NSF Award Search: Award # 1751736

Award Abstract # 1751736

CAREER: Fundamentals of Complex Chalcogenide Electronic Materials

NSF Org:	DMR Division Of Materials Research
Recipient:	MASSACHUSETTS INSTITUTE OF TECHNOLOGY
Initial Amendment Date:	January 5, 2018
Latest Amendment Date:	May 17, 2022
Award Number:	1751736
Award Instrument:	Continuing Grant
Program Manager:	Paul Lane plane@nsf.gov (703)292-2453 DMR Division Of Materials Research MPS Directorate for Mathematical and Physical Sciences
Start Date:	June 1, 2018
End Date:	May 31, 2023 (Estimated)
Total Intended Award Amount:	$500,000.00
Total Awarded Amount to Date:	$510,411.00
Funds Obligated to Date:	FY 2018 = $100,000.00 FY 2019 = $100,000.00 FY 2020 = $210,411.00 FY 2022 = $100,000.00
History of Investigator:	Rafael Jaramillo (Principal Investigator) rjaramil@MIT.EDU
Recipient Sponsored Research Office:	Massachusetts Institute of Technology 77 MASSACHUSETTS AVE CAMBRIDGE MA US 02139-4301 (617)253-1000
Sponsor Congressional District:	07
Primary Place of Performance:	Massachusetts Institute of Technology MA US 02139-4301
Primary Place of Performance Congressional District:	07
Unique Entity Identifier (UEI):	E2NYLCDML6V1
Parent UEI:	E2NYLCDML6V1
NSF Program(s):	DMR SHORT TERM SUPPORT, ELECTRONIC/PHOTONIC MATERIALS
Primary Program Source:	01001819DB NSF RESEARCH & RELATED ACTIVIT 01001920DB NSF RESEARCH & RELATED ACTIVIT 01002021DB NSF RESEARCH & RELATED ACTIVIT 01002122DB NSF RESEARCH & RELATED ACTIVIT 01002223DB NSF RESEARCH & RELATED ACTIVIT 01002021DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s):	1045, 8396, 8397, 8611
Program Element Code(s):	171200, 177500
Award Agency Code:	4900
Fund Agency Code:	4900
Assistance Listing Number(s):	47.049

ABSTRACT

Non-technical description: New and improved materials are essential for development of new technologies. This project focuses on the development of semiconductors containing the elements barium, zirconium, sulfur, and selenium. The research team is motivated by theoretical predictions that certain combinations of these elements will produce semiconductors with properties that are useful for applications including energy conversion, lighting, and chemical manufacturing. The team tests these predictions by producing thin films of these materials and measuring the properties of the resulting materials. Reflecting the importance of new generation workforce to the economy, this project also includes the launch of a new internship program - the Guided Academic Industry Network (GAIN) - that introduces students at local community colleges to opportunities in materials science. The goals of GAIN are to create opportunities for students, and to enhance the workforce pipeline for materials-focused industries.

Technical description: This project focuses on fundamental studies of chalcogenide perovskites in the Ba-Zr-S-Se system, which are predicted by theory to be mixed-anion semiconductors with band gap in the range 1.3 - 1.8 eV. The research is enabled by the development of techniques for the epitaxial growth of complex chalcogenide thin films, using hydride gas precursors and a molecular beam deposition system that was custom-designed for this purpose. Detailed structural and optoelectronic characterization is used to address issues such as the effect of tuning the ionic-to-covalent balance of chemical bonds on the optoelectronic properties of a semiconductor, and the ability of the perovskite structure to accommodate anion alloying. The potential for this semiconducting alloy to be used in minority-carrier devices is assessed by measuring recombination rates, and by evaluating the performance of thin films in two energy-conversion technologies: solar cells and photo-electrochemical hydrogen production.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Filippone, Stephen A. and Sun, Yi-Yang and Jaramillo, R. "Determination of adsorption-controlled growth windows of chalcogenide perovskites" MRS Communications , v.8 , 2018 10.1557/mrc.2018.10 Citation Details

Filippone, Stephen A. and Sun, Yi-Yang and Jaramillo, R. "The effect of an improved density functional on the thermodynamics and adsorption-controlled growth windows of chalcogenide perovskites" MRS Advances , v.3 , 2018 10.1557/adv.2018.497 Citation Details

Filippone, Stephen and Song, Samuel and Jaramillo, R. "High densification of BaZrS3 powder inspired by the cold-sintering process" Journal of Materials Research , v.36 , 2021 https://doi.org/10.1557/s43578-021-00404-1 Citation Details

Filippone, Stephen and Zhao, Boyang and Niu, Shanyuan and Koocher, Nathan Z. and Silevitch, Daniel and Fina, Ignasi and Rondinelli, James M. and Ravichandran, Jayakanth and Jaramillo, R. "Discovery of highly polarizable semiconductors

BaZr S_{3}

and

{Ba}_{3} {Zr}_{2"Physical Review Materials, v.4, 2020https://doi.org/10.1103/PhysRevMaterials.4.091601Citation
                                        DetailsJaramillo, R. and Ravichandran, J. "In praise and in search of highly-polarizable semiconductors: Technological promise and discovery strategies" APL Materials, v.7, 2019 https://doi.org/10.1063/1.5124795 Citation
                                        DetailsNiu, Shanyuan E. and Zhao, Boyang and Ye, Kevin and Bianco, Elisabeth and Zhou, Jieyang and McConney, Michael and Settens, Charles and Haiges, Ralf and Jaramillo, Rafael and Ravichandran, Jayakanth "Crystal growth and structural analysis of perovskite chalcogenide BaZrS 3 and RuddlesdenPopper phase Ba 3 Zr 2 S 7 " Journal of Materials Research, v.34, 2019 10.1557/jmr.2019.348 Citation
                                        DetailsSadeghi, Ida and Ye, Kevin and Xu, Michael and Li, Yifei and LeBeau, James M. and Jaramillo, Rafael "Making BaZrS 3 Chalcogenide Perovskite Thin Films by Molecular Beam Epitaxy" Advanced Functional Materials, v.31, 2021 https://doi.org/10.1002/adfm.202105563 Citation
                                        DetailsYe, Kevin and Zhao, Boyang and Diroll, Benjamin T. and Ravichandran, Jayakanth and Jaramillo, R. "Time-resolved photoluminescence studies of perovskite chalcogenides" Faraday Discussions, v.239, 2022 https://doi.org/10.1039/D2FD00047D Citation
                                        DetailsPROJECT OUTCOMES REPORT Disclaimer This Project Outcomes Report for the General Public is displayed verbatim as submitted by the
                        Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or
                        recommendations expressed in this Report are those of the PI and do not necessarily reflect the
                        views of the National Science Foundation; NSF has not approved or endorsed its content. This project established chalcogenides in the perovskite crystal structure as a new family of semiconductor alloys with direct and tunable band gap, of interest for opto-electronic and energy conversion applications. The experimentally-demonstrated band gap range for BaZr(S,Se) 3 alloys is 1.5 – 1.9 eV, and a wider range is likely possible by expanding the set of alloying elements. Chalcogenide perovskites are stable, are made of Earth-abundant elements, and do not include highly-toxic elements, and therefore are an enticing alternative to lead-based halide perovskites for thin-film solar cells.
Project outcomes included first-of-a-kind epitaxial thin film growth of chalcogenide perovskites, characterization of chalcogenide perovskites by electrical and optical methods, and a detailed study of dielectric properties. These efforts address basic research questions of how electron-phonon coupling and crystal structure predict semiconductor materials performance. Results also illuminate the path towards developing chalcogenide perovskite-based technology. Further applied development will require lower film synthesis temperature without sacrificing material quality; this research is underway, with continued funding from the NSF and elsewhere.
Results were made possible by the development of gas-source molecular beam epitaxy (MBE) to make high-quality chalcogenide perovskite thin films. The gas sources for sulfur and selenium allowed composition tuning over the full range of sulfur-selenium alloys. This represents a revival of gas-source chalcogenide MBE, which is of relevance to a broad spectrum of current research activity worldwide on layered and two-dimensional (2D) materials. The methods developed for this project have already benefitted other, separate research on 2D materials for photonic integrated circuits.
This project supported the training of a team of graduate students and postdoctoral associates. The project also fostered interest and proficiency in materials research and career opportunities among community college students by establishing the Guided Academic Industry Network (GAIN) outreach program. GAIN is a two-year internship program that provides experiences in materials research and development both in academia and industry for Boston-area community college students. The twin goals of GAIN are to create opportunities for students and to enhance the workforce pipeline for materials-focused industries. Over the course of this project, we introduced five participants (from two community colleges) to materials research during summer internships at MIT, and subsequently placed students in industry internships at four partner companies. The success of the GAIN program has been recognized by continued NSF funding, to continue the program at MIT and to double the program size by expanding to a second research university (Tufts University).

				      	Last Modified: 07/24/2023
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