Award Abstract # 1609973
GOALI: Fundamental Approaches to Atomic Layer Etching

NSF Org: DMR
Division Of Materials Research
Recipient: UNIVERSITY OF DELAWARE
Initial Amendment Date: July 5, 2016
Latest Amendment Date: August 22, 2018
Award Number: 1609973
Award Instrument: Continuing Grant
Program Manager: Birgit Schwenzer
bschwenz@nsf.gov
 (703)292-4771
DMR
 Division Of Materials Research
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: August 1, 2016
End Date: July 31, 2020 (Estimated)
Total Intended Award Amount: $500,000.00
Total Awarded Amount to Date: $500,000.00
Funds Obligated to Date: FY 2016 = $180,030.00
FY 2017 = $166,660.00

FY 2018 = $153,310.00
History of Investigator:
  • S. Ismat Shah (Principal Investigator)
    ismat@udel.edu
  • Andrew Teplyakov (Co-Principal Investigator)
  • Venkateswara Pallem (Co-Principal Investigator)
  • Robert Opila (Former Principal Investigator)
  • Rahul Gupta (Former Co-Principal Investigator)
Recipient Sponsored Research Office: University of Delaware
550 S COLLEGE AVE
NEWARK
DE  US  19713-1324
(302)831-2136
Sponsor Congressional District: 00
Primary Place of Performance: University of Delaware
210 Hullihen Hall
Newark
DE  US  19716-2150
Primary Place of Performance
Congressional District:
00
Unique Entity Identifier (UEI): T72NHKM259N3
Parent UEI:
NSF Program(s): SOLID STATE & MATERIALS CHEMIS
Primary Program Source: 01001617DB NSF RESEARCH & RELATED ACTIVIT
01001718DB NSF RESEARCH & RELATED ACTIVIT

01001819DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 1504, 8037, 9150
Program Element Code(s): 176200
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

NON-TECHNICAL ABSTRACT:

This project will develop the science and technology for etching metallic films one atomic later at a time. This know-how is most important in the field of memory devices, specifically based on magnetic principles used in computers, digital cameras, mobile phones and other similar devices. These devices based on the technology developed should demonstrate lower power consumption, smaller sizes, and lower cost of production compared to the other modern alternatives. However, to achieve this goal, very high level of control over making very thin metallic layers is necessary. The thickness of these layers must be highly reproducible to ensure reliable memory performance. For the metal components required, it is difficult to deposit them by traditional methods; however, it is possible to deposit relatively thick layers of these materials and then partially etch them away with the atomic layer precision.
In addition to the obvious advantages of capabilities to make simpler, cheaper, faster, and more reliable memory devices this work can affect a wide variety of the systems that are at the core of national interests, including aerospace and military systems, image storage and analysis, data logging and many other applications. The combination of university and industrial research in this grant will offer special educational and training opportunities to the students and facilitate this development to reach the marketplace more quickly.


TECHNICAL ABSTRACT:

This GOALI project will target new approaches for removal of deposited metals in a layer-by-layer manner through atomic layer etching (ALEt). One of the prime targets for potential application of ALEt is in the field of Magnetic Random Access Memory (MRAM). Atomic Layer Etching (ALEt) requires reacting a metallic surface with a precursor molecule that saturates the surface and reduces the binding of the first layer of atoms to the bulk. A second input, be it chemical, energetic, or some combination of the two, will cause the first layer of metal atoms (with their associated ligands) to desorb. The second layer of atoms will now be exposed to the saturating precursor, followed by the desorption steps. As the process proceeds, the atoms will be removed from the surface layer by layer. Fe, Co, Ni, and Pt thin films deposited on a Si substrate will be used as the initial targets. The experimental approach will take two tracks. First, model systems will be designed, modeled, and tested. This approach will build on the understanding obtained through studying atomic layer deposition (ALD). A suite of surface characterization techniques will be coupled with high-resolution microscopies to understand these processes at the atomic level. In the second approach, work with American Air Liquide will study the ALEt process in manufacturing systems including temperature controlled wafer chucks, mass flow controllers for the reactants, and plasma sources. These systems will also be equipped so that the ALEt process can be monitored in operando. A model processing system will be constructed at the University of Delaware so that the composition and chemistry of the surface can be studied at any point in the process, in-situ studies. At the end of the proposal, working processes for various materials, including those of importance in MRAM application, will be developed. A deeper understanding of the physical components of the ALEt process will also be achieved.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 17)
Duan, Y., Rani, S., Zhang, Y., Ni, C., Newberg, J. T., and Teplyakov, A. V. "Silver Deposition onto Modified Silicon Substrates" J. Phys. Chem. C , v.121 , 2017 , p.7240 10.1021/acs.jpcc.6b12896
He, C., Abraham, B., Fan, H., Harmer, R., Li, Z., Galoppini, E., Gundlach, L, and Teplyakov, A. V. "Morphology-Preserving Sensitization of ZnO Nanorod Surfaces via Click-Chemistry" J. Phys. Chem. Lett. , v.9 , 2018 , p.768 10.1021/acs.jpclett.7b03388
Barry, S. T., Teplyakov, A. V., and Zaera, F. "The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces" Acc. Chem. Res. , v.51 , 2018 , p.800 10.1021/acs.accounts.8b00012
Duan, Y. and Teplyakov, A. V. "Deposition of Copper from Cu(I) and Cu(II) Precursors onto HOPG Surface: Role of Surface Defects and Choice of a Precursor." J. Chem. Phys. , v.146 , 2017 , p.052814-1- http://dx.doi.org/10.1063/1.4971287
Duan, Y., Rani, S., Newberg, J. T., and Teplyakov, A. V. "Investigation of the influence of oxygen plasma on supported silver nanoparticles" J. Vac. Sci. Technol. A , v.35 , 2018 , p.01B101 10.1116/1.4986208
He, C., Janzen, R., and Teplyakov, A. V. "?Clickable? Metal Oxide Nanomaterials Surface-Engineered by Gas-Phase Covalent Functionalization with Prop-2-ynoic Acid." Chem. Mater. , v.31 , 2019 , p.2068 10.1021/acs.chemmater.8b05124.
He, C., Janzen, R., and Teplyakov, A. V. "Clickable Metal Oxide Nanomaterials Surface-Engineered by Gas-Phase Covalent Functionalization with Prop-2-ynoic Acid" Chem. Mater. , v.31 , 2019 , p.2068 10.1021/acs.chemmater.8b05124
Konh, M., He, C., Lin, X., Guo, X., Pallem, V., Opila, R. L., Teplyakov, A. V., Wang, Z., and Yuan, B "Molecular Mechanisms of Atomic Layer Etching of Cobalt with Molecular Chlorine and Diketones" J. Vac. Sci. Technol. A , v.37 , 2019 , p.021004 10.1116/1.5082187
Konh, M., He, C., Li, Z., Bai, S., Galoppini, E., Gundlach, L., and Teplyakov, A. V. "Comparison of ZnO Surface Modification with Gas-Phase Propiolic Acid at High and Medium Vacuum Conditions" J. Vac. Sci. Technol. A , v.36 , 2018 , p.041404 10.1116/1.5031945
Konh, M., Lien, C., Cai, X., Wei, S.-H., Janotti, A., Zaera, F, and Teplyakov, A. V. "ToF-SIMS Investigation of the Initial Stages of MeCpPt(CH3)3 Adsorption and Decomposition on Nickel Oxide Surfaces: Exploring the Role and Location of the Ligands" Organometallics , v.39 , 2020 , p.1024 10.1021/acs.organomet.9b00781
Konh, M., Lien, C., Zaera, F, and Teplyakov, A. V. "Application of Time-of-Flight Secondary Ion Mass Spectrometry to the Detection of Surface Intermediates during the First Cycle of Atomic Layer Deposition (ALD) of Platinum on Silica Surfaces" Appl. Surf. Sci. , v.488 , 2019 , p.468 10.1016/j.apsusc.2019.05.209
(Showing: 1 - 10 of 17)

PROJECT 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.

The difficulty of reliably depositing thin layers of metal films makes the fabrication of Magnetic Random Access Memory (MRAM)  very challenging. Atomic layer etching (ALE) of magnetic materials is a cutting-edge method to do so, but the mechanisms are extremely difficult to understand. This GOALI proposal combines expertise in engineering, materials and chemistry from the University of Delaware and the industrial partner American Air Liquide, Inc.

Intellectual Merit:

  •  Elemental processing steps for ALE of cobalt and iron have been understood;
  •  Origins of surface smoothing mechanism were proposed;
  •  Computational investigations have been initiated and selected results published;
  • Studies of CoFeB alloys have been started;
  •  General mechanisms of metal atom removal have been proposed.

Broader Impacts:

  •  Five of the graduate students involved in this project have graduated, four of them are employed in semiconductor industrial companies (including one at Air Liquide, Inc.) and one in academia;
  •  A publication on the project was chosen to be promoted as an Editor's Pick in 2019;
  • Application of Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) for pinpointing surface species in ALD and ALE has been demonstrated and published;
  •  Extensive international collaboration with Peru (UTEC) has been established, but participation in a capstone international conference has been delayed because of COVID-19;
  •  The first computational external grant has been received by co-PI Teplyakov to continue the theoretical work on the project;

Last Modified: 08/21/2020
Modified by: S. Ismat Shah

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