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Saturday, January 5, 2019

Concentrator photovoltaics

From Wikipedia, the free encyclopedia

This Amonix system in Las Vegas, USA consists of thousands of small Fresnel lenses, each focusing sunlight to ~500X higher intensity onto a tiny, high-efficiency multi-junction solar cell. A Tesla Roadster is parked beneath for scale.
 
Concentrator photovoltaics (CPV) modules on dual axis solar trackers in Golmud, China

Concentrator photovoltaics (CPV) (also known as Concentration Photovoltaics) is a photovoltaic technology that generates electricity from sunlight. Contrary to conventional photovoltaic systems, it uses lenses and curved mirrors to focus sunlight onto small, but highly efficient, multi-junction (MJ) solar cells. In addition, CPV systems often use solar trackers and sometimes a cooling system to further increase their efficiency. Ongoing research and development is rapidly improving their competitiveness in the utility-scale segment and in areas of high insolation. This sort of solar technology can be thus used in smaller areas.

Systems using high-concentration photovoltaics (HCPV) especially have the potential to become competitive in the near future. They possess the highest efficiency of all existing PV technologies, and a smaller photovoltaic array also reduces the balance of system costs. Currently, CPV is not used in the PV rooftop segment and is far less common than conventional PV systems. For regions with a high annual direct normal irradiance of 2000 kilowatt-hour (kWh) per square meter or more, the levelized cost of electricity is in the range of $0.08–$0.15 per kWh and installation cost for a 10-megawatt CPV power plant was identified to lie between €1.40–€2.20 (~$1.50-$2.30) per watt-peak (Wp).

In 2016, cumulative CPV installations reached 350 megawatts (MW), less than 0.2% of the global installed capacity of 230,000 MW. Commercial HCPV systems reached instantaneous ("spot") efficiencies of up to 42% under standard test conditions (with concentration levels above 400) and the International Energy Agency sees potential to increase the efficiency of this technology to 50% by the mid-2020s. As of December 2014, the best lab cell efficiency for concentrator MJ-cells reached 46% (four or more junctions). Under outdoor, operating conditions, CPV module efficiencies have exceeded 33% ("one third of a sun"). System-level AC efficiencies are in the range of 25-28%. CPV installations are located in China, the United States, South Africa, Italy and Spain.

HCPV directly competes with concentrated solar power (CSP) as both technologies are suited best for areas with high direct normal irradiance, which are also known as the Sun Belt region in the United States and the Golden Banana in Southern Europe. CPV and CSP are often confused with one another, despite being intrinsically different technologies from the start: CPV uses the photovoltaic effect to directly generate electricity from sunlight, while CSP – often called concentrated solar thermal – uses the heat from the sun's radiation in order to make steam to drive a turbine, that then produces electricity using a generator. Currently, CSP is more common than CPV.

History

Research into concentrator photovoltaics has taken place since the mid 1970s, initially spurred on by the energy shock from a mideast oil embargo. Sandia National Laboratories in Albuquerque, New Mexico was the site for most of the early work, with the first modern-like photovoltaic concentrating system produced there late in the decade. Their first system was a linear-trough concentrator system that used a point focus acrylic Fresnel lens focusing on water-cooled silicon cells and two axis tracking. Cell cooling with a passive heat sink and use of silicone-on-glass Fresnel lenses was demonstrated in 1979 by the Ramón Areces Project at the Institute of Solar Energy of the Technical University of Madrid. The 350 kW SOLERAS project in Saudi Arabia—the largest until many years later—was constructed by Sandia/Martin Marietta in 1981.

Research and development continued through the 1980s and 1990s without significant industry interest. Improvements in cell efficiency were soon recognized as essential to making the technology economical. However the improvements to Si-based cell technologies used by both concentrators and flat PV failed to favor the system-level economics of CPV. The introduction of III-V Multi-junction solar cells starting in the early 2000s has since provided a clear differentiator. MJ cell efficiencies have improved from 34% (3-junctions) to 46% (4-junctions) at research-scale production levels. A substantial number of multi-MW CPV projects have also been commissioned worldwide since 2010.

Challenges

Modern CPV systems operate most efficiently in highly concentrated sunlight (i.e. concentration levels equivalent to hundreds of suns), as long as the solar cell is kept cool through the use of heat sinks. Diffuse light, which occurs in cloudy and overcast conditions, cannot be highly concentrated using conventional optical components only (i.e. macroscopic lenses and mirrors). Filtered light, which occurs in hazy or polluted conditions, has spectral variations which produce mismatches between the electrical currents generated within the series-connected junctions of spectrally "tuned" multi-junction (MJ) photovoltaic cells. These CPV features lead to rapid decreases in power output when atmospheric conditions are less than ideal.

To produce equal or greater energy per rated watt than conventional PV systems, CPV systems must be located in areas that receive plentiful direct sunlight. This is typically specified as average DNI greater than 5.5-6 kWh/m2/day or 2000kWh/m2/yr. Otherwise, evaluations of annualized DNI vs. GNI/GHI irradiance data have concluded that conventional PV should still perform better over time than presently available CPV technology in most regions of the world. 

CPV Strengths CPV Weaknesses
High efficiencies under direct normal irradiance HCPV cannot utilize diffuse radiation. LCPV can only utilize a fraction of diffuse radiation.
Low cost per watt of manufacturing capital Power output of MJ solar cells is more sensitive to shifts in radiation spectra caused by changing atmospheric conditions.
Low temperature coefficients Tracking with sufficient accuracy and reliability is required.
No cooling water required for passively cooled systems May require frequent cleaning to mitigate soiling losses, depending on the site
Additional use of waste heat possible for systems with active cooling possible (e.g.large mirror systems) Limited market – can only be used in regions with high DNI, cannot be easily installed on rooftops
Modular – kW to GW scale Strong cost decrease of competing technologies for electricity production
Increased and stable energy production throughout the day due to (two-axis) tracking Bankability and perception issues
Low energy payback time New generation technologies, without a history of production (thus increased risk)
Potential double use of land e.g. for agriculture, low environmental impact Optical losses
High potential for cost reduction Lack of technology standardization
Opportunities for local manufacturing
Smaller cell sizes could prevent large fluctuations in module price due to variations in semiconductor prices
Greater potential for efficiency increase in the future compared to single-junction flat plate systems could lead to greater improvements in land area use, BOS costs, and BOP costs

Ongoing research and development

International CPV-x Conference - Historical Participation Statistics. Data Source - CPV-x Proceedings
 
CPV research and development has been pursued in over 20 countries for more than a decade. The annual CPV-x conference series has served as a primary networking and exchange forum between university, government lab, and industry participants. Government agencies have also continued to encourage a number of specific technology thrusts. 

ARPA-E announced a first round of R&D funding in late 2015 for the MOSAIC Program (Microscale Optimized Solar-cell Arrays with Integrated Concentration) to further combat the location and expense challenges of existing CPV technology. As stated in the program description: "MOSAIC projects are grouped into three categories: complete systems that cost effectively integrate micro-CPV for regions such as sunny areas of the U.S. southwest that have high Direct Normal Incident (DNI) solar radiation; complete systems that apply to regions, such as areas of the U.S. Northeast and Midwest, that have low DNI solar radiation or high diffuse solar radiation; and concepts that seek partial solutions to technology challenges."

In Europe the CPVMATCH Program (Concentrating PhotoVoltaic Modules using Advanced Technologies and Cells for Highest efficiencies) aims "to bring practical performance of HCPV modules closer to theoretical limits". Efficiency goals achievable by 2019 are identified as 48% for cells and 40% for modules at greater than 800x concentration.

The Australian Renewable Energy Agency (ARENA) extended its support in 2017 for further commercialization of the HCPV technology developed by Raygen. Their 250kW dense array receivers are the most powerful CPV receivers thus far created, with demonstrated PV efficiency of 40.4% and include usable heat co-generation.

Optical design

The design of macroscopic sunlight concentrators for CPV introduces a very specific optical design problem, with features that makes it different from any other optical design. It has to be efficient, suitable for mass production, capable of high concentration, insensitive to manufacturing and mounting inaccuracies, and capable of providing uniform illumination of the cell. All these reasons make nonimaging optics the most suitable for CPV. 

For very low concentrations, the wide acceptance angles of nonimaging optics avoid the need for active solar tracking. For medium and high concentrations, a wide acceptance angle can be seen as a measure of how tolerant the optic is to imperfections in the whole system. It is vital to start with a wide acceptance angle since it must be able to accommodate tracking errors, movements of the system due to wind, imperfectly manufactured optics, imperfectly assembled components, finite stiffness of the supporting structure or its deformation due to aging, among other factors. All of these reduce the initial acceptance angle and, after they are all factored in, the system must still be able to capture the finite angular aperture of sunlight.

Efficiency

Reported records of solar cell efficiency since 1975. As of December 2014, best lab cell efficiency reached 46% (for multi-junction concentrator, 4+ junctions).
 
All CPV systems have a concentrating optic and a solar cell. Generally, active solar tracking is necessary. Low-concentration systems often have a simple booster reflector, which can increase solar electric output by over 30% from that of non-concentrator PV systems. Experimental results from such LCPV systems in Canada resulted in energy gains over 40% for prismatic glass and 45% for traditional crystalline silicon PV modules.

Semiconductor properties allow solar cells to operate more efficiently in concentrated light, as long as the cell Junction temperature is kept cool by suitable heat sinks. Efficiency of multi-junction photovoltaic cells developed in research is upward of 44% today, with the potential to approach 50% in the coming years. The theoretical limiting efficiency under concentration approaches 65% for 5 junctions, which is a likely practical maximum.

Types

CPV systems are categorized according to the amount of their solar concentration, measured in "suns" (the square of the magnification).

Low concentration PV (LCPV)

An example of a Low Concentration PV Cell's surface, showing the glass lensing
 
Low concentration PV are systems with a solar concentration of 2–100 suns. For economic reasons, conventional or modified silicon solar cells are typically used, and, at these concentrations, the heat flux is low enough that the cells do not need to be actively cooled. There is now modeling and experimental evidence that standard solar modules do not need any modification, tracking or cooling if the concentration level is low and yet still have increased output of 35% or more.

Medium concentration PV

From concentrations of 100 to 300 suns, the CPV systems require two-axis solar tracking and cooling (whether passive or active), which makes them more complex. 

A 10×10 mm HCPV solar cell

High concentration photovoltaics (HCPV)

High concentration photovoltaics (HCPV) systems employ concentrating optics consisting of dish reflectors or fresnel lenses that concentrate sunlight to intensities of 1,000 suns or more. The solar cells require high-capacity heat sinks to prevent thermal destruction and to manage temperature related electrical performance and life expectancy losses. To further exacerbate the concentrated cooling design, the heat sink must be passive, otherwise the power required for active cooling will reduce the overall conversion efficiency and economy. Multi-junction solar cells are currently favored over single junction cells, as they are more efficient and have a lower temperature coefficient (less loss in efficiency with an increase in temperature). The efficiency of both cell types rises with increased concentration; multi-junction efficiency rises faster. Multi-junction solar cells, originally designed for non-concentrating PV on space-based satellites, have been re-designed due to the high-current density encountered with CPV (typically 8 A/cm2 at 500 suns). Though the cost of multi-junction solar cells is roughly 100 times that of conventional silicon cells of the same area, the small cell area employed makes the relative costs of cells in each system comparable and the system economics favor the multi-junction cells. Multi-junction cell efficiency has now reached 44% in production cells. 

The 44% value given above is for a specific set of conditions known as "standard test conditions". These include a specific spectrum, an incident optical power of 850 W/m², and a cell temperature of 25 °C. In a concentrating system, the cell will typically operate under conditions of variable spectrum, lower optical power, and higher temperature. The optics needed to concentrate the light have limited efficiency themselves, in the range of 75–90%. Taking these factors into account, a solar module incorporating a 44% multi-junction cell might deliver a DC efficiency around 36%. Under similar conditions, a crystalline silicon module would deliver an efficiency of less than 18%.

When high concentration is needed (500–1000 times), as occurs in the case of high efficiency multi-junction solar cells, it is likely that it will be crucial for commercial success at the system level to achieve such concentration with a sufficient acceptance angle. This allows tolerance in mass production of all components, relaxes the module assembling and system installation, and decreasing the cost of structural elements. Since the main goal of CPV is to make solar energy inexpensive, there can be used only a few surfaces. Decreasing the number of elements and achieving high acceptance angle, can be relaxed optical and mechanical requirements, such as accuracy of the optical surfaces profiles, the module assembling, the installation, the supporting structure, etc. To this end, improvements in sunshape modelling at the system design stage may lead to higher system efficiencies.

Reliability requirements

The maximum operating temperatures (Tmax cell) of CPV systems are limited to less than approximately 100–125 °C on account of the intrinsic reliability limitation of their multi-junction PV cells. This contrasts to CSP and other CHP systems which may be designed to function at temperatures in excess of several hundred degrees. More specifically, the cells are fabricated from a layering of thin-film III-V semiconductor materials having intrinsic lifetimes during operation that rapidly decrease with an Arrhenius-type temperature dependence. The system receiver must therefore provide for highly efficient and uniform cell cooling, where an ideal receiver would provide Tmax coolant ~ Tmax cell. In addition to material and design limitations in receiver heat-transfer performance, numerous extrinsic factors, such as the frequent system thermal cycling, further reduce the practical Tmax coolant compatible with long system life to below about 80 °C. 

The higher capital costs, lesser standardization, and added engineering & operational complexities (in comparison to zero and low-concentration PV technologies) make long-life performance a critical demonstration goal for the first generations of CPV technologies. Performance certification standards (e.g. IEC 62108, UL 8703, IEC 62789, IEC 62670) include stress testing conditions that may be useful to uncover some predominantly infant and early life (less than 1–2 year) failure modes at the system, module, and sub-component levels. However, such standardized tests – as typically performed on only a small sampling of units – are generally incapable to evaluate comprehensive long-term lifetimes (10 to 25 or more years) for each unique system design and application under its broader range of actual operating conditions. Reliability of these complex systems is therefore assessed in the field, and is improved through aggressive product development cycles which are guided by the results of accelerated component/system aging, performance monitoring diagnostics, and failure analysis. Significant growth in the deployment of CPV can be anticipated once these concerns are better addressed to build confidence in system bankability.

Installations

Concentrator photovoltaics technology has established its presence in the solar industry over the last several years. The first CPV power plant that exceeded 1 MW-level was commissioned in Spain in 2006. By the end of 2015, the number of CPV power plants around the world accounted for a total installed capacity of 350 MW. Field data collected over six years is also starting to benchmark the prospects for long-term system reliability.

The emerging CPV segment has comprised ~0.1% of the fast-growing utility market for PV installations over the past decade. Unfortunately, by the end of 2015, the near term outlook for CPV industry growth has faded with closure of all of the largest CPV manufacturing facilities: including those of Suncore, Soitec, Amonix, and Solfocus. Nevertheless, the growth outlook for the overall PV industry continues to appear strong.

Cumulative CPV Installations in MW by country by November 2014
 
Yearly Installed CPV Capacity in MW from 2002 to 2015.
 
Yearly Installed PV Capacity in GW from 2002 to 2015.

List of large CPV systems

The largest CPV power plant currently in operation is of 80 MWp capacity located in Golmud, China, hosted by Suncore Photovoltaics.

Power station Capacity (MWp) Location Vendor/Builder
Golmud 2 79.83 in Golmud/Qinghai province/China Suncore
Golmud 1 57.96 in Golmud/Qinghai province/China Suncore
Touwsrivier 44.19 in Touwsrivier/Western Cape/South Africa Soitec
Alamosa Solar Project 35.28 in Alamosa, Colorado/San Luis Valley/United States Amonix

Concentrated photovoltaics and thermal

Concentrator photovoltaics and thermal (CPVT), also sometimes called combined heat and power solar (CHAPS) or hybrid thermal CPV, is a cogeneration or micro cogeneration technology used in the field of concentrator photovoltaics that produces usable heat and electricity within the same system. CPVT at high concentrations of over 100 suns (HCPVT) utilizes similar components as HCPV, including dual-axis tracking and multi-junction photovoltaic cells. A fluid actively cools the integrated thermal–photovoltaic receiver, and simultaneously transports the collected heat. 

Typically, one or more receivers and a heat exchanger operate within a closed thermal loop. To maintain efficient overall operation and avoid damage from thermal runaway, the demand for heat from the secondary side of the exchanger must be consistently high. Under such optimal operating conditions, collection efficiencies exceeding 70% (up to ~35% electric, ~40% thermal for HCPVT) are anticipated. Net operating efficiencies may be substantially lower depending on how well a system is engineered to match the demands of the particular thermal application.

The maximum temperature of CPVT systems is typically too low alone to power a boiler for additional steam-based cogeneration of electricity. Such systems may be economical to power lower temperature applications having a constant high heat demand. The heat may be employed in district heating, water heating and air conditioning, desalination or process heat. For applications having lower or intermittent heat demand, a system may be augmented with a switchable heat dump to the external environment in order to maintain reliable electrical output and safeguard cell life, despite the resulting reduction in net operating efficiency. 

HCPVT active cooling enables the use of much higher power thermal–photovoltaic receiver units, generating typically 1–100 kilowatts electric, as compared to HCPV systems that mostly rely upon passive cooling of single ~20W cells. Such high-power receivers utilize dense arrays of cells mounted on a high-efficiency heat sink. Minimizing the number of individual receiver units is a simplification that should ultimately yield improvement in the overall balance of system costs, manufacturability, maintainability/upgradeability, and reliability.

This 240 x 80 mm 1,000 suns CPV heat sink design thermal animation, was created using high resolution CFD analysis, and shows temperature contoured heat sink surface and flow trajectories as predicted.

Demonstration projects

The economics of a mature CPVT industry is anticipated to be competitive, despite the large recent cost reductions and gradual efficiency improvements for conventional silicon PV (which can be installed alongside conventional CSP to provide for similar electrical+thermal generation capabilities). CPVT may currently be economical for niche markets having all of the following application characteristics:
  • high solar direct normal incidence (DNI)
  • tight space constraints for placement of a solar collector array
  • high and constant demand for low-temperature (less than 80 °C) heat
  • high cost of grid electricity
  • access to backup sources of power or cost-efficient storage (electrical and thermal)
Utilization of a power purchase agreement (PPA), government assistance programs, and innovative financing schemes are also helping potential manufacturers and users to mitigate the risks of early CPVT technology adoption.

CPVT equipment offerings ranging from low (LCPVT) to high (HCPVT) concentration are now being deployed by several startup ventures. As such, longer-term viability of the technical and/or business approach being pursued by any individual system provider is typically speculative. Notably, the minimum viable products of startups can vary widely in their attention to reliability engineering. Nevertheless, the following incomplete compilation is offered to assist with the identification of some early industry trends.

LCPVT systems at ~14x concentration using reflective trough concentrators, and receiver pipes clad with silicon cells having dense interconnects, have been assembled by Cogenra with a claimed 75% efficiency (~15-20% electric, 60% thermal). Several such systems are in operation for more than 5 years as of 2015, and similar systems are being produced by Absolicon  and Idhelio at 10x and 50x concentration, respectively.

HCPVT offerings at over 700x concentration have more recently emerged, and may be classified into three power tiers. Third tier systems are distributed generators consisting of large arrays of ~20W single-cell receiver/collector units, similar to those previously pioneered by Amonix and SolFocus for HCPV. Second tier systems utilize localized dense-arrays of cells that produce 1-100 kW of electrical power output per receiver/generator unit. First tier systems exceed 100 kW of electrical output and are most aggressive in targeting the utility market.

Several HCPVT system providers are listed in the following table. Nearly all are early demonstration systems which have been in service for under 5 years as of 2015. Collected thermal power is typically 1.5x-2x the rated electrical power. 

Provider Country Concentrator Type Unit Size in  kWe
Generator Receiver


- Tier 1 -

Raygen Australia Large Heliostat Array 250 250


- Tier 2 -

Airlight Energy/dsolar Switzerland Large Dish 12 12
Rehnu United States Large Dish 6.4 0.8
Solartron Canada Large Dish 20 20
Southwest Solar United States Large Dish 20 20
Sun Oyster Germany Large Trough + Lens 4.7 2.35
Zenith Solar/Suncore Israel/China/USA Large Dish 4.5 2.25


- Tier 3 -

BSQ Solar Spain Small Lens Array 13,44 0.02
Silex Power Malta Small Dish Array 16 0.04
Solergy Italy/USA Small Lens Array 20 0.02

Perovskite solar cell (updated)

From Wikipedia, the free encyclopedia

A perovskite solar cell is a type of solar cell which includes a perovskite structured compound, most commonly a hybrid organic-inorganic lead or tin halide-based material, as the light-harvesting active layer. Perovskite materials such as methylammonium lead halides and all-inorganic cesium lead halide, are cheap to produce and simple to manufacture.

Solar cell efficiencies of devices using these materials have increased from 3.8% in 2009 to 23.3% in late 2018 in single-junction architectures, and, in silicon-based tandem cells 27.3% exceeding the maximum efficiency achieved in single-junction silicon solar cells. Perovskite solar cells are therefore the fastest-advancing solar technology to date. With the potential of achieving even higher efficiencies and the very low production costs, perovskite solar cells have become commercially attractive, with start-up companies already promising modules and powerbanks on the market by 2017.

Advantages

Metal halide perovskites possess unique features that make them exciting for solar cell applications. The raw materials used, and the possible fabrication methods (such as various printing techniques) are both low cost. Their high absorption coefficient enables ultrathin films of around 500 nm to absorb the complete visible solar spectrum. These features combined result in the possibility to create low cost, high efficiency, thin, lightweight and flexible solar modules.

Materials

Crystal structure of CH3NH3PbX3 perovskites (X=I, Br and/or Cl). The methylammonium cation (CH3NH3+) is surrounded by PbX6 octahedra.
 
The name 'perovskite solar cell' is derived from the ABX3 crystal structure of the absorber materials, which is referred to as perovskite structure. The most commonly studied perovskite absorber is methylammonium lead trihalide (CH3NH3PbX3, where X is a halogen atom such as iodine, bromine or chlorine), with an optical bandgap between 1.5 and 2.3 eV depending on halide content. Formamidinum lead trihalide (H2NCHNH2PbX3) has also shown promise, with bandgaps between 1.5 and 2.2 eV. The minimum bandgap is closer to the optimal for a single-junction cell than methylammonium lead trihalide, so it should be capable of higher efficiencies. The first use of perovskite in a solid state solar cell was in a dye-sensitized cell using CsSnI3 as a p-type hole transport layer and absorber. A common concern is the inclusion of lead as a component of the perovskite materials; solar cells based on tin-based perovskite absorbers such as CH3NH3SnI3 have also been reported with lower power-conversion efficiencies.

In another recent development, solar cells based on transition metal oxide perovskites and heterostructures thereof such as LaVO3/SrTiO3 are studied.

Rice University scientists have discovered a novel phenomenon of light-induced lattice expansion in perovskite materials.

In order to overcome the instability issues with lead-based organic perovskite materials in ambient air and reduce the use of lead, perovskite derivatives, such as Cs2SnI6 double perovskite, have also been investigated.

Processing

Perovskite solar cells hold an advantage over traditional silicon solar cells in the simplicity of their processing. Traditional silicon cells require expensive, multistep processes, conducted at high temperatures (>1000 °C) in a high vacuum in special clean room facilities. Meanwhile, the organic-inorganic perovskite material can be manufactured with simpler wet chemistry techniques in a traditional lab environment. Most notably, methylammonium and formamidinium lead trihalides have been created using a variety of solvent techniques and vapor deposition techniques, both of which have the potential to be scaled up with relative feasibility.

In one-step solution processing, a lead halide and a methylammonium halide can be dissolved in a solvent and spin coated onto a substrate. Subsequent evaporation and convective self-assembly during spinning results in dense layers of well crystallized perovskite material, due to the strong ionic interactions within the material (The organic component also contributes to a lower crystallization temperature). However, simple spin-coating does not yield homogenous layers, instead requiring the addition of other chemicals such as GBL, DMSO, and toluene drips. Simple solution processing results in the presence of voids, platelets, and other defects in the layer, which would hinder the efficiency of a solar cell. 

Recently, a new approach for forming the PbI2 nanostructure and the use of high CH3NH3I concentration have been adopted to form high quality (large crystal size and smooth) perovskite film with better photovoltaic performances. On one hand, self-assembled porous PbI2 is formed by incorporating small amounts of rationally chosen additives into the PbI2 precursor solutions, which significantly facilitate the conversion of perovskite without any PbI2 residue. On the other hand, through employing a relatively high CH3NH3I concentration, a firmly crystallized and uniform CH3NH3PbI3 film is formed. 

Another technique using room temperature solvent-solvent extraction produces high-quality crystalline films with precise control over thickness down to 20 nanometers across areas several centimeters square without generating pinholes. In this method "perovskite precursors are dissolved in a solvent called NMP and coated onto a substrate. Then, instead of heating, the substrate is bathed in diethyl ether, a second solvent that selectively grabs the NMP solvent and whisks it away. What's left is an ultra-smooth film of perovskite crystals."

In another solution processed method, the mixture of lead iodide and methylammonium halide dissolved in DMF is preheated. Then the mixture is spin coated on a substrate maintained at higher temperature. This method produces uniform films of up to 1 mm grain size.

In vapor assisted techniques, spin coated or exfoliated lead halide is annealed in the presence of methylammonium iodide vapor at a temperature of around 150 °C. This technique holds an advantage over solution processing, as it opens up the possibility for multi-stacked thin films over larger areas. This could be applicable for the production of multi-junction cells. Additionally, vapor deposited techniques result in less thickness variation than simple solution processed layers. However, both techniques can result in planar thin film layers or for use in mesoscopic designs, such as coatings on a metal oxide scaffold. Such a design is common for current perovskite or dye-sensitized solar cells.

Both processes hold promise in terms of scalability. Process cost and complexity is significantly less than that of silicon solar cells. Vapor deposition or vapor assisted techniques reduce the need for use of further solvents, which reduces the risk of solvent remnants. Solution processing is cheaper. Current issues with perovskite solar cells revolve around stability, as the material is observed to degrade in standard environmental conditions, suffering drops in efficiency. 

In 2014, Olga Malinkiewicz presented her inkjet printing manufacturing process for perovskite sheets in Boston (US) during the MRS fall meeting – for which she received MIT Technology review's innovators under 35 award. The University of Toronto also claims to have developed a low-cost Inkjet solar cell in which the perovskite raw materials are blended into a Nanosolar ‘ink’ which can be applied by an inkjet printer onto glass, plastic or other substrate materials.

Physics

An important characteristic of the most commonly used perovskite system, the methylammonium lead halides, is a bandgap controllable by the halide content. The materials also display a diffusion length for both holes and electrons of over one micron. The long diffusion length means that these materials can function effectively in a thin-film architecture, and that charges can be transported in the perovskite itself over long distances. It has recently been reported that charges in the perovskite material are predominantly present as free electrons and holes, rather than as bound excitons, since the exciton binding energy is low enough to enable charge separation at room temperature.

Efficiency limits

Perovskite solar cell bandgaps are tunable and can be optimised for the solar spectrum by altering the halide content in the film (i.e., by mixing I and Br). The Shockley–Queisser limit radiative efficiency limit, also known as the detailed balance limit, is about 31% under an AM1.5G solar spectrum at 1000W/m2, for a Perovskite bandgap of 1.55 eV. This is slightly smaller than the radiative limit of gallium arsenide of bandgap 1.42 eV which can reach a radiative efficiency of 33%. 

Values of the detailed balance limit are available in tabulated form and a MATLAB program for implementing the detailed balance model has been written.

In the meantime, the drift-diffusion model has found to successfully predict the efficiency limit of perovskite solar cells, which enable us to understand the device physics in-depth, especially the radiative recombination limit and selective contact on device performance. There are two prerequisites for predicting and approaching the perovskite efficiency limit. First, the intrinsic radiative recombination needs to be corrected after adopting optical designs which will significantly affect the open-circuit voltage at its Shockley–Queisser limit. Second, the contact characteristics of the electrodes need to be carefully engineered to eliminate the charge accumulation and surface recombination at the electrodes. With the two procedures, the accurate prediction of efficiency limit and precise evaluation of efficiency degradation for perovskite solar cells are attainable by the drift-diffusion model.

Along with analytical calculations, there have been many first principle studies to find the characteristics of the perovskite material numerically. These include but are not limited to bandgap, effective mass, and defect levels for different perovskite materials. Also there have some efforts to cast light on the device mechanism based on simulations where Agrawal et al. suggests a modeling framework, presents analysis of near ideal efficiency, and talks about the importance of interface of perovskite and hole/electron transport layers. However, Sun et al. tries to come up with a compact model for perovskite different structures based on experimental transport data.

Architectures

Schematic of a sensitized perovskite solar cell in which the active layer consist of a layer of mesoporous TiO2 which is coated with the perovskite absorber. The active layer is contacted with an n-type material for electron extraction and a p-type material for hole extraction. b) Schematic of a thin-film perovskite solar cell. In this architecture in which just a flat layer of perovskite is sandwiched between two selective contacts. c) Charge generation and extraction in the sensitized architecture. After light absorption in the perovskite absorber the photogenerated electron is injected into the mesoporous TiO2 through which it is extracted. The concomitantly generated hole is transferred to the p-type material. d) Charge generation and extraction in the thin-film architecture. After light absorption both charge generation as well as charge extraction occurs in the perovskite layer.
 
Perovskite solar cells function efficiently in a number of somewhat different architectures depending either on the role of the perovskite material in the device, or the nature of the top and bottom electrode. Devices in which positive charges are extracted by the transparent bottom electrode (cathode), can predominantly be divided into 'sensitized', where the perovskite functions mainly as a light absorber, and charge transport occurs in other materials, or 'thin-film', where most electron or hole transport occurs in the bulk of the perovskite itself. Similar to the sensitization in dye-sensitized solar cells, the perovskite material is coated onto a charge-conducting mesoporous scaffold – most commonly TiO2 – as light-absorber. The photogenerated electrons are transferred from the perovskite layer to the mesoporous sensitized layer through which they are transported to the electrode and extracted into the circuit. The thin film solar cell architecture is based on the finding that perovskite materials can also act as highly efficient, ambipolar charge-conductor. After light absorption and the subsequent charge-generation, both negative and positive charge carrier are transported through the perovskite to charge selective contacts. Perovskite solar cells emerged from the field of dye-sensitized solar cells, so the sensitized architecture was that initially used, but over time it has become apparent that they function well, if not ultimately better, in a thin-film architecture. More recently, some researchers also successfully demonstrated the possibility of fabricating flexible devices with perovskites, which makes it more promising for flexible energy demand. Certainly, the aspect of UV-induced degradation in the sensitized architecture may be detrimental for the important aspect of long-term stability

There is another different class of architectures, in which the transparent electrode at the bottom acts as cathode by collecting the photogenerated p-type charge carriers.

History

These perovskite materials have been well known for many years, but the first incorporation into a solar cell was reported by Miyasaka et al. in 2009. This was based on a dye-sensitized solar cell architecture, and generated only 3.8% power conversion efficiency (PCE) with a thin layer of perovskite on mesoporous TiO2 as electron-collector. Moreover, because a liquid corrosive electrolyte was used, the cell was only stable for a matter of minutes. Park et al. improved upon this in 2011, using the same dye-sensitized concept, achieving 6.5% PCE.

A breakthrough came in 2012, when Henry Snaith and Mike Lee from the University of Oxford realised that the perovskite was stable if contacted with a solid-state hole transporter such as spiro-OMeTAD and did not require the mesoporous TiO2 layer in order to transport electrons. They showed that efficiencies of almost 10% were achievable using the 'sensitized' TiO2 architecture with the solid-state hole transporter, but higher efficiencies, above 10%, were attained by replacing it with an inert scaffold. Further experiments in replacing the mesoporous TiO2 with Al2O3 resulted in increased open-circuit voltage and a relative improvement in efficiency of 3–5% more than those with TiO2 scaffolds. This led to the hypothesis that a scaffold is not needed for electron extraction, which was later proved correct. This realisation was then closely followed by a demonstration that the perovskite itself could also transport holes, as well as electrons. A thin-film perovskite solar cell, with no mesoporous scaffold, of > 10% efficiency was achieved.

In 2013 both the planar and sensitized architectures saw a number of developments. Burschka et al. demonstrated a deposition technique for the sensitized architecture exceeding 15% efficiency by a two-step solution processing, At a similar time Olga Malinkiewicz et al, and Liu et al. showed that it was possible to fabricate planar solar cells by thermal co-evaporation, achieving more than 12% and 15% efficiency in a p-i-n and an n-i-p architecture respectively. Docampo et al. also showed that it was possible to fabricate perovskite solar cells in the typical 'organic solar cell' architecture, an 'inverted' configuration with the hole transporter below and the electron collector above the perovskite planar film.

A range of new deposition techniques and even higher efficiencies were reported in 2014. A reverse-scan efficiency of 19.3% was claimed by Yang Yang at UCLA using the planar thin-film architecture. In November 2014, a device by researchers from KRICT achieved a record with the certification of a non-stabilized efficiency of 20.1%.

In December 2015, a new record efficiency of 21.0% was achieved by researchers at EPFL.

As of March 2016, researchers from KRICT and UNIST hold the highest certified record for a single-junction perovskite solar cell with 22.1%.

In 2018, a new record was set by researchers at the Chinese Academy of Sciences with a certified efficiency of 23.3%.

Stability

One big challenge for perovskite solar cells (PSCs) is the aspect of short-term and long-term stability. The instability of PSCs is mainly related to environmental influence (moisture and oxygen), thermal influence (intrinsic stability), heating under applied voltage, photo influence (Ultraviolet light) (Visible light) and mechanical fragility. Several studies about PSCs stability have been performed and some elements have been proven to be important to the PSCs stability. However, there is no standard "operational" stability protocol for PSCs. But a method to quantify the intrinsic chemical stability of hybrid halide perovskites has been recently proposed.

The water-solubility of the organic constituent of the absorber material make devices highly prone to rapid degradation in moist environments. The degradation which is caused by moisture can be reduced by optimizing the constituent materials, the architecture of the cell, the interfaces and the environment conditions during the fabrication steps. Encapsulating the perovskite absorber with a composite of carbon nanotubes and an inert polymer matrix has been demonstrated to successfully prevent the immediate degradation of the material when exposed to moist ambient air at elevated temperatures. However, no long term studies and comprehensive encapsulation techniques have yet been demonstrated for perovskite solar cells. Besides moisture instability, it has also been shown that the embodiment of devices in which a mesoporous TiO2 layer is sensitized with the perovskite absorber exhibits UV light induced instability. The cause for the observed decline in device performance of those solar cells is linked to the interaction between photogenerated holes inside the TiO2 and oxygen radicals on the surface of TiO2. The measured ultra low thermal conductivity of 0.5 W/(Km) at room temperature in CH3NH3PbI3 can prevent fast propagation of the light deposited heat, and keep the cell resistive on thermal stresses that can reduce its life time. The PbI2 residue in perovskite film has been experimentally demonstrated to have a negative effect on the long-term stability of devices. The stabilization problem is claimed to be solved by replacing the organic transport layer with a metal oxide layer, allowing the cell to retain 90% capacity after 60 days. Besides, the two instabilities issues can be solved by using multifunctional fluorinated photopolymer coatings that confer luminescent and easy-cleaning features on the front side of the devices, while concurrently forming a strongly hydrophobic barrier toward environmental moisture on the back contact side. The front coating can prevent the UV light of the whole incident solar spectrum from negatively interacting with the PSC stack by converting it into visible light, and the back layer can prevent water from permeation within the solar cell stack. The resulting devices demonstrated excellent stability in terms of power conversion efficiencies during a 180-day aging test in the lab and a real outdoor condition test for more than 3 months.

In July 2015 major hurdles were that the largest perovskite solar cell was only the size of a fingernail and that they degraded quickly in moist environments. However, researchers from EPFL published in June 2017, a work successfully demonstrating large scale perovskite solar modules with no observed degradation over one year. Now, together with other organizations, the research team aims to develop a fully printable perovskite solar cell with 22% efficiency and with 90% of performance after ageing tests.

Apart from the moisture and oxygen, UV light is a critical problem. The UV light will cause the perovskite layer CH3NH3PbI3 to decompose and dramatically decrease the efficiency of the solar cell. The basic idea to address this problem is to block the UV light when we absorb the sun light. The more effective method is to aid another layer on the solar layer, which is YVO4:EU3+ material. This material has a very unique band gap which can block the UV light and let other light goes through. By using this material, the efficiency of the solar will be higher than 50% even after it is exposed to the sunlight for a very long time. Advancements in the engineering of interfaces allowed the creation of a 2D / 3D mixed perovskite, which enabled the creation of a solar cell with over 10000 hour (more than 1 year) stable performance without any loss in efficiency, pointing towards the viability of commercialization. The intrinsic fragility of the perovskite material requires extrinsic reinforcement to shield this crucial layer from mechanical stresses. Insertion of mechanically reinforcing scaffolds directly into the active layers of perovskite solar cells resulted in the compound solar cell formed exhibiting a 30-fold increase in fracture resistance, repositioning the fracture properties of perovskite solar cells into the same domain as conventional c-Si, CIGS and CdTe solar cells.

Hysteretic current-voltage behavior

Another major challenge for perovskite solar cells is the observation that current-voltage scans yield ambiguous efficiency values. The power-conversion efficiency of a solar cell is usually determined by characterizing its current-voltage (IV) behavior under simulated solar illumination. In contrast to other solar cells, however, it has been observed that the IV-curves of perovskite solar cells show a hysteretic behavior: depending on scanning conditions – such as scan direction, scan speed, light soaking, biasing – there is a discrepancy between the scan from forward-bias to short-circuit (FB-SC) and the scan from short-circuit to forward bias (SC-FB). Various causes have been proposed such as ion movement, polarization, ferroelectric effects, filling of trap states, however, the exact origin for the hysteretic behavior is yet to be determined. But it appears that determining the solar cell efficiency from IV-curves risks producing inflated values if the scanning parameters exceed the time-scale which the perovskite system requires in order to reach an electronic steady-state. Two possible solutions have been proposed: Unger et al. show that extremely slow voltage-scans allow the system to settle into steady-state conditions at every measurement point which thus eliminates any discrepancy between the FB-SC and the SC-FB scan. Henry Snaith et al. have proposed 'stabilized power output' as a metric for the efficiency of a solar cell. This value is determined by holding the tested device at a constant voltage around the maximum power-point (where the product of voltage and photocurrent reaches its maximum value) and track the power-output until it reaches a constant value. Both methods have been demonstrated to yield lower efficiency values when compared to efficiencies determined by fast IV-scans. However, initial studies have been published that show that surface passivation of the perovskite absorber is an avenue with which efficiency values can be stabilized very close to fast-scan efficiencies. Initial reports suggest that in the 'inverted architecture', which has a transparent cathode, little to no hysteresis is observed. This suggests that the interfaces might play a crucial role with regards to the hysteretic IV behavior since the major difference of the inverted architecture to the regular architectures is that an organic n-type contact is used instead of a metal oxide. 

The observation of hysteretic current-voltage characteristics has thus far been largely underreported. Only a small fraction of publications acknowledge the hysteretic behavior of the described devices, even fewer articles show slow non-hysteretic IV curves or stabilized power outputs. Reported efficiencies, based on rapid IV-scans, have to be considered fairly unreliable and make it currently difficult to genuinely assess the progress of the field.

The ambiguity in determining the solar cell efficiency from current-voltage characteristics due to the observed hysteresis has also affected the certification process done by accredited laboratories such as NREL. The record efficiency of 20.1% for perovskite solar cells accepted as certified value by NREL in November 2014, has been classified as 'not stabilized'. To be able to compare results from different institution, it is necessary to agree on a reliable measurement protocol, as it has been proposed by  including the corresponding Matlab code which can be found at GitHub.

Perovskites for tandem applications

A perovskite cell combined with bottom cell such as Si or copper indium gallium selenide (CIGS) as a tandem design can suppress individual cell bottlenecks and take advantage of the complementary characteristics to enhance the efficiency. This type of cells have higher efficiency potential, and therefore attracted recently a large attention from academic researchers.

4-terminal tandems

Using a four terminal configuration in which the two sub-cells are electrically isolated, Bailie et al. obtained a 17% and 18.6% efficient tandem cell with mc-Si (η ~ 11%) and copper indium gallium selenide (CIGS, η ~ 17%) bottom cells, respectively. A 13.4% efficient tandem cell with a highly efficient a-Si:H/c-Si heterojunction bottom cell using the same configuration was obtained. The application of TCO-based transparent electrodes to perovskite cells allowed to fabricate near-infrared transparent devices with improved efficiency and lower parasitic absorption losses. The application of these cells in 4-terminal tandems allowed improved efficiencies up to 26.7% when using a silicon bottom cell and up to 23.9% with a CIGS bottom cell.

2-terminal tandems

Mailoa et al. started the efficiency race for monolithic 2-terminal tandems using an homojunction c-Si bottom cell and demonstrate a 13.7% cell, largely limited by parasitic absorption losses. Then, Albrecht et al. developed a low-temperature processed perovskite cells using a SnO2 electron transport layer. This allowed the use of silicon heterojunction solar cells as bottom cell and tandem efficiencies up to 18.1%. Werner et al. then improved this performance replacing the SnO2 layer with PCBM and introducing a sequential hybrid deposition method for the perovskite absorber, leading to a tandem cell with 21.2% efficiency. Important parasitic absorption losses due to the use of Spiro-OMeTAD were still limiting the overall performance. An important change was demonstrated by Bush et al., who inverted the polarity of the top cell (n-i-p to p-i-n). They used a bilayer of SnO2 and zinc tin oxide (ZTO) processed by ALD to work as a sputtering buffer layer, which enables the following deposition of a transparent top indium tin oxide (ITO) electrode. This change helped to improve the environmental and thermal stability of the perovskite cell and was crucial to further improve the perovskite/silicon tandem performance to 23.6% In the continuity, using a p-i-n perovskite top cell, Sahli et al. demonstrated in June 2018 a fully textured monolithic tandem cell with 25.2% efficiency, independently certified by Fraunhofer ISE CalLab. This improved efficiency can largely be attributed to the massively reduced reflection losses (below 2% in the range 360 nm-1000 nm, excluding metallization) and reduced parasitic absorption losses, leading to certified short-circuit currents of 19.5mA/cm2. Also in June 2018 the company Oxford Photovoltaics presented a cell with 27.3% efficiency.

Theoretical modelling

There have been some efforts to predict the theoretical limits for these traditional tandem designs using a perovskite cell as top cell on a c-Si or a-Si/c-Si heterojunction bottom cell. To show that the output power can be even further enhanced, bifacial structures were studied as well. It was concluded that extra output power can be extracted from the bifacial structure as compared to a bifacial HIT cell when the albedo reflection takes on values between 10 and 40%, which are realistic.

Up-scaling

In May 2016, IMEC and its partner Solliance announced a tandem structure with a semi-transparent perovskite cell stacked on top of a back-contacted silicon cell. A combined power conversion efficiency of 20.2% was claimed, with the potential to exceed 30%.

All-perovskite tandems

In 2016, the development of efficient low-bandgap (1.2 - 1.3eV) perovskite materials and the fabrication of efficient devices based on these enabled a new concept: all-perovskite tandem solar cells, where two perovskite compounds with different bandgaps are stacked on top of each other. The first two- and four-terminal devices with this architecture reported in the literature achieved efficiencies of 17% and 20.3%. All-perovskite tandem cells offer the prospect of being the first fully solution-processable architecture that has a clear route to exceeding not only the efficiencies of silicon, but also GaAs and other expensive III-V semiconductor solar cells. 

In 2017, Dewei Zhao et al. fabricated low-bandgap (~1.25 eV) mixed Sn-Pb perovskite solar cells (PVSCs) with the thickness of 620 nm, which enables larger grains and higher crystallinity to extend the carrier lifetimes to more than 250 ns, reaching a maximum power conversion efficiency (PCE) of 17.6%. Furthermore, this low-bandgap PVSC reached an external quantum efficiency (EQE) of more than 70% in the wavelength range of 700–900 nm, the essential infrared spectral region where sunlight transmitted to bottom cell. They also combined the bottom cell with a ~1.58 eV bandgap perovskite top cell to create an all-perovskite tandem solar cell with four terminals, obtaining a steady-state PCE of 21.0%, suggesting the possibility of fabricating high-efficiency all-perovskite tandem solar cells.

Inequality (mathematics)

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