phase, present at the CIGS grain boundaries, acts as a fluxing agent for the growth of photovoltaic quality CIGS. Real time optical feedback via RTSE combined with the growth temperature dielectric functions presented here could play an important role in improving material fabrication on both the laboratory and industrial scales.

The InAs/InGaAs DWELL solar cell grown by MBE is a standard pin diode structure with six layers of InAs QDs embedded in InGaAs quantum wells placed within a 200-nm intrinsic GaAs region. The GaAs control wafer consists of the same pin configuration but without the DWELL structure. The typical DWELL solar cell exhibits higher short current density while maintaining nearly the same open-circuit voltage for different scales, and the advantage of higher short current density is more obvious in the smaller cells. In contrast, the smaller size cells, which have a higher perimeter to area ratio, make edge recombination current dominant in the GaAs control cells, and thus their open circuit voltage and efficiency severely degrade. The open-circuit voltage and efficiency under AM1.5G of the GaAs control cell decrease from 0.914V and 8.85% to 0.834V and 7.41%, respectively, as the size shrinks from 5*5mm2 to 2*2mm2, compared to the increase from 0.665V and 7.04% to 0.675V and 8.17%, respectively, in the DWELL solar cells. The lower open-circuit voltage in the smaller GaAs control cells is caused by strong Shockley-Read-Hall (SRH) recombination on the perimeter, which leads to a shoulder in the semi-logarithmic dark IV curve. However, despite the fact that the DWELL and GaAs control cells were processed simultaneously, the shoulders on the dark IV curve disappear in all the DWELL cells over the whole processed wafer. As has been discussed in previous research on transport in QDs, it is believed that the DWELL cells inhibit lateral diffusion current and thus edge recombination by collection first in the InGaAs quantum well and then trapping in the embedded InAs dots. This conclusion is further supported by the almost constant current densities of the different area DWELL devices as a function of voltage.

Incorporating O2 in the closed space sublimation (CSS) of CdTe thin film has resulted in improved cell efficiencies. Many studies have been undertaken to understand this effect on cell efficiency. In this work we study the effect of oxygen on lateral uniformity of the deposited CdTe film. A finite element model has been developed to represent the mass and heat transfers involved in the CSS process. The model takes into consideration the effect of O2 by modeling its reaction with Cd vapors in the space between the source and the substrates and with the CdTe source. So a gradient of O2 from the edges to the center of the substrate can result in non-uniform oxidation of the source and subsequently a laterally non-uniform film. A steady state model solved at various temperatures, pressures, and separation distances. O2 concentration gradient was found to depend on the oxidation rate of Cd vapors and thus on temperature, total pressure, and oxygen partial pressure in the system.

In order to reduce the power-generating cost of silicon solar cells, it is necessary to achieve a high conversion efficiency using a thinner crystalline silicon (c-Si) substrate. The HIT (Heterojunction with Intrinsic Thin-layer) solar cell is an amorphous silicon (a-Si) / c-Si heterojunction solar cell that exhibits the potential to make this possible. Our recent R&D activities have achieved the world’s highest conversion efficiency of 23.0% with a practical sized (100.4 cm2) HIT solar cell, by improving the quality of the surface passivation, reducing the optical absorption loss and reducing the resistance loss. We have also developed a HIT solar cell with a thickness of only 98 mm, which has a very high conversion efficiency of 22.8%. This value is comparable to that of the conventional HIT solar cell, which has a thickness of more than 200 mm. Moreover, we have fabricated HIT solar cells using thinner c-Si substrates (96 to 58 μm), and found that the Voc increased with decreases in the substrate thickness, and reached an extremely high value of 0.745 V with a thickness of only 58 μm. This indicates that the surface recombination velocity of the HIT structure is extremely low due to the excellent passivation of the c-Si surface.

Thin films of CuInSe2 (CIS) and CuGaSe2 (CGS) were deposited on (100) Si substrates by RF magnetron sputtering using stoichiometric targets, at various substrate temperatures. Prior to film deposition, the Si substrates were cleaned using the RCA cleaning procedure and treated in a buffered oxide etch (BOE) solution. Deposited films were characterized using Rutherford backscattering spectroscopy (RBS), transmission electron microscopy (TEM) of cross-sectional samples and Hall measurements. Rutherford backscattering analysis indicated that the CIS films had a composition of Cu0.8In1.1Se1.9, whereas CGS films were Cu-poor and Ga-rich with a composition of Cu0.3Ga1.5Se1.5. Clean Cu-chalcopyrite/Si interfaces were obtained using BOE treated Si substrates. Transmission electron micrographs of cross-sectional samples indicated a polycrystalline film structure and that the native oxide on the Si substrate was eliminated. Energy dispersive X-ray spectroscopy (EDS) conducted in the TEM showed that contamination levels in the films were low. The Hall-mobility experiments performed the CIS film indicated that the material was of p-type conductivity with a carrier concentration of 9.6 x 1020/cm3 and a Hall mobility of 390 cm2V-1s-1.

The relation between impurity content in Solar Grade Silicon (SGS) and solar cell quality is the subject of intensive research. The PV industry has developed around the use of silicon made by the Siemens process for the semiconductor industry, with impurity levels typically in the parts per billion by weight (ppbw) range. There is a growing consensus that SGS with impurities in the parts per million range (ppmw) can be obtained cost effectively from Metallurgical Grade Silicon (MGS) and used to yield solar cells with comparable performance (see for example ‘Beneficial Effects of Dopant Compensation on Carrier Lifetime in Upgraded Metallurgical Silicon’ by S. Dubois et al. in the 23rd European Photovoltaic Solar Energy Conference, Valencia, September, 2008). This provides insight on the success encountered by Timminco, an early SGS market entrant, in commercializing silicon material with [P] levels of the order of 2 ppmw. Current Work We have successfully reduced P to about 2 ppmw, a level that appears acceptable for solar cell fabrication, by application of a novel unidirectional solidification (UDS) technique at a 50% material yield. This is important as UDS, by its nature, implies a loss of silicon, while little or no silicon is lost in B reduction, partially achieved in this furnace using a glass slagging process. Figure 1 shows [P] data from 16 UDS runs on samples taken from the melt, before and after UDS, and a solid sample taken from the silicon frozen on the cold silicon collection surface. The error bars represent a standard 20% error value. We note that the average values of [P] in the molten silicon samples increase from 11.9 ppmw before UDS to 15.9 ppmw after UDS. The average value of [P] in the solid silicon sample is 4.9 ppmw. The average value of the solid silicon, 4.9 ppmw P, taken with the average value of the starting silicon, 11.9 ppmw P, demonstrates an effective refining ratio of 0.41, even at a 50% solid fraction. Performing a second UDS on silicon obtained from runs in Figure 1, yields [P] around 2 ppmw (Figure 2).In addition to P and B reduction, in this paper we also discuss the hardware designed to implement this process in commercial production in volumes exceeding 4,000 MT per year. MB Scientific, the original process developer, and NC Consulting, an engineering company, have developed a plant design that can produce SGS at an estimated cost that will allow for profitable large scale production, and have joined in a new company, Silicon Forge, to commercialize the large-scale production technology.

In this paper, fired and non-fired direct PECVD deposited Si-SiNx interface properties with and without NH3 pretreatment on both n- and p-type mono-crystalline silicon samples were investigated with deep-level transient spectroscopy (DLTS) measurements. A and B defect states are identified at the Si-SiNx interface. Energy-dependent electron and hole capture cross sections were measured by small-pulse DLTS. Fired samples with NH3 pretreatment show the lowest DLTS signals, which suggests the lowest overall Dit. The combination of NH3 pretreatment and firing is also suggested for application in the solar cell fabrication.

There are several ways to nanostructure Si. Some of them, e.g. nanoscale Si-layerd systems buried within the n+ layer of a crystalline Si can provide an initial material with unpredicted optoelectronic behavior. Such a transformation leads to a PV Si metamaterial, whose optoelectronic properties arise from qualitatively new response functions that are (i) not observed in the constituent materials and (ii) result from the inclusion of artificially fabricated, intrinsic and extrinsic, low-dimensional components. We show that an extremely strong c-Si:P absorptance, is larger than can result from conventional conversion because the surface population increases by injection of additional carriers from a nanostratum (transformed up to a Si-metamaterial) lying just behind the top c-Si:P-layer.

CuInGaSe2 (CIGS) is a prominent thin-film photovoltaic material. However, commonly used physical vapour deposition and sputtering techniques used to fabricate CIGS thin-film photovoltaic (PV) devices are complex and expensive. Therefore non-vacuum deposition techniques such as paste coating, spray pyrolysis and electro deposition are gaining more attention in recent years. Our intention is to choose a low cost non-vacuum technique like mechano-chemical synthesis of CIGS powder, followed by screen printing. Mechano chemical synthesis is a process that induces physical and/or chemical change in the compounds by mechanical energy, such as pulverization, friction or compression. This method has some advantages for the mass production of CIGS solar cells, high productivity and short processing cycle time. In the present work CIGS powders suitable for screen-printing ink has been prepared by ball milling. High purity elemental copper granules (>99.9% pure), selenium and indium powders (>99.9% pure) and fine chips of gallium (>99.9% pure) were used as the starting materials. Ball milling was carried out for an optimized composition of CuIn0.75Ga0.25Se2 using a SPEX-8000 mixer/mill at 1200 rpm for 1.5 hours. X-ray diffraction analysis of the milled powder shows the presence of (112), (220)/ (204), (312)/ (116), (400) and (332) peaks corresponding to CIGS chalcopyrite structure with a preferential orientation along (112) peak. The average grain size calculated by Scherrer’s formula is about 12.24 nm. Crystallographic structure of the prepared CIGS powder was analyzed by Rietveld analysis using X-ray powder diffraction data. Geometry optimization of the structure was performed and the basic structural properties have been evaluated by density functional approximation and compared with experimental results. Density of states has been simulated for the same structure inorder to have a better understanding of the distribution of atomic orbitals. FESEM analysis shows the agglomeration of nano particles. Particle size varied from 11 to 30nm. Final composition of the milled powder studied by Energy dispersive X-ray analysis gives 24.39 at% Cu, 21.42 at% In, 7.22 at% Ga and 46.97 at% Se. HRTEM analysis reveals the presence of nano crystalline particles. The interplanar distance (d-spacing) corresponding to (112), (220)/ (204), (512)/ (417) and (620)/ (604) diffraction peaks has been estimated and compared with standard values and the corresponding diffraction pattern has been simulated with simulaTEM software. CIGS ink is prepared by proper mixing of the powder with a suitable organic binder (ethyl cellulose). Screen printing is carried out on glass substrates, followed by annealing at 5 different temperatures of 300,350,400,450 and 500 degrees, in order to form a porous CIGS film. XRD analysis was carried out to study the structure of screen printed CIGS.