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The technical and economic feasibility of producing solar-cell-quality sheet silicon was investigated. The sheets were made by coating one surface of carbonized ceramic substrates with a thin layer of large-grain polycrystalline silicon from the melt. Significant progress was made in all areas of the program.
Closely-spaced crucible cover speeds up solidification. Growth rate of dendritic-web silicon ribbon from molten silicon increased by controlling distance between crucible susceptor lid and liquid/solid interface. Lid held in relatively high position when crucible newly filled with chunks of polycrystalline silicon. As silicon melts and forms pool of liquid at lower level, lid gradually lowered.
The technical and economic feasibility of producing solar cell quality sheet silicon was investigated. It was hoped this could be done by coating one surface of carbonized ceramic substrates with a thin layer of large-grain polycrystalline silicon from the melt. Work was directed towards the solution of unique cell processing/design problems encountered with the silicon-ceramic (SOC) material due to its intimate contact with the ceramic substrate. Significant progress was demonstrated in the following areas; (1) the continuous coater succeeded in producing small-area coatings exhibiting unidirectional solidification and substatial grain size; (2) dip coater succeeded in producing thick (more than 500 micron) dendritic layers at coating speeds of 0.2-0.3 cm/sec; and (3) a standard for producing total area SOC solar cells using slotted ceramic substrates was developed.
The results of the study form a basis for silicon producers, wafer manufacturers, and cell fabricators to develop appropriate cost-benefit relationships for the use of less pure, less costly solar grade silicon. Cr is highly mobile in silicon even at temperatures as low as 600 C. Contrasting with earlier data for Mo, Ti, and V, Cr concentrations vary from place to place in polycrystalline silicon wafers and the electrically-active Cr concentration in the polysilicon is more than an order of magnitude smaller than would be projected from single crystal impurity data. We hypothesize that Cr diffuses during ingot cooldown after growth, preferentially segregates to grain and becomes electrically deactivated. Accelerated aging data from Ni-contaminated silicon imply that no significant impurity-induced cell performance reduction should be expected over a twenty year device lifetime.
Due to its many excellent properties, diamond is being explored as a material for MicroElectroMechanical Systems (MEMS). However, as is true in the case of silicon, a large amount of basic material characterization issues still warrant investigation. This paper presents preliminary results from charged particle irradiation of Chemical Vapor Deposited (CVD) polycrystalline diamond films. The films were simultaneously dosed to a level of 9.4 x l0(exp 13)/sq cm using 700 keV protons and 1 MeV electrons. The samples were then subject to cross-sectional nanoindention analysis and Raman spectroscopy. Polycrystalline silicon was also investigated for comparison purposes. The diamond was unaffected by the irradiation. However, the silicon did indicate a slight decrease in the Young's Modulus.
A detailed cost analysis of solar cell module manufacturing, utilizing process sequences incorporating near-term technology, has been performed. The entire structuring of a factory to manufacture solar cell modules, starting from supplied polycrystalline silicon and other raw materials, was specified. This analysis then formed the basis for a sensitivity analysis of the major cost factors. The results of the cost and sensitivity analyses are presented here.
A continuous Flow Reactor (CFR) process based on the hydrogen reduction of the bromosilanes SiBr4 and SiHBr3 was proposed. Initial experiments carried and directed at obtaining overall yield data for bromosilane reduction in the CFR, indicated the need for increased reactor residence time and deposition substrate particle packing density to fully characterize the kinetics (rate) and thermodynamics (yield) of observed silicon production. Fluidized bed experiments were therefore initiated to overcome these experimental difficulties, which showed both thermal decomposition and hydrogen reduction of SiHBr3 in a fluid bed reactor to present attractive closed-loop processes for producing solar cell grade polycrystalline silicon. No process selection could be made however due to the fact that preliminary optimization of 2 of 3 process stages in each case during the course of the experimental program showed comparable attainment of cost element objectives.
Silicon tetrachloride, hydrogen and metallurgical silicon are reacted at about 400.degree.-600.degree. C. and at pressures in excess of 100 psi, and specifically from about 300 up to about 600 psi to form di- and trichlorosilane that is subjected to disproportionation in the presence of an anion exchange resin to form high purity silane. By-product and unreacted materials are recycled, with metallurgical silicon and hydrogen being essentially the only consumed feed materials. The silane product may be further purified, as by means of activated carbon or cryogenic distillation, and decomposed in a fluid bed or free space reactor to form high purity polycrystalline silicon and by-product hydrogen which can be recycled for further use. The process results in simplified waste disposal operations and enhances the overall conversion of metallurgical grade silicon to silane and high purity silicon for solar cell and semiconductor silicon applications.
The background and progress to date of EFG ribbon growth for solar cell applications are briefly reviewed. The design and operation of a multiple ribbon-per-operator manufacturing system are then described. Results are presented of cost studies of this system at three stages of development. In the latter stage, believed to be attainable by 1986, conversion costs for polycrystalline silicon into wafers are attained which are consistent with manufacture of photovoltaic systems at $0.50 per peak watt. Principal technological problems in the ribbon growth process are discussed.
We demonstrate the relationship between Si solar cell passivation and hydrogen content of various passivating films, including hydrogenated amorphous silicon (a-Si:H), aluminum oxide (Al2O3), silicon nitride (SiNx) and combinations thereof. Through isotopic studies using quadrupole mass spectrometry (QMS), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, we determine how hydrogen content and stability within each type of film relates to final passivation quality of solar cell test structures. Si solar cells using polycrystalline silicon on silicon oxide (poly-Si/SiOx) passivating contacts are at the forefront of Si solar cell research and emerging as top performers within industrial production. Performance of passivating contact Si solar cells is largely determined by a parameter known as the open-circuit voltage Voc, which directly relates to material quality within the bulk of the device and at surfaces. High Voc is achieved when defects within the bulk crystalline silicon (c-Si) and at interfaces are passivated, preventing them from acting as charge carrier recombination centers. One of the most important means of passivating defects within Si solar cells is via hydrogenation, injecting the cells with large amounts of H to satisfy dangling bonds in the bulk and at interfaces. Hydrogen is especially important in deactivating a prevalent defect in industrial p-type devices which leads to decreased device performance over long-term exposure to light, called light-induced degradation (LID). Some of the most common materials used to supply H to devices are a-Si:H, Al2O3, and SiNx, which can contain very large amounts of H. Upon annealing at elevated temperatures, the hydrogen becomes mobile enough to find and disable defect sites. However, too much hydrogen can also be problematic, sometimes leading to an effect called light and elevated temperature induced degradation (LeTID). It has been shown that these films passivate the interfaces of poly-Si passivating contacts differently, leading to differing performance. Though Al2O3 is a well-defined dielectric material, SiNx can have many different values of x depending on precursor gases and deposition conditions. We observe different FTIR and Raman spectra from different SiNx over a range of x values films to determine the bonding environments within them and further correlate the relative concentrations of Si, N, and H to the stability of H within SiNx and the passivation performance of each film. Because deuterium is chemically identical to hydrogen within these systems, but gives different signals in FTIR and Raman spectroscopy as well as in QMS, isotopic substitution can be used as an excellent tool to probe the H within films. In addition to measuring the H and D bonding within films using FTIR and Raman spectroscopy, we will use such isotopic experiments to observe H and D movement out of these hydrogenating films at elevated temperatures using QMS to determine the stability of H bonding within such systems. With these films characterized based on elemental composition, we will relate such measurements to passivation quality of these films and combinations thereof on poly-Si/SiOx contact structures using quasi-steady state photoconductance decay measurements to obtain implied open-circuit voltage (iVoc) and saturation current density J0 values. Such investigations into the performance of different passivating films and film stacks will lead to greater understanding of dielectrics in semiconductor devices, further improvements in passivated contact design, and eventually, greater proliferation of renewable solar energy worldwide.
High area output rates and continuous, automated growth are two key technical requirements for the growth of low-cost silicon ribbons for solar cells. By means of computer-aided furnace design, silicon dendritic web output rates as high as 27 sq cm/min have been achieved, a value in excess of that projected to meet a $0.50 per peak watt solar array manufacturing cost. The feasibility of simultaneous web growth while the melt is replenished with pelletized silicon has also been demonstrated. This step is an important precursor to the development of an automated growth system. Solar cells made on the replenished material were just as efficient as devices fabricated on typical webs grown without replenishment. Moreover, web cells made on a less-refined, pelletized polycrystalline silicon synthesized by the Battelle process yielded efficiencies up to 13% (AM1).
Measurements of minority carrier diffusion lengths were made on the small mesa diodes from HEM Si and SILSO Si. The results were consistent with previous Voc and Isc measurements. Only the medium grain SILSO had a distinct advantage for the non grain boundary diodes. Substantial variations were observed for the HEM ingot 4141C. Also a quantitatively scaled light spot scan was being developed for localized diffusion length measurements in polycrystalline silicon solar cells. A change to a more monochromatic input for the light spot scan results in greater sensitivity and in principle, quantitative measurement of local material qualities is now possible.
High-efficiency single crystalline silicon (c-Si) solar cells require precise control of dopant diffusion profiles and highly active doping concentrations through thermal annealing. Conventional furnace annealing has been successfully employed for dopant diffusion in aluminum back-surface field (Al-BSF), passivated emitter and rear contact (PERC), and Topcon cells. However, furnace annealing limits some next-generation polycrystalline silicon (poly-Si) on SiOx passivating contacts. This limitation largely affects p-type passivating contacts by not being able to: 1) control the dopant diffusion accurately to prevent B segregation at the SiOx and c-Si interface; and 2) provide highly activated doping concentrations for low contact resistivity. In this contribution, we use a nanosecond excimer laser to examine the passivation quality and electrical performance of both B- and Ga-doped poly-Si/SiOx passivating contacts. The core of this method is to take advantage of the nonequilibrium nature of the anneal through rapid melting and recrystallizing the poly-Si in a short timescale and to achieve doping concentrations above the solid solubility limit. Simulations were performed on polished surfaces to visualize the doping diffusion profiles under different laser conditions, and secondary ion mass spectrometry (SIMS) was used to verify the experimental diffusion profiles post pulsed laser melting (PLM). The results show the dopant diffusion profiles can be tuned precisely through PLM. The electrical analysis using VdP-Hall measurements reveals that the active doping concentration reached 10^21 cm-3 for B and ~2×10^21 cm-3 for Ga in poly-Si, far exceeding their solid solubility limit in Si, with a nearly 100% dopant activation achieved for B, and 20% for Ga. This highly activated dopant profile results in a low contact resistivity of <15 mO·cm^2 for B-doped contacts and <40 mO·cm^2 for Ga-doped contacts. We demonstrate that the passivation quality of the laser annealed contacts shows a linear dependency with the laser energy density and the number of pulses. PLM was also performed on random pyramid textured samples, and we found that preferential melting exists for the tips of pyramids, which can be pursued further for selective pinhole opening. Additionally, we perform thermal stability tests of these hyperdoped passivating contacts and show that under certain laser conditions, the B-doped samples exhibit good thermal stability with near full activation for temperatures up to 800°C. Lastly, we transfer this technique to a larger area by overlapping laser spots and show uniform passivation quality and electrical performance. We are currently implementing this PLM annealed p-type passivating contacts into double-side back-junction poly-Si/SiOx passivating contact devices. Our results show that PLM can not only enable the next generation of high-efficiency c-Si photovoltaics technology but can also benefit the c-Si integrated circuit industry through hyperdoping other semiconductors with atoms that may otherwise have a low solubility.
The degradation of photocarrier bulk lifetime in Si wafer substrates during the heteroepitaxial growth of III-V materials has been widely reported and is known to limit the efficiency of III-V/Si tandem solar cells. There have been prior strategies to protect Si lifetime in III-V growth chambers, but most require the use of a protective layer that must be removed in subsequent device processing. It would be advantageous for protective layers to remain an active part of the device. In this work, we demonstrate that a polycrystalline silicon (poly-Si) passivated contact can protect the minority carrier lifetime of the Si base wafer during the organometallic vapor phase epitaxy of III-V materials on silicon substrates.
In crystalline silicon photovoltaics (c-Si PV), a pulsed laser can be used as a substitute for a high-temperature furnace dopant diffusion/activation step. In contrast to furnace-based activation, lasers can be used to achieve highly localized doping with controlled dopant concentrations, useful in advanced architectures such as the interdigitated back contact (IBC) solar cell. In this study, a pulsed ultraviolet (UV) laser is utilized for phosphorus dopant activation within a low-pressure chemical vapor deposited (LPCVD) polycrystalline silicon (poly-Si) passivated contact layer. The highest implied open-circuit voltage iV oc values achieved using this approach reach 726 mV. However, this comes at the expense of high specific contact resistivities ρ c , which is attributed to a lower dopant concentration across the poly-Si(n + )/SiO x /c-Si interface. Regardless, the optimum iV oc , ρ c combination is measured at a laser fluence of 0.78 J cm -2 producing values of 712 mV and 89 mΩ-cm 2 , respectively. These values are still compatible with high-efficiency solar cell designs, underscoring the feasibility and effectiveness of this approach.
Perovskite solar cells are among the most promising new solar technologies, already surpassing polycrystalline silicon solar cell efficiencies. The stability of the highest efficiency devices at elevated temperature is, however, poor. These cells typically use Spiro-MeOTAD as the hole transporting layer. It is generally believed that additives, required for enhancing electrical conductivity and optimizing energy level alignment, are responsible for the reduced stability—inferring that Spiro-MeOTAD based hole transporting layers are intrinsically unstable. Here, a reliable noble metal free synthesis of Spiro-MeOTAD (bis(trifluoromethane)sulfonimide) 4 is presented which is used as the oxidizing agent. No additives are added to the partially oxidized Spiro-MeOTAD hole-transporting layer. Device efficiencies up to 24.2% are achieved. Electrical conductivity is largely developed by the first 1% oxidation. Further oxidation shifts the energy levels away from the vacuum level, which allows tuning of the energy level alignment without the use of additives—contradicting the current understanding of this system. Without additives, devices demonstrate significant improvement in stability at elevated temperatures up to 85 °C under one sun over 1400 h continuous illumination. The remaining degradation is pinpointed to ion migration and reactions in the perovskite layer which may be further suppressed with compositional engineering and adequate ion barrier layers.
In this work, we study how crystallographic structures, optoelectronic properties, and nanoscale surface morphologies of ex situ phosphorus-doped polycrystalline silicon (poly-Si)/SiO x passivating contacts, formed by different deposition methods (sputtering, plasma-enhanced chemical vapour deposition [PECVD], and low-pressure chemical vapour deposition [LPCVD]), are investigated and compared. Across all these deposition technologies, we noted the same trend: higher diffusion temperatures yield films that are more crystalline but that have rougher surface morphologies due to bigger surface crystal grains. Also, the recrystallization process of the as-deposited Si films starts from the SiO x interface, rather than from the film surface and bulk. However, there are some distinct differences among these technologies. First, the LPCVD method yields the lowest deposition rate, roughest surfaces, and smallest degree of crystallinity on finished poly-Si films. In contrast, the PECVD method has the highest deposition rate and smoothest surfaces for both as-deposited Si and annealed poly-Si films. Second, as-deposited sputtered and PECVD Si films contain only an amorphous phase, whereas as-deposited LPCVD films already has some crystalline phase. Third, the LPCVD phosphorus in-diffusion into the substrate depends strongly on the initial film thickness, whereas for the other two methods, it is weakly dependent on thickness. Finally, the passivation quality of every poly-Si film type has different responses to the film thickness and diffusion temperature, suggesting that the ex situ doping optimization should be performed independently.
Doped polycrystalline silicon (poly-Si), when coupled with a thin SiO 2 interlayer, is of large interest for crystalline silicon ( c -Si) solar cells due to its outstanding passivating contact properties. To reach high levels of surface passivation, it is pivotal to hydrogenate the poly-Si and the underlying c -Si/SiO 2 interface. This can be done by capping the poly-Si with a hydrogen-containing dielectric layer such as Al 2 O 3 or SiN x , followed by a thermal anneal. On the basis of recent research, this work addresses several aspects of such hydrogenation by dielectric materials, including the effect of the annealing ambient, the thermal stability and reversibility of hydrogenation, the poly-Si doping level and c -Si surface texture. Additionally, the implementation of hydrogenation of poly-Si by dielectric materials in solar cells is discussed.