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Title: Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

Nucleation is a core scientific concept that describes the formation of new phases and materials. While classical nucleation theory is applied across wide-ranging fields, nucleation energy landscapes have never been directly measured at the atomic level, and experiments suggest that nucleation rates often greatly exceed the predictions of classical nucleation theory. Multistep nucleation via metastable states could explain unexpectedly rapid nucleation in many contexts, yet experimental energy landscapes supporting such mechanisms are scarce, particularly at nanoscale dimensions. In this paper, we measured the nucleation energy landscape of diamond during chemical vapor deposition, using a series of diamondoid molecules as atomically defined protonuclei. We find that 26-carbon atom clusters, which do not contain a single bulk atom, are postcritical nuclei and measure the nucleation barrier to be more than four orders of magnitude smaller than prior bulk estimations. These data support both classical and nonclassical concepts for multistep nucleation and growth during the gas-phase synthesis of diamond and other semiconductors. Finally, more broadly, these measurements provide experimental evidence that agrees with recent conceptual proposals of multistep nucleation pathways with metastable molecular precursors in diverse processes, ranging from cloud formation to protein crystallization, and nanoparticle synthesis.
Authors:
ORCiD logo [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [4] ;  [5] ;  [5] ;  [6] ;  [7] ;  [8] ;  [4] ;  [1]
  1. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences; Tokyo Inst. of Technology (Japan). Dept. of Electrical and Electronic Engineering
  3. Czech Academy of Sciences, Prague (Czech Republic). Inst. of Physics
  4. Univ. of Hasselt, Diepenbeek (Belgium). Inst. of Materials Research; Interuniversity Microelectronics Centre (IMEC), Diepenbeek (Belgium). Inst. for Materials Research in Microelectronics
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
  6. Justus Liebig Univ. Giessen (Germany). Inst. of Organic Chemistry; Igor Sikorsky Kyiv Polytechnic Inst., Kiev (Ukraine). Dept. of Organic Chemistry
  7. Justus Liebig Univ. Giessen (Germany). Inst. of Organic Chemistry
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences; Stanford Univ., CA (United States). Applied Physics
Publication Date:
Grant/Contract Number:
AC02-76SF00515; ECCS-1542152; G0E7417N
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States); Univ. of Hasselt, Diepenbeek (Belgium); Interuniversity Microelectronics Centre (IMEC), Diepenbeek (Belgium)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Research Foundation - Flanders (FWO) (Belgium)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; nucleation; diamond; nanomaterials; thermodynamics; plasma synthesis
OSTI Identifier:
1462355
Alternate Identifier(s):
OSTI ID: 1462457