Tag Archives: Carlos Silva

The mystifying physics of paint-on semiconductors

I was not expecting a Canadian connection but it seems we are heavily invested in this research at the Georgia Institute of Technology (Georgia Tech), from a March 19, 2018 news item on ScienceDaily,

Some novel materials that sound too good to be true turn out to be true and good. An emergent class of semiconductors, which could affordably light up our future with nuanced colors emanating from lasers, lamps, and even window glass, could be the latest example.

These materials are very radiant, easy to process from solution, and energy-efficient. The nagging question of whether hybrid organic-inorganic perovskites (HOIPs) could really work just received a very affirmative answer in a new international study led by physical chemists at the Georgia Institute of Technology.

A March 19,. 2018 Georgia Tech news release (also on EurekAlert), which originated the news item, provides more detail,

The researchers observed in an HOIP a “richness” of semiconducting physics created by what could be described as electrons dancing on chemical underpinnings that wobble like a funhouse floor in an earthquake. That bucks conventional wisdom because established semiconductors rely upon rigidly stable chemical foundations, that is to say, quieter molecular frameworks, to produce the desired quantum properties.

“We don’t know yet how it works to have these stable quantum properties in this intense molecular motion,” said first author Felix Thouin, a graduate research assistant at Georgia Tech. “It defies physics models we have to try to explain it. It’s like we need some new physics.”

Quantum properties surprise

Their gyrating jumbles have made HOIPs challenging to examine, but the team of researchers from a total of five research institutes in four countries succeeded in measuring a prototypical HOIP and found its quantum properties on par with those of established, molecularly rigid semiconductors, many of which are graphene-based.

“The properties were at least as good as in those materials and may be even better,” said Carlos Silva, a professor in Georgia Tech’s School of Chemistry and Biochemistry. Not all semiconductors also absorb and emit light well, but HOIPs do, making them optoelectronic and thus potentially useful in lasers, LEDs, other lighting applications, and also in photovoltaics.

The lack of molecular-level rigidity in HOIPs also plays into them being more flexibly produced and applied.

Silva co-led the study with physicist Ajay Ram Srimath Kandada. Their team published the results of their study on two-dimensional HOIPs on March 8, 2018, in the journal Physical Review Materials. Their research was funded by EU Horizon 2020, the Natural Sciences and Engineering Research Council of Canada, the Fond Québécois pour la Recherche, the [National] Research Council of Canada, and the National Research Foundation of Singapore. [emphases mine]

The ‘solution solution’

Commonly, semiconducting properties arise from static crystalline lattices of neatly interconnected atoms. In silicon, for example, which is used in most commercial solar cells, they are interconnected silicon atoms. The same principle applies to graphene-like semiconductors.

“These lattices are structurally not very complex,” Silva said. “They’re only one atom thin, and they have strict two-dimensional properties, so they’re much more rigid.”

“You forcefully limit these systems to two dimensions,” said Srimath Kandada, who is a Marie Curie International Fellow at Georgia Tech and the Italian Institute of Technology. “The atoms are arranged in infinitely expansive, flat sheets, and then these very interesting and desirable optoelectronic properties emerge.”

These proven materials impress. So, why pursue HOIPs, except to explore their baffling physics? Because they may be more practical in important ways.

“One of the compelling advantages is that they’re all made using low-temperature processing from solutions,” Silva said. “It takes much less energy to make them.”

By contrast, graphene-based materials are produced at high temperatures in small amounts that can be tedious to work with. “With this stuff (HOIPs), you can make big batches in solution and coat a whole window with it if you want to,” Silva said.

Funhouse in an earthquake

For all an HOIP’s wobbling, it’s also a very ordered lattice with its own kind of rigidity, though less limiting than in the customary two-dimensional materials.

“It’s not just a single layer,” Srimath Kandada said. “There is a very specific perovskite-like geometry.” Perovskite refers to the shape of an HOIPs crystal lattice, which is a layered scaffolding.

“The lattice self-assembles,” Srimath Kandada said, “and it does so in a three-dimensional stack made of layers of two-dimensional sheets. But HOIPs still preserve those desirable 2D quantum properties.”

Those sheets are held together by interspersed layers of another molecular structure that is a bit like a sheet of rubber bands. That makes the scaffolding wiggle like a funhouse floor.

“At room temperature, the molecules wiggle all over the place. That disrupts the lattice, which is where the electrons live. It’s really intense,” Silva said. “But surprisingly, the quantum properties are still really stable.”

Having quantum properties work at room temperature without requiring ultra-cooling is important for practical use as a semiconductor.

Going back to what HOIP stands for — hybrid organic-inorganic perovskites – this is how the experimental material fit into the HOIP chemical class: It was a hybrid of inorganic layers of a lead iodide (the rigid part) separated by organic layers (the rubber band-like parts) of phenylethylammonium (chemical formula (PEA)2PbI4).

The lead in this prototypical material could be swapped out for a metal safer for humans to handle before the development of an applicable material.

Electron choreography

HOIPs are great semiconductors because their electrons do an acrobatic square dance.

Usually, electrons live in an orbit around the nucleus of an atom or are shared by atoms in a chemical bond. But HOIP chemical lattices, like all semiconductors, are configured to share electrons more broadly.

Energy levels in a system can free the electrons to run around and participate in things like the flow of electricity and heat. The orbits, which are then empty, are called electron holes, and they want the electrons back.

“The hole is thought of as a positive charge, and of course, the electron has a negative charge,” Silva said. “So, hole and electron attract each other.”

The electrons and holes race around each other like dance partners pairing up to what physicists call an “exciton.” Excitons act and look a lot like particles themselves, though they’re not really particles.

Hopping biexciton light

In semiconductors, millions of excitons are correlated, or choreographed, with each other, which makes for desirable properties, when an energy source like electricity or laser light is applied. Additionally, excitons can pair up to form biexcitons, boosting the semiconductor’s energetic properties.

“In this material, we found that the biexciton binding energies were high,” Silva said. “That’s why we want to put this into lasers because the energy you input ends up to 80 or 90 percent as biexcitons.”

Biexcitons bump up energetically to absorb input energy. Then they contract energetically and pump out light. That would work not only in lasers but also in LEDs or other surfaces using the optoelectronic material.

“You can adjust the chemistry (of HOIPs) to control the width between biexciton states, and that controls the wavelength of the light given off,” Silva said. “And the adjustment can be very fine to give you any wavelength of light.”

That translates into any color of light the heart desires.

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Coauthors of this paper were Stefanie Neutzner and Annamaria Petrozza from the Italian Institute of Technology (IIT); Daniele Cortecchia from IIT and Nanyang Technological University (NTU), Singapore; Cesare Soci from the Centre for Disruptive Photonic Technologies, Singapore; Teddy Salim and Yeng Ming Lam from NTU; and Vlad Dragomir and Richard Leonelli from the University of Montreal. …

Three Canadian science funding agencies plus European and Singaporean science funding agencies but not one from the US ? That’s a bit unusual for research undertaken at a US educational institution.

In any event, here’s a link to and a citation for the paper,

Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder by Félix Thouin, Stefanie Neutzner, Daniele Cortecchia, Vlad Alexandru Dragomir, Cesare Soci, Teddy Salim, Yeng Ming Lam, Richard Leonelli, Annamaria Petrozza, Ajay Ram Srimath Kandada, and Carlos Silva. Phys. Rev. Materials 2, 034001 – Published 8 March 2018

This paper is behind a paywall.

The evolution of molecules as observed with femtosecond stimulated Raman spectroscopy

A July 3, 2014 news item on Azonano features some recent research from the Université de Montréal (amongst other institutions),

Scientists don’t fully understand how ‘plastic’ solar panels work, which complicates the improvement of their cost efficiency, thereby blocking the wider use of the technology. However, researchers at the University of Montreal, the Science and Technology Facilities Council, Imperial College London and the University of Cyprus have determined how light beams excite the chemicals in solar panels, enabling them to produce charge.

A July 2, 2014 University of Montreal news release, which originated the news item, provides a fascinating description of the ultrafast laser process used to make the observations,

 “We used femtosecond stimulated Raman spectroscopy,” explained Tony Parker of the Science and Technology Facilities Council’s Central Laser Facility. “Femtosecond stimulated Raman spectroscopy is an advanced ultrafast laser technique that provides details on how chemical bonds change during extremely fast chemical reactions. The laser provides information on the vibration of the molecules as they interact with the pulses of laser light.” Extremely complicated calculations on these vibrations enabled the scientists to ascertain how the molecules were evolving. Firstly, they found that after the electron moves away from the positive centre, the rapid molecular rearrangement must be prompt and resemble the final products within around 300 femtoseconds (0.0000000000003 s). A femtosecond is a quadrillionth of a second – a femtosecond is to a second as a second is to 3.7 million years. This promptness and speed enhances and helps maintain charge separation.  Secondly, the researchers noted that any ongoing relaxation and molecular reorganisation processes following this initial charge separation, as visualised using the FSRS method, should be extremely small.

As for why the researchers’ curiosity was stimulated (from the news release),

The researchers have been investigating the fundamental beginnings of the reactions that take place that underpin solar energy conversion devices, studying the new brand of photovoltaic diodes that are based on blends of polymeric semiconductors and fullerene derivatives. Polymers are large molecules made up of many smaller molecules of the same kind – consisting of so-called ‘organic’ building blocks because they are composed of atoms that also compose molecules for life (carbon, nitrogen, sulphur). A fullerene is a molecule in the shape of a football, made of carbon. “In these and other devices, the absorption of light fuels the formation of an electron and a positive charged species. To ultimately provide electricity, these two attractive species must separate and the electron must move away. If the electron is not able to move away fast enough then the positive and negative charges simple recombine and effectively nothing changes. The overall efficiency of solar devices compares how much recombines and how much separates,” explained Sophia Hayes of the University of Cyprus, last author of the study.

… “Our findings open avenues for future research into understanding the differences between material systems that actually produce efficient solar cells and systems that should as efficient but in fact do not perform as well. A greater understanding of what works and what doesn’t will obviously enable better solar panels to be designed in the future,” said the University of Montreal’s Carlos Silva, who was senior author of the study.

Here’s a link to and a citation for the paper,

Direct observation of ultrafast long-range charge separation at polymer–fullerene heterojunctions by Françoise Provencher, Nicolas Bérubé, Anthony W. Parker, Gregory M. Greetham, Michael Towrie, Christoph Hellmann, Michel Côté, Natalie Stingelin, Carlos Silva & Sophia C. Hayes. Nature Communications 5, Article number: 4288 doi:10.1038/ncomms5288 Published 01 July 2014

This article is behind a paywall but there is a free preview available vie ReadCube Access.

Université de Montréal (Canada) collaborates with University of Houston (US) for a new theory and better solar cells

Solar cell efficiency is not good as researchers from  l’Université de Montréal (UdeM, located in Quebec, Canada) and the University of Houston (UH, located Texas, US) note in a Jan. 29, 2014 joint UH/UdeM news release written by Lisa Merkl (UH) on EurekAlert,

“Scientists don’t fully understand what is going on inside the materials that make up solar cells. We were trying to get at the fundamental photochemistry or photophysics that describes how these cells work,” Bittner said [Eric Bittner, a John and Rebecca Moores Professor of Chemistry and Physics in UH’s College of Natural Sciences and Mathematics,].

Solar cells are made out of organic semiconductors – typically blends of materials. However, solar cells made of these materials have about 3 percent efficiency. Bittner added that the newer materials, the fullerene/polymer blends, only reach about 10 percent efficiency.

“There is a theoretical limit for the efficiency of the ideal solar cell – the Shockley-Queisser limit. The theory we published describes how we might be able to get above this theoretical limit by taking advantage of quantum mechanical effects,” Bittner said. “By understanding these effects and making use of them in the design of a solar cell, we believe you can improve efficiency.”

Silva [Carlos Silva, an associate professor at the Université de Montréal and Canada Research Chair in Organic Semiconductor Materials] added, “In polymeric semiconductors, where plastics form the active layer of solar cells, the electronic structure of the material is intimately correlated with the vibrational motion within the polymer chain. Quantum-mechanical effects due to such vibrational-electron coupling give rise to a plethora of interesting physical processes that can be controlled to optimize solar cell efficiencies by designing materials that best exploit them.”

Unfortunately, there’s no more information about this model other than this (from the news release),

“Our theoretical model accomplishes things that you can’t get from a molecular model,” he [Bittner] said. “It is mostly a mathematical model that allows us to look at a much larger system with thousands of molecules. You can’t do ordinary quantum chemistry calculations on a system of that size.”

The calculations have prompted a series of new experiments by Silva’s group to probe the outcomes predicted by their model.

Bittner and Silva’s next steps involve collaborations with researchers who are experts in making the polymers and fabricating solar cells.

Here’s a link to and a citation for the paper,

Noise-induced quantum coherence drives photo-carrier generation dynamics at polymeric semiconductor heterojunctions by Eric R. Bittner & Carlos Silva. Nature Communications 5, Article number: 3119 doi:10.1038/ncomms4119 Published 29 January 2014

This article is behind a paywall although you can get a free preview via ReadCube Access.