Recrystallization of Cu(In,Ga)Se2 Semiconductor Thin Films via InCl3 Treatment
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Inorganic-based thin-film photovoltaics (TFPV) represents an important component of the growing low-carbon energy market and plays a vital role in the drive toward lower cost and increased penetration of solar energy. Yet, commercialized thin-film absorber technologies suffer from some non-ideal characteristics, such as toxic or non-abundant element use (e.g., CdTe and Cu(In,Ga)(S,Se) 2 , which bring into question their suitability for terawatt deployment. Numerous promising chalcogenide, halide, pnictide and oxide semiconductors are being pursued to bridge these concerns for TFPV and several promising paths have emerged, both as prospective replacements for the entrenched technologies, and to serve as partner (i.e., higher bandgap) absorbers for tandem junction devices—e.g., to be used with a lower bandgap Si bottom cell. The current perspective will primarily focus on emerging chalcogenide-based technologies and provide both an overview of absorber candidates that have been of recent interest and a deeper dive into an exemplary Cu 2 BaSnS 4 -related family. Altogether, considering the combined needs of high-performance, low-cost, and operational stability, as well as the experiences gained from existing commercialized thin-film absorber technologies, chalcogenide-based semiconductors represent a promising direction for future PV development and also serve to highlight common themes and needs among the broader TFPV materials family.
Photovoltaic arrays have played a key role in power generation in space. The current technology will continue to evolve but is limited in the important mass specific power metric (MSP or power/weight ratio) because it is based on bulk crystal technology. Solar cells based on thin-film materials offer the promise of much higher MSP and much lower cost. However, for many space applications, a 20% or greater AM0 efficiency (eta) may be required. The leading thin-film materials, amorphous Si, CuInSe, and CdTe have seen significant advances in efficiency over the last decade but will not achieve the required efficiency in the near future. Several new technologies are herein described to maximize both device eta and MSP. We will discuss these technologies in the context of space exploration and commercialization. One novel approach involves the use of very lightweight polyimide substrates. We describe efforts to enable this advance including materials processing and device fabrication and characterization. Another approach involves stacking two cells on top of each other. These tandem devices more effectively utilize solar radiation by passing through non-absorbed longer wavelength light to a narrow-bandgap bottom cell material. Modeling of current devices in tandem format indicates that AM0 efficiencies near 20% can be achieved with potential for 25% in the near future. Several important technical issues need to be resolved to realize the benefits of lightweight technologies for solar arrays, such as: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. Recent advances will be stressed.
A thin layer of Al 2 O 3 at the back of CdSe x T e1-x /CdTe devices is shown to passivate the back interface and drastically improve surface recombination lifetimes and photoluminescent response. Despite this, such devices do not show an improvement in open-circuit voltage (VOC.) Adding a p + amorphous silicon layer behind the Al 2 O 3 bends the conduction band upward, reducing the barrier to hole extraction and improving collection. Further optimization of the Al 2 O 3 , amorphous silicon (a-Si), and indium-doped tin oxide (ITO) layers, as well as their interaction with the CdCl 2 passivation process, are necessary to translate these electro-optical improvements into gains in voltage.
This project aimed to generate the characterization tools needed for accurate and systematic loss analysis in non-silicon photovoltaic solar cell technologies and, through the use of these tools and analysis techniques, contribute to the development of a novel class of hetero-contacts to II-VI absorbers, with the final goal of demonstrating record-breaking CdSeTe devices. CdSeTe solar cells provide a prime example of the potential impact of the techniques we proposed to develop and implement: record poly-CdSeTe cells have bandgap-voltage deficits (W oc ) of approximately 550 mV, as compared with below 400 mV for all other mature PV technologies. Similarly, these record CdSeTe devices have FFs below 80%, when other mature cells are near or above 85%. Frustratingly, a systematic identification of the origin of these sub-par performances—for example recombination or resistive losses—has been lacking, thus slowing down the development of these technologies. Similarly, it is often asserted that CdSeTe cells need a better back (hole) contact. Although most believe this is true, no one knew—at the start of this project—how high the V oc and FF could be for a given cell if it had a perfect back contact. Such characterization techniques and loss analysis methods exist and are routinely performed on c-Si solar cells (e.g. injection-dependent lifetime, Suns-V oc , transfer length method, etc). Over the years, they have been instrumental in the development of silicon devices that operate at 91% of their theoretical (Auger) limit. Lifetime testing, and the associated reconstruction of the implied-J-V curve, can moreover be performed at every cell-processing step, thus allowing a direct peek into the impact of that step on cell performance. Therefore, adapting these techniques and tools to non-Si devices would greatly improve their learning rate. In this project, we developed a Suns-ERE technique—the equipment, methodology, and know-how—to measure the implied-J-V curve, the pseudo-J-V curve, and the actual J-V curve of a thin-film solar cell, allowing an accurate assessment of the quality of the bulk material and its surface passivation, the selectivity of the contact, and its resistivity. We used this technique to show that the absorber of present CdSeTe solar cells is capable of achieving 1 V Voc,, that passivation layers exist (e.g., Al2O3) that can support such high voltages, and that the barrier is identifying contact layers that are both passivating and carrier-selective. The characterization platform created in this project and the understanding generated using it will accelerate the progress of non-silicon PV technologies. In particular, the project will contribute to CdSeTe solar cells with Voc > 1 V and cell efficiency > 24%. Such cells provide a pathway to module-level efficiencies >23%. As CdSeTe presently competes with silicon on module cost (in $\$ $/W) and yet has significantly more room for efficiency gains, the potential for LCOE reduction is particularly large. For example, CdTe modules with an efficiency of 21% would allow an LCOE below $\$ $0.04kWh -1 in average US climates.
Since excellent carrier lifetimes and front interface electronic quality are now achieved, rear interface recombination can limit V OC in CdSexTe1-x/CdTe solar cells. Several back-contact structures for devices were fabricated using combinations of tellurium, aluminum oxide, amorphous silicon, and indium tin oxide (ITO). Time-resolved photoluminescence was used to characterize such structures. We show increasingly improved interface passivation through the subsequent use of aluminum oxide, amorphous silicon, and ITO. Additionally, we show that arsenic-doped absorbers form a more passive interface with numerous back contact structures.
In order to meet aggressive decarbonization goals, photovoltacs (PV) need to expand substantially. The current technology that heavily dominates the market, silicon (Si), comprises 95% of the world's PV production, is energy intensive to make, and can take up a substantial portion of the remaining carbon budget if expanded. Conversely, cadmium telluride (CdTe) comprises much of the remaining 5% of the global PV market and has a significantly lower carbon footprint than Si, historically costs less to produce, and is critically important to U.S. competitiveness in the global market. Importantly, CdTe still has room to grow, particularly related to efficiency because voltage has historically been much lower than what we calculate it should be. My research is focused in part on understanding this voltage deficit from a fundamental perspective by studying bulk materials and interfaces. One of the most important regions of the device is buried within the stack, so I developed a technique to cleave and reveal buried interfaces. This cleave technique has enabled a much better scientific understanding and allows us to make lightweight, flexible PV while maintaining low costs, high efficiency, and high throughput associated with standard module processing.
Progress of state-of-the-art and next-generation thin-film photovoltaic devices is often stymied by open-circuit voltage (𝑉 oc ) that is significantly lower than theoretical and practical limits. Yet, effectively diagnosing the primary sources of voltage loss remains challenging. Herein, a sequence of device-level characterization techniques and simulations are employed to identify and rank loss mechanisms. For the research-based Cd(Se,Te) device under study, most of the loss was at the front semiconductor heterointerface due to a clifflike conduction-band offset that lowered the recombination activation energy. Additional losses due to band tails were quantified by photoluminescence analysis. The latter provided the absorption coefficient and activation energy reduction associated with band tails as inputs to device models. Simulations showed that alleviating front-interface issues would improve 𝑉 oc , but it would then be limited by bulk recombination. Further improvement of the bulk would then lead to back-contact limitations. Reducing band tails is beneficial in any circumstance. In conclusion, this analysis provides guidance for reaching toward the radiative 𝑉 oc limit.
This is one of a series of reports and deep dive assessments produced in response to Executive Order 14017 “America’s Supply Chains,” which directs the Secretary of Energy to submit a report on supply chains for the energy sector industrial base. The Executive Order is helping the federal government to build more secure and diverse U.S. supply chains, including energy supply chains. Over the past decade, solar power has gone from an emerging, niche technology to a mature energy industry. By 2035, solar power could supply 40% or more of U.S. electricity demand, dramatically accelerating the decarbonization of buildings, transportation, and industry; and, if current technology trends continue, it could do so without increasing the price of electricity. The rapid expansion of solar energy has the potential to yield broad benefits in the form of economic activity and workforce development. The solar industry already employs roughly 230,000 people in the United States, at an average wage that is higher than the national average for most comparable positions. By decarbonizing the electricity sector by 2035, the U.S. solar industry could employ 500,000–1,500,000 people by 2030. The components that are assembled to install a photovoltaic power system are produced by a global supply chain. Photovoltaic (PV) modules (also called panels) are made of cells that use a variety of technologies. There are two leading types of solar modules used in the United States, with crystalline silicon (c-Si) modules representing 84% of the market and cadmium telluride (CdTe) modules representing 16% of the market. Modules of either type require mounting structures to provide mechanical support (racking), which may be configured to follow the sun (tracking). The output of any PV module is direct current (dc), which is almost always converted to alternating current (ac) by an inverter.
Copper barium thioselenostannate, Cu 2 BaSnS 4-x Se x (CBTSSe), absorbers employ low-toxicity and abundant metals while offering low-cost manufacturing options, controllable stoichiometry and band gap tunability (from 2 eV at x = 0 to 1.55 eV at x = 3). CBTSSe can therefore be considered a prospective candidate for maintaining or improving upon the advantages of already commercialized Cu(In,Ga)(S,Se) 2 (CIGSSe) and CdTe absorbers. Here, we focus on solution-deposited stoichiometric CBTSSe films with band gap of 1.59 eV (x ≈ 3) and explore the fundamental film properties. Temperature- and excitation-dependent photoluminescence studies reveal a dominant defect emission at ~1.5 eV and a second deep defect feature at 1.15 eV. From time-resolved terahertz measurements, we find a charge carrier (electron and hole sum) mobility of ~140 cm 2 /Vs—i.e., comparable to values in CIGSSe or Cu 2 ZnSnS 4-x Se x (CZTSSe)—as well as a two-component minority carrier lifetime. A longer-lived lifetime component (~2 ns) arises from bulk recombination. However, strong recombination at the (bare) surface leads to a ~50 ps lifetime, inferior to state-of-the-art CIGSSe or CZTSSe absorbers. This recombination issue may worsen for CBTSSe/CdS interfaces, due to a cliff-like band alignment with 0.6 eV band offset, as revealed by ultraviolet photoemission spectroscopy. A low number of charge carriers within the absorber further contributes to a high series resistance. Employing these films, we also report the highest performance achieved from solution-processed trigonal CBTSSe thin-film photovoltaic devices, with open circuit voltage, short-circuit current density, fill factor and efficiency of 470 mV, 14.3 mA/cm 2 , 43.6% and 2.9%, respectively. The physical measurements provided on the stoichiometric solution-processed CBTSSe absorber further point to critical areas for future improvement of CBTSSe and related photovoltaic cells in the quest for higher efficiency devices based on earth abundant metals.
A historical view of the research and development in photovoltaics from the perspective of both the terrestrial and the space communities is presented from the early days through the '70s and '80s and the '90s and beyond. The synergy of both communities in the beginning and once again in the present and hopefully future are highlighted, with examples of the important features in each program. The space community which was impressed by the light-weight and reliability of photovoltaics drove much of the early development. Even up to today, nearly every satellites and other scientific space probe that has been launched has included some solar power. However, since the cost of these power systems were only a small fraction of the satellite and launch cost, the use of much of this technology for the terrestrial marketplace was not feasible. It was clear that the focus of the terrestrial community would be best served by reducing costs. This would include addressing a variety of manufacturing issues and raising the rate of production. Success in these programs and a resulting globalization of effort resulted in major strides in the reduction of PV module costs and increased production. Although, the space community derived benefit from some of these advancements, its focus was on pushing the envelope with regard to cell efficiency. The gap between theoretical efficiencies and experimental efficiencies for silicon, gallium arsenide and indium phosphide became almost non-existent. Recent work by both communities have focused on the development thin film cells of amorphous silicon, CuInSe2 and CdTe. These cells hold the promise of lower costs for the terrestrial community as well as possible flexible substrates, better radiation resistance, and higher specific power for the space community. It is predicted that future trends in both communities will be directed toward advances through the application of nanotechnology. A picture is emerging in which the space and terrestrial solar cell communities shall once again share many common goals and, in fact, companies may manufacture both space and terrestrial solar cells in III-V materials and thin film materials. Basic photovoltaics research including these current trends in nanotechnology provides a valuable service for both worlds in that fundamental understanding of cell processes is still vitally important, particularly with new materials or new cell structures. It is entirely possible that one day we might have one solar array design that will meet the criteria for success in both space and on the Earth or perhaps the Moon or Mars.
Our oceans are vast, mostly unexplored and difficult to monitor. Large-scale implementation of a fully autonomous 'Internet of Underwater Things' would transform how we collect and share data from this domain; however, deployment is prohibited by the lack of persistent power sources. In principle, underwater solar-energy generation can complement the use of batteries and provide a solution, although dedicated research is needed since traditional silicon solar cells do not perform well underwater due to water's strong absorption of near-infrared light. In this Perspective we present examples of solar-powered underwater applications and discuss which types of solar-harvesting materials could be appropriate, including GaInP variants, CdTe, organic semiconductors, and perovskite semiconductors. We also discuss challenges that need to be addressed, such as the development of effective antifouling coatings and new certification standards given that underwater conditions are starkly different from those in terrestrial environments.
This study systematically documents defect levels in n-type iodine-doped cadmium telluride (CdTe:I) crystals as measured by thermoelectric effect spectroscopy, Hall-effect measurements, and photoluminescence and calculated by density functional theory. The primary donor, I Te , was identified with an activation energy of ∼0.05 eV (measured)/∼0.13 eV (calculated). Deep acceptor states, V Cd and I Te –V Cd complex, exhibited activation energies of ∼0.1 eV (measured)/∼0.19 eV (calculated) and ∼0.12 eV (measured)/∼0.24 eV (calculated), respectively. Self-compensation and Fermi level pinning were observed at ∼0.7 eV (measured)/∼1.08 eV (calculated), contributing to high resistivity in as-grown samples. Post-growth Cd annealing effectively removes compensation centers, releases iodine donors, and significantly reduces resistivity, resulting in an ideal n-type solar cell material.
The ability to predict the likelihood of impurity incorporation and their electronic energy levels in semiconductors is crucial for controlling its conductivity, and thus the semiconductor's performance in solar cells, photodiodes, and optoelectronics. The difficulty and expense of experimental and computational determination of impurity levels makes a data-driven machine learning approach appropriate. In this work, we show that a density functional theory-generated dataset of impurities in Cd-based chalcogenides CdTe, CdSe, and CdS can lead to accurate and generalizable predictive models of defect properties. By converting any semiconductor + impurity system into a set of numerical descriptors, regression models are developed for the impurity formation enthalpy and charge transition levels. These regression models can subsequently predict impurity properties in mixed anion CdX compounds (where X is a combination of Te, Se and S) fairly accurately, proving that although trained only on the end points, they are applicable to intermediate compositions. We make machine-learned predictions of the Fermi-level-dependent formation energies of hundreds of possible impurities in 5 chalcogenide compounds, and we suggest a list of impurities which can shift the equilibrium Fermi level in the semiconductor as determined by the dominant intrinsic defects. Machine learning predictions for the dominating impurities compare well with DFT predictions, revealing the power of machine-learned models in the quick screening of impurities likely to affect the optoelectronic behavior of semiconductors.
Temperature and solar irradiance are among the most relevant parameters that affect the energy yield of photovoltaic cells and modules. A rise in the module temperature leads to a significant decrease in the open circuit voltage and a small increase in the short circuit current. Here we use a new tool to determine temperature coefficients as well as to assess power rating of multi c-Si, mono c-Si, CdTe, and CIGS-based PV modules in controlled indoor conditions per IEC 60891 and IEC 61853-1. We use the tool to explore how nonuniformities in module temperature affect the accuracy of the temperature coefficients.
Photovoltaics (PV), also known as solar cells, are now found everywhere - in utility plants; on roofs of homes and commercial buildings; on platforms at sea; in agricultural fields; on vehicles, buildings, drones, and backpacks; and, in their longest running application, providing power in space. Continuous device innovation has led to increased efficiency and improved reliability for multiple PV technologies. Confronted with an urgent need to deploy PV at multiterawatt (TW) scale over the next two decades to mitigate greenhouse gas emissions, PV device innovation takes on new urgency and impact. This perspective reviews recent progress in device design and performance for PV technologies that are currently in commercial production at greater than 1 GW/year or enabling significant space-based power generation - Si, CdTe, CIGS, and multijunction III-V - and looks ahead to the next 5 years. In conclusion, we also identify device-related topics requiring cross-cutting research and innovation.
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