Harnessing the Functionality and ‘Power’ of Perovskites for Better Solar and LED’s

Originally a mineral, the perovskite used in today’s technology is quite different from the rock found in the Earth mantle. 

A “perovskite structure” uses a different combination of atoms but keep the general 3-dimensional structure originally observed in the mineral, which possesses superb optoelectronic properties such as strong light absorption and facilitated charge transport. These advantages qualify the perovskite structure as particularly suited for the design of electronic devices, from solar cells to lights.

The accelerating progress in perovskite technology over the past few years suggest new perovskite-based devices will soon outperform current technology in the energy sector. 

The Energy Materials and Surface Sciences Unit at OIST led by Prof. Yabing Qi is at the forefront of this development, with now two new scientific publications focusing on the improvement of perovskite solar cells and a cheaper and smarter way to produce emerging perovskite-based LED lights.

An extra layer in a solar cell “sandwich”

Perovskite-based solar cells is a rising technology forecast to replace the classic photovoltaic cells currently dominating the industry. 

In just seven years of development, the efficiency of perovskite solar cells increased to almost rival – and is expected to soon overtake – commercial photovoltaic cells, but the perovskite structure still plagued by a short lifespan due to stability issues. 

OIST scientists have made constant baby steps in improving the cells stability, identifying the degradations factors and providing solutions towards better solar cell architecture.

The new finding, reported in the Journal of Physical Chemistry B (“Engineering Interface Structure to Improve Efficiency and Stability of Organometal Halide Perovskite Solar Cells”), suggests interactions between components of the solar cell itself are responsible for the rapid degradation of the device. 

More precisely, the titanium oxide layer extracting electrons made available through solar energy – effectively creating an electric current – causes unwanted deterioration of the neighboring perovskite layer. 

Imagine the solar cell as a multi-layered club sandwich: if not properly assembled, fresh and juicy vegetables in contact with the bread slices will make the bread very soggy in a matter of hours. 

But if you add a layer of ham or turkey between the vegetables and the bread, then your sandwich stays crisp all day in the lunchroom refrigerator.

A perovskite-based layer includes many layers, including for example the electrodes on both sides, and the perovskite in the middle. The addition of a polystyrene layer in-between prevents the titanium oxide layer to deteriorate the perovskite, but does not affect the overall power conversion efficiency. (© American Chemical Society)

This is exactly what the OIST researchers achieved: they inserted in the solar cell an additional layer made from a polymer to prevent direct contact between the titanium oxide and the perovskite layers. 
This polymer layer is insulating but very thin, which means it lets the electron current tunnel through yet does not diminish the overall efficiency of the solar cell, while efficiently protecting the perovskite structure.

“We added a very thin sheet, only a few nanometers wide, of polystyrene between the perovskite layer and the titanium oxide layer,” explained Dr. Longbin Qiu. 

“Electrons can still tunnel cross this new layer and it does not affect the light absorption of the cell. This way, we were able to extend the lifetime of the cell four-fold without loss in energy conversion efficiency”.

The lifespan of the new perovskite device was extended to over 250 hours – still not enough to compete with commercial photovoltaic cells regarding stability, but an important step forward toward fully functional perovskite solar cells.

Manufacturing LED lights from gasses

The bipolar electronic properties of the perovskite structure not only confer them the ability to generate electricity from solar energy but also can convert electricity into vivid light. Light-Emitting Diode – LED – technology, omnipresent in our daily life from laptop and smartphone screens to car lights and ceiling tubes, currently relies on semi-conductors that are difficult and expensive to manufacture. Perovskite LEDs are envisaged to become the new industry standard in the near future due to the lower cost and their efficiency to convert power into light. Moreover, by changing the atomic composition in the perovskite structure, perovskite LED can be easily tuned to emit specific colors.

The manufacturing of these perovskite LEDs is currently based on dipping or covering the targeted surface with liquid chemicals, a process which is difficult to setup, limited to small areas and with low consistency between samples. To overcome this issue, OIST researchers reported in the Journal of Physical Chemistry Letters (“Methylammonium Lead Bromide Perovskite Light-Emitting Diodes by Chemical Vapor Deposition”) the first perovskite LED assembled with gasses, a process called chemical vapor deposition or CVD.

“Chemical vapor deposition is already compatible with the industry, so in principle it would be easy to use this technology to produce LEDs,” commented Prof. Yabing Qi. “The second advantage in using CVD is a much lower variation from batch to batch compared to liquid-based techniques. Finally, the last point is scalability: CVD can achieve a uniform surface over very large areas”.

Like the solar cell, the perovskite LED also comprises many layers working in synergy. First, an indium tin oxide glass sheet and a polymer layer allow electrons into the LED. The chemicals required for the perovskite layer – lead bromide and methylammonium bromide – are then successively bound to the sample using CVD, in which the sample is exposed to gasses in order to convert to perovskite instead of typically solution-coating processes with liquid. In this process, the perovskite layer is composed of nanometer-small grains, whose sizes play a critical role in the efficiency of the device. Finally, the last step involves the deposition of two additional layers and a gold electrode, forming a complete LED structure. The LED can even form specific patterns using lithography during the manufacturing process.

Perovskite LED fabrication

Top: the perovskite LED sits in a furnace, where the Methylammonium Bromide (MABr) in gaseous form will be introduced into the system and deposit on the LED surface. Bottom left: a glass-based LED, glowing green when electricity is applied. Bottom right: size and shapes of the perovskite grains on the surface of the LED. (© American Chemical Society)

“With large grains, the surface of the LED is rough and less efficient in emitting light. The smaller the grain size, the higher the efficiency and the brighter the light,” explained Dr. Lingqiang Meng. “By changing the assembly temperature, we can now control the growth process and the size of the grains for the best efficiency”.

Controlling the grain size is not the only challenge for this first-of-its-kind assembling technique of LED lights.

“Perovskite is great, but the choice in the adjacent layers is really important too,” added Dr. Luis K. Ono. “To achieve high electricity-to-light conversion rates, every layer should be working in harmony with the others.”

The result is a flexible, thick film-like LED with a customizable pattern. The luminance, or brightness, currently reaches 560 cd/m2, while a typical computer screen emits 100 to 1000 cd/m2 and a ceiling fluorescent tube around 12,000 cd/m2.

Perovskite-LED

This large perovskite-LED was produced using chemical vapor deposition and connect to a 5V current, illuminating through an OIST pattern etched on the surface. (© American Chemical Society)

“Our next step is to improve the luminance a thousand-fold or more,” concluded Dr. Meng. “In addition, we have achieved a CVD-based LED emitting green light but we are now trying to repeat the process with different combinations of perovskite to obtain a vivid blue or red light”.

Source: By Wilko Duprez, Okinawa Institute of Technology

Third-Generation Solar Cells using Metalorganic Perovskites Challenges silicon based Solar Cells

An illustration of a perovskite solar cell. Credit: Photo by Aalto University / University of Uppsala / EPFL

Five years ago, the world started to talk about third-generation solar cells that challenged the traditional silicon cells with a cheaper and simpler manufacturing process that used less energy.

Methylammonium lead iodide is a metal-organic material in the perovskite crystal structure that captures light efficiently and conducts electricity well—both important qualities in solar cells. However, the lifetime of solar cells made of metalorganic perovskites has proven to be very short compared to cells made of silicon.

Now researchers from Aalto University, Uppsala University and École polytechnique fédérale de Lausanne (EPFL) in Switzerland have managed to improve the long term stability of solar cells made of perovskite using “random network” nanotube films developed under the leadership of Professor Esko Kauppinen at Aalto University. Random network nanotube films are films composed of single-walled carbon nanotubes that in an electron microscope image look like spaghetti on a plate.

‘In a traditional perovskite solar cell, the hole conductor layer consists of organic material and, on top of it, a thin layer of gold that easily starts to disintegrate and diffuse through the whole solar cell structure. We replaced the gold and also part of the organic material with films made of carbon nanotubes and achieved good cell stability in 60 degrees and full one sun illumination conditions‘, explains Kerttu Aitola, who defended her doctoral dissertation at Aalto University and now works as a researcher at Uppsala University

In the study, thick black films with conductivity as high as possible were used in the back contact of the solar cell where light does not need to get through. According to Aitola, nanotube films can also be made transparent and thin, which would make it possible to use them as the front contact of the cell, in other words as the contact that lets light through.

‘The solar cells were prepared in Uppsala and the long-term stability measurement was carried out at EPFL. The leader of the solar cell group at EPFL is Professor Michael Grätzel, who was awarded the Millennium Prize 2010 for dye-sensitised solar cells, on which the perovskite solar cells are also partly based on’, says Aitola.

Cross-section of the solar cell in an electron microscope image. The fluff seen in the front of the image is composed of bundles of nanotubes that have become half-loose when the samples have been prepared for imaging. Credit: Photo by Aalto University / University of Uppsala / EPFL

 

The lifetime of solar cells made of silicon is 20-30 years and their industrial production is very efficient. Still, alternatives are needed as reducing the silicon dioxide in sand to silicon consumes a huge amount of energy. It is estimated that a silicon solar cell needs two or three years to produce the energy that was used to manufacture it, whereas a perovskite solar cell would only need two or three months to do it.

‘In addition, the silicon used in solar cells must be extremely pure’, says Aitola.

‘Perovskite solar cell is also interesting because its efficiency, in other words how efficiently it converts sunlight energy into electrical energy, has very quickly reached the level of silicon solar cells. That is why so much research is conducted on perovskite solar cells globally.’

The alternative solar cells are even more interesting because of their various application areas. Flexible solar cells have until now been manufactured on conductive plastic. Compared with the conductive layer of plastic, the flexibility of nanotube films is superior and the raw materials are cheaper. Thanks to their flexibility, solar cells could be produced using the roll-to-roll processing method known from the paper industry.

‘Light and flexible solar cells would be easy to integrate in buildings and you could also hang them in windows by yourself’, says Aitola.

Explore further: New way to make low-cost solar cell technology

More information: Kerttu Aitola et al, High Temperature-Stable Perovskite Solar Cell Based on Low-Cost Carbon Nanotube Hole Contact, Advanced Materials (2017). DOI: 10.1002/adma.201606398

Journal reference: Advanced Materials

Provided by: Aalto University

ASU and Stanford Researchers Achieve Record Breaking Efficiency with Tandem (Perovskite + Silicon) Solar Cell

Above: A perovskite/silicon tandem solar cell, created by research teams from Arizona State University and Stanford University, capable of record-breaking sunlight-to-electricity conversion efficiency. Photographer: Pete Zrioka/ASU

Some pairs are better together than their individual counterparts — peanut butter and chocolate, warm weather and ice cream, and now, in the realm of photovoltaic technology, silicon and perovskite.

As existing solar energy technologies near their theoretical efficiency limits, researchers are exploring new methods to improve performance — such as stacking two photovoltaic materials in a tandem cell. Collaboration between researchers at Arizona State University and Stanford University has birthed such a cell with record-breaking conversion efficiency — effectively finding the peanut butter to silicon’s chocolate.

The results of their work, published February 17 in Nature Energy, outline the use of perovskite and silicon to create a tandem solar cell capable of converting sunlight to energy with an efficiency of 23.6 percent, just shy of the all-time silicon efficiency record.

“The best silicon solar cell alone has achieved 26.3 percent efficiency,” says Zachary Holman, an assistant professor of electrical engineering at the Ira A. Fulton Schools of Engineering. “Now we’re gunning for 30 percent with these tandem cells, and I think we could be there within two years.”

Assistant Professor Zachary Holman, holds one of the many solar cells his research group has created. Photographer: Jessica Hochreiter/ASU

Silicon solar cells are the backbone of a $30 billion a year industry, and this breakthrough shows that there’s room for significant improvement within such devices by finding partner materials to boost efficiency.

The high-performance tandem cell’s layers are each specially tuned to capture different wavelengths of light. The top layer, composed of a perovskite compound, was designed to excel at absorbing visible light. The cell’s silicon base is tuned to capture infrared light.

Perovskite, a cheap, easily manufacturable photovoltaic material, has emerged as a challenger to silicon’s dominance in the solar market. Since its introduction to solar technology in 2009, the efficiency of perovskite solar cells has increased from 3.8 percent to 22.1 percent in early 2016, according to the National Renewable Energy Laboratory.

The perovskite used in the tandem cell came courtesy of Stanford researchers Professor Michael McGehee and doctoral student Kevin Bush, who fabricated the compound and tested the materials.

The research team at ASU provided the silicon base and modeling to determine other material candidates for use in the tandem cell’s supporting layers.

OVERCOMING CHALLENGES WITH PEROVSKITES

Though low-cost and highly efficient, perovskites have been limited by poor stability, degrading at a much faster rate than silicon in hot and humid environments. Additionally, perovskite solar cells have suffered from parasitic absorption, in which light is absorbed by supporting layers in the cell that don’t generate electricity.

“We have improved the stability of the perovskite solar cells in two ways,” says McGehee, a materials science and engineering professor at Stanford’s School of Engineering. “First, we replaced an organic cation with cesium. Second, we protected the perovskite with an impermeable indium tin oxide layer that also functions as an electrode.”

Though McGehee’s compound achieves record stability, perovskites remain delicate materials, making it difficult to employ in tandem solar technology.

“In many solar cells, we put a layer on top that is both transparent and conductive,” says Holman, a faculty member in the School of Electrical, Computer and Energy Engineering. “It’s transparent so light can go through and conductive so we can take electrical charges off it.”

This top conductive layer is applied using a process called sputtering deposition, which historically has led to damaged perovskite cells. However, McGehee was able to apply a tin oxide layer with help from chemical engineering Professor Stacey Bent and doctoral student Axel Palmstrom of Stanford. The pair developed a thin layer that protects the delicate perovskite from the deposition of the final conductive layer without contributing to parasitic absorption, further boosting the cell’s efficiency.

The deposition of the final conductive layer wasn’t the only engineering challenge posed by integrating perovskites and silicon.

“It was difficult to apply the perovskite itself without compromising the performance of the silicon cell,” says Zhengshan (Jason) Yu, an electrical engineering doctoral student at ASU.

Silicon wafers are placed in a potassium hydroxide solution during fabrication, which creates a rough, jagged surface. This texture, ideal for trapping light and generating more energy, works well for silicon, but perovskite prefers a smooth — and unfortunately reflective — surface for deposition.

Additionally, the perovskite layer of the tandem cell is less than a micron thick, opposed to the 250-micron thick silicon layer. This means when the thin perovskite layer was deposited, it was applied unevenly, pooling in the rough silicon’s low points and failing to adhere to its peaks.

Yu developed a method to create a planar surface only on the front of the silicon solar cell using a removable, protective layer. This resulted in a smooth surface on one side of the cell, ideal for applying the perovskite, while leaving the backside rough, to trap the weakly-absorbed near-infrared light in the silicon.

“With the incorporation of a silicon nanoparticle rear reflector, this infrared-tuned silicon cell becomes an excellent bottom cell for tandems,” says Yu.

BUILDING ON PREVIOUS SUCCESSES

The success of the tandem cell is built on existing achievements from both teams of researchers. In October 2016, McGehee and post-doctoral scholar Tomas Leijtens fabricated an all-perovskite cell capable of 20.3 percent efficiency. The high-performance cell was achieved in part by creating a perovskite with record stability, marking McGehee’s group as one of the first teams to devote research efforts to fabricating stable perovskite compounds.

Likewise, Holman has considerable experience working with silicon and tandem cells.

“We’ve tried to position our research group as the go-to group in the U.S. for silicon bottom cells for tandems,” says Holman, who’s been pursuing additional avenues to create high-efficiency tandem solar cells.

In fact, Holman and Yu published a comment in Nature Energy in September 2016 outlining the projected efficiencies of different cell combinations in tandems.

“People often ask, ‘given the fundamental laws of physics, what’s the best you can do?’” says Holman. “We’ve asked and answered a different, more useful question: Given two existing materials, if you could put them together, ideally, what would you get?”’

The publication is a sensible guide to designing a tandem solar cell, specifically with silicon as the bottom solar cell, according to Holman.

It calculates what the maximum efficiency would be if you could pair two existing solar cells in a tandem without any performance loss. The guide has proven useful in directing research efforts to pursue the best partner materials for silicon.

“We have eight projects with different universities and organizations, looking at different types of top cells that go on top of silicon,” says Holman. “So far out of all our projects, our perovskite/silicon tandem cell with Stanford is the leader.”

Perovskite solar cells hit new world efficiency record

Dr. Anita Ho-Baillie, a Senior Research Fellow at the Australian Centre for Advanced Photovoltaics at UNSW, with the new perovskite cell. Credit: Rob Largent/UNSW

They’re flexible, cheap to produce and simple to make – which is why perovskites are the hottest new material in solar cell design. And now, engineers at Australia’s University of New South Wales in Sydney have smashed the trendy new compound’s world efficiency record.

Speaking at the Asia-Pacific Solar Research Conference in Canberra on Friday 2 December, Anita Ho-Baillie, a Senior Research Fellow at the Australian Centre for Advanced Photovoltaics (ACAP), announced that her team at UNSW has achieved the highest efficiency rating with the largest perovskite solar cells to date.

The 12.1% efficiency rating was for a 16 cm2 perovskite solar cell, the largest single perovskite photovoltaic cell certified with the highest energy conversion efficiency, and was independently confirmed by the international testing centre Newport Corp, in Bozeman, Montana.
The new cell is at least 10 times bigger than the current certified high-efficiency perovskite solar cells on record.

Her team has also achieved an 18% efficiency rating on a 1.2 cm2 single perovskite cell, and an 11.5% for a 16 cm2 four-cell perovskite mini-module, both independently certified by Newport.

“This is a very hot area of research, with many teams competing to advance photovoltaic design,” said Ho-Baillie. “Perovskites came out of nowhere in 2009, with an efficiency rating of 3.8%, and have since grown in leaps and bounds.

These results place UNSW amongst the best groups in the world producing state-of-the-art high-performance perovskite solar cells. And I think we can get to 24% within a year or so.”

Perovskite is a structured compound, where a hybrid organic-inorganic lead or tin halide-based material acts as the light-harvesting active layer. They are the fastest-advancing solar technology to date, and are attractive because the compound is cheap to produce and simple to manufacture, and can even be sprayed onto surfaces.

“The versatility of solution deposition of perovskite makes it possible to spray-coat, print or paint on solar cells,” said Ho-Baillie. “The diversity of chemical compositions also allows cells be transparent, or made of different colours. Imagine being able to cover every surface of buildings, devices and cars with solar cells.”

Most of the world’s commercial solar cells are made from a refined, highly purified silicon crystal and, like the most efficient commercial silicon cells (known as PERC cells and invented at UNSW), need to be baked above 800?C in multiple high-temperature steps.

Perovskites, on the other hand, are made at low temperatures and 200 times thinner than silicon cells.

But although perovskites hold much promise for cost-effective solar energy, they are currently prone to fluctuating temperatures and moisture, making them last only a few months without protection. Along with every other team in the world, Ho-Baillie’s is trying to extend its durability.

Thanks to what engineers learned from more than 40 years of work with layered silicon, they’re are confident they can extend this.

 

Nevertheless, there are many existing applications where even disposable low-cost, high-efficiency solar cells could be attractive, such as use in disaster response, device charging and lighting in electricity-poor regions of the world.
Perovskite solar cells also have the highest power to weight ratio amongst viable photovoltaic technologies.

“We will capitalise on the advantages of perovskites and continue to tackle issues important for commercialisation, like scaling to larger areas and improving cell durability,” said Martin Green, Director of the ACAP and Ho-Baillie’s mentor. The project’s goal is to lift perovskite solar cell efficiency to 26%.

The research is part of a collaboration backed by $3.6 million in funding through the Australian Renewable Energy Agency’s (ARENA) ‘solar excellence’ initiative. ARENA’s CEO Ivor Frischknecht said the achievement demonstrated the importance of supporting early stage renewable energy technologies:
“In the future, this world-leading R&D could deliver efficiency wins for households and businesses through rooftop solar as well as for big solar projects like those being advanced through ARENA’s investment in large-scale solar.”

To make a perovskite solar cells, engineers grow crystals into a structure known as ‘perovskite’, named after Lev Perovski, the Russian mineralogist who discovered it. They first dissolve a selection of compounds in a liquid to make the ‘ink’, then deposit this on a specialised glass which can conduct electricity. When the ink dries, it leaves behind a thin film that crystallises on top of the glass when mild heat is applied, resulting in a thin layer of perovskite crystals.

The tricky part is growing a thin film of perovskite crystals so the resulting solar cell absorbs a maximum amount of light.

Worldwide, engineers are working to create smooth and regular layers of perovskite with large crystal grain sizes in order to increase photovoltaic yields.

Ho-Baillie, who obtained her PhD at UNSW in 2004, is a former chief engineer for Solar Sailor, an Australian company which integrates solar cells into purpose-designed commercial marine ferries which currently ply waterways in Sydney, Shanghai and Hong Kong.

Perovskite phosphor boosts visible light communication: Flashy nanocrystals help LEDs send data in the blink of an eye

A green-emitting perovskite nanocrystal phosphor mixed with a red-emitting nitride phosphor looks yellow under ambient light (left). When excited by blue laser light, the phosphor combination produces white light (right).

Credit: Osman Bakr

 

Light-emitting diodes (LEDs) are increasingly used to illuminate homes and offices; soon, the same lights could also transmit data to your computer or smartphone in photon pulses so fast the eye can’t see them. But this form of visible light communication faces two key challenges: The light must flicker fast enough to carry sizeable amounts of data; and at the same time it should provide the warm, balanced color tones needed for pleasant ambient lighting.

 

Nanocrystals of cesium lead bromide (CsPbBr₃) could help to solve both problems, according to a team led by Boon S. Ooi and Osman M. Bakr at King Abdullah University of Science & Technology (KAUST). They have found that LEDs coated with the material can reach high data transmission rates of 2 gigabits per second, comparable to the fastest Wi-Fi, while producing a quality of light that matches commercial white-light LEDs (ACS Photonics 2016, DOI: 10.1021/acsphotonics.6b00187).

 

Visible light communication, sometimes called Li-Fi, is already finding real-world applications. Last year, for example, Dutch company Phillips installed a smart LED system in a French supermarket that uses Li-Fi to transmit discount offers to shoppers’ cellphones, based on their location in the store. If data rates could be increased significantly, Li-Fi might add much-needed capacity to congested Wi-Fi networks that rely on radio waves.

 

And since the smart LEDs are doing double duty, by providing both lighting and communication, they offer an economical solution, says Bakr. Ooi adds that these systems do not even need a direct line of sight between LED and computer: “As long as your device can see light, you can detect a signal,” he says.

 

White-light LEDs typically contain a blue LED coated with phosphors that turn some of the light into green and red. But most phosphors take too long to recover between excitation and emission, pulsing no more than a few million times per second. Last year, other researchers showed that polymer semiconductors could reach more than 200 MHz (ACS Photonics2015, DOI: 10.1021/ph500451y).

 

The KAUST team instead turned to CsPbBr₃, part of a family of materials known as perovskites that have become the darling of the photovoltaic research community. Perovskite solar cells have seen remarkable efficiency gains over the past seven years, and the materials are cheap and relatively easy to prepare in solution.

 

The team created nanocrystals of the perovskite, roughly 8 nm across, and found that their green emission faded in just seven nanoseconds. This allowed them to pulse reliably at almost 500 MHz, setting what the researchers believe is a new record for LED phosphors. “It is an extremely impressive and important achievement,” says Ted Sargent of the University of Toronto, who works on optoelectronic materials and has collaborated with the KAUST group in the past.

 

The rapid response is partly due to the size of the crystals, Bakr explains. When blue light excites an electron in the material, it forms an electron-hole pair called an exciton. The confines of the tiny crystal change the exciton’s energy levels, making the electron more likely to recombine with its hole and emit a photon.

 

When the researchers teamed the perovskite phosphor with a commercial red-emitting phosphor and a blue gallium nitride LED, the device produced a warm white light with a color rendering index of 89, as good as white LEDs already on the market (natural sunlight itself is rated at 100). “This quality makes this material ideal for low-power indoor illumination,” Sargent says.

 

Jakoah Brgoch of the University of Houston, who develops novel phosphors for LED lighting, says that it is relatively easy to fine-tune the chemistry of perovskites by substituting different halides or metal ions. “That means there’s a lot of potential to improve these properties,” he says.

Chemical & Engineering News ISSN 0009-2347 Copyright © 2016 American Chemical Society

MIT: Light can “heal” defects in some solar cells

A sample of the mineral perovskite is shown in the foreground, while behind it is an image the researchers used to prove the effects of intense light on a thin film of perovskite. Fluorescence imaging shows that areas that received more light became more purified, as revealed by brighter fluorescence from those regions.

Image: MIT News. Fluorescence image courtesy of the researchers.

Defects in some new electronic materials can be removed by making ions move under illumination.

A family of compounds known as perovskites, which can be made into thin films with many promising electronic and optical properties, has been a hot research topic in recent years. But although these materials could potentially be highly useful in applications such as solar cells, some limitations still hamper their efficiency and consistency.

Now, a team of researchers at MIT and elsewhere say they have made significant inroads toward understanding a process for improving perovskites’ performance, by modifying the material using intense light. The new findings are being reported in the journal Nature Communications, in a paper by Samuel Stranks, a researcher at MIT; Vladimir Bulović, the Fariborz Maseeh (1990) Professor of Emerging Technology and associate dean for innovation; and eight colleagues at other institutions in the U.S. and the U.K. The work is part of a major research effort on perovskite materials being led by Stranks, within MIT’s Organic and Nanostructured Electronics Laboratory.

Tiny defects in perovskite’s crystalline structure can hamper the conversion of light into electricity in a solar cell, but “what we’re finding is that there are some defects that can be healed under light,” says Stranks, who is a Marie Curie Fellow jointly at MIT and Cambridge University in the U.K. The tiny defects, called traps, can cause electrons to recombine with atoms before the electrons can reach a place in the crystal where their motion can be harnessed.

Under intense illumination, the researchers found that iodide ions — atoms stripped of an electron so they carry an electric charge — migrated away from the illuminated region, and in the process apparently swept away most of the defects in that region along with them.

“This is the first time this has been shown,” Stranks says, “where just under illumination, where no [electric or magnetic] field has been applied, we see this ion migration that helps to clean the film. It reduces the defect density.”While the effect had been observed before, this work is the first to show that the improvement was caused by the ions moving as a result of the illumination.

This work is focused on particular types of the material, known as organic-inorganic metal halide perovskites, which are considered promising for applications including solar cells, light-emitting diodes (LEDs), lasers, and light detectors. They excel in a property called the photoluminescence quantum efficiency, which is key to maximizing the efficiency of solar cells. But in practice, the performance of different batches of these materials, or even different spots on the same film, has been highly variable and unpredictable. The new work was aimed at figuring out what caused these discrepancies and how to reduce or eliminate them.

Stranks explains that “the ultimate aim is to make defect-free films,” and the resulting improvements in efficiency could also be useful for applications in light emission as well as light capture.

Previous work reducing defects in thin-film perovskite materials has focused on electrical or chemical treatments, but “we find we can do the same with light,” Stranks says. One advantage of that is that the same technique used to improve the material’s properties can at the same time be used as a sensitive probe to observe and better understand the behavior of these promising materials.

Another advantage of this light-based processing is it doesn’t require anything to come in physical contact with the film being treated — for example, there is no need to attach electrical contacts or to bathe the material in a chemical solution. Instead, the treatment can simply be applied by turning on the source of illumination. The process, which they call photo-induced cleaning, could be “a way forward” for the development of useful perovskite-based devices, Stranks says.

The effects of the illumination tend to diminish over time, Stranks says, so “the challenge now is to maintain the effect” long enough to make it practical. Some forms of perovskites are already “looking to be commercialized by next year,” he says, and this research “raises questions that need to be addressed, but it also shows there are ways to address” the phenomena that have been limiting this material’s performance.

“I think the paper provides valuable insight that is likely to help people make more efficient solar cells by figuring out how to reduce the number of iodine vacancies,” says Michael McGehee, a professor of materials science and engineering at Stanford University, who was not involved in this research. “I think it is fascinating that illuminating the perovskites improves their photoluminescence efficiency by enabling iodine to move around and eliminate iodine vacancies. … This research does not make solar cells better, but it does greatly increase our understanding of how these complex materials function in solar cells.”

In addition to Stranks and Bulović, the team included Anna Osherov of MIT, Dane deQuilettes, Daniel Graham, and David Ginger of the University of Washington, and Wei Zhang, Victor Burlakov, Tomas Leitjens, and Henry Snaith of Oxford University in the U.K. The work was supported by the European Union Seventh Framework Programme, the U.S. National Science Foundation, the Center for Excitonics, an Energy Frontier Research Center at MIT funded by the U.S. Department of Energy, and the National Institutes of Health. 

Berkeley Lab: Hybrid Ultra-Thin Perovskite: A Different Type of 2D Semiconductor

Berkeley Lab Researchers Produce First Ultrathin Sheets of Perovskite Hybrids

To the growing list of two-dimensional semiconductors, such as graphene, boron nitride, and molybdenum disulfide, whose unique electronic properties make them potential successors to silicon in future devices, you can now add hybrid organic-inorganic perovskites. However, unlike the other contenders, which are covalent semiconductors, these 2D hybrid perovskites are ionic materials, which gives them special properties of their own.

Researchers at the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) have successfully grown atomically thin 2D sheets of organic-inorganic hybrid perovskites from solution. The ultrathin sheets are of high quality, large in area, and square-shaped. They also exhibited efficient photoluminescence, color-tunability, and a unique structural relaxation not found in covalent semiconductor sheets.

“We believe this is the first example of 2D atomically thin nanostructures made from ionic materials,” says Peidong Yang, a chemist with Berkeley Lab’s Materials Sciences Division and world authority on nanostructures, who first came up with the idea for this research some 20 years ago. “The results of our study open up opportunities for fundamental research on the synthesis and characterization of atomically thin 2D hybrid perovskites and introduces a new family of 2D solution-processed semiconductors for nanoscale optoelectronic devices, such as field effect transistors and photodetectors.”

Yang, who also holds appointments with the University of California (UC) Berkeley and is a co-director of the Kavli Energy NanoScience Institute (Kavli-ENSI), is the corresponding author of a paper describing this research in the journal Science. The paper is titled “Atomically thin two-dimensional organic-inorganic hybrid perovskites.” The lead authors are Letian Dou, Andrew Wong and Yi Yu, all members of Yang’s research group. Other authors are Minliang Lai, Nikolay Kornienko, Samuel Eaton, Anthony Fu, Connor Bischak, Jie Ma, Tina Ding, Naomi Ginsberg, Lin-Wang Wang and Paul Alivisatos.

Traditional perovskites are typically metal-oxide materials that display a wide range of fascinating electromagnetic properties, including ferroelectricity and piezoelectricity, superconductivity and colossal magnetoresistance. In the past couple of years, organic-inorganic hybrid perovskites have been solution-processed into thin films or bulk crystals for photovoltaic devices that have reached a 20-percent power conversion efficiency. Separating these hybrid materials into individual, free-standing 2D sheets through such techniques as spin-coating, chemical vapor deposition, and mechanical exfoliation has met with limited success.

In 1994, while a PhD student at Harvard University, Yang proposed a method for preparing 2D hybrid perovskite nanostructures and tuning their electronic properties but never acted upon it. This past year, while preparing to move his office, he came upon the proposal and passed it on to co-lead author Dou, a post-doctoral student in his research group. Dou, working mainly with the other lead authors Wong and Yu, used Yang’s proposal to synthesize free-standing 2D sheets of CH3NH3PbI3, a hybrid perovskite made from a blend of lead, bromine, nitrogen, carbon and hydrogen atoms.

“Unlike exfoliation and chemical vapor deposition methods, which normally produce relatively thick perovskite plates, we were able to grow uniform square-shaped 2D crystals on a flat substrate with high yield and excellent reproducibility,” says Dou. “We characterized the structure and composition of individual 2D crystals using a variety of techniques and found they have a slightly shifted band-edge emission that could be attributed to structural relaxation. A preliminary photoluminescence study indicates a band-edge emission at 453 nanometers, which is red-shifted slightly as compared to bulk crystals. This suggests that color-tuning could be achieved in these 2D hybrid perovskites by changing sheet thickness as well as composition via the synthesis of related materials.”

The well-defined geometry of these square-shaped 2D crystals is the mark of high quality crystallinity, and their large size should facilitate their integration into future devices.

“With our technique, vertical and lateral heterostructures can also be achieved,” Yang says. “This opens up new possibilities for the design of materials/devices on an atomic/molecular scale with distinctive new properties.”

This research was supported by DOE’s Office of Science. The characterization work was carried out at the Molecular Foundry’s National Center for Electron Microscopy, and at beamline 7.3.3 of the Advanced Light Source. Both the Molecular Foundry and the Advanced Light Source are DOE Office of Science User Facilities hosted at Berkeley Lab.

Graphene – Silicon-Perovskite Tandem Solar Cells = Greater Conversion Efficiency

Silicon absorbers primarily convert the red portion of the solar spectrum very effectively into electrical energy, whereas the blue portions are partially lost as heat. To reduce this loss, the silicon cell can be combined with an additional solar cell that primarily converts the blue portions. Teams at Helmholtz Zentrum Berlin (HZB) have already acquired extensive experience with these kinds of tandem cells. A particularly effective complement to conventional silicon is the hybrid material called perovskite. It has a band gap of 1.6 electron volts with organic as well as inorganic components. However, it is very difficult to provide the perovskite layer with a transparent front contact. While sputter deposition of indium tin oxide (ITO) is common practice for inorganic silicon solar cells, this technique destroys the organic components of a perovskite cell.

Graphene as transparent front contact

Now a group headed by Prof. Norbert Nickel has introduced a new solution. Dr. Marc Gluba and PhD student Felix Lang have developed a process to cover the perovskite layer evenly with graphene (“Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells”). Graphene consists of carbon atoms that have arranged themselves into a two-dimensional honeycomb lattice forming an extremely thin film that is highly conductive and highly transparent.

The perovskite film (black, 200-300 nm) is covered by Spiro.OMeTAD, Graphene with gold contact at one edge, a glass substrate and an amorphous/crystalline silicon solar cell. (Image: F. Lang / HZB)

Fishing for graphene

As a first step, the scientists promote growth of the graphene onto copper foil from a methane atmosphere at about 1000 degrees Celsius. For the subsequent steps, they stabilise the fragile layer with a polymer that protects the graphene from cracking. In the following step, Felix Lang etches away the copper foil. This enables him to transfer the protected graphene film onto the perovskite.

“This is normally carried out in water. The graphene film floats on the surface and is fished out by the solar cell, so to speak. However, in this case this technique does not work, because the performance of the perovskite degrades with moisture. Therefore we had to find another liquid that does not attack perovskite, yet is as similar to water as possible”, explains Gluba.

Ideal front contact

Subsequent measurements showed that the graphene layer is an ideal front contact in several respects. Thanks to its high transparency, none of the sunlight’s energy is lost in this layer. But the main advantage is that there are no open-circuit voltage losses, that are commonly observed for sputtered ITO layers. This increases the overall conversion efficiency.

“This solution is comparatively simple and inexpensive to implement”, says Nickel. “For the first time, we have succeeded in implementing graphene in a perovskite solar cell. This enabled us to build a high-efficiency tandem device.”

Source: Helmholtz Zentrum Berlin

Graphene-perovskite hybrids make new super-detectors: Turning Light into Energy

EPFL scientists have created the first perovskite nanowire-graphene hybrid phototransistors. Even at room temperature, the devices are highly sensitive to light, making them outstanding photodetectors.

The lead-containing perovskite materials can turn light into electricity with high efficiency, which is why they have revolutionized solar cell technologies. On the other hand, graphene is known for its super-strength as well as its excellent electrical conductivity. Combining the two materials, EPFL scientists have created the first ever class of hybrid transistors that turn light into electricity with high sensitivity and at room temperature. The work is published in Small.

The lab of László Forró at EPFL, where the chemical activity is led by Endre Horváth, used its expertise in microengineering to create nanowires of the perovskite methylammonium lead iodide. This highly non-trivial route for the synthesis of nanowires was developed by him in 2014 and called slip-coating method. The advantage of nanowires is their consistency, while their manufacturing can be controlled to modify their architecture and explore different designs.

Making a device by depositing the perovskite nanowires onto graphene has increased the efficiency in converting light to electrical current at room temperature. “Such a device shows almost 750,000 times higher photoresponse compared to detectors made only with perovskite nanowires,” added Massimo Spina who fabricated the miniature photodetectors. Because of this exceptionally high sensitivity, the graphene/perovskite nanowire hybrid device is considered to be a superb candidate for even a single-photon detection.

This work was founded by the Swiss National Science Foundation. The hybrid devices were fabricated in part at EPFL’s Center for Micro/Nanotechnology.

Reference

Argonne National Laboratory: Perovskite Solar Technology Shows Quick Energy Returns: As little as 2 to 3 Months

This graphic shows the semi-cubic structure of perovskite materials, and how they would fit into a solar power device. An Argonne-Northwestern study found that perovskite-based solar technology has the quickest energy payback time of all …more

Solar panels are an investment—not only in terms of money, but also energy. It takes energy to mine, process and purify raw materials, and then to manufacture and install the final product.

Silicon-based panels, which dominate the market for solar power, usually need about two years to return this energy investment. But for technology made with perovskites—a class of materials causing quite a buzz in the solar research community—the energy payback time could be as quick as two to three months.

By this metric, perovskite modules are better than any solar technology that is commercially available today.

These are the findings of a study by scientists at Northwestern University and the U.S. Department of Energy’s Argonne National Laboratory. The study took a broad perspective in evaluating solar technology: In what’s called a cradle-to-grave life cycle assessment, scientists traced a product from the mining of its raw materials until its retirement in a landfill. They determined the ecological impacts of making a solar panel and calculated how long it would take to recover the energy invested.

Perovskite technology has yet to be commercialized, but researchers everywhere are excited about the materials. Most projects, however, have been narrowly focused on conversion efficiency—how effectively the technology transforms sunlight into useable energy.

“People see 11 percent efficiency and assume it’s a better product than something that’s 9 percent efficient,” said Fengqi You, corresponding author on the paper and assistant professor of chemical and biological engineering at Northwestern. “But that’s not necessarily true.”

A more comprehensive way to compare solar technology is the energy payback time, which also considers the energy that went into creating the product.

This study looked at the energy inputs and outputs of two perovskite modules. A solar panel consists of many parts, and the module is the piece directly involved in converting energy from one form into another—sunlight into electricity.

Perovskites lag behind silicon in conversion efficiency, but they require much less energy to be made into a solar module. So perovskite modules pull ahead with a substantially shorter energy payback time—the shortest, in fact, among existing options for solar power.

“Appreciating energy payback times is important if we want to move perovskites from the world of scientific curiosity to the world of relevant commercial technology,” said Seth Darling, an Argonne scientist and co-author on the paper.

To get a complete picture of the environmental impacts a perovskite panel could have, the researchers also analyzed metals used for electrodes and other parts of the device.

One of the modules tested includes lead and gold, among other metals. Many perovskite models have lead in their active layer, which absorbs sunlight and plays a leading role in conversion efficiency. People in the research community have expressed concern because everyone knows lead can be toxic, Darling said.

Surprisingly, the team’s assessment showed that gold was much more problematic.

Gold isn’t typically perceived as hazardous, but the process of mining the precious metal is extremely damaging to the environment. The module in this study uses gold in its positive electrode, where charges are collected in the process of generating electricity.

The harmful effects of gold mining, an indirect impact of this particular perovskite technology, is something that could only be uncovered by a cradle-to-grave investigation, said Jian Gong, the study’s first author and a PhD student in You’s research group at Northwestern.

The team hopes that future projects use this same zoomed-out approach to identify the best materials and manufacturing processes for the next generation of solar technology—products that will have to be environmentally sustainable and commercially viable.

“Soon, we’re going to need to produce an extremely high number of solar panels,” You said. “We don’t have time for trial-and-error in finding the ideal design. We need a more rigorous approach, a method that systematically considers all variables.”

While this paper featured a thorough environmental assessment of different solar power options, further studies are needed to factor in economic costs. Before putting a perovskite panel on the market, scientists will likely have to replace gold and other unsustainable materials, for both environmental and economic reasons, Darling said.

In addition, extending the lifetime of perovskite modules will be important in order to make sure they are stable enough for long-term commercial use, You said. Despite a few necessary improvements, he said perovskite technology could be commercialized within two years if researchers use comprehensive analysis to optimize the selection of raw materials and manufacturing.

One of the motivations for this study, according to the authors, was the need to improve technology so that solar energy can be scaled up in a big way.

Global energy demand is expected to nearly double by 2050, and Darling said there’s no question that solar power must contribute a significant fraction.

The real question, Darling said, is “How quickly do we have to get a technology to market to save the planet? And how can we make that happen?”

Explore further: Solar panel manufacturing is greener in Europe than China, study says

More information: “Perovskite photovoltaics: life-cycle assessment of energy and environmental impacts.” Energy Environ. Sci., 2015,8, 1953-1968 DOI: 10.1039/C5EE00615E

Provided by: Argonne National Laboratory