Featured paper: Additivated perovskites for more stable solar cells.

[Paper: Effect of the incorporation of poly(ethylene oxide) copolymer on the stability of perovskite solar cells. Jeann Carlos da Silva, Francineide Lopes de Araújo, Rodrigo Szostak, Paulo Ernesto Marchezi, Raphael Fernando Moral, Jilian Nei de Freitas  and  Ana Flávia Nogueira. J. Mater. Chem. C, 2020,8, 9697-9706].

"Sandwich" of materials that form the perovskite solar cell developed by the Brazilian team.
“Sandwich” of materials that form the perovskite solar cell developed by the Brazilian team.

Thanks to the contributions of research groups from different countries, perovskite-based solar cells have quickly become competitive in terms of energy conversion efficiency – the percentage of solar energy that is converted into electrical energy – reaching values above 25%. Unfortunately, the good efficiency achieved for these solar cells does not remain throughout their use, mainly because of the instability of their active layer. Composed of materials from the perovskite family, this layer of the sandwich-like solar cell is responsible for absorbing light. Due to moisture, as well as light itself, perovskite degrades and threatens the life cycle of a solar cell.

The problem has been the focus of many researchers in the area, among them, those from the Laboratory of Nanotechnology and Solar Energy (LNES) at Unicamp (Brazil), led by Professor Ana Flávia Nogueira. In recently reported research in the Journal of Materials Chemistry C (impact factor 7.059), LNES members were able to produce more stable perovskite films which allowed manufacturing solar cells with lower efficiency losses over time.

The addition of copolymer P(EO/EP) improved the stability of MAPbI3 perovskite.
The addition of copolymer P(EO/EP) improved the stability of MAPbI3 perovskite.

The strategy adopted was to add to the perovskite a compound that gives it stability without affecting its crystalline structure, from which important properties emerge for solar cell performance. The chosen additive, a copolymer (polymer formed by two different monomers), was added in different concentrations to a solution of lead iodide and methylammonium iodide, which, when crystallized, formed a modified and more stable perovskite film.

The researchers used the spin coating technique to prepare filmes of pure perovskite and “additivated” perovskite. In a material degradation test, the authors exposed the samples to ambient light and humidity for nine days and observed their degradation, which was visible to the naked eye by the yellowing of the films, whose original color is almost black. In the samples with additive, the degradation was delayed by a few days when compared to the pure perovskite samples.

Another test carried out by the team showed the films’ ability to regenerate after an initial degradation caused by exposure to a humidifier. The samples with the additive not only degraded less, but also spontaneously regenerated, almost entirely, thirty seconds after removing the moisture source – a phenomenon known as healing – as can be seen in this video.

“This work demonstrated that incorporating a copolymer based on poly(ethylene oxide) to the perovskite layer can delay and, in some cases, even reverse the degradation process of the film with relation to moisture and lighting,” summarizes Jeann Carlos da Silva, co-author of the article.

box_enTo study in detail the structure and composition of the films, the authors used a series of characterization techniques, including an X-ray diffraction technique (in situ GWAXS), available at the Brazilian National Synchrotron Light Laboratory (LNLS), which allowed to monitor the manufacturing process of the films. Based on the set of characterization results, the authors were able to explain the mechanism that generates the protective effect in perovskite films with additives. According to them, the effect occurs mainly due to the interaction performed by the copolymer, through hydrogen bonds, with the methylammonium cation of the perovskite.  In films without the additive, light and moisture cause part of the methylammonium to shift into the gas state and then leave the perovskite structure, generating the degradation, which is partially irreversible. In the films with the additive, the copolymer retains the methylammonium, which generates films that are more stable and have greater regenerative capacity.

“This study also allowed to investigate the crystallization dynamics of the perovskite containing the copolymer, as well as to understand the formation mechanisms of perovskite/copolymer in humidity and lighting conditions,” highlights Francineide Lopes de Araújo, co-author of the article. “In addition, through characterization techniques such as in situ X-ray diffraction, the study explores an important area in order to understand the material, offering an important contribution to the scientific community and opening new investigation perspectives for the application of polymers in the process of forming and manufacturing perovskite solar cells,” she adds.

Finally, the scientific team manufactured solar cells using perovskite films with and without additives as active layer, and compared their energy conversion efficiency. Initially, the presence of the copolymer decreased the efficiency of the devices, since, as it is an insulating material, it impairs the transfer of electrical charges. However, in the stability tests, when the devices were exposed to humidity and light for twenty days, the perovskite cells with additives performed better.

In numbers: while pure perovskite solar cells started at 17% efficiency and maintained 47% of that value at the end of the test, perovskite devices containing 1.5 mg mL-1% copolymer had an initial efficiency of around 15 %, but retained 68% of efficiency after the 20 days of testing.

“Unfortunately, the problem of stability of perovskite solar cells could not be definitively solved through this research, however, an important way to protect the material was explored, mainly against aggressive exposure to moisture and light, which in the future can be combined with other protection mechanisms,” summarizes Jeann Carlos da Silva. “The research also reinforces the feasibility of incorporating extrinsic compounds to perovskite as protective agents,” he adds.

This study began at LNES in 2016, in the master’s research of Jeann Carlos da Silva, shortly after the development, in that same laboratory, of the first perovskite solar cell prototype in Brazil. The research was completed with the collaboration of the postdoctoral fellow Francineide Lopes de Araújo and other members and former members of the group, always under the guidance of Professor Ana Flávia.

The study was funded by Brazilian agencies FAPESP, CNPq and CAPES, and is the subject of the project “Perovskite Solar Cells for Artificial Photosynthesis” of the Center for Innovation on New Energies (CINE) with support from Shell and Fapesp.

Authors of the paper. From the left: Jeann Carlos da Silva, Francineide Lopes de Araújo, Rodrigo Szostak, Paulo Ernesto Marchezi, Raphael Fernando Moral, Jilian Nei de Freitas and Ana Flávia Nogueira.
Authors of the paper. From the left: Jeann Carlos da Silva, Francineide Lopes de Araújo, Rodrigo Szostak, Paulo Ernesto Marchezi, Raphael Fernando Moral, Jilian Nei de Freitas and Ana Flávia Nogueira.

B-MRS newsletter. Year 4, issue 2.


The newsletter of the Brazilian Materials Research Society 

News update from Brazil for the Materials community

English edition. Year 4, issue 2.

B-MRS (SBPMat) news
Young Researcher Award. SBPMat launches an award for postdocs in partnership with E-MRS. Application submission is open. Here.
Registration exemption for the E-MRS Meeting. Meet the selected students who will attend the 2017 E-MRS Spring Meeting exempt from registration fee. Here.
SBPMat Membership. The discount period for the 2017 annuity is still open. See the reasons and advantages of being a member of SBPMat and how to pay the annuity. Here.
Institutional members. Companies and organizations of all types are also welcome to SBPMat’s membership community. Meet the new institutional partners of SBPMat: Altmann and Interprise. Here.
XVI B-MRS Meeting (Gramado, Brazil, September 10-14)
  • Symposia. The list of approved symposia will be on the event’s website soon. 
  • Organization. Meet the organizing committee. Here.
  • Exhibitors. The event website shows the 14 companies that have already confirmed their participation. Companies interested in participating in the event with booths and other means of dissemination should contact Alexandre via this e-mail: comercial@sbpmat.org.br.   
Featured paper

A team of researchers from Unicamp has developed an innovative “formula” to manufacture luminescent perovskite nanocrystals (quantum dots) that can be purified without degradation. With the robust nanocrystals, the team prepared brilliant and efficient LEDs with innovative architecture. The work was reported in a paper published in Advanced Functional Materials. See our news article.

People from our community

We interviewed Aloísio Nelmo Klein, professor at UFSC and one of the architects of Materials research and teaching at that university. With more than 60 patents and a history of interaction with companies, Klein defines himself as a researcher who is convinced that science is one of the main driving forces for a nation’s development. Learn more about this researcher and his background, starting with his childhood in a village of German descendants in Rio Grande do Sul, and see the message he left for the younger audience and readers. See the interview.

Two new laboratories of the Federal University of Pelotas are named after former presidents of SBPMat Elson Longo (UNESP, UFSCar) and José Arana Varela (in memoriam). Know more. 

Reading tips
  • Technological innovations made in Brazil in steels used in electric motors and transformers improve energy efficiency.  Here.
  • Collaboration of LNNano (CNPEM) with alcohol plant generates technology for the transformation of sugarcane bagasse into active coal, which can be used in the purification of water and air. Here.
  • Striving for aerospace applications, a team with Brazilian participation studies what happens with nanotubes during high-speed impacts and improves the material.
  • Pan-American Polymer Science Conference (PanPoly). Guarujá (Brazil). March 22 – 24, 2017. Site.
  • 9th International Conference on Materials for Advanced Technologies. Suntec (Singapore). June 18 – 23, 2017. Site. 
  • XXXVIII Congresso Brasileiro de Aplicações de Vácuo na Indústria e na Ciência (CBRAVIC) + III Workshop de Tratamento e Modificação de Superfícies (WTMS). São José dos Campos (Brazil). August, 21 – 25, 2017. Facebook.
  • IUMRS-ICAM 2017. Kyoto (Japan). August 27 – Setember 1, 2017. Site.
  • International Conference on Luminescence (ICL-2017).  João Pessoa (Brazil). August 27 – September 1, 2017.
  • XVI Encontro da SBPMat/ XVI B-MRS Meeting. Gramado (Brazil). September 10 – 14, 2017. Site.

Submit your suggestion for any section of our newsletter: comunicacao@sbpmat.org.br


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Featured paper: How to make more stable perovskite nanocrystals for more efficient LEDs.

Paper: Amine-Free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient Light-Emitting Diodes. Emre Yassitepe, Zhenyu Yang, Oleksandr Voznyy, Younghoon Kim, Grant Walters, Juan Andres Castañeda, Pongsakorn Kanjanaboos, Mingjian Yuan, Xiwen Gong, Fengjia Fan, Jun Pan, Sjoerd Hoogland, Riccardo Comin, Osman M. Bakr, Lazaro A. Padilha, Ana F. Nogueira, and Edward H. Sargent. Adv. Funct. Mater. 2016. DOI: 10.1002/adfm.201604580.

How to make more stable perovskite nanocrystals for more efficient LEDs.

Nesta imagem ilustrativa, enviada por Emre Yassitepe, pontos quânticos azuis, verdes e vermelhos excitados por radiação ultravioleta exibem uma brilhante luminescência.
In this illustrative image, sent by Emre Yassitepe, blue, green and red quantum dots excited by ultraviolet radiation exhibit a brilliant luminescence.

Perovskite quantum dots have been seen as great candidates to compose a next generation of displays and lighting devices. In fact, these luminescent nanoparticles are able to emit high brightness light and very vivid and pure colors when receiving external energy. But the technological use of perovskite quantum dots still runs into some limitations, mainly linked to their instability, for these tiny particles can quickly react with the medium, agglomerate or increase in size, for example.

A team of scientists from institutions in Canada, Brazil and Saudi Arabia has found a solution to one of the problems limiting the advance of research and development in the field, the degradation of perovskite quantum dots during their synthesis. The study was reported in an article recently published in the journal Advanced Functional Materials (impact factor: 11.38).

The manufacture of perovskite quantum dots is traditionally carried out by placing in a flask a solution with a series of compounds which react among them and generate perovskite nanoparticles coated (passivated) with oleic acid (C18H34O2) and oleylamine (C18H35NH2).

The team performed experiments and computational simulations to understand how the formation of perovskite quantum dots occurred step by step and thus formulate a manufacturing method that would avoid the problem of degradation. The scientists realized that the key to the solution was to reformulate the “ingredients” of the process in order to remove the oleylamine that eventually created the conditions for the degradation of the quantum dots, which precipitated to the bottom of the flask.

“We focused on developing the new synthetic technique to passivate perovskite quantum dots with oleic acid,” says Emre Yassitepe, postdoc at the Nanotechnology and Solar Energy Laboratory of the Institute of Chemistry of Unicamp, who signs the article as the first author. “Oleic acid is one of the most common ligands to date to stabilize the quantum dots and we wanted to see the impact on stabilization and LED performance between different ligands.”

Following the new “recipe”, the team was able to produce quantum dots of about 8 nm, coated only with oleic acid, made of cesium, lead and elements of the group of halogens and having perovskite structure (which is a certain organization of the atoms). Green quantum dots (CsPbBr3), blue (CsPb (Br, Cl) 3) and red (CsPb (Br, I) 3) were produced and characterized.

One of the main gains achieved with the new method was the colloidal stability of the quantum dots: they remained intact more than oleylamine capped perovskite quantum dots after the purification step, which removes from the nanocrystals the residual compounds that usually remain from the manufacturing process.

The team went beyond the manufacturing and experimental analysis of quantum dots and built with them LED devices (light-emitting diodes, now widely used in lamps and displays) emitting green, blue and red light, in order to check their efficiency. They made thin films with the obtained perovskite quantum dots and placed a layer of this material “sandwiched” between a layer of titanium dioxide, in charge of transporting electrons (carriers of negative charge) and a polymer layer, destined to transport the so-called “holes” (positive charge carriers). In this LED, when applying an electric field, electrons and holes move to the quantum dots layer and excite them, causing them to emit photons and thus generate the desired light.

The use of polymer transport layers processed from solution instead of layers processed from evaporation to make perovskite LEDs was also an innovation made possible by the new “recipe”, which made quantum dots more robust against this type of processing.

As a final result, the team of scientists achieved bright and efficient blue and green LEDs. Perovskite LEDs made with oleylamine-free quantum dots demonstrated better performance in some respects than conventional perovskite LEDs produced with oleylamine coated quantum dots.

Pictures from the authors of the paper from Brazilian institutions. From the left: Ana Flávia Nogueira and Emre Yassitepe (Institute of Chemistry, Unicamp), Juan Andrés Castañeda and Lázaro Padilha (Institute of Physics, Unicamp).
Pictures from the authors of the paper from Brazilian institutions. From the left: Ana Flávia Nogueira and Emre Yassitepe (Institute of Chemistry, Unicamp), Juan Andrés Castañeda and Lázaro Padilha (Institute of Physics, Unicamp).

“We have demonstrated a new synthetic method that enhances the colloidal stability of perovskite quantum dots by capping them solely by oleic acid”, summarizes Yassitepe. “The enhancement of stability of oleic acid capped perovskite quantum dots allows us to remove excess organic content in thin films. The excess inorganic content acts as an insulator between quantum dots reducing performance. By reducing the excessive ligands we are able to make more efficient and solution-processed perovskite quantum dot light emitting diodes” concludes the postdoc.

The work was funded by Canadian agencies, FAPESP (São Paulo State Research Foundation) and King Abdullah University of Science and Technology (Saudi Arabia). The experiments of transient ultra-fast absorption and analysis by transmission electron microscopy were carried out at Unicamp to characterize the quantum dots. The synthesis of the nanocrystals and the manufacture of LEDs were carried out at the University of Toronto in the group of Professor Edward H. Sargent, where Yassitepe performed a one-year internship during within his post-doc at Unicamp. “I am grateful to FAPESP- Bolsa Estágio de Pesquisa no Exterior project for giving me this opportunity,” says Yassitepe.

Science without Borders Postdoctoral Fellowship for NREL-USA in Perovskite or Organic semiconductors.

The National Renewable Energy Laboratory (NREL), located at the foothills of the Rocky Mountains in Golden, Colorado is the U.S. primary laboratory for research and development of renewable energy and energy efficiency technologies.

The Science without Borders is a large scale nationwide scholarship program primarily funded by the Brazilian federal government. The program seeks to strengthen and expand the initiatives of science and technology, innovation and competitiveness through international mobility of undergraduate and graduate students and researchers.

We would like to offer the opportunity for outstanding Postdoctoral Researchers to come to NREL through the Brazil-US Consortium for Innovation in Energy Materials (CINEMA) initiative under the Brazilian Science Without Borders program to develop research activities within NREL’s Chemical Sciences and Nanoscience Division in the area of Perovskites and Organic semiconductors.

1) Our current research activities on perovskite-based PVs focuses on (a) solution processing of halide perovskites, (b) fabrication of planar and mesostructured perovskite cells, and (c) fundamental understanding of charge transport and recombination. Our objective is to understand material effects on the basic physical and chemical processes that are important to device operations. The insight learned from the basic studies will be used as guide to control material properties and to develop more effective device architectures. Examples of our recent publications on perovskites include [1] J. Phys. Chem. Lett., 5, 490–494 (2014); [2] Chem. Commun., 50, 1605–1607 (2014); [3] J. Phys. Chem. Lett., 4, 2880–2884 (2013).

2) Fundamental research topics of particular interest for organic semiconductors include the structural characterization of organic materials in the solid state by X-ray or Neutron scattering methods, transient photoconductivity for the study of photoinduced charge generation and decay dynamics in novel donor:acceptor materials and device-based methods for charge mobility and recombination studies. As to more applied device level research, we are also interested in developing novel electrical contact architectures for upscaling OPV devices. Some of our relevant publications in organic semiconductors and devices include [1] ChemPhysChem (2014), accepted. DOI: 10.1002/cphc.201301022; [2] Adv. Funct. Mater., 22 (2012) 4115; [3] Macromolecules 46 (2013) 1350; [4] Organic Electronics 12 (2011) 108.

Postdoctoral candidates from Brazil willing to develop research activities in areas relevant to the projects above are strongly encouraged to apply. Candidates will be expected to communicate their results through journal publications and conference presentations. In general, to be considered, candidates should have a demonstrated track record of success in addressing fundamental science questions and devising solutions to challenging problems, a Ph.D degree in related field and a strong record of publications/presentations will be a plus.

Send inquires to alexandre.nardes@nrel.gov and to apply, please, send CV along with a list of publications, and the names of at least three professional references to the same e-mail address (subject: “PostDoc Brazil”). Note deadlines for applications at http://www.cienciasemfronteiras.gov.br