Plastron Regeneration on Submerged ... - ACS Publications

Sep 5, 2018 - We perform drag-reduction experiments under turbulent flow conditions in a Taylor−Couette cell (TC cell), which show that more than half...
0 downloads 0 Views 3MB Size
Subscriber access provided by University of South Dakota

Surfaces, Interfaces, and Applications

Plastron Regeneration on Submerged Superhydrophobic Surfaces using in-situ Gas Generation by Chemical Reaction Divya Panchanathan, Anoop Rajappan, Kripa K Varanasi, and Gareth H. McKinley ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b12471 • Publication Date (Web): 05 Sep 2018 Downloaded from http://pubs.acs.org on September 6, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

P❧❛str♦♥ ❘❡❣❡♥❡r❛t✐♦♥ ♦♥ ❙✉❜♠❡r❣❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s ✉s✐♥❣ ✐♥✲s✐t✉ ●❛s ●❡♥❡r❛t✐♦♥ ❜② ❈❤❡♠✐❝❛❧ ❘❡❛❝t✐♦♥ ❉✐✈②❛ P❛♥❝❤❛♥❛t❤❛♥✱ ❆♥♦♦♣ ❘❛❥❛♣♣❛♥✱ ❑r✐♣❛ ❑✳ ❱❛r❛♥❛s✐✱ ❛♥❞ ●❛r❡t❤ ❍✳



▼❝❑✐♥❧❡②

❉❡♣❛rt♠❡♥t ♦❢ ▼❡❝❤❛♥✐❝❛❧ ❊♥❣✐♥❡❡r✐♥❣✱ ▼❛ss❛❝❤✉s❡tts ■♥st✐t✉t❡ ♦❢ ❚❡❝❤♥♦❧♦❣②✱ ❈❛♠❜r✐❞❣❡ ❊✲♠❛✐❧✿ ❣❛r❡t❤❅♠✐t✳❡❞✉

❑❡②✇♦r❞s✿ ♣❧❛str♦♥✱ ❞r❛❣ r❡❞✉❝t✐♦♥✱ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✱ ❝❛t❛❧②s✐s✱ s✉♣❡r❤②❞r♦♣❤♦❜✐❝✱ r❡✲ ❣❡♥❡r❛t✐♦♥✱ s❡❧❢✲r❡❝♦✈❡r②

❆❜str❛❝t ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s s✉❜♠❡r❣❡❞ ✉♥❞❡r ✇❛t❡r ❛♣♣❡❛r s❤✐♥② ❞✉❡ t♦ t♦t❛❧ ✐♥t❡r✲ ♥❛❧ r❡✢❡❝t✐♦♥ ♦❢ ❧✐❣❤t ❢r♦♠ ❛ t❤✐♥ ❧❛②❡r ♦❢ ❛✐r ✭♣❧❛str♦♥✮ tr❛♣♣❡❞ ✐♥ t❤❡✐r s✉r❢❛❝❡ t❡①t✉r❡✳ ❚❤✐s ❡♥tr❛♣♣❡❞ ❛✐r ✐s ❛❞✈❛♥t❛❣❡♦✉s ❢♦r ❢r✐❝t✐♦♥❛❧ ❞r❛❣ r❡❞✉❝t✐♦♥ ✐♥ ✈❛r✐♦✉s ❛♣♣❧✐❝❛t✐♦♥s r❛♥❣✐♥❣ ❢r♦♠ ♠✐❝r♦✢✉✐❞✐❝ ❝❤❛♥♥❡❧s t♦ ♠❛r✐♥❡ ✈❡ss❡❧s✳ ❍♦✇❡✈❡r✱ t❤❡s❡ ❛❡r♦♣❤✐❧✐❝ t❡①t✉r❡s ❛r❡ ♣r♦♥❡ t♦ ✐♠♣r❡❣♥❛t✐♦♥ ❜② ✇❛t❡r ❞✉❡ t♦ t✉r❜✉❧❡♥t ♣r❡ss✉r❡ ✢✉❝t✉❛t✐♦♥s ❢r♦♠ ❡①t❡r✲ ♥❛❧ ✢♦✇s ❛♥❞ ❞✐ss♦❧✉t✐♦♥ ♦❢ t❤❡ tr❛♣♣❡❞ ❣❛s ✐♥t♦ t❤❡ ✇❛t❡r✳ ❲❡ ❞❡♠♦♥str❛t❡ ❛ ♥♦✈❡❧ ❝❤❡♠✐❝❛❧ ♠❡t❤♦❞ t♦ r❡♣❧❡♥✐s❤ t❤❡ ♣❧❛str♦♥ ✐♥✲s✐t✉ ❜② ✉s✐♥❣ t❤❡ ❞❡❝♦♠♣♦s✐t✐♦♥ r❡❛❝t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ♦♥ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s ♣r❡♣❛r❡❞ ✇✐t❤ ❛ ❝❛t❛❧②t✐❝ ❝♦❛t✐♥❣✳ ❲❡ ❛❧s♦ ♣r♦✈✐❞❡ ❛ t❤❡r♠♦❞②♥❛♠✐❝ ❢r❛♠❡✇♦r❦ ❢♦r ❞❡s✐❣♥✐♥❣ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s ✇✐t❤ ♦♣t✐♠❛❧ t❡①t✉r❡ ❛♥❞ ❝❤❡♠✐str② ❢♦r ✉♥❞❡r✇❛t❡r ♣❧❛str♦♥ r❡❣❡♥❡r❛t✐♦♥✳ ❲❡ ✜♥❛❧❧② ❞❡♠♦♥str❛t❡ t❤❡ ♣r❛❝t✐❝❛❧ ✉t✐❧✐t② ♦❢ t❤✐s ♠❡t❤♦❞ ❜② ❢❛❜r✐❝❛t✐♥❣ ♣❡r✐♦❞✐❝ ♠✐❝r♦t❡①t✉r❡s ✶

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

♦♥ ❛❧✉♠✐♥✉♠ s✉r❢❛❝❡s t❤❛t ✐♥❝♦r♣♦r❛t❡ ❛ ❝❤❡❛♣ ❝❛t❛❧②st✱ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡✳ ❲❡ ♣❡r✲ ❢♦r♠ ❞r❛❣ r❡❞✉❝t✐♦♥ ❡①♣❡r✐♠❡♥ts ✉♥❞❡r t✉r❜✉❧❡♥t ✢♦✇ ❝♦♥❞✐t✐♦♥s ✐♥ ❛ ❚❛②❧♦r✲❈♦✉❡tt❡ ❝❡❧❧ ✭❚❈ ❝❡❧❧✮ ✇❤✐❝❤ s❤♦✇ t❤❛t ♠♦r❡ t❤❛♥ ❤❛❧❢ ♦❢ t❤❡ ❞r❛❣ ✐♥❝r❡❛s❡ ❡♥s✉✐♥❣ ❢r♦♠ ♣❧❛str♦♥ ❝♦❧❧❛♣s❡ ❝❛♥ ❜❡ r❡❝♦✈❡r❡❞ s♣♦♥t❛♥❡♦✉s❧② ❜② ✐♥❥❡❝t✐♦♥ ♦❢ ❞✐❧✉t❡ ❍2 ❖2 ✐♥t♦ t❤❡ ❚❈ ❝❡❧❧✳ ❚❤✉s✱ ✇❡ ♣r❡s❡♥t ❛ ❧♦✇✲❝♦st s❝❛❧❛❜❧❡ ♠❡t❤♦❞ t♦ ❡♥❛❜❧❡ ✐♥✲s✐t✉ ♣❧❛str♦♥ r❡❣❡♥❡r❛t✐♦♥ ♦♥ ❧❛r❣❡ s✉r❢❛❝❡s ❢♦r ♠❛r✐♥❡ ❛♣♣❧✐❝❛t✐♦♥s✳

■♥tr♦❞✉❝t✐♦♥ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s ❛r❡ ✇❡❧❧ ❦♥♦✇♥ ❢♦r t❤❡✐r ♣r♦♣❡rt✐❡s ♦❢ s❡❧❢✲❝❧❡❛♥✐♥❣✱ ✶ ❢♦❣ ❝♦❧❧❡❝✲ t✐♦♥✱ ✷ ❛♥t✐✲✐❝✐♥❣✱ ✸ ❛♥❞ ❛♥t✐✲❜✐♦❢♦✉❧✐♥❣✳ ✹ ❚❤❡ ❞❡s✐❣♥ ♦❢ s②♥t❤❡t✐❝ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s ✐s ♦❢t❡♥ ✐♥s♣✐r❡❞ ❜② ♥❛t✉r❛❧❧② ♦❝❝✉rr✐♥❣ ✇❛t❡r r❡♣❡❧❧❡♥t s✉r❢❛❝❡s s✉❝❤ ❛s ❧♦t✉s ❧❡❛✈❡s ❛♥❞ ✇❛✲ t❡rstr✐❞❡r ❢❡❡t✳ ✺ ❚❤❡s❡ ♥❛t✉r❛❧❧② ♦❝❝✉rr✐♥❣ s✉r❢❛❝❡s ❤❛✈❡ ❛ ❤✐❡r❛r❝❤✐❝❛❧ t❡①t✉r❡ ✇✐t❤ ♠✐❝r♦✲ ❛♥❞ ♥❛♥♦s❝❛❧❡ ❢❡❛t✉r❡s✱ ❝♦✉♣❧❡❞ ✇✐t❤ ❛ ❤②❞r♦♣❤♦❜✐❝ ❝❤❡♠✐❝❛❧ ❝♦❛t✐♥❣ ✭❨♦✉♥❣✬s ❝♦♥t❛❝t ❛♥❣❧❡

θw > 90◦ ✮ ✇❤✐❝❤ ❝♦❧❧❡❝t✐✈❡❧② ✐♠♣❛rt t❤❡ ♣r♦♣❡rt② ♦❢ s✉♣❡r✲r❡♣❡❧❧❡♥❝② t♦✇❛r❞s ✇❛t❡r ✭❤❡r❡ s✉♣❡r✲r❡♣❡❧❧❡♥❝② ✐s t❛❦❡♥ t♦ ♠❡❛♥ ❛♣♣❛r❡♥t ❝♦♥t❛❝t ❛♥❣❧❡ θw∗ > 150◦ ✱ ❛♥❞ ❛ r♦❧❧✲♦✛ ❛♥❣❧❡

< 5 − 10◦ ✮✳ ✶✱✻✱✼ ❲❤❡♥ ❛ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡ ✐s s✉❜♠❡r❣❡❞ ✉♥❞❡r✇❛t❡r✱ ❛ t❤✐♥ ❧❛②❡r ♦❢ ❛✐r ✐s tr❛♣♣❡❞ ✇✐t❤✐♥ ✐ts ♠✐❝r♦t❡①t✉r❡ ❝♦rr❡s♣♦♥❞✐♥❣ t♦ t❤❡ t❤r❡❡ ♣❤❛s❡ ❝♦♥✜❣✉r❛t✐♦♥ ❦♥♦✇♥ ❛s t❤❡ ❈❛ss✐❡ st❛t❡✳ ✽ ❍❡♥❝❡✱ t❤❡s❡ t❡①t✉r❡s ❛r❡ ❛❧s♦ ❦♥♦✇♥ ❛s ✉♥❞❡r✇❛t❡r s✉♣❡r❛❡r♦♣❤✐❧✐❝ s✉r❢❛❝❡s✳ ✾✱✶✵ ❚❤❡ ❛✐r ❡♥tr❛♣♣❡❞ ✇✐t❤✐♥ t❤❡ t❡①t✉r❡ ✐s t❡r♠❡❞ ❛ ♣❧❛str♦♥ ✐♥ t❤❡ ❜✐♦❧♦❣✐❝❛❧ ❝♦♠✲ ♠✉♥✐t② ❛♥❞ t❤✐s ♣❤❡♥♦♠❡♥❛ ✐s ♦❜s❡r✈❡❞ ✐♥ ♥❛t✉r❡ ❛♠♦♥❣ ♠❛♥② ✐♥s❡❝ts ❛♥❞ ♣❧❛♥ts ✇❤✐❝❤ ❤❛✈❡ ❡✈♦❧✈❡❞ t❤❡ ❛❜✐❧✐t② t♦ ❜r❡❛t❤❡ ✉♥❞❡r✇❛t❡r✳ ✶✶✕✶✸ ■♥ ❛❞❞✐t✐♦♥ t♦ ♣r❡✈❡♥t✐♥❣ ✇❛t❡r ❢r♦♠ ✇❡tt✐♥❣ t❤❡ ✉♥❞❡r❧②✐♥❣ s✉❜str❛t❡✱ t❤❡ ♣❧❛str♦♥ ❛❝ts ❛s ❛ ❜❛rr✐❡r t♦✇❛r❞s ❝♦rr♦s✐♦♥ ♦♥ ♠❡t❛❧ s✉r❢❛❝❡s ✶✹ ❛♥❞ t❤❡ s✉r❢❛❝❡ ❛✐r ❧❛②❡r r❡❞✉❝❡s t❤❡ s❦✐♥ ❢r✐❝t✐♦♥ ❞r❛❣ ❡①♣❡r✐❡♥❝❡❞ ❜② s✉♣❡r❤②✲ ❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡s ✉♥❞❡r✇❛t❡r✳ ✶✺✱✶✻ ❈♦♥t✐♥✉❡❞ st❛❜✐❧✐t② ♦❢ t❤❡ ❈❛ss✐❡ st❛t❡ ✐s ❡ss❡♥t✐❛❧ ❢♦r ❡①♣❧♦✐t✐♥❣ t❤❡ ❞❡s✐r❛❜❧❡ ♣r♦♣❡rt✐❡s ♦❢ ✉♥❞❡r✇❛t❡r s✉♣❡r❛❡r♦♣❤✐❧✐❝ s✉r❢❛❝❡s✳ ❇✉t t❤❡ ❛✐r ✐♥ t❤✐s t❤r❡❡✲♣❤❛s❡ st❛t❡ ✐s ❡❛s✐❧② ❞✐s♣❧❛❝❡❞ ❜② ✇❛t❡r ✉♥❞❡r ♣r❡ss✉r❡ ✢✉❝t✉❛t✐♦♥s✱ s❤❡❛r ✢♦✇✱ ❛♥❞ ❧♦✇ ❞✐ss♦❧✈❡❞ ❣❛s ❝♦♥❝❡♥tr❛t✐♦♥s ✶✼✕✷✶ ✷

ACS Paragon Plus Environment

Page 2 of 35

Page 3 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

❝❛✉s✐♥❣ t❤❡♠ t♦ tr❛♥s✐t✐♦♥ ✐♥t♦ t❤❡ ❲❡♥③❡❧ ♦r ❢✉❧❧②✲✇❡tt❡❞ st❛t❡✳ ✷✷ ■♥ ♦r❞❡r ❢♦r s✉❝❤ ❛ s✉r✲ ❢❛❝❡ t♦ r❡❝♦✈❡r ✐ts ❞r❛❣✲r❡❞✉❝✐♥❣ ❛♥❞ ❛♥t✐✲❝♦rr♦s✐♦♥ ♣r♦♣❡rt✐❡s✱ ✐t ✐s ♥❡❝❡ss❛r② t♦ ✐♥❞✉❝❡ ❛ ❲❡♥③❡❧✲t♦✲❈❛ss✐❡ st❛t❡ tr❛♥s✐t✐♦♥ ♦♥ t❤❡ t❡①t✉r❡❞ s✉r❢❛❝❡ ✇❤✐❧❡ ✐t r❡♠❛✐♥s s✉❜♠❡r❣❡❞ ✐♥ t❤❡ ❧✐q✉✐❞ ♣❤❛s❡✳ ❲❡♥③❡❧✲t♦✲❈❛ss✐❡ st❛t❡ tr❛♥s✐t✐♦♥s ♦♥ t❡①t✉r❡❞ s✉r❢❛❝❡s ❤❛✈❡ ❜❡❡♥ ❛❝❤✐❡✈❡❞ ❢♦r s❡ss✐❧❡ ✇❛t❡r ❞r♦♣❧❡ts ✐♥ ❛✐r ✉s✐♥❣ ❡❧❡❝tr♦✇❡tt✐♥❣✱ ✷✸✱✷✹ ❜♦✐❧✐♥❣✱ ✷✺ ♠♦❞✉❧❛t✐♦♥ ♦❢ t❤❡ ▲❛♣❧❛❝❡ ♣r❡ss✉r❡✱ ✷✻ ✈✐❜r❛t✐♦♥✱ ✷✼ ❛♥❞ ✈♦❧❛t✐❧❡ ❧♦✇ s✉r❢❛❝❡ t❡♥s✐♦♥ ❧✐q✉✐❞s✳ ✷✽ ❍♦✇❡✈❡r✱ t❤❡s❡ ♠❡t❤♦❞s ✭❡①❝❡♣t ❜♦✐❧✐♥❣✮ ❝❛♥♥♦t ❡❛s✐❧② ❜❡ ❛♣♣❧✐❡❞ ✇❤❡♥ t❤❡ s✉r❢❛❝❡ ✐s s✉❜♠❡r❣❡❞ ✉♥❞❡r✇❛t❡r ❜❡❝❛✉s❡ t❤❡r❡ ✐s ♥♦ s♦✉r❝❡ ♦❢ ❛✐r ❛✈❛✐❧❛❜❧❡ ✐♥ t❤❡ s✉rr♦✉♥❞✐♥❣s t♦ ❞✐s♣❧❛❝❡ t❤❡ ✇❛t❡r ✐♥ t❤❡ t❡①t✉r❡✳ ❚❤❡r❡❢♦r❡ ✐♥ ♦r❞❡r t♦ ❛❝t✐✈❡❧② r❡st♦r❡ ❛ ♣❧❛str♦♥ ❜② r❡♣❧❡♥✐s❤✐♥❣ t❤❡ ❈❛ss✐❡ st❛t❡✱ t❤❡r❡ ✐s ❛ ❝❧❡❛r ♥❡❡❞ t♦ ✐♠♣❧❡♠❡♥t ❛ ❣❛s ♦r ✈❛♣♦r s♦✉r❝❡ ✉♥❞❡r✇❛t❡r✳ ▼❡t❤♦❞s t❤❛t ❤❛✈❡ ❜❡❡♥ ❞❡✈❡❧✲ ♦♣❡❞ t♦ ❛❞❞r❡ss t❤✐s ♥❡❡❞ ❝❛♥ ❜❡ ❜r♦❛❞❧② ❝❧❛ss✐✜❡❞ ✐♥t♦ t❤r❡❡ ❝❛t❡❣♦r✐❡s✿ ✭✐✮ ✐♥✲s✐t✉ ❣❛s✴✈❛♣♦r ❣❡♥❡r❛t✐♦♥✱ ✭✐✐✮ ❣❛s ✐♥❥❡❝t✐♦♥✱ ❛♥❞ ✭✐✐✐✮ ✐♥❝r❡❛s✐♥❣ t❤❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ ❞✐ss♦❧✈❡❞ ❣❛s ✐♥ t❤❡ ❝♦♥t❛❝t✐♥❣ ❧✐q✉✐❞✳ ❚❤❡ ✜rst ❛♣♣r♦❛❝❤ ✉s❡s ✐♥✲s✐t✉ ❣❡♥❡r❛t✐♦♥ ♦❢ ❣❛s✴✈❛♣♦r t♦ r❡♣❧❡♥✐s❤ t❤❡ ❣❛s❡♦✉s✴✈❛♣♦r ♣❤❛s❡ t❤❛t ✐♥✐t✐❛❧❧② ❢♦r♠❡❞ t❤❡ ❧♦st ♣❧❛str♦♥✳ ❚❤❡s❡ r❡❣❡♥❡r❛t✐✈❡ t❡❝❤♥✐q✉❡s ✐♥❝❧✉❞❡ ❡❧❡❝tr♦❧②✲ s✐s✱ ✷✾✱✸✵ ♣❤♦t♦❡❧❡❝tr♦❝❛t❛❧②t✐❝ ✇❛t❡r s♣❧✐tt✐♥❣✱ ✸✶ ❛♥❞ ✜❧♠ ❜♦✐❧✐♥❣✳ ✸✷✱✸✸ ▲❡❡ ❡t ❛❧✳ ❞❡♠♦♥str❛t❡❞

✐♥✲s✐t✉ ♣❧❛str♦♥ r❡❝♦✈❡r② ✉s✐♥❣ ❡❧❡❝tr♦❧②s✐s ♦♥ Pt✴❆✉ ❝♦❛t❡❞ s✐❧✐❝♦♥ ♣✐❧❧❛rs✳ ✷✾ ❆❧t❤♦✉❣❤ t❤✐s ♠❡t❤♦❞ ❤❛s t❤❡ ❛❞✈❛♥t❛❣❡ ♦❢ ❜❡✐♥❣ s❡❧❢✲❧✐♠✐t✐♥❣✱ ✐t ✐s ❡①♣❡♥s✐✈❡ t♦ ♣❡r❢♦r♠ ✇❛t❡r✲s♣❧✐tt✐♥❣ ✉s✐♥❣ ♥♦❜❧❡ ♠❡t❛❧s✳ ❖♥ t❤❡ ♦t❤❡r ❤❛♥❞✱ ✜❧♠ ❜♦✐❧✐♥❣ ❤❛s ♥♦ ♠❛t❡r✐❛❧ ❧✐♠✐t❛t✐♦♥s ❜✉t ✐s ❡♥❡r❣② ✐♥t❡♥s✐✈❡ t♦ ♣❡r❢♦r♠ ♦♥ ❛ ❧❛r❣❡ s❝❛❧❡✳ ✸✹ ❚❤❡ s❡❝♦♥❞ ♠❡t❤♦❞✱ ❣❛s ✐♥❥❡❝t✐♦♥✱ r❡❧✐❡s ♦♥ ♣r♦✈✐❞✲ ✐♥❣ ❛ ❝♦♥t✐♥✉♦✉s s✉♣♣❧② ♦❢ ❣❛s✴❛✐r t♦ t❤❡ ♣❧❛str♦♥✳ ❚❤✐s ❝❛♥ ❜❡ ❛❝❤✐❡✈❡❞ ✉s✐♥❣ ❛ ❝♦♥♥❡❝t❡❞

♣❧❛str♦♥ ✭♣❧❛str♦♥ ❝♦♥♥❡❝t❡❞ t♦ ❛♥ ❛✐r r❡s❡r✈♦✐r t❤r♦✉❣❤ ❛ ♣♦r♦✉s ♠✐❝r♦str✉❝t✉r❡✱ ✸✺ ❛ ❧❛r❣❡ ❜✉❜❜❧❡✱ ✸✻ ♦r ❛ r❡❣✐♦♥ ♦❢ ❝♦♠♣r❡ss❡❞ ❣❛s ✸✼ ✮✱ ♦r ❜② ✐♥❥❡❝t✐♥❣ ❣❛s ❜✉❜❜❧❡s ❞✐r❡❝t❧② ✐♥t♦ t❤❡ ❜♦✉♥❞❛r② ❧❛②❡r ♦❢ t❤❡ ✢♦✇✳ ✸✽ ❈♦♥♥❡❝t✐♥❣ ❛ ♣❧❛str♦♥ t♦ ❛♥ ❡①t❡r♥❛❧ r❡s❡r✈♦✐r ❞♦❡s ♥♦t r❡q✉✐r❡ ❛♥② ❡①♣❡♥s✐✈❡ ♠❛t❡r✐❛❧s ♦r ❡♥❡r❣② ✐♥♣✉t✱ ❜✉t ♥❡❡❞s ♣r❡❝✐s❡ ❝♦♥tr♦❧ ♦❢ ♣r❡ss✉r❡ ✐♥ t❤❡ r❡s❡r✈♦✐r t♦ ❢❛✈♦r ♣❧❛str♦♥ s♣r❡❛❞✐♥❣✳ ❆❧s♦✱ ❜✉❜❜❧❡s ✐♥❥❡❝t❡❞ ✐♥t♦ t❤❡ ❜♦✉♥❞❛r② ❧❛②❡r ❞♦ ♥♦t ❛❞❤❡r❡ t♦ t❤❡ s✉r❢❛❝❡ ✐♠♠❡❞✐❛t❡❧② ❞✉❡ t♦ t❤❡ ❧✉❜r✐❝❛t✐♦♥ ♣r❡ss✉r❡ ❡①❡rt❡❞ ♦♥ t❤❡ ❜✉❜❜❧❡ ❜② t❤❡ ✸

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 35

❞r❛✐♥✐♥❣ ❧✐q✉✐❞ ✜❧♠✳ ✸✾ ❚❤❡s❡ ♠❡t❤♦❞s ❛r❡ t②♣✐❝❛❧❧② ♥♦t s❡❧❢✲❧✐♠✐t✐♥❣ ❛♥❞ ❛r❡ s✉s❝❡♣t✐❜❧❡ t♦ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ ❧❛r❣❡ ❜✉❜❜❧❡s t❤❛t r❡s✐❞❡ ♦♥ t❤❡ t❡①t✉r❡ ✐♥st❡❛❞ ♦❢ ❢♦r♠✐♥❣ ❛ t❤✐♥ ♣❧❛str♦♥ ❧❛②❡r ✇✐t❤✐♥ t❤❡ t❡①t✉r❡✳ ✸✽ ❚❤❡s❡ ♠❛❝r♦s❝♦♣✐❝ ❜✉❜❜❧❡s ✐♥❝r❡❛s❡ t❤❡ ❢♦r♠ ❞r❛❣ ❜② ❞✐sr✉♣t✐♥❣ t❤❡ ❜♦✉♥❞❛r② ❧❛②❡r✱ ❡✈❡♥ t❤♦✉❣❤ t❤❡ s❦✐♥ ❢r✐❝t✐♦♥ ❞r❛❣ ❝♦♥tr✐❜✉t✐♦♥ ✐s ❧♦✇❡r✳ ✹✵ ❚❤❡ ✜♥❛❧ ❛♣♣r♦❛❝❤ ✐s t♦ s❛t✉r❛t❡ t❤❡ ✇❛t❡r ✇✐t❤ ❞✐ss♦❧✈❡❞ ❛✐r✴❣❛s t♦ ❛❝❤✐❡✈❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ❜② ❞✐❢✲ ❢✉s✐♦♥ t❤r♦✉❣❤ t❤❡ ❧✐q✉✐❞ ❛♥❞ ♠❛ss tr❛♥s❢❡r ❛t t❤❡ ✐♥t❡r❢❛❝❡✳ ✹✶✱✹✷ ❚❤✐s t❡❝❤♥✐q✉❡ r❡q✉✐r❡s t❤❡ ❣❛s ❝♦♥❝❡♥tr❛t✐♦♥ t♦ ❜❡ ❝♦♥tr♦❧❧❡❞ ❧♦❝❛❧❧② ♥❡❛r t❤❡ s✉r❢❛❝❡ ❜② ✐♥❝r❡❛s✐♥❣ t❤❡ t❡♠♣❡r❛t✉r❡ ♦r ❞❡❝r❡❛s✐♥❣ t❤❡ ♣r❡ss✉r❡ ♦❢ t❤❡ ✇❛t❡r ✐♥ s✐t✉✳ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ❞❡♠♦♥str❛t❡ ❛ ♥♦✈❡❧ ❝❤❡♠✐❝❛❧ ♠❡t❤♦❞ t♦ r❡♣❧❡♥✐s❤ ❛✐r ❧♦ss ❢r♦♠ ❛♥ ❡st❛❜✲ ❧✐s❤❡❞ ♣❧❛str♦♥ ❜② ✉s✐♥❣ ❝❛t❛❧②t✐❝ ❞❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✳ ❍②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✐s ❛♥ ✉♥st❛❜❧❡ ❝♦♠♣♦✉♥❞ ✇❤✐❝❤ s❧♦✇❧② ❞❡❝♦♠♣♦s❡s ✐♥t♦ ✇❛t❡r ❛♥❞ ♦①②❣❡♥ ✭❊q✉❛t✐♦♥ ✶✮ ❡✈❡♥ ❛t r♦♦♠ t❡♠♣❡r❛t✉r❡ ❛♥❞ ♣r❡ss✉r❡✳ ❝❛t❛❧②st✴❤❡❛t

✷❍2 ❖2 −−−−−−−→ ✷❍2 ❖ + ❖2

✭✶✮

❚❤✐s r❡❛❝t✐♦♥ ✐s s❧♦✇ ✉♥❞❡r r♦♦♠ t❡♠♣❡r❛t✉r❡ ❝♦♥❞✐t✐♦♥s ✭✇✐t❤ ❛ ❞❡❝♦♠♣♦s✐t✐♦♥ ❤❛❧❢✲ ❧✐❢❡ ♦❢ t1/2 ∼ ✸ ②❡❛rs ✹✸ ✮ ❜✉t ❝❛♥ ❜❡ ❛❝❝❡❧❡r❛t❡❞ ❜② ✐♥❝r❡❛s✐♥❣ t❤❡ t❡♠♣❡r❛t✉r❡ ♦r ✉s✐♥❣ ❛ s✉✐t❛❜❧❡ ❝❛t❛❧②st✳ ❚❤❡r❡ ❛r❡ ❛ r❛♥❣❡ ♦❢ ♣♦ss✐❜❧❡ ❝❛t❛❧②sts ✐♥❝❧✉❞✐♥❣ t❤❡ ❡♥③②♠❡ ❝❛t❛❧❛s❡✱ ✹✹ ♣❧❛t✐♥✉♠ ❛♥❞ ✐ts ❛❧❧♦②s✱ ✹✺ ✐♦❞✐❞❡ ✹✻ ❛♥❞ ♠❡t❛❧ ♦①✐❞❡s✳ ✹✼ ❚❤❡ ✐♥t❡r♠❡❞✐❛t❡s ♦❢ t❤✐s r❡❛❝t✐♦♥ ❞❡♣❡♥❞ ♦♥ t❤❡ ❦✐♥❞ ♦❢ ❝❛t❛❧②st ✉s❡❞ ❢♦r t❤❡ ❞❡❝♦♠♣♦s✐t✐♦♥ r❡❛❝t✐♦♥✳ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ✉s❡ Pt ❛♥❞ ▼♥❖2 ❛s ❝❛t❛❧②sts✳ ❆ r❡❝❡♥t st✉❞② ❤❛s s❤♦✇♥ t❤❛t t❤❡ r❡❛❝t✐♦♥ ♦❢ ♣❧❛t✐♥✉♠ ✇✐t❤ ❍2 ❖2 t♦ ❣✐✈❡ Pt✭❖✮ ✐s t❤❡ r❛t❡ ❧✐♠✐t✐♥❣ st❡♣ ✐♥ t❤❡ r❡❛❝t✐♦♥✳ ✹✽ ❖♥ t❤❡ ♦t❤❡r ❤❛♥❞✱ ❝❛t❛❧②s✐s ❜② ▼♥❖2 ♣r♦❝❡❡❞s ✈✐❛ ❤②❞r♦♣❡r♦①✐❞❡✴s✉♣❡r♦①✐❞❡ ❛♥✐♦♥ ✐♥t❡r♠❡❞✐❛t❡s✳ ✹✾ ❘❡❣❛r❞❧❡ss ♦❢ t❤❡ ✐♥t❡r♠❡❞✐❛t❡s✱ t❤❡ ✜♥❛❧ r❡❛❝t✐♦♥ ♣r♦❞✉❝ts ❛r❡ ✇❛t❡r ❛♥❞ ♦①②❣❡♥ ❣❛s✳ ❚❤✐s r❡❛❝t✐♦♥ ❤❛s ❜❡❡♥ ♣r❡✈✐♦✉s❧② ❡①♣❧♦✐t❡❞ ✐♥ st✉❞✐❡s ♦❢ ❛❝t✐✈❡ ♠❛tt❡r ✇❤✐❝❤ ✉s❡ ❣❛s ❣❡♥❡r❛t✐♦♥ t♦ ♣r♦♣❡❧ ♥❛♥♦r♦❞s ❛♥❞ ♠✐❝r♦t✉❜❡s ✉♥❞❡r✇❛t❡r✳ ✺✵✱✺✶ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ✉s❡ t❤❡ ♦✈❡r♣r❡ss✉r❡ ♦❢ t❤❡ ♦①②❣❡♥ ❣❛s ❣❡♥❡r❛t❡❞ ❜② t❤❡ ❞❡❝♦♠♣♦s✐t✐♦♥ r❡❛❝t✐♦♥ t♦ ❞❡✇❡t t❤❡ ♠✐❝r♦t❡①t✉r❡ ❛♥❞ ❞r✐✈❡ ❛ ✇❡tt✐♥❣ st❛t❡ tr❛♥s✐t✐♦♥ ❢r♦♠ t❤❡ ❲❡♥③❡❧ st❛t❡ ❜❛❝❦ t♦ t❤❡ ❈❛ss✐❡ st❛t❡✳ ❋✐❣✉r❡ ✶ ❞❡♣✐❝ts t❤❡ st❛❣❡s ✹

ACS Paragon Plus Environment

Page 5 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

♦❜t❛✐♥❡❞ ❛♥♦t❤❡r ❝♦♥❞✐t✐♦♥ ♦♥ t❤❡ ♣r❡♠✐s❡ t❤❛t t❤❡ ❧❛t❡r❛❧ ❢r♦♥t ♦❢ t❤❡ ♣❧❛str♦♥ ♠✉st t♦✉❝❤ t❤❡ s✉❝❝❡ss✐✈❡ ♣✐❧❧❛r ❜❡❢♦r❡ t❤❡ ✈❡rt✐❝❛❧ ❢r♦♥t r❡❛❝❤❡s t❤❡ t♦♣ ♦❢ t❤❡ ♠✐❝r♦t❡①t✉r❡✳ ▲❡❡ ❡t ❛❧✳ ✷✾ ❛♥❞ ❱❡r❤♦ ❡t ❛❧✳ ✸✻ ❢♦✉♥❞ t❤❛t ❛ s✉♣❡r✐♠♣♦s❡❞ ♥❛♥♦t❡①t✉r❡ ✐s ❛ ♥❡❝❡ss❛r② ❝♦♥❞✐t✐♦♥ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②❀ ❜② ❝♦♥tr❛st✱ ❋♦rs❜❡r❣ ❡t✳ ❛❧✳ ♦❜t❛✐♥❡❞ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ ♣✐❧❧❛r❡❞ ♠✐❝r♦t❡①t✉r❡s ✇✐t❤ s♠♦♦t❤ ✇❛❧❧s✳ ❖♥❡ ♦❢ t❤❡ r❡❛s♦♥s ❢♦r t❤❡ ✐♥❝♦♥s✐st❡♥❝② ✐♥ t❤❡s❡ ♦❜s❡r✈❛✲ t✐♦♥s ✐s t❤❛t t❤❡ ❝♦rr❡s♣♦♥❞✐♥❣ t❤❡♦r✐❡s ✇❡r❡ ❞❡r✐✈❡❞ ❜❛s❡❞ ♦♥ ❣❡♦♠❡tr✐❝ ♣r✐♥❝✐♣❧❡s ❛♥❞ t❤❡ ✐♥❤❡r❡♥t t❤❡r♠♦❞②♥❛♠✐❝ st❛❜✐❧✐t② ♦❢ t❤❡ ♣❧❛str♦♥ ✐♥ t❤❡ t❡①t✉r❡ ✇❛s ✐❣♥♦r❡❞✳ ❏♦♥❡s ❡t ❛❧✳ ✺✷ ❛♥❞ ▼❛r♠✉r ❡t ❛❧✳ ✺✸ s❤♦✇ t❤❛t t❤❡ st❛❜✐❧✐t② ♦❢ t❤❡ ❈❛ss✐❡ st❛t❡ ✐s t❤❡ ♣r✐♠❛r② ❝♦♥❞✐t✐♦♥ ❢♦r ✉♥❞❡r✇❛t❡r st❛❜✐❧✐t② ♦❢ t❤❡ ♣❧❛str♦♥✳ ❲❡ ❡①♣❧♦r❡ t❤❡ ✐♠♣♦rt❛♥❝❡ ♦❢ t❤✐s ❝♦♥❞✐t✐♦♥ ❢♦r t❤❡ ❧❛t❡r❛❧ s♣r❡❛❞✐♥❣ ♦❢ t❤❡ ♣❧❛str♦♥ ✐♥ ❛♥ ✉♥❞❡r✇❛t❡r s✉♣❡r❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡✳ ❲❡ ❢❛❜r✐❝❛t❡ ♠✐❝r♦♣✐❧❧❛rs ✐♥t❡rs♣❡rs❡❞ ✇✐t❤ ♣❧❛t✐♥✉♠ ❝❛t❛❧②st ♦♥ s✐❧✐❝♦♥ ✇❛❢❡rs✱ ❤②❞r♦♣❤♦✲ ❜✐③❡ t❤❡♠ ✇✐t❤ ❛ ❚❡✢♦♥ ❧❛②❡r✱ ❛♥❞ ❞❡♠♦♥str❛t❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ✉♥❞❡r✇❛t❡r ✇❤❡♥ ❞✐❧✉t❡ ❝♦♥❝❡♥tr❛t✐♦♥s ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ❛r❡ ✐♥tr♦❞✉❝❡❞✳ ❲❡ ♣r♦♣♦s❡ ❛ t❤❡r♠♦❞②♥❛♠✐❝ ♠♦❞❡❧ ❜❛s❡❞ ♦♥ ❡♥❡r❣❡t✐❝s ♦❢ ❣❛s ❤❡♠✐✇✐❝❦✐♥❣ ✉♥❞❡r✇❛t❡r✱ ❛♥❞ ❞❡r✐✈❡ ❛ ❝r✐t❡r✐♦♥ ❢♦r ♣❧❛str♦♥ r❡✲ ❝♦✈❡r②✳ ❲❡ ❡①♣❧♦r❡ t❤✐s ❝r✐t❡r✐♦♥ ✉s✐♥❣ ♣❧❛t✐♥✉♠✲❝♦❛t❡❞ ♠✐❝r♦♣✐❧❧❛r ❛rr❛②s ♦❢ ✈❛r②✐♥❣ ❤❡✐❣❤t ❛♥❞ ♣✐t❝❤✳ ❋✐♥❛❧❧②✱ ✇❡ ❛❧s♦ ❞❡♠♦♥str❛t❡ ♣r❛❝t✐❝❛❧ ♣❧❛str♦♥ r❡❝♦✈❡r② ❞✉r✐♥❣ ♠❡❛s✉r❡♠❡♥ts ♦❢ ❢r✐❝t✐♦♥❛❧ ❞r❛❣ ♦♥ ❛♥ ✐♥❡①♣❡♥s✐✈❡ ❛♥❞ s❝❛❧❛❜❧❡ ❛❧✉♠✐♥✉♠ s✉r❢❛❝❡ ✇✐t❤ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡ ❝❛t❛❧②st ✉s✐♥❣ ❛ ❚❛②❧♦r✲❈♦✉❡tt❡ ❝❡❧❧✳ ✺✹

❚❤❡r♠♦❞②♥❛♠✐❝ ❙t❛t❡s ♦❢ ●❛s ❇✉❜❜❧❡s ♦♥ ❆❡r♦♣❤✐❧✐❝ ❚❡①✲ t✉r❡s ❇✉❜❜❧❡s ✐♥t❡r❛❝t ✇✐t❤ t❡①t✉r❡❞ s♦❧✐❞ s✉r❢❛❝❡s ✐♥ ❞✐✛❡r❡♥t ✇❛②s ❞❡♣❡♥❞✐♥❣ ♦♥ t❤❡ r♦✉❣❤♥❡ss ❛♥❞ ❝❤❡♠✐str② ♦❢ t❤❡ s✉r❢❛❝❡✳ ✺✺ ❲❡ ❝❧❛ss✐❢② t❤❡ st❛t❡s ♦❢ ✇❡tt✐♥❣ ♦❢ ❛ ❣❛s ❜✉❜❜❧❡ ❣❡♥❡r❛t❡❞ ♦♥ ❛ t❡①t✉r❡❞ s♦❧✐❞ s✉r❢❛❝❡ ✐♠♠❡rs❡❞ ✉♥❞❡r✇❛t❡r ❜❛s❡❞ ♦♥ t❤❡✐r t❤❡r♠♦❞②♥❛♠✐❝ st❛❜✐❧✐t②✳ ❈♦♠♣❛r✐s♦♥ ✇✐t❤ t❤❡ ❝♦rr❡s♣♦♥❞✐♥❣ s②st❡♠ ✐♥ ✇❤✐❝❤ ❛ ❞r♦♣ ♦❢ ❧✐q✉✐❞ ✇❡ts ❛ t❡①t✉r❡❞ s♦❧✐❞ s✉r❢❛❝❡ ✐♥ ❛✐r ❡♥❛❜❧❡s t❤❡ ✐❞❡♥t✐✜❝❛t✐♦♥ ♦❢ ❢♦✉r ❞✐st✐♥❝t r❡❣✐♠❡s✱ ❛♥❞ t❤❡ st❛❜✐❧✐t② ♦❢ ❡❛❝❤ ♦❢ ✻

ACS Paragon Plus Environment

Page 6 of 35

Page 7 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

t❤❡s❡ ❣❛s ❜✉❜❜❧❡✲✐♥✲✇❛t❡r st❛t❡s ❞❡♣❡♥❞s ♦♥ ❜♦t❤ t❤❡ s✉r❢❛❝❡ ❝❤❡♠✐str② ❛♥❞ r♦✉❣❤♥❡ss ♦❢ t❤❡ t❡①t✉r❡✳ ❋✐❣✉r❡ ✷❛ s❤♦✇s ❛ s❝❤❡♠❛t✐❝ ✐❧❧✉str❛t✐♥❣ t❤❡ ❢♦✉r r❡❣✐♠❡s ♦♥ ❛ ♠✐❝r♦t❡①t✉r❡❞ s♦❧✐❞ s✉r❢❛❝❡ ✲ ❜✉❜❜❧❡✱ ❜❧✐st❡r✱ ❤❡♠✐✇✐❝❦✐♥❣ ❜❧✐st❡r✱ ❛♥❞ ♣❧❛str♦♥✳ ❇✉❜❜❧❡ ✐❞❡♥t✐✜❡s t❤❡ st❛t❡ ✐♥ ✇❤✐❝❤ t❤❡ ❣❛s ❞♦❡s ♥♦t ✇❛♥t t♦ ✇❡t t❤❡ s♦❧✐❞ s✉r❢❛❝❡ ❛♥❞ ✐s ♣✐♥♥❡❞ t♦ t❤❡ s✉r❢❛❝❡ ✇✐t❤ ♠✐♥✐♠❛❧ s♦❧✐❞✲❛✐r ❝♦♥t❛❝t ❛r❡❛✳ ❇❧✐st❡rs ❛r❡ ❜✉❜❜❧❡s t❤❛t ♣❛rt✐❛❧❧② s♣r❡❛❞ ♦♥ t❤❡ s♦❧✐❞ s✉r❢❛❝❡ ✉♥t✐❧ t❤❡② ❡st❛❜❧✐s❤ ❛♥ ❡q✉✐❧✐❜r✐✉♠ ♣r❡ss✉r❡ ❛♥❞ ❛♣♣❛r❡♥t ❝♦♥t❛❝t ❛♥❣❧❡✳ ❚❤❡② ❞♦ ♥♦t ✐♠❜✐❜❡ s♣♦♥t❛♥❡♦✉s❧② ✐♥t♦ t❤❡ t❡①t✉r❡✳ ❚❤❡ P❧❛str♦♥ ✐s t❤❡ st❛t❡ ✐♥ ✇❤✐❝❤ t❤❡ ❣❛s ✐s ❝♦♠♣❧❡t❡❧② ✐♠❜✐❜❡❞ ✐♥ t❤❡ t❡①t✉r❡ ❛♥❞ ♦♥❧② t❤❡ t♦♣ ♦❢ t❤❡ s✉r❢❛❝❡ t❡①t✉r❡ ❝♦♥t❛❝ts t❤❡ ❧✐q✉✐❞ ♣❤❛s❡✳ ❋✐♥❛❧❧②✱ t❤❡ ✐♥t❡r♠❡❞✐❛t❡ st❛t❡ ✐❞❡♥t✐✜❡❞ ❛s ❍❡♠✐✇✐❝❦✐♥❣ ❇❧✐st❡rs ❛r❡ ❜❧✐st❡rs t❤❛t s♣r❡❛❞ ♦♥ t♦♣ ♦❢ ❛ ♠✐❝r♦t❡①t✉r❡ ✐♠❜✐❜❡❞ ✇✐t❤ ❛✐r ✐✳❡✳ ♣❧❛str♦♥✳ ❚❤❡ ❞✐st✐♥❝t✐♦♥ ❜❡t✇❡❡♥ ❛ ❜❧✐st❡r ❛♥❞ ❛ ❤❡♠✐✇✐❝❦✐♥❣ ❜❧✐st❡r ✐s t❤❛t t❤❡ ✢✉✐❞ ♣❤❛s❡ ♣r❡❢❡r❡♥t✐❛❧❧② ✐♠❜✐❜❡❞ ✐♥ t❤❡ t❡①t✉r❡ s✉rr♦✉♥❞✐♥❣ t❤❡ ❣❛s ❜❧✐st❡r ✐s ❞✐✛❡r❡♥t✳ ❲❡ ❞❡✜♥❡ t❤✐s st❛t❡ ✉s✐♥❣ ❛ ♥♦♠❡♥❝❧❛t✉r❡ ❞❡r✐✈❡❞ ❢r♦♠ t❤❡ ✇♦r❦ ♦❢ ❇✐❝♦ ❡t ❛❧✳ ✇❤♦ ❝♦♥s✐❞❡r❡❞ ❝♦rr❡s♣♦♥❞✐♥❣ st❛t❡s ❢♦r ❧✐q✉✐❞ ❞r♦♣❧❡ts ✇❡tt✐♥❣ ♠✐❝r♦t❡①t✉r❡❞ ❞r② s✉❜str❛t❡s ✐♥ ❛✐r✳ ✺✻ ■t ❝❛♥ ❜❡ s❡❡♥ ❢r♦♠ ❞❡t❛✐❧❡❞ ❡①❛♠✐♥❛t✐♦♥ ♦❢ ❋✐❣✉r❡ ✷❛ ✭✐✮✲✭✐✈✮ t❤❛t t❤❡ ♣✐❧❧❛rs ❛r❡ ✈✐s✐❜❧❡ ❢♦r t❤❡ ❜✉❜❜❧❡ ❛♥❞ ❜❧✐st❡r st❛t❡s ✇❤✐❧❡ t❤❡ ♣✐❧❧❛rs ❛r❡ ❤✐❞❞❡♥ ✐♥s✐❞❡ t❤❡ ❣❛s ❧❛②❡r ❢♦r t❤❡ ❤❡♠✐✇✐❝❦✐♥❣ ❜❧✐st❡r ❛♥❞ ♣❧❛str♦♥ st❛t❡s✳ ❲❤❡♥ ❣❛s ✐s ♣r♦❞✉❝❡❞ ✐♥ t❤❡ t❡①t✉r❡ t❤r♦✉❣❤ t❤❡ ❞❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✱ ✐t ♠❛② ❧❡❛✈❡ t❤❡ s✉r❢❛❝❡ t❤r♦✉❣❤ ❜✉♦②❛♥❝② ❡✛❡❝ts ❛s ❛ ♠❛❝r♦s❝♦♣✐❝ ❜✉❜❜❧❡✱ ♦r s♣r❡❛❞ t❤r♦✉❣❤ t❤❡ ♠✐❝r♦s❝♦♣✐❝ t❡①t✉r❡ ✐♥ ♦♥❡ ♦❢ t❤❡ ♦t❤❡r st❛t❡s ❞❡♣❡♥❞✐♥❣ ♦♥ t❤❡ t❡①t✉r❡ ❝❤❡♠✐str② ❛♥❞ r♦✉❣❤♥❡ss✱ ❛♥❞ t❤❡ r❛t❡ ♦❢ ❣❡♥❡r❛t✐♦♥ ❝♦♠♣❛r❡❞ t♦ t❤❡ r❛t❡ ♦❢ s♣r❡❛❞✐♥❣✳ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ❢♦❧❧♦✇ ◗✉éré✬s ❤❡♠✐✇✐❝❦✐♥❣ ♠♦❞❡❧ ❢♦r ❤②❞r♦♣❤✐❧✐❝ t❡①t✉r❡s ✺✻ t♦ ♦❜t❛✐♥ ❛♥ ❡q✉✐✈❛❧❡♥t ❤❡♠✐✇✐❝❦✐♥❣ ♠♦❞❡❧ ❢♦r s✉♣❡r❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡s ✉♥❞❡r✇❛t❡r✳ ■♥ ✐❞❡❛❧ ♣❧❛str♦♥ r❡❝♦✈❡r②✱ t❤❡ ❣❛s ✇♦✉❧❞ s♣r❡❛❞ ❛❧♦♥❣ t❤❡ s✉r❢❛❝❡ ♠✐❝r♦t❡①t✉r❡ ✇✐t❤♦✉t ❞✐s♣❧❛❝✐♥❣ t❤❡ ✇❛t❡r ♦♥ t♦♣ ♦❢ t❤❡ t❡①t✉r❡ ❛s ❞❡♣✐❝t❡❞ ✐♥ ❋✐❣✉r❡ ✶✳ ❚❤✐s ♣r♦❝❡ss ✐♥✈♦❧✈❡s t❤❡ ❝r❡❛t✐♦♥ ♦❢ ♥❡✇ s♦❧✐❞✲ ❛✐r ❛♥❞ ✇❛t❡r✲❛✐r ✐♥t❡r❢❛❝❡s ✇❤✐❧❡ r❡♣❧❛❝✐♥❣ t❤❡ ✇❛t❡r✲s♦❧✐❞ ✐♥t❡r❢❛❝❡s ❞✉r✐♥❣ ❞❡✲✇❡tt✐♥❣✳ ❚❤❡ ❝❤❛♥❣❡ ✐♥ ❡♥❡r❣② ♦❢ t❤❡ s②st❡♠ ✇❤❡♥ t❤❡ ❣❛s ❢r♦♥t ❞✐s♣❧❛❝❡s ✇❛t❡r ❢r♦♠ ❛ s♠❛❧❧ ❛r❡❛ ldx ✐s ❣✐✈❡♥ ❜② t❤❡ ❢♦❧❧♦✇✐♥❣ ❡q✉❛t✐♦♥✳ ✼

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 8 of 35

Page 9 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

dE = γw,g (1 − φs )ldx + γs,g (r − φs )ldx − γs,w (r − φs )ldx

✭✷✮

✇❤❡r❡ γw,g ✱ γs,g ❛♥❞ γs,w r❡♣r❡s❡♥t t❤❡ r❡s♣❡❝t✐✈❡ ✐♥t❡r❢❛❝✐❛❧ ❡♥❡r❣✐❡s ❜❡t✇❡❡♥ t❤❡ t❤r❡❡ ♣❤❛s❡s✱

r ❛♥❞ φs ❞❡♥♦t❡ t❤❡ ❲❡♥③❡❧ r♦✉❣❤♥❡ss ❛♥❞ t❤❡ ♣r♦❥❡❝t❡❞ s♦❧✐❞ ❢r❛❝t✐♦♥ r❡s♣❡❝t✐✈❡❧②✱ ❛♥❞ l ✐s t❤❡ ❧❡♥❣t❤ ✐♥t♦ t❤❡ ♣❧❛♥❡ ♦❢ ❋✐❣✉r❡ ✶✳ ❚❤❡ ❲❡♥③❡❧ r♦✉❣❤♥❡ss r ✐s ❞❡✜♥❡❞ ❛s t❤❡ t♦t❛❧ s✉r❢❛❝❡ ❛r❡❛ ♣❡r ✉♥✐t ♣r♦❥❡❝t❡❞ ❛r❡❛ ♦❢ s♦❧✐❞ s✉r❢❛❝❡✱ ❛♥❞ s♦❧✐❞ ❢r❛❝t✐♦♥ φs ✐s ❞❡✜♥❡❞ ❛s t❤❡ ❛r❡❛ ✇❡tt❡❞ ❜② t❤❡ ❧✐q✉✐❞ ✐♥ t❤❡ ❈❛ss✐❡ st❛t❡ ♣❡r ✉♥✐t ♣r♦❥❡❝t❡❞ s✉r❢❛❝❡ ❛r❡❛ ♦❢ s♦❧✐❞✳ ❋♦r ❡①❛♠♣❧❡ ♦♥ ❛ ♠✐❝r♦t❡①t✉r❡ ✇✐t❤ ❝✐r❝✉❧❛r ♣✐❧❧❛rs✱ r ❛♥❞ φs ❛r❡ ❝❛❧❝✉❧❛t❡❞ ❜② ✉s✐♥❣ t❤❡ ❢♦❧❧♦✇✐♥❣ ❡q✉❛t✐♦♥s✳

r =1+

2πRH L2

πR2 φs = 2 L

✭✸✮

✭✹✮

❚❤❡ ❝❤❛♥❣❡ ✐♥ ❡♥❡r❣② dE ♦❢ t❤❡ s②st❡♠ ♠✉st ❜❡ ♥❡❣❛t✐✈❡ ✐♥ ♦r❞❡r ❢♦r t❤❡ ❣❛s t♦ ♣r❡❢❡r❡♥✲ t✐❛❧❧② ✇✐❝❦ ✐♥t♦ t❤❡ t❡①t✉r❡✳ ❍❡♥❝❡ ❜② s❡tt✐♥❣ dE < 0 ❛♥❞ s✐♠♣❧✐❢②✐♥❣ t❤❡ ❡①♣r❡s✐♦♥ ✉s✐♥❣ t❤❡ ❡①♣r❡ss✐♦♥ ❢♦r ❨♦✉♥❣✬s t❤r❡❡ ♣❤❛s❡ ❝♦♥t❛❝t ❛♥❣❧❡ ❡q✉❛t✐♦♥✱ ✺✼ ✇❡ ♦❜t❛✐♥ t❤❡ t❤❡r♠♦❞②♥❛♠✐❝ ❝♦♥❞✐t✐♦♥ ❢♦r s♣♦♥t❛♥❡♦✉s ♣❧❛str♦♥ r❡❝♦✈❡r②✳

cos θw < −

1 − φs r − φs

✭✺✮

❊q✉❛t✐♦♥ ✺ ✐♠♣❧✐❡s t❤❛t ♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ♦♥❧② ♣♦ss✐❜❧❡ ❢♦r t❡①t✉r❡s ✇✐t❤ ❤②❞r♦♣❤♦❜✐❝ ❝❤❡♠✐str✐❡s ✭θw > 90◦ ✮ s✐♥❝❡ t❤❡ ❡①♣r❡ss✐♦♥ ♦♥ t❤❡ r✐❣❤t ✐s ❛❧✇❛②s ♥❡❣❛t✐✈❡✳ ❚❤❡ ❢❛✈♦r❛❜❧❡ r❡❣✐♠❡s ♦❢ ✉♥❞❡r✇❛t❡r ❣❛s ✇❡tt✐♥❣ ❝❛♥ ❜❡ r❡♣r❡s❡♥t❡❞ ♦♥ t❤❡ ♣❧♦t ✐❧❧✉str❛t✐♥❣ t❤❡ r❡❧❛t✐♦♥s❤✐♣ ❜❡t✇❡❡♥ t❤❡ ❝♦s✐♥❡ ♦❢ t❤❡ ❛♣♣❛r❡♥t ❝♦♥t❛❝t ❛♥❣❧❡ ♦❢ ❛ ✇❛t❡r ❞r♦♣❧❡t ♦♥ ❛ t❡①t✉r❡❞ s♦❧✐❞ ✐♥ ❛✐r✱ cos θw∗ ❛♥❞ t❤❡ ❝♦s✐♥❡ ♦❢ t❤❡ ❨♦✉♥❣✬s ❝♦♥t❛❝t ❛♥❣❧❡ ♦❢ ❛ ✇❛t❡r ❞r♦♣❧❡t ♦♥ ❛ ✢❛t s✉r❢❛❝❡ ✐♥ ❛✐r✱ cos θw ❛s s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ✷❜✳ ❍❡r❡ ✐t ❝❛♥ ❜❡ s❡❡♥ t❤❛t ♣❧❛str♦♥ ❛♥❞ ❤❡♠✐✲✇✐❝❦✐♥❣ ❜❧✐st❡rs ❛r❡ ❢❛✈♦r❛❜❧❡ ✐♥ t❤❡ t❡①t✉r❡s ✇❤✐❝❤ ❛r❡ ❈❛ss✐❡✲st❛❜❧❡ t♦✇❛r❞s s❡ss✐❧❡ ✇❛t❡r ❞r♦♣❧❡ts



ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 35

✐♥ ❛✐r✱ ❜❧✐st❡rs ❛r❡ ❢❛✈♦r❛❜❧❡ ✐♥ t❤❡ t❡①t✉r❡s ✇❤✐❝❤ ❛r❡ ❲❡♥③❡❧✲st❛❜❧❡ t♦✇❛r❞s s❡ss✐❧❡ ✇❛t❡r ❞r♦♣❧❡ts ✐♥ ❛✐r✱ ❛♥❞ ❜✉❜❜❧❡s ❛r❡ ❢❛✈♦r❡❞ ✐♥ t❤❡ t❡①t✉r❡s ✇❤✐❝❤ ❛r❡ ❤❡♠✐✇✐❝❦✐♥❣ t♦✇❛r❞s s❡ss✐❧❡ ✇❛t❡r ❞r♦♣❧❡ts ✐♥ ❛✐r✳ ❙✐♥❝❡ ❣❛s ❞✐s♣❧❛❝❡s ✇❛t❡r ✐♥ t❤❡ t❡①t✉r❡ ❞✉r✐♥❣ ♣❧❛str♦♥ s♣r❡❛❞✐♥❣✱ ✐t ✐s ♠♦st ❛♣♣r♦♣r✐❛t❡ ✐♥ ❊q✉❛t✐♦♥ ✺ t♦ ✉s❡ t❤❡ r❡❝❡❞✐♥❣ ❝♦♥t❛❝t ❛♥❣❧❡ ♦❢ ❛ s❡ss✐❧❡ ✇❛t❡r ❞r♦♣❧❡t ♦♥ ❛ s♠♦♦t❤ s✉r❢❛❝❡ ✇✐t❤ t❤❡ s❛♠❡ ❝❤❡♠✐str②✳ ❘❡❛rr❛♥❣✐♥❣ ❊q✉❛t✐♦♥ ✺ ✉s✐♥❣ t❤❡ r❡❝❡❞✐♥❣ ✇❛t❡r ❝♦♥t❛❝t ❛♥❣❧❡ ❣✐✈❡s ✉s t❤❡ ❝♦♥❞✐t✐♦♥ t❤❛t ♥❡❡❞s t♦ ❜❡ s❛t✐s✜❡❞ ❢♦r t❡①t✉r❛❧ ❞❡s✐❣♥ ♣❛r❛♠❡t❡rs s✉❝❤ ❛s t❤❡ s♦❧✐❞ ❛r❡❛ ❢r❛❝t✐♦♥ φs ❛♥❞ t❤❡ s♦❧✐❞ r♦✉❣❤♥❡ss r✳ ❚❤✐s ❛❧s♦ ♠❛t❝❤❡s ✇✐t❤ t❤❡ ♠♦♥♦st❛❜❧❡ ❈❛ss✐❡ st❛t❡ ❝♦♥❞✐t✐♦♥ ❞❡r✐✈❡❞ ❜② ▲✐ ❡t ❛❧✳ ❢♦r t❤❡ ❲❡♥③❡❧✲t♦✲ ❈❛ss✐❡ tr❛♥s✐t✐♦♥ ♦❢ ❧✐q✉✐❞ ❞r♦♣❧❡ts ♦♥ ♠✐❝r♦t❡①t✉r❡s✳ ✷✻ ❋♦r ♣❧❛str♦♥ r❡❝♦✈❡r② t♦ ❜❡ ❢❛✈♦r❛❜❧❡ ♦✈❡r ❜❧✐st❡r ❢♦r♠❛t✐♦♥✱ ✇❡ t❤❡r❡❢♦r❡ r❡q✉✐r❡ ♠✐❝r♦t❡①t✉r❡s ✇✐t❤ r♦✉❣❤♥❡ss ❡①❝❡❡❞✐♥❣ ❛ ❝r✐t✐❝❛❧ ✈❛❧✉❡✿

r >1−



 1 + 1 (1 − φs ) cos θwrec

∀ θwrec > 90◦

✭✻✮

✇❤❡r❡ t❤❡ ❝♦s✐♥❡ ♦❢ t❤❡ r❡❝❡❞✐♥❣ ❛♥❣❧❡ ✐s ♥❡❣❛t✐✈❡✱ −1 < cos θwrec < 0✱ ❛♥❞ ❤❡♥❝❡ t❤❡ r✐❣❤t ❤❛♥❞ s✐❞❡ ❡①♣r❡ss✐♦♥ ✐s ❛❧✇❛②s ♣♦s✐t✐✈❡✳

❘❡s✉❧ts ❛♥❞ ❉✐s❝✉ss✐♦♥ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ✉s❡ t✇♦ t②♣❡s ♦❢ t❡①t✉r❡❞ s✉r❢❛❝❡s ❢♦r t❡st✐♥❣ ♣❧❛str♦♥ r❡❝♦✈❡r② ✲ ❧✐t❤♦✲ ❣r❛♣❤✐❝❛❧❧② ♣❛tt❡r♥❡❞ s✐❧✐❝♦♥ ❛♥❞ ❧❛s❡r✲t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ ✭❙❡❡ ❋✐❣✉r❡ ✸✮✳ ■♥ ♦r❞❡r t♦ s②s✲ t❡♠❛t✐❝❛❧❧② st✉❞② t❤❡ ❡✛❡❝t ♦❢ s✉r❢❛❝❡ r♦✉❣❤♥❡ss ♦♥ ♣❧❛str♦♥ r❡❝♦✈❡r②✱ ♠✐❝r♦✲♣✐❧❧❛r ❛rr❛②s ✇✐t❤ ✈❛r②✐♥❣ ♣✐❧❧❛r ❤❡✐❣❤ts ❛♥❞ s♣❛❝✐♥❣ ✇❡r❡ ❢❛❜r✐❝❛t❡❞ ♦♥ s✐❧✐❝♦♥ ✇❛❢❡rs ✉s✐♥❣ ♣❤♦t♦❧✐t❤♦❣✲ r❛♣❤②✳ P❧❛t✐♥✉♠✱ ❛ ✇❡❧❧✲❦♥♦✇♥ ❝❛t❛❧②st ❢♦r t❤❡ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ❞❡❝♦♠♣♦s✐t✐♦♥ r❡❛❝t✐♦♥✱ ✇❛s s❡❧❡❝t✐✈❡❧② ❞❡♣♦s✐t❡❞ ♦♥ t❤❡ ❜♦tt♦♠ ❛♥❞ t❤❡ s✐❞❡s ♦❢ t❤❡ ♠✐❝r♦✲♣✐❧❧❛rs ✉s✐♥❣ ❧✐❢t✲♦✛ ♣❤♦✲ t♦❧✐t❤♦❣r❛♣❤② ✭s❡❡ t❤❡ ❡①♣❡r✐♠❡♥t❛❧ ♠❡t❤♦❞s s❡❝t✐♦♥ ❢♦r ♠♦r❡ ❞❡t❛✐❧s✮✱ t♦ ❡♥s✉r❡ t❤❛t t❤❡ ♣❧❛str♦♥ r❡✲✐♥✢❛t✐♦♥ ♣r♦❝❡ss ✐s s❡❧❢✲❧✐♠✐t✐♥❣✳ ❚❤❡ t❡①t✉r❡s ✇❡r❡ t❤❡♥ s♣✐♥✲❝♦❛t❡❞ ✇✐t❤ ❛ ✶ ✇t✳✪ ❚❡✢♦♥ s♦❧✉t✐♦♥ ❛♥❞ ❝✉r❡❞ t♦ r❡♥❞❡r t❤❡♠ ❤②❞r♦♣❤♦❜✐❝✳ ✶✵

ACS Paragon Plus Environment

Page 11 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

❙✐✲Pt✲❚❡✢♦♥ s✉r❢❛❝❡ tr❛♥s✐t✐♦♥✐♥❣ ❢r♦♠ ❛ ♣❛rt✐❛❧❧②✲✇❡tt❡❞ st❛t❡ t♦ ❛ ❢✉❧❧②✲r❡❝♦✈❡r❡❞ ♣❧❛str♦♥ st❛t❡✳ ❙✉♣♣❧❡♠❡♥t❛r② ❱✐❞❡♦ ❙✶ s❤♦✇s t❤❡ ♣r♦❝❡ss ♦❢ ♣❧❛str♦♥ ♥✉❝❧❡❛t✐♦♥ ❛♥❞ ❧❛t❡r❛❧ s♣r❡❛❞✐♥❣ t❤r♦✉❣❤ t❤❡ t❡①t✉r❡✳ ❊①♣❡r✐♠❡♥ts ✇❡r❡ ❛❧s♦ ♣❡r❢♦r♠❡❞ ♦♥ s✐❧✐❝♦♥ ♠✐❝r♦♣✐❧❧❛rs ✇❤♦s❡ t♦♣s ✇❡r❡ ♥♦t str✐♣♣❡❞ ♦❢ ♣❧❛t✐♥✉♠ ❝❛t❛❧②st ✭❙❡❡ ❙✉♣♣❧❡♠❡♥t❛r② ❋✐❣✉r❡ ❙✷✮ ❛♥❞ ✐t ✇❛s ❢♦✉♥❞ t❤❛t ♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ♣♦ss✐❜❧❡ ✐♥ t❤❡s❡ ❝❛s❡s t♦♦✳ ❲❡ ❜❡❧✐❡✈❡ t❤❛t t❤✐s ✐s ♣♦ss✐❜❧❡ ❜❡❝❛✉s❡ t❤❡ ♥✉❝❧❡❛t✐♦♥ ♦❢ ❣❛s ✐s ❢❛✈♦r❡❞ ❛t t❤❡ s❤❛r♣ ❝♦r♥❡rs ❛t t❤❡ ❜♦tt♦♠ ♦❢ t❤❡ t❡①t✉r❡✱ ❡✈❡♥ t❤♦✉❣❤ t❤❡r❡ ✐s ❝❛t❛❧②st ❛t t❤❡ t♦♣✳ ❲❡ ❛❧s♦ ♥♦t❡ t❤❛t ❙✐ ♠✐❝r♦♣✐❧❧❛rs ❢❛❜r✐❝❛t❡❞ ✉s✐♥❣ t❤❡ ❇♦s❝❤ ❘■❊ ♣r♦❝❡ss ❛❧s♦ ❤❛✈❡ ❛ ♥❛♥♦s❝❛❧❡ t❡①t✉r❡ ✇❤✐❝❤ ❝❛♥ ♣r♦♠♦t❡ ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❍❡♥❝❡✱ ❢✉rt❤❡r t❡sts ✇❡r❡ ❝♦♥❞✉❝t❡❞ ✉s✐♥❣ s♠♦♦t❤✲✇❛❧❧❡❞ ♠✐❝r♦♣✐❧❧❛rs ♠❛❞❡ ♦❢ ❙❯✽ ♣❤♦t♦r❡s✐st ✭❙❡❡ ❙✉♣♣❧❡♠❡♥t❛r② ❋✐❣✉r❡ ❙✹✮✳ ■t ✇❛s ♦❜s❡r✈❡❞ t❤❛t s♠♦♦t❤✲✇❛❧❧❡❞ ♠✐❝r♦♣✐❧❧❛r t❡①t✉r❡s ❛❧s♦ s❤♦✇ ♣❧❛str♦♥ r❡❝♦✈❡r② s✐♠✐❧❛r t♦ t❤❡ ❞r②✲❡t❝❤❡❞ ❙✐ ♠✐❝r♦♣✐❧❧❛rs✱ ❢✉rt❤❡r s✉♣♣♦rt✐♥❣ ♦✉r ♦❜s❡r✈❛t✐♦♥ t❤❛t ♥❛♥♦s❝❛❧❡ r♦✉❣❤♥❡ss ✐s ♥♦t ♥❡❝❡ss❛r② ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❍♦✇❡✈❡r ❛s ♣r❡❞✐❝t❡❞ ❜② t❤❡ t❤❡r♠♦❞②♥❛♠✐❝ ❛♥❛❧②s✐s✱ ✐t ✇❛s ♦❜s❡r✈❡❞ t❤❛t s♦♠❡ t❡①t✉r❡s ❞♦ ♥♦t ♣r♦♠♦t❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ❡✈❡♥ ✐❢ t❤❡② ❛r❡ ❤②❞r♦♣❤♦❜✐❝✳ ❋✐❣✉r❡ ❙✺ s❤♦✇s ❛♥ ✐♠❛❣❡ ♦❢ ❛ s✉❜♠❡r❣❡❞ ❙✐✲Pt✲❚❡✢♦♥ t❡①t✉r❡ ✭✷✺ µ♠ ❞❡♣t❤✱ ✺✵ µ♠ ♣✐❧❧❛r ✇✐❞t❤✱ ✶✺✵ µ♠ ♣✐t❝❤ ❝♦rr❡s♣♦♥❞✐♥❣ t♦ φs ❂ ✵✳✵✽✼✱ r ❂ ✶✳✶✼✺✮ ♦♥ ✇❤✐❝❤ ❜❧✐st❡rs ❛r❡ ❢♦r♠❡❞ ✉♣♦♥ t❤❡ ❛❞❞✐t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✉♥❞❡r s✐♠✐❧❛r ❝♦♥❞✐t✐♦♥s✳ ❋✐❣✉r❡ ✹ s❤♦✇s ❛ r❡❣✐♠❡ ♠❛♣ ❝❧❛ss✐❢②✐♥❣ t❤❡ s✐❧✐❝♦♥ ♠✐❝r♦✲♣✐❧❧❛r ❡①♣❡r✐♠❡♥ts ✐♥t♦ t✇♦ ❝❛t❡❣♦r✐❡s ❜❛s❡❞ ♦♥ ✇❤❡t❤❡r ♣❧❛str♦♥ s♣r❡❛❞✐♥❣ ♦r ❜❧✐st❡r ❢♦r♠❛t✐♦♥ ✇❛s ❢❛✈♦r❡❞ ❜❛s❡❞ ♦♥ t❤❡ t❡①t✉r❡ ♣❛r❛♠❡t❡rs ❝❤❛r❛❝t❡r✐③✐♥❣ ❡❛❝❤ s✉r❢❛❝❡✳ ❚❤❡ r❡❝❡❞✐♥❣ ❝♦♥t❛❝t ❛♥❣❧❡ ♦❢ ❛ ✇❛t❡r ❞r♦♣❧❡t ♦♥ ❛ ❚❡✢♦♥ ❝♦❛t❡❞ s♠♦♦t❤ s✐❧✐❝♦♥ ✇❛❢❡r ✇❛s ♠❡❛s✉r❡❞ t♦ ❜❡ θwrec = 111◦ ± 2◦ ❛♥❞ t❤✐s ✈❛❧✉❡ ❤❛s ❜❡❡♥ ✉s❡❞ t♦ ♣❧♦t t❤❡ r❡❝♦✈❡r② ❝♦♥❞✐t✐♦♥ ❣✐✈❡♥ ❜② ❊q✉❛t✐♦♥ ✻✳ ❚❤❡ s❤❛❞❡❞ r❡❣✐♦♥ ❛r♦✉♥❞ t❤❡ t❤❡♦r❡t✐❝❛❧ ♣r❡❞✐❝t✐♦♥ ❧✐♥❡ ✐♥❞✐❝❛t❡s t❤❡ s❡♥s✐t✐✈✐t② ♦❢ ❊q✉❛t✐♦♥ ✻ t♦ ❛ r❡❝❡❞✐♥❣ ❝♦♥t❛❝t ❛♥❣❧❡ ✈❛r✐❛t✐♦♥ ♦❢ ±2◦ ✳ ■t ❝❛♥ ❜❡ s❡❡♥ ❢r♦♠ ❜♦t❤ t❤❡ t❤❡♦r② ❛♥❞ t❤❡ ❡①♣❡r✐♠❡♥ts t❤❛t t❡①t✉r❡s ✇✐t❤ ❧❛r❣❡r r♦✉❣❤♥❡ss ❛♥❞ ❤✐❣❤❡r s♦❧✐❞ ❢r❛❝t✐♦♥ ❢❛✈♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✱ ✇❤✐❧❡ t❤♦s❡ ✇✐t❤ ❧♦✇❡r r♦✉❣❤♥❡ss ❛♥❞ s♠❛❧❧❡r s♦❧✐❞ ❢r❛❝t✐♦♥ ♣r♦♠♦t❡ ❜❧✐st❡r ❢♦r♠❛t✐♦♥✳ ❲❡ ❛❧s♦ s❡❡ t❤❛t t❤❡ t❡①t✉r❡s ✇❤✐❝❤ ❤❛✈❡ ❝❛t❛❧②st ♦♥ t♦♣ ♦❢ t❤❡ ♣✐❧❧❛rs ❢❛✈♦r ♣❧❛str♦♥ r❡❝♦✈❡r② ❛s ✇❡❧❧✳ ✶✷

ACS Paragon Plus Environment

Page 12 of 35

Page 13 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

❆❧t❤♦✉❣❤ ✐t ❤❛s ❜❡❡♥ r❡♣♦rt❡❞ ✐♥ ♣r❡✈✐♦✉s st✉❞✐❡s t❤❛t t❤❡ ♣r❡s❡♥❝❡ ♦❢ ❛ ♥❛♥♦✲❈❛ss✐❡ st❛t❡ ✐s ♥❡❝❡ss❛r② ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✱ ✷✾✱✸✻ ✇❡ ♦❜s❡r✈❡ t❤❛t s❛t✐s❢②✐♥❣ t❤❡ t❤❡r♠♦❞②♥❛♠✐❝ ❝♦♥❞✐t✐♦♥ ❢♦r ♣❧❛str♦♥ ❣❛s s♣r❡❛❞✐♥❣ ❛❧♦♥❡ ✐s s✉✣❝✐❡♥t t♦ ❛❧❧♦✇ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ ♠✐❝r♦t❡①t✉r❡s ❡✈❡♥ ✇✐t❤♦✉t ❛ ♥❛♥♦s❝❛❧❡ t❡①t✉r❡ t♦ ❤♦❧❞ ❛ st❛❜❧❡ ♣❧❛str♦♥✳ ❚❤✐s ✐s ❛❧s♦ ✐♥ ❛❣r❡❡♠❡♥t ✇✐t❤ t❤❡ ♦❜s❡r✈❛t✐♦♥ ❜② ❋♦rs❜❡r❣ ❡t✳ ❛❧✳✱ ✸✼ ✇❤♦ r❡♣♦rt❡❞ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ s♠♦♦t❤✲✇❛❧❧❡❞ ♣♦❧②♠❡r ♣✐❧❧❛rs✳ ■t ❝❛♥ ❜❡ ♦❜s❡r✈❡❞ t❤❛t ❛ ❢❡✇ t❡①t✉r❡s s❤♦✇ r❡❝♦✈❡r② ❡✈❡♥ t❤♦✉❣❤ t❤❡② ❧✐❡ ❜❡❧♦✇ t❤❡ t❤❡♦r❡t✐❝❛❧❧② ❝♦♥❞✐t✐♦♥ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❚❤✐s ❝❛♥ ❜❡ ❡①♣❧❛✐♥❡❞ ❜② t❤❡ ❢❛❝t t❤❛t t❤❡s❡ t❡①t✉r❡s ❝❛♥ tr❛♥s✐t✐♦♥ ❢r♦♠ ❛ ♠❡t❛st❛❜❧❡ ❲❡♥③❡❧ st❛t❡ t♦ ❛ st❛❜❧❡ ❈❛ss✐❡ st❛t❡ ✐❢ t❤❡② s❛t✐s❢② ❊q✉❛t✐♦♥ ✻ ✇✐t❤ θwrec = θwy ✱ t❤❡ ❨♦✉♥❣ ❝♦♥t❛❝t ❛♥❣❧❡ ❢♦r ❚❡✢♦♥✳ ❚❤✐s ❝✉r✈❡ ✇♦✉❧❞ ❧✐❡ ✐♥ ❜❡t✇❡❡♥ t❤❡ t❤❡♦r❡t✐❝❛❧ ❝✉r✈❡s ❢♦r θwadv ❛♥❞ θwrec s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ✹✱ ❛♥❞ ❞❡✜♥❡ t❤❡ ❜✐✲st❛❜❧❡ r❡❣✐♦♥ ✇❤❡r❡ t❤❡ ❲❡♥③❡❧ st❛t❡ ✐s ♠❡t❛st❛❜❧❡✳ ✷✻ ■♥ ✉♥❞❡r✇❛t❡r ❲❡♥③❡❧✲t♦✲❈❛ss✐❡ tr❛♥s✐t✐♦♥s✱ t❤❡ ❡♥❡r❣② ❜❛rr✐❡r ❜❡t✇❡❡♥ t❤❡ ❈❛ss✐❡ ❛♥❞ ❲❡♥③❡❧ st❛t❡s ✐♥ t❤❡ ❜✐st❛❜❧❡ r❡❣✐♦♥ ❝❛♥ ❜❡ ♦✈❡r❝♦♠❡ ❜② t❤❡ ❣❛s ♦✈❡r✲♣r❡ss✉r❡ ✐♥ t❤❡ ♣❧❛str♦♥ ❞✉❡ t♦ ❝♦♥t✐♥✉♦✉s ❣❡♥❡r❛t✐♦♥ ♦❢ ❣❛s✳ ❲❡ ❜❡❧✐❡✈❡ t❤❛t t❤✐s t❤❡r♠♦❞②♥❛♠✐❝ ❝♦♥❞✐t✐♦♥ ❞❡r✐✈❡❞ ❛ss✉♠✐♥❣ ❛ s✐♠♣❧❡ ♣❛tt❡r♥❡❞ t❡①t✉r❡ ✐s ❛ ♥❡❝❡ss❛r② ❜✉t ♥♦t ❛ s✉✣❝✐❡♥t ❝♦♥❞✐t✐♦♥ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❲❤✐❧❡ t❤✐s ❝♦♥❞✐t✐♦♥ ✐s ❛♥ ✐♠♣♦rt❛♥t ❣❧♦❜❛❧ ❢❛❝t♦r✱ t❤❡r❡ ❛r❡ ✈❛r✐♦✉s ♦t❤❡r ❧♦❝❛❧ ❢❛❝t♦rs ✇❤✐❝❤ ❝❛♥ ❛❧s♦ ✐♥✢✉❡♥❝❡ t❤❡ ❞②♥❛♠✐❝s ♦❢ ♣❧❛str♦♥ s♣r❡❛❞✐♥❣ s✉❝❤ ❛s t❤❡ ♣✐❧❧❛r ❜r❡❛❦t❤r♦✉❣❤ ♣r❡ss✉r❡✱ ✷✾ ❝♦♥t❛❝t ♦❢ ❣❛s ♠❡♥✐s❝✉s ✇✐t❤ ♣✐❧❧❛rs ✐♥ t❤❡ ❞✐r❡❝t✐♦♥ ♦❢ s♣r❡❛❞✐♥❣✱ ✸✼ ❝♦♥t❛❝t ❧✐♥❡ ♣✐♥♥✐♥❣✱ ❛♥❞ t❡①t✉r❡ r❡✲❡♥tr❛♥❝❡✳ ✺✽ ■♥ ♦r❞❡r t♦ ♠❛❦❡ t❤✐s ♠❡t❤♦❞ s❝❛❧❛❜❧❡ ❢♦r ❧❛r❣❡ s❝❛❧❡ ❞r❛❣ r❡❞✉❝t✐♦♥ ❛♣♣❧✐❝❛t✐♦♥s✱ ❝❛t❛❧②t✲ ✐❝❛❧❧② ❛❝t✐✈❡ t❡①t✉r❡s ✇❡r❡ ❢❛❜r✐❝❛t❡❞ ♦♥ t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ ✉s✐♥❣ ❛♥ ✐♥❡①♣❡♥s✐✈❡ ❝❛t❛❧②st✱ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡✳ ❋❧❛t ♣♦❧✐s❤❡❞ ❛❧✉♠✐♥✉♠ ♣❧❛t❡s ✇❡r❡ ❧❛s❡r t❡①t✉r❡❞✱ ❡❧❡❝tr♦♣❧❛t❡❞ ✇✐t❤ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡✱ ❛♥❞ ❝♦♥❢♦r♠❛❧❧② ❝♦❛t❡❞ ✇✐t❤ ❛ ✢✉♦r✐♥❛t❡❞ s✐❧❛♥❡ t♦ ♦❜t❛✐♥ ❝❛t❛❧②t✐❝❛❧❧② ❛❝t✐✈❡ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡s ✭❉❡t❛✐❧s ♦❢ t❤❡ ♣r♦❝❡❞✉r❡ ❛r❡ ❡①♣❧❛✐♥❡❞ ✐♥ t❤❡ ❡①♣❡r✐♠❡♥t❛❧ s❡❝t✐♦♥✮✳ ❋✐❣✉r❡ ✸❝ s❤♦✇s ❛ ♠✐❝r♦❣r❛♣❤ ♦❢ ❛ s♦✲❝❛❧❧❡❞ ❡❣❣✲❝r❛t❡ ✺✾ ❛❧✉♠✐♥✉♠ ♠✐❝r♦t❡①t✉r❡ ❝♦❛t❡❞ ✇✐t❤ ▼♥❖2 ❛♥❞ s✐❧❛♥❡✳ ❚❤❡ ❲❡♥③❡❧ r♦✉❣❤♥❡ss ♦❢ t❤✐s t❡①t✉r❡ ✇❛s ❝❛❧❝✉❧❛t❡❞ ❢r♦♠ t❤❡ s✉r❢❛❝❡ ❛r❡❛ ♠❡❛s✉r❡❞ ✉s✐♥❣ ❛♥ ♦♣t✐❝❛❧ ♣r♦✜❧♦♠❡t❡r ❛♥❞ ❝♦rr❡s♣♦♥❞s t♦ r ❂ ✺✳✶✳ ❚❤❡ ✶✹

ACS Paragon Plus Environment

Page 14 of 35

Page 15 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

❡❧❡❝tr♦♣❧❛t❡❞ ▼♥❖2 ❞❡♣♦s✐t ❤❛s ❜♦t❤ ♠✐❝r♦s❝❛❧❡ ❛♥❞ ♥❛♥♦s❝❛❧❡ ❢❡❛t✉r❡s ❛s ❝❛♥ ❜❡ s❡❡♥ ✐♥ ❙✉♣♣❧❡♠❡♥t❛r② ❋✐❣✉r❡ ❙✸✳ ❙✐♥❝❡ t❤❡ t❡①t✉r❡ ❤❛s ❛ ❞✉❛❧ s❝❛❧❡ r♦✉❣❤♥❡ss✱ ✐t ✐s ❡①♣❡❝t❡❞ t❤❛t t❤❡ ♥❛♥♦✲❈❛ss✐❡ st❛t❡ ❝❛♥ ❜❡ s✉♣♣♦rt❡❞ ✐♥ t❤❡ ♥❛♥♦❢❡❛t✉r❡s ♦❢ t❤❡ t❡①t✉r❡ ❡✈❡♥ ❛❢t❡r ✐♠♣r❡❣✲ ♥❛t✐♦♥ ❛t t❤❡ ♠✐❝r♦✲s❝❛❧❡✳ ✸✻ ❙✉♣♣❧❡♠❡♥t❛r② ❱✐❞❡♦ ❙✷ s❤♦✇s t❤❡ ✐♥✢❛t✐♦♥ ♦❢ ♣❧❛str♦♥ ✇✐t❤✐♥ t❤❡ ❡❣❣✲❝r❛t❡ ❛❧✉♠✐♥✉♠ ♠✐❝r♦t❡①t✉r❡✳ ■♥ ♦r❞❡r t♦ ❡♥s✉r❡ ♠❛①✐♠✉♠ ✇❛t❡r ✐♠♣r❡❣♥❛t✐♦♥ ✐♥ t❤❡ t❡①t✉r❡✱ t❤❡ s❛♠♣❧❡s ✇❡r❡ ✐♠♠❡rs❡❞ ✐♥t♦ ❜♦✐❧❡❞ ❞❡✐♦♥✐s❡❞ ✇❛t❡r ✉♥❞❡r ✈❛❝✉✉♠ ❢♦r ✶✷ ❤♦✉rs ❜❡❢♦r❡ t❤❡ ✐♥tr♦❞✉❝t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✳ ❋✐❣✉r❡ ✸❞ s❤♦✇s t❤❡ ♣r♦❝❡ss ♦❢ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ s✉❝❤ ❛ t❡①t✉r❡ ❛t ❛ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ ✶✳✺ ✇t✳✪✳ ◆♦t❡ t❤❛t t❤❡ ▼♥❖2 ❝♦❛t✐♥❣ ✇❛s ♥♦t r❡♠♦✈❡❞ ❢r♦♠ t❤❡ t♦♣s ♦❢ t❤❡ ❛❧✉♠✐♥✉♠ ♣②r❛♠✐❞s ✐♥ t❤✐s ❡①♣❡r✐♠❡♥t❀ ❤♦✇❡✈❡r✱ ♣❧❛str♦♥ r❡❝♦✈❡r② ✇❛s st✐❧❧ ❢❛✈♦r❡❞ ♦✈❡r ❜❧✐st❡r ❢♦r♠❛t✐♦♥✳ ❚❤✐s ✐s ✐♥ ❛❣r❡❡♠❡♥t ✇✐t❤ ♦✉r ♣r❡✈✐♦✉s ♦❜s❡r✈❛t✐♦♥ ♦♥ s✐❧✐❝♦♥ ♣✐❧❧❛rs ✇✐t❤ ♣❧❛t✐♥✉♠✲❝♦❛t❡❞ t♦♣s✳ ■♥ ❛❧❧ ♦❢ t❤❡ ❡①♣❡r✐♠❡♥ts ❢♦r ✇❤✐❝❤ ♣❧❛str♦♥ r❡❝♦✈❡r② ✇❛s ♦❜s❡r✈❡❞✱ t❤❡ ❣❛s s♣r❡❛❞s ❧❛t❡r❛❧❧② ❛❧♦♥❣ t❤❡ t❡①t✉r❡ ✉♥t✐❧ t❤❡ ❝♦♥t❛❝t ❧✐♥❡ ❜❡❝♦♠❡s s✉✣❝✐❡♥t❧② ♣✐♥♥❡❞ t♦ ♣r❡✈❡♥t ❢✉rt❤❡r ❛❞✈❛♥❝❡♠❡♥t✳ ❲❤❡♥ t❤❡ ❝♦♥t❛❝t ❧✐♥❡ ✐s ✉♥❛❜❧❡ t♦ ❞❡✲♣✐♥ ❢✉rt❤❡r✱ t❤❡ ❣❛s ❜r❡❛❦s t❤r♦✉❣❤ t❤❡ t♦♣ ♦❢ t❤❡ ♣✐❧❧❛rs ❛♥❞ ❢♦r♠s ❛ ❤❡♠✐✇✐❝❦✐♥❣ ❜❧✐st❡r✳ ❆t t❤✐s ♣♦✐♥t t❤❡ ❣❛s ❣❡♥❡r❛t❡❞ ✇✐t❤✐♥ t❤❡ t❡①t✉r❡ ✐s ♣r❡❢❡r❡♥t✐❛❧❧② ❝❤❛♥♥❡❧❡❞ ✐♥t♦ t❤❡ ❤❡♠✐✇✐❝❦✐♥❣ ❜❧✐st❡r ✇❤✐❝❤ ❤❛s ❛ ❧♦✇ ▲❛♣❧❛❝❡ ♣r❡ss✉r❡ ❞✉❡ t♦ t❤❡ ❧❛r❣❡ r❛❞✐✉s ♦❢ ❝✉r✈❛t✉r❡ ♦❢ t❤❡ ❜❧✐st❡r✳ ❚❤✐s st♦♣s t❤❡ ❝♦♥♥❡❝t❡❞ ♣❧❛str♦♥ ❢r♦♠ s♣r❡❛❞✐♥❣ ❢✉rt❤❡r ✐♥t♦ ♦t❤❡r ✇❡tt❡❞ ♣❛rts ♦❢ t❤❡ t❡①t✉r❡✳ ❍❡♥❝❡✱ ✐t ✐s ✐♠♣♦rt❛♥t t♦ ❢❛❜r✐❝❛t❡ s✉r❢❛❝❡ t❡①t✉r❡s ✇✐t❤ ❤✐❣❤ ♣❧❛str♦♥ ❝♦♥♥❡❝t✐✈✐t② ❛♥❞ ❧♦✇ ♣✐♥♥✐♥❣ ❞❡❢❡❝ts ❢♦r ❝♦♠♣❧❡t❡ ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❚♦ ♠❡❛s✉r❡ t❤❡ ❞r❛❣ r❡❞✉❝t✐♦♥ ♣❡r❢♦r♠❛♥❝❡ ❛♥❞ s❧✐♣ r❡❝♦✈❡r② ❝❛♣❛❜✐❧✐t✐❡s ♦❢ t❤❡s❡ ♣❧❛str♦♥ ♣r♦♠♦t✐♥❣ t❡①t✉r❡s✱ ❛❧✉♠✐♥✉♠ r♦t♦rs ✇✐t❤ ❝❛t❛❧②t✐❝❛❧❧② ❛❝t✐✈❡ t❡①t✉r❡s ✇❡r❡ t❡st❡❞ ✐♥ ❛ ❚❛②❧♦r✲❈♦✉❡tt❡ ❝❡❧❧ ✉♥❞❡r t✉r❜✉❧❡♥t ✢♦✇ ❝♦♥❞✐t✐♦♥s✳ ✶✻ ❈②❧✐♥❞r✐❝❛❧ r♦t♦rs ✭Rrotor ❂ ✶✹ ♠♠✮ ✇❡r❡ t❡①t✉r❡❞ ❜② ♠❛❝❤✐♥✐♥❣ ♠✐❝r♦❣r♦♦✈❡s ♦♥t♦ t❤❡ s✉r❢❛❝❡ ✐♥ ❜♦t❤ t❤❡ ❝✐r❝✉♠❢❡r❡♥t✐❛❧ ❛♥❞ ❧♦♥❣✐t✉❞✐♥❛❧ ❞✐r❡❝t✐♦♥s t♦ ♦❜t❛✐♥ ❛ r❡❣✉❧❛r ❛rr❛② ♦❢ sq✉❛r❡ ♠✐❝r♦♣✐❧❧❛rs ♦❢ ✇✐❞t❤ ✶✵✵ µ♠✱ ❤❡✐❣❤t ✷✵✵ µ♠✱ ❛♥❞ s♣❛❝✐♥❣ ✶✵✵ µ♠ ✭r ❂ ✷✱ φs ❂ ✵✳✷✺✮✳ ❚❤❡ r♦t♦r ✇❛s t❤❡♥ ❡❧❡❝tr♦♣❧❛t❡❞ ✇✐t❤ ▼♥❖2 ❛♥❞ ❤②❞r♦♣❤♦❜✐③❡❞ ✉s✐♥❣ ❛ ✢✉♦r✐♥❛t❡❞ s✐❧❛♥❡ ✐♥ ❛ s✐♠✐❧❛r ♠❛♥♥❡r t♦ t❤❡ ✢❛t ✶✺

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

❧❛s❡r✲t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ s❛♠♣❧❡s✳ ❋✐❣✉r❡ ✺❛ s❤♦✇s ❛ ♠✐❝r♦❣r❛♣❤ ♦❢ t❤✐s t❡①t✉r❡❀ ✇❤❡r❡ t❤❡ ♠✐❝r♦✲❞❡♣♦s✐ts ♦♥ t❤❡ ♣✐❧❧❛rs ❝♦rr❡s♣♦♥❞ t♦ ▼♥❖2 ❡❧❡❝tr♦♣❧❛t❡❞ ♦♥ t❤❡ t❡①t✉r❡✱ ✇❤✐❧❡ ❋✐❣✉r❡ ✺❜ s❤♦✇s ❛ ❞r♦♣❧❡t ♦❢ ✇❛t❡r s✐tt✐♥❣ ♦♥ t❤❡ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ s✉r❢❛❝❡ ♦❢ t❤❡ t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ r♦t♦r✳ ❆❧❧ ❞r❛❣ r❡❞✉❝t✐♦♥ ❡①♣❡r✐♠❡♥ts ✇❡r❡ ♣❡r❢♦r♠❡❞ ✉♥❞❡r ❢✉❧❧② t✉r❜✉❧❡♥t ✢♦✇ ❝♦♥❞✐t✐♦♥s ✐♥ ❛ ❝✉st♦♠✲❢❛❜r✐❝❛t❡❞ ❚❛②❧♦r✲❈♦✉❡tt❡ ❈❡❧❧ ✭s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ✺❝✮ ❛t ❘❡ = ✹✼✱✵✵✵✱ ✇❤❡r❡ t❤❡ ❘❡②♥♦❧❞s ♥✉♠❜❡r ✐s ❝❛❧❝✉❧❛t❡❞ ❛s ❘❡ = Ri Ω∆R/ν ✳ ❍❡r❡ Ri ✐s t❤❡ r♦t♦r r❛❞✐✉s✱

∆R ✐s t❤❡ ❝❡❧❧ ❣❛♣✱ Ω ✐s t❤❡ ❛♥❣✉❧❛r ✈❡❧♦❝✐t② ♦❢ t❤❡ r♦t♦r ✭Rrotor ✮✱ ❛♥❞ ν ✐s t❤❡ ❦✐♥❡♠❛t✐❝ ✈✐s❝♦s✐t② ♦❢ t❤❡ ✇♦r❦✐♥❣ ✢✉✐❞✳ ❚❤❡ ♠❡❛♥ ✈❛❧✉❡ ♦❢ t❤❡ ❢r✐❝t✐♦♥❛❧ ✇❛❧❧ s❤❡❛r str❡ss ✭τw ✮ ♦♥ t❤❡ r♦t♦r ✐s ❞❡✜♥❡❞ ❛s τw = T /2πRi2 L ✇❤❡r❡ T ❛♥❞ L ❛r❡ t❤❡ ❛✈❡r❛❣❡❞ t♦rq✉❡ ❡①♣❡r✐❡♥❝❡❞ ❜② t❤❡ r♦t♦r ❛♥❞ t❤❡ ❧❡♥❣t❤ ♦❢ t❤❡ r♦t♦r r❡s♣❡❝t✐✈❡❧②✳ ❚❤❡ ♣❡r❝❡♥t❛❣❡ ❞r❛❣ r❡❞✉❝t✐♦♥ ✐s ❞❡✜♥❡❞ ❛s DR = 100 × (τ❙♠♦♦t❤ − τ❈❛ss✐❡ )/τ❙♠♦♦t❤ ✱ ✇❤❡r❡ τ❙♠♦♦t❤ ✐s t❤❡ s❤❡❛r str❡ss ♦♥ ❛♥ ✉♥t❡①t✉r❡❞ ❝②❧✐♥❞r✐❝❛❧ r♦t♦r ❛♥❞ τ❈❛ss✐❡ ✐s t❤❡ s❤❡❛r str❡ss ♦♥ t❤❡ ♣❛tt❡r♥❡❞ r♦t♦r ✇✐t❤ ❛ ❢✉❧❧② ✐♥✢❛t❡❞ ♣❧❛str♦♥✳ ◆♦t❡ t❤❛t t❤❡ s♦❧✐❞ ❢r❛❝t✐♦♥ φs ♦❢ t❤❡ ❣r♦♦✈❡❞ r♦t♦r ✐s ❤✐❣❤ ✭φs = 0.25✮ t♦ ♣r♦♠♦t❡ ♣❧❛str♦♥ r❡❣❡♥❡r❛t✐♦♥ ✭❙❡❡ ❋✐❣✉r❡ ✹✮✱ ❜✉t t❤❡ ❡①♣❡r✐♠❡♥t❛❧❧② ♠❡❛s✉r❡❞ t✉r❜✉❧❡♥t ❞r❛❣ r❡❞✉❝t✐♦♥ ✐s ♦♥❧② ❛❜♦✉t ✸✪ ❝♦♠♣❛r❡❞ t♦ ❛ s♠♦♦t❤ ✉♥t❡①t✉r❡❞ ❤②❞r♦♣❤✐❧✐❝ r♦t♦r ❛t t❤❡ s❛♠❡ ❘❡②♥♦❧❞s ♥✉♠❜❡r ♦❢ ❘❡ ❂ ✹✼✱✵✵✵✳ ❍♦✇❡✈❡r✱ t❤✐s r♦t♦r ❝❛♥ st✐❧❧ ❜❡ ✉s❡❞ t♦ ❡✈❛❧✉❛t❡ t❤❡ ❡✛❡❝t✐✈❡♥❡ss ♦❢ t❤❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ♠❡t❤♦❞ ❜② ❝♦♠♣❛r✐♥❣ t❤❡ t♦rq✉❡s ♦♥ t❤❡ r♦t♦r ✐♥ ✐ts ♦r✐❣✐♥❛❧ ♣❧❛str♦♥ ✐♥✢❛t❡❞ st❛t❡ ✭❈❛ss✐❡✮✱ ✐ts ✇❡tt❡❞ st❛t❡ ✭❲❡♥③❡❧✮ ❛♥❞ ✐ts ✜♥❛❧ r❡❝♦✈❡r❡❞ st❛t❡✳ ❚❤❡ ♣❧❛str♦♥ r❡❝♦✈❡r② t❡sts ✇❡r❡ ♣❡r❢♦r♠❡❞ ✐♥ t❤r❡❡ st❛❣❡s ❛s s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ✺❡✳ ❚❤❡ ♣❧❛str♦♥ ✐s ✐♥✐t✐❛❧❧② t❡st❡❞ ❢♦r ✐ts st❛❜✐❧✐t② ❜② r✉♥♥✐♥❣ ❛ ❧♦♥❣ t❡st ✭✹ ❤♦✉rs✮ ✉♥❞❡r ❛✐r✲s❛t✉r❛t❡❞ ✇❛t❡r ❝♦♥❞✐t✐♦♥s✳ ❚❤❡r❡ ✐s ♠✐♥✐♠❛❧ ❝❤❛♥❣❡ ✐♥ t❤❡ s❤❡❛r str❡ss✱ τ❈❛ss✐❡ ✱ ❛s t❤❡ ♣❧❛str♦♥ ✐s st❛❜❧❡ ❞✉r✐♥❣ t❤✐s t✐♠❡ ♣❡r✐♦❞✳ ❆ ✇❡tt✐♥❣ tr❛♥s✐t✐♦♥ ✇❛s t❤❡♥ ❛rt✐✜❝✐❛❧❧② ✐♥❞✉❝❡❞ ❜② ✢✉s❤✐♥❣ ❞❡✲ ❛❡r❛t❡❞ ✇❛t❡r t❤r♦✉❣❤ t❤❡ s②st❡♠ ✉♥t✐❧ t❤❡ s❤❡❛r str❡ss r✐s❡s ❛♥❞ r❡❛❝❤❡s ❛ ♥❡✇ st❡❛❞② st❛t❡ ✈❛❧✉❡ ❝♦rr❡s♣♦♥❞✐♥❣ t♦ ❛ ❢✉❧❧② ✇❡tt❡❞ ❲❡♥③❡❧ st❛t❡✱ τ❲❡♥③❡❧ ✳ ❱✐s✉❛❧ ✐♥s♣❡❝t✐♦♥ ♦❢ t❤❡ t❡①t✉r❡❞ r♦t♦r ✐♥ t❤❡ ❝❡❧❧ ❛❧s♦ s❤♦✇❡❞ ❛❧♠♦st ❝♦♠♣❧❡t❡ ❧♦ss ♦❢ t❤❡ s✐❧✈❡r② ♣❧❛str♦♥ ✜❧♠✳ ❚❤❡ r♦t♦r ✇❛s ♠❛✐♥t❛✐♥❡❞ ✐♥ t❤✐s st❛t❡ ❢♦r ❛ ❢❡✇ ♠✐♥✉t❡s ❜❡❢♦r❡ ✐♥tr♦❞✉❝✐♥❣ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✐♥t♦ ✶✻

ACS Paragon Plus Environment

Page 16 of 35

Page 17 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

t❤❡ s②st❡♠✳ ✶ ♠❧ ♦❢ ✼✳✺ ✇t✪ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✇❛s ✐♥tr♦❞✉❝❡❞ ✐♥t♦ t❤❡ ❝❡❧❧ ♦✈❡r ❛ ♣❡r✐♦❞ ♦❢ ✺ ♠✐♥s t♦ ✐♥❝r❡❛s❡ t❤❡ ❍2 ❖2 ❜✉❧❦ ❝♦♥❝❡♥tr❛t✐♦♥ ✉♣ t♦ 1.3 × 10−5 ♠♦❧ ♠❧−1 ✳ ❚❤❡ ❛✈❡r❛❣❡ s❤❡❛r str❡ss ❡①❡rt❡❞ ♦♥ t❤❡ ✐♥♥❡r r♦t♦r ✐s ♦❜s❡r✈❡❞ t♦ ❞❡❝r❡❛s❡ s❧♦✇❧② ❛♥❞ r❡❛❝❤❡s ❛ st❡❛❞② st❛t❡ ✈❛❧✉❡✱ τ❘❡❝♦✈❡r❡❞ ✱ ♦✈❡r ❛ ♣❡r✐♦❞ ♦❢ ✷✵ ♠✐♥ ❛❢t❡r ✇❤✐❝❤ ❛♥② ❛❞❞✐t✐♦♥❛❧ ♦①②❣❡♥ ♣r♦❞✉❝❡❞ ♦♥❧② ❝♦♥tr✐❜✉t❡❞ t♦ ❜❧✐st❡r ❢♦r♠❛t✐♦♥ ♦♥ t❤❡ r♦t♦r✳ ❚❤❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ♦❜s❡r✈❡❞ t♦ ❜❡ ♣❛t❝❤② ✐♥ ♠♦st ♣❛rts ❞✉❡ t♦ ♣✐♥♥✐♥❣ ❞❡❢❡❝ts ❛s ❝❛♥ ❜❡ s❡❡♥ ✐♥ ❙✉♣♣❧❡♠❡♥t❛r② ❋✐❣✉r❡ ❙✻✳ ❋✐❣✉r❡ ✺❞ s❤♦✇s ✧✉♥✇r❛♣♣❡❞✧ ✈✐❡✇s ♦❢ t❤❡ r♦t♦r ✐♥ ✐ts ❈❛ss✐❡ st❛t❡✱ ❲❡♥③❡❧ st❛t❡ ❛♥❞ ❛❢t❡r ♣❛rt✐❛❧ r❡❝♦✈❡r② ✭r❡❝♦♥str✉❝t❡❞ ❢r♦♠ ❛ s❡q✉❡♥❝❡ ♦❢ ✐♠❛❣❡s✮✳ ❆❧t❤♦✉❣❤ t❤❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ✐♠♣❡r❢❡❝t✱ t❤❡ ♣r❡s❡♥❝❡ ♦❢ t❤❡ ❛✐r ❧❛②❡r ❝♦♥tr✐❜✉t❡s t♦ ✐♠♣r♦✈✐♥❣ t❤❡ ❛✈❡r❛❣❡ ❧❡✈❡❧ ♦❢ ✇❛❧❧ s❧✐♣ ✐♥❞✉❝❡❞ ♦♥ t❤❡ r♦t♦r s✉r❢❛❝❡✳ ❚❤❡ ♣❡r❝❡♥t❛❣❡ s❧✐♣ r❡❝♦✈❡r② ✐s ❝❛❧❝✉❧❛t❡❞ ❛s SR =

100 × (τ❲❡♥③❡❧ − τ❘❡❝♦✈❡r❡❞ )/(τ❲❡♥③❡❧ − τ❈❛ss✐❡ )✱ ✇❤❡r❡ τ❲❡♥③❡❧ ✐s t❤❡ t♦rq✉❡ ♦♥ t❤❡ ❝♦♠♣❧❡t❡❧② ✇❡tt❡❞ r♦t♦r ❛♥❞ τ❘❡❝♦✈❡r❡❞ ✐s t❤❡ t♦rq✉❡ ♦♥ t❤❡ r♦t♦r ❛❢t❡r ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❚❤❡ ❛✈❡r❛❣❡ s❧✐♣ r❡❝♦✈❡r② ♣❡r❝❡♥t❛❣❡ ♦✈❡r ❢♦✉r r❡♣❡❛t❡❞ ❡①♣❡r✐♠❡♥ts ✇❛s ❢♦✉♥❞ t♦ ❜❡ ✺✶ ± ✶✹ ✪✳ ■t ❝❛♥ ❜❡ ❡st✐♠❛t❡❞ ❢r♦♠ t❤❡ r♦t♦r t❡①t✉r❡ ♣❛r❛♠❡t❡rs t❤❛t 6.1 × 10−7 ♠♦❧ ♦❢ ♦①②❣❡♥ ✐s r❡q✉✐r❡❞ ❢♦r ❡✈❡r② sq✉❛r❡ ❝❡♥t✐♠❡t❡r ♦❢ r♦t♦r s✉r❢❛❝❡ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r② t♦ ♦❝❝✉r ♦✈❡r t❤❡ ❝♦♠♣❧❡t❡ s✉r❢❛❝❡ ❛r❡❛ ♦❢ t❤❡ r♦t♦r ❛ss✉♠✐♥❣ ♥❡❛r ❛t♠♦s♣❤❡r✐❝ ♣r❡ss✉r❡ ❝♦♥❞✐t✐♦♥s ❛♥❞ ❛ t❡①t✉r❡ ❞❡♣t❤ ♦❢ ❍ ❂ ✷✵✵ µ♠✳ ❍♦✇❡✈❡r✱ s✐♥❝❡ ❛❧❧ t❤❡ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✐♥❥❡❝t❡❞ ❞♦❡s ♥♦t ❝♦♠❡ ✐♥t♦ ❝♦♥t❛❝t ✇✐t❤ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛♥❞ t❤✉s ❞♦❡s ♥♦t ❝♦♥tr✐❜✉t❡ t♦ ♣❧❛str♦♥ r❡❝♦✈❡r②✱ ✐t ✐s ♥❡❝❡ss❛r② t♦ ✐♥❥❡❝t ❛♥ ❛♠♦✉♥t ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✱ n✐♥❥❡❝t❡❞ ❍2 ❖2 ✱ ❤✐❣❤❡r t❤❛♥ t❤❡ r❡q✉✐r❡❞ st♦✐❝❤✐♦♠❡tr✐❝ q✉❛♥t✐t②✱ n✉t✐❧✐③❡❞ ❍2 ❖2 ✱ ✐♥ ♦r❞❡r t♦ ❛❝❤✐❡✈❡ ❛ s✐❣♥✐✜❝❛♥t r❛t❡ ♦❢ ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❚❤❡ ♠❛①✐♠✉♠ ❡✣❝✐❡♥❝② ♦❢ ❝❤❡♠✐❝❛❧ r❡❣❡♥❡r❛t✐♦♥ ♦❢ ♣❧❛str♦♥ ❝❛♥ ❜❡ ❝❛❧❝✉❧❛t❡❞ ❛s ✐♥❥❡❝t❡❞ ηmax = n✉t✐❧✐③❡❞ ❍2 ❖2 /n❍2 ❖2 ✱ ❛♥❞ ✐t ✇❛s ❢♦✉♥❞ t♦ ❜❡ ✶✳✶✪ ✐♥ t❤❡ ❝✉rr❡♥t ❝♦♥✜❣✉r❛t✐♦♥✳ ❙✐♥❝❡ t❤❡

♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ♣❛rt✐❛❧✱ t❤✐s ❡✣❝✐❡♥❝② ♠✉st ❛❧s♦ ❜❡ ♠✉❧t✐♣❧✐❡❞ ❜② t❤❡ ♣❡r❝❡♥t❛❣❡ ❛r❡❛ r❡❝♦✈❡r❡❞ t♦ ❣❡t t❤❡ ❡✛❡❝t✐✈❡ ❡✣❝✐❡♥❝②✳ ❋♦r ❡①❛♠♣❧❡✱ ✐♥ ❋✐❣✉r❡ ✺❞✱ t❤❡ ♣❡r❝❡♥t❛❣❡ ♦❢ t❤❡ ✇❡tt❡❞ ❛r❡❛ ♦✈❡r ✇❤✐❝❤ ♣❧❛str♦♥ r❡❝♦✈❡r② ✐s ♦❜s❡r✈❡❞ ✐s ♦♥❧② ❡st✐♠❛t❡❞ t♦ ❜❡ ✺✽✪✱ ❛♥❞ ❤❡♥❝❡ t❤❡ ❡✣❝✐❡♥❝② η ❂ ✵✳✻✪✳ ❚❤❡ ♣❧❛str♦♥ r❡❝♦✈❡r② ❝♦✈❡r❛❣❡ ❝♦✉❧❞ ❜❡ ✐♥❝r❡❛s❡❞ ❜② ✐♥❝♦r♣♦r❛t✐♥❣ ❛ ❞✉❛❧✲s❝❛❧❡❞ t❡①t✉r❡ ❧✐❦❡ t❤❛t ✐♥ t❤❡ ❧❛s❡r t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ s✉❜str❛t❡s✱ ✇❤✐❝❤ ❛❧❧♦✇s ❢♦r t❤❡ ✶✽

ACS Paragon Plus Environment

Page 18 of 35

Page 19 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

❣❛s t♦ s♣r❡❛❞ ♠♦r❡ ❡❛s✐❧② t❤r♦✉❣❤ t❤❡ ♥❛♥♦t❡①t✉r❡ ✇✐t❤♦✉t ♣✐♥♥✐♥❣✱ t❤✉s r❡❞✉❝✐♥❣ ❝♦♥t❛❝t ❛♥❣❧❡ ❤②st❡r❡s✐s✳ ❚❤❡ ♠❛ss tr❛♥s❢❡r ❡✣❝✐❡♥❝② ❝♦✉❧❞ ❜❡ ❛❧s♦ ♣♦t❡♥t✐❛❧❧② ✐♠♣r♦✈❡❞ ❜② ✐♥❥❡❝t✐♥❣ t❤❡ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ❞✐r❡❝t❧② ✐♥t♦ t❤❡ ❜♦✉♥❞❛r② ❧❛②❡r ❢r♦♠ ✇✐t❤✐♥ ❛ ♣♦r♦✉s s✉r❢❛❝❡✳

❈♦♥❝❧✉s✐♦♥ ❲❡ ❤❛✈❡ ❞❡♠♦♥str❛t❡❞ ❛ ♥♦✈❡❧ ❝❤❡♠✐❝❛❧ ♠❡t❤♦❞ t♦ r❡♣❧❡♥✐s❤ ❛ s✉r❢❛❝❡ ❛✐r ❧❛②❡r ♦r ♣❧❛str♦♥ ✐♥✲s✐t✉ ♦♥ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡s t❤❛t ❛r❡ ❢✉❧❧② ✐♠♠❡rs❡❞ ✉♥❞❡r✇❛t❡r ✉s✐♥❣ ❝❛t❛❧②t✐❝ ❞❡✲ ❝♦♠♣♦s✐t✐♦♥ ♦❢ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✳ ❲❡ ❛❧s♦ s❤♦✇❡❞ t❤❛t ♣❧❛str♦♥ s♣r❡❛❞✐♥❣ ✐s ♣♦ss✐❜❧❡ ♦♥ ♠✐❝r♦t❡①t✉r❡s ✇✐t❤♦✉t ❛ ♥❛♥♦✲❈❛ss✐❡ st❛t❡ ❜② ♣❡r❢♦r♠✐♥❣ ❡①♣❡r✐♠❡♥ts ♦♥ s✐❧✐❝♦♥ ♠✐❝r♦t❡①✲ t✉r❡s ✇✐t❤ ♣❧❛t✐♥✉♠ ❝❛t❛❧②st ✇✐t❤♦✉t ❛ s❡❝♦♥❞ ❧❡✈❡❧ ♦❢ ♥❛♥♦✲t❡①t✉r❡✳ ❖✉r t❤❡r♠♦❞②♥❛♠✐❝ ❢r❛♠❡✇♦r❦ ❢♦r ♣r❡❞✐❝t✐♥❣ r❡❝♦✈❡r② ♦♥ ❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡s ❝❛♥ ❜❡ ✉s❡❞ t♦ ❞❡s✐❣♥ t❡①t✉r❡s ✇✐t❤ ♦♣t✐♠❛❧ r♦✉❣❤♥❡ss ❛♥❞ s✉r❢❛❝❡ ❝❤❡♠✐str② ❢✉♥❝t✐♦♥❛❧✐③❛t✐♦♥ ❢♦r ♣❧❛str♦♥ r❡❝♦✈❡r②✳ ❲❡ ❛❧s♦ ❞❡♠♦♥str❛t❡ t❤❡ s❝❛❧❛❜✐❧✐t② ♦❢ t❤✐s ♠❡t❤♦❞ ❜② ❢❛❜r✐❝❛t✐♥❣ ❛ s✉✐t❛❜❧❡ ✬❡❣❣ ❝r❛t❡✬ str✉❝✲ t✉r❡ ♦♥ ❧❛s❡r✲t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ s✉r❢❛❝❡s ✇✐t❤ ❛♥ ✐♥❡①♣❡♥s✐✈❡ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡ ❝❛t❛❧②st ❛♥❞ ❞❡♠♦♥str❛t✐♥❣ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ t❤✐s s✉r❢❛❝❡✳ ❋✐♥❛❧❧② ✇❡ ❤❛✈❡ ♣❡r❢♦r♠❡❞ ✢✉✐❞ ❢r✐❝✲ t✐♦♥❛❧ ❞r❛❣ ♠❡❛s✉r❡♠❡♥ts ♦♥ ❛ ♠✐❝r♦t❡①t✉r❡❞ ❛❧✉♠✐♥✉♠ r♦t♦r ❧♦❛❞❡❞ ✇✐t❤ ▼♥❖2 ❝❛t❛❧②st✳ ❙❦✐♥ ❢r✐❝t✐♦♥ ♠❡❛s✉r❡♠❡♥ts ✐♥ ❛ t✉r❜✉❧❡♥t ❚❛②❧♦r✲❈♦✉❡tt❡ ✢♦✇ s❤♦✇❡❞ t❤❛t ✐t ✐s ♣♦ss✐❜❧❡ t♦ ♦❜t❛✐♥ ❛♥ ❛✈❡r❛❣❡ s❧✐♣ r❡❝♦✈❡r② ♦❢ ✺✶ ± ✶✹✪ ❢r♦♠ t❤❡ t❡①t✉r❡✬s ❢✉❧❧② ✇❡tt❡❞ st❛t❡ ✇❤❡♥ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✇❛s ❛❞❞❡❞ t♦ t❤❡ s②st❡♠✳ ❲❡ ❛♥t✐❝✐♣❛t❡ t❤❛t t❤❡s❡ ❝❛t❛❧②t✐❝❛❧❧②✲❛❝t✐✈❡ ❞r❛❣✲r❡❞✉❝✐♥❣ s✉r❢❛❝❡ ♠✐❝r♦t❡①t✉r❡s ❝❛♥ ❜❡ s❝❛❧❡❞✲✉♣ ❢✉rt❤❡r ❛♥❞ ✐♠♣❧❡♠❡♥t❡❞ ✐♥ t❤❡ ♠❛r✐♥❡ ❡♥✈✐r♦♥❡♠♥t t♦ ❡①t❡♥❞ t❤❡ st❛❜❧❡ ❧✐❢❡t✐♠❡s ♦❢ ❢r✐❝t✐♦♥❛❧ ❞r❛❣ r❡❞✉❝t✐♦♥ ❛♥❞ ❛♥t✐✲❝♦rr♦s✐♦♥✳

✶✾

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

❊①♣❡r✐♠❡♥t❛❧ ▼❡t❤♦❞s ❋❛❜r✐❝❛t✐♦♥ ♦❢ ❙✐❧✐❝♦♥ ▼✐❝r♦♣✐❧❧❛rs ✇✐t❤ ❈❛t❛❧②st✲❢r❡❡ ❚♦♣s

❲❡ ❢❛❜r✐❝❛t❡❞ ♠✐❝r♦t❡①t✉r❡s ✇✐t❤ s❡❧❡❝t✐✈❡ ❝❛t❛❧②st ❝♦✈❡r❛❣❡ ♦♥ s✐❧✐❝♦♥ ✇❛❢❡rs ✉s✐♥❣ ✐♠❛❣❡ r❡✈❡rs❛❧ ♣❤♦t♦❧✐t❤♦❣r❛♣❤②✱ r❡❛❝t✐✈❡ ✐♦♥ ❡t❝❤✐♥❣ ✭❘■❊✮✱ ❡✲❜❡❛♠ ❡✈❛♣♦r❛t✐♦♥ ♦❢ ❝❛t❛❧②st ♦♥t♦ t❤❡ ♣✐❧❧❛rs✱ ❛♥❞ s✉❜s❡q✉❡♥t ❧✐❢t✲♦✛ ♦❢ t❤❡ ❝❛t❛❧②st ❢r♦♠ t❤❡ t♦♣s ♦❢ t❤❡ ♠✐❝r♦♣✐❧❧❛rs✳ ✻✧ ❙✐❧✐❝♦♥ ✇❛❢❡rs ✭❯♥✐✈❡rs✐t② ✇❛❢❡rs✮ ✇❡r❡ ✜rst ❝♦❛t❡❞ ✇✐t❤ t❤❡ ✐♠❛❣❡ r❡✈❡rs❛❧ ♣❤♦t♦r❡s✐st✱ ❆❩✺✷✶✹✱ ❛♥❞ ❛♥ ❛rr❛② ♦❢ ❝✐r❝✉❧❛r ♣✐❧❧❛rs ♦❢ ♣❤♦t♦r❡s✐st ✇❛s ❝r❡❛t❡❞ ♦♥ t❤❡ ✇❛❢❡r ❜② ✉s✐♥❣ ✐♠❛❣❡ r❡✈❡rs❛❧ ♣❤♦t♦❧✐t❤♦❣r❛♣❤②✳ ❘■❊ ✭❙❚❙ P❡❣❛s✉s✮ ✇❛s t❤❡♥ ✉s❡❞ t♦ ❡t❝❤ t❤❡ ❡①♣♦s❡❞ ❙✐ ✐♥ t❤❡ ♣❤♦t♦r❡s✐st ♠❛s❦ t♦ ❝r❡❛t❡ ♠✐❝r♦♣✐❧❧❛rs ✐♥ t❤❡ s✐❧✐❝♦♥✳ ❚❤❡ ❞❡♣t❤ ♦❢ t❤❡ ♣✐❧❧❛rs ✇❛s ❝♦♥tr♦❧❧❡❞ ❜② ❛❞❥✉st✐♥❣ t❤❡ ❘■❊ ♣r♦❝❡ss t✐♠❡✳ P❧❛t✐♥✉♠ ✇❛s ✉♥✐❢♦r♠❧② ❞❡♣♦s✐t❡❞ ♦♥t♦ t❤❡ ♣✐❧❧❛rs ✉s✐♥❣ ❡✲❜❡❛♠ ❡✈❛♣♦r❛t✐♦♥ ✭t❤✐❝❦♥❡ss ❂ ✷✵ ♥♠✮✳ ❚❤❡ ❝❛t❛❧②st ♦♥ t❤❡ t♦♣s ♦❢ t❤❡ ♠✐❝r♦♣✐❧❧❛rs ✇❛s s✉❜s❡q✉❡♥t❧② r❡♠♦✈❡❞ ✉s✐♥❣ ❛ ❧✐❢t✲♦✛ ♣r♦❝❡❞✉r❡✳ ❚❤❡s❡ ♣✐❧❧❛rs ✇❡r❡ t❤❡♥ s♣✐♥✲❝♦❛t❡❞ ✇✐t❤ ❚❡✢♦♥ ❆❋ s♦❧✉t✐♦♥ ✭✶ ✇t✳✪✱ ❈❤❡♠♦✉rs✮ ❛t ✸✵✵✵ r♣♠ t♦ r❡♥❞❡r t❤❡ s✉r❢❛❝❡ ❝❤❡♠✐str② ♦❢ t❤❡ ♠✐❝r♦t❡①t✉r❡ ❛rr❛② ❤②❞r♦♣❤♦❜✐❝✳ ❋✐❣✉r❡ ✸❛ s❤♦✇s ❛ ♠✐❝r♦❣r❛♣❤ ♦❢ ❛ ❙✐✲Pt✲❚❡✢♦♥ t❡①t✉r❡ ✇✐t❤ ✶✺✵ µ♠ ❞❡♣t❤✱ ❛♥❞ Pt✲❧❡ss t♦♣s✳ ❚❤❡ ❧✐❢t✲♦✛ st❡♣ ✇❛s ♦♠✐tt❡❞ ❢♦r t❡st✐♥❣ t❤❡ s❛♠♣❧❡s ✐♥ ✇❤✐❝❤ t❤❡ ❝❛t❛❧②st ✇❛s r❡t❛✐♥❡❞ ♦♥ t❤❡ t♦♣s ♦❢ t❤❡ ♣✐❧❧❛rs ❛♥❞ t❤❡s❡ ❛r❡ s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ❙✷✳ ❚❤❡ ❞✐♠❡♥s✐♦♥s ♦❢ t❤❡s❡ ♣✐❧❧❛rs ❛r❡ ❣✐✈❡♥ ✐♥ ❚❛❜❧❡ ❙✶ ✐♥ t❤❡ s✉♣♣❧❡♠❡♥t❛r② ♠❛t❡r✐❛❧✳ ❙♠♦♦t❤✲ ✇❛❧❧❡❞ ♠✐❝r♦♣✐❧❧❛r ❛rr❛②s ✇❡r❡ ❢❛❜r✐❝❛t❡❞ ✉s✐♥❣ ♣❤♦t♦❧✐t❤♦❣r❛♣❤② ✇✐t❤ ❙❯✽ ♣❤♦t♦r❡s✐st ♦♥ Pt✲❝♦❛t❡❞ ❙✐ ✇❛❢❡rs✳

❋❛❜r✐❝❛t✐♦♥ ♦❢ ❛❧✉♠✐♥✉♠ ▼✐❝r♦♣✐❧❧❛rs ✇✐t❤ ❈❛t❛❧②st ❈♦❛t✐♥❣

❲❡ ❢❛❜r✐❝❛t❡❞ ❝❛t❛❧②st✲✐♠♣r❡❣♥❛t❡❞ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❛❧✉♠✐♥✉♠ ♠✐❝r♦t❡①t✉r❡s ❜② ✉s✐♥❣ ❧❛s❡r t❡①t✉r✐♥❣✱ ❡❧❡❝tr♦♣❧❛t✐♥❣ ❛♥❞ s✐❧❛♥✐③❛t✐♦♥✳ ❆♥ ❡❣❣✲❝r❛t❡ ♠✐❝r♦t❡①t✉r❡ ✭r ❂ ✺✳✶✮ ✇❛s ♣❛tt❡r♥❡❞ ♦♥t♦ ✢❛t s❤❡❡ts ♦❢ ❛❧✉♠✐♥✉♠ ✭❆❧ ✻✵✻✶✲❚✻✮ ❜② s❝r✐❜✐♥❣ ❡q✉❛❧❧② s♣❛❝❡❞ ❧✐♥❡s ✭♣✐t❝❤ ❂ ✼✺ µ♠✮ ✐♥ t❤❡ ❤♦r✐③♦♥t❛❧ ❛♥❞ ✈❡rt✐❝❛❧ ❞✐r❡❝t✐♦♥s ✉s✐♥❣ ❛ ❧❛s❡r s❝r✐❜❡r ✭❊❧❡❝tr♦① ❙❝r✐❜❛ ❊✲❇♦①✱ ✷✵✵ ♠♠✴s✱ ✷✵ r❡♣❡t✐t✐♦♥s✮✳ ❚❤✐s s✉r❢❛❝❡ ✇❛s t❤❡♥ ❞✐♣♣❡❞ ✐♥t♦ ✺ ✇t✪ s♦❞✐✉♠ ❤②✲ ✷✵

ACS Paragon Plus Environment

Page 20 of 35

Page 21 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

❞r♦①✐❞❡ ❢♦r ✹✺ s t♦ r❡♠♦✈❡ ❛♥② ♦r❣❛♥✐❝ ❝♦♥t❛♠✐♥❛♥ts✳ ❚❤❡ s✉❜str❛t❡ ✇❛s t❤❡♥ ❡❧❡❝tr♦♣❧❛t❡❞ ✇✐t❤ ♠❛♥❣❛♥❡s❡ ❞✐♦①✐❞❡ ❜② ✉s✐♥❣ ❛♥♦❞✐❝ ❡❧❡❝tr♦❧②t✐❝ ❞❡♣♦s✐t✐♦♥✳ ✻✵ ❚❤❡ s✉❜str❛t❡ ❛♥❞ ❝♦✉♥t❡r ❡❧❡❝tr♦❞❡ ✭❛ ✢❛t ❆❧ ♣❧❛t❡ ❝❧❡❛♥❡❞ ✉s✐♥❣ t❤❡ s♦❞✐✉♠ ❤②❞r♦①✐❞❡ ♣r♦t♦❝♦❧ ❞❡s❝r✐❜❡❞ ❡❛r❧✐❡r✮ ✇❡r❡ ❞✐♣♣❡❞ ✐♥t♦ ✶✵✵ ♠❧ ♦❢ ✵✳✵✺ ▼ ♠❛♥❣❛♥❡s❡ ❛❝❡t❛t❡ s♦❧✉t✐♦♥ ✇✐t❤ ❛ ❣❛♣ ♦❢ ✷✵ ♠♠ ❜❡t✇❡❡♥ t❤❡♠✳ ❚❤❡ s♦❧✉t✐♦♥ ✇❛s ♠❛✐♥t❛✐♥❡❞ ❛t ✻✵ ◦ ❈ ❛♥❞ st✐rr❡❞ ✉s✐♥❣ ❛ st✐r ❜❛r ❛t ✻✵ r♣♠✳ ❊❧❡❝tr♦❧②t✐❝ ❞❡♣♦s✐t✐♦♥ ✇❛s ♣❡r❢♦r♠❡❞ ❛t ✺ ♠❆✴❝♠2 ❢♦r ✺ ♠✐♥✱ ❛♥❞ t❤❡♥ t❤❡ ❡❧❡❝tr♦❞❡s ✇❡r❡ ✐♠♠❡❞✐❛t❡❧② r❡♠♦✈❡❞ ❢r♦♠ t❤❡ s♦❧✉t✐♦♥ ❛♥❞ ❞r✐❡❞ ❛t ✶✵✵ ◦ ❈ ✐♥ ❛✐r✳ ❋r❡s❤ s♦❧✉t✐♦♥s ♦❢ ▼♥✭❈❍3 ❈❖❖✮2 ✇❡r❡ ✉s❡❞ ❢♦r ❡✈❡r② ♥❡✇ ❞❡♣♦s✐t✐♦♥✳ ❋✐❣✉r❡ ❙✸ s❤♦✇s ▼♥❖2 ❡❧❡❝tr♦❞❡♣♦s✐t❡❞ ♦♥ ❛ ✢❛t ❆❧ s✉❜str❛t❡ ✉♥❞❡r s✐♠✐❧❛r ❞❡♣♦s✐t✐♦♥ ❝♦♥❞✐t✐♦♥s ✭❝❛t❛❧②st ❧♦❛❞✐♥❣ ≃ ✺ ♠❣ ❝♠−2 ✮✳ ❚❤❡ ❡❧❡❝✲ tr♦♣❧❛t❡❞ s✉❜str❛t❡s ✇❡r❡ t❤❡♥ ❝❧❡❛♥❡❞ ✉s✐♥❣ ❛ ♣❧❛s♠❛ ❝❧❡❛♥❡r ✭❍❛rr✐❝❦✮ ❢♦r ✺ ♠✐♥s ❛♥❞ ♣❧❛❝❡❞ ✐♥t♦ ❛ ❣❧❛ss ❜❡❛❦❡r ❢♦r s✐❧❛♥❡ ❝❤❡♠✐❝❛❧ ✈❛♣♦r ❞❡♣♦s✐t✐♦♥✳ ❆♥ ♦♣❡♥ ✈✐❛❧ ✇✐t❤ ✸ ♠❧ ♦❢ ❛ ✢✉♦r✐♥❛t❡❞ s✐❧❛♥❡ ✭❚r✐❝❤❧♦r♦✭✶❍✱✶❍✱✷❍✱✷❍✲♣❡r✢✉♦r♦♦❝t②❧✮s✐❧❛♥❡✮ ✇❛s ♣❧❛❝❡❞ ✐♥t♦ t❤❡ ❣❧❛ss ❜❡❛❦❡r ❛❧♦♥❣ ✇✐t❤ t❤❡ ♦t❤❡r s✉❜str❛t❡s✳ ❚❤❡ ❜❡❛❦❡r ✇❛s t❤❡♥ ❝♦✈❡r❡❞ ✇✐t❤ ❛♥ ❛❧✉♠✐♥✉♠ ❢♦✐❧ ❛♥❞ ♣❧❛❝❡❞ ♦♥ ❛ ❤♦t♣❧❛t❡ ❛t ✶✷✵ ◦ ❈ ❢♦r ✸ ❤♦✉rs✳ ❚❤❡ s✉❜str❛t❡s ✇❡r❡ t❤❡♥ r✐♥s❡❞ ✇✐t❤ ✐s♦♣r♦♣❛♥♦❧ t♦ r❡♠♦✈❡ ❡①❝❡ss s✐❧❛♥❡ ❛♥❞ ❞r✐❡❞ ✐♥ ❛✐r✱ t♦ ♦❜t❛✐♥ ❛ s✉♣❡r❤②❞r♦♣❤♦❜✐❝ t❡①t✉r❡ ✇✐t❤ ✭θadv = 162◦ ± 3◦ , θrec = 148◦ ± 4◦ ✮

■♠❛❣✐♥❣ ♦❢ ♣❧❛str♦♥ r❡❝♦✈❡r②

❚❤❡ s✉❜str❛t❡s ✇❡r❡ ✐♠♠❡rs❡❞ ✐♥t♦ ❛ q✉❛rt③ ❝❡❧❧ ✭✷✧▲ × ✶✧❲ × ✷✧❍✱ r❛♠é✲❤❛rt✮ ❝♦♥t❛✐♥✐♥❣ ✸✵ ♠❧ ♦❢ ❞❡✲✐♦♥✐③❡❞ ✭❉■✮ ✇❛t❡r ❛♥❞ s✉♣♣♦rt❡❞ ❛t ❛♣♣r♦①✐♠❛t❡❧② ✹✺◦ t♦ t❤❡ ❤♦r✐③♦♥t❛❧ ♣❧❛♥❡✳ ❆ ♠✐❝r♦s❝♦♣❡ ✭❩❊■❙❙ ❆①✐♦ ❩♦♦♠✳❱✶✻✮ ✇❛s ✉s❡❞ t♦ ♦❜s❡r✈❡ t❤❡ ♣❧❛str♦♥ ❛t ❤✐❣❤ ♠❛❣♥✐✜❝❛t✐♦♥✳ ❆ s♣♦t ❧✐❣❤t s♦✉r❝❡ ✭❉♦❧❛♥✲❏❡♥♥❡r ▼■✲✶✺✵✮ ✇❛s ✉s❡❞ t♦ ✐❧❧✉♠✐♥❛t❡ t❤❡ ♣❧❛str♦♥ ❛t ❛♥ ❛♥❣❧❡ ❣r❡❛t❡r t❤❛♥ t❤❡ ❝r✐t✐❝❛❧ ❛♥❣❧❡ ❢♦r t♦t❛❧ ✐♥t❡r♥❛❧ r❡✢❡❝t✐♦♥ ✭θc = 48.75◦ ✮ t♦ ✈✐s✉❛❧✐③❡ t❤❡ ❛✐r✲ ✇❛t❡r ✐♥t❡r❢❛❝❡ ❛s s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ❙✶✳ ❚❤❡ ♣❧❛str♦♥ t❤❛t ✐s ✐♥✐t✐❛❧❧② ♣r❡s❡♥t ♦♥ t❤❡ s✉❜str❛t❡ ❛❢t❡r ✐♠♠❡rs✐♦♥ ✐♥t♦ ❉■ ✇❛t❡r ✇❛s r❡♠♦✈❡❞ ❢r♦♠ t❤❡ s✉❜str❛t❡s ❜② ❛♣♣❧②✐♥❣ s✉❝t✐♦♥✴♣r❡ss✉r❡ ❛t t❤❡ s✉r❢❛❝❡ ✉s✐♥❣ ❛ ♣✐♣❡tt❡✳ ❚♦ tr✐❣❣❡r ♣❧❛str♦♥ r❡❝♦✈❡r②✱ ✶✲✸ ♠❧ ♦❢ ✸✵ ✇t✳✪ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✭✐♥❤✐❜✐t❡❞ ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡✱ ❙✐❣♠❛ ❆❧❞r✐❝❤✮ ✇❛s ❣❡♥t❧② ❛❞❞❡❞ t♦ t❤❡ ✇❛t❡r ❛♥❞ ✷✶

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

❛❧❧♦✇❡❞ t♦ ❞✐✛✉s❡ t♦ t❤❡ s✉r❢❛❝❡✳ ❱✐❞❡♦s ✇❡r❡ t❤❡♥ r❡❝♦r❞❡❞ ✉s✐♥❣ ❛ ❈❈❉ ❝❛♠❡r❛ ❛t ✷✹ ❢♣s✳

❉r❛❣ ❘❡❞✉❝t✐♦♥ ❊①♣❡r✐♠❡♥ts

❉r❛❣ r❡❞✉❝t✐♦♥ ❡①♣❡r✐♠❡♥ts ✇❡r❡ ♣❡r❢♦r♠❡❞ ♦♥ ❛ ❝♦♥tr♦❧❧❡❞ str❡ss r❤❡♦♠❡t❡r ✭❚❆ ■♥str✉✲ ♠❡♥ts ❆❘✲●✷✮ ✉s✐♥❣ ❛ ❜❡s♣♦❦❡ ❚❛②❧♦r✲❈♦✉tt❡ ❝❡❧❧ ✇✐t❤ r♦t♦r r❛❞✐✉s ✶✹ ♠♠✱ ❝❡❧❧ ❣❛♣ ✷✵ ♠♠ ❛♥❞ r♦t♦r ❧❡♥❣t❤ ✹✷ ♠♠✱ ✶✻ ❛♥❞ ❛ ✢✉✐❞ ✐♥❧❡t ♣♦rt t♦ ✐♥❥❡❝t ❤②❞r♦❣❡♥ ♣❡r♦①✐❞❡ ✐♥t♦ t❤❡ ❝❡❧❧ ❞✉r✐♥❣ t❤❡ ❡①♣❡r✐♠❡♥t ❛s s❤♦✇♥ ✐♥ ❋✐❣✉r❡ ✺❝✳ ■♥ t❤✐s ❚❛②❧♦r✲❈♦✉tt❡ ❝❡❧❧✱ tr❛♥s✐t✐♦♥ t♦ ❢✉❧❧② t✉r❜✉❧❡♥t ✢♦✇ ♦❝❝✉rs ❛t ❘❡ > ✶✵✱✵✵✵✳ ▼✐❝r♦❣r♦♦✈❡s ✇❡r❡ ♠❛❝❤✐♥❡❞ ♦♥t♦ t❤❡ r♦t♦r ✭❆❧ ✻✵✻✶✲❚✻✮ ✉s✐♥❣ ❛ ❈◆❈ ❧❛t❤❡ ✭❇✉r❧✐♥❣t♦♥ ▼❛❝❤✐♥❡✱ ❲✐❧♠✐♥❣t♦♥✱ ▼❆✮✳ ❚❤❡ r♦t♦r ✇❛s t❤❡♥ ❡❧❡❝tr♦♣❧❛t❡❞ ✐♥ ♠❛♥❣❛♥❡s❡ ❛❝❡t❛t❡ s♦❧✉t✐♦♥ ✭✵✳✵✺ ▼✱ ✻✵ ◦ ❈✱ st✐rr✐♥❣ ❛t ✻✵ r♣♠✮ ✇✐t❤ ❛ ❝②❧✐♥❞r✐❝❛❧ ❝♦✉♥t❡r ❡❧❡❝tr♦❞❡ ❛t ❛ ❝✉rr❡♥t ❞❡♥s✐t② ♦❢ ✺ ♠❆✴❝♠2 ❢♦r ✺ ♠✐♥✳ ■t ✇❛s t❤❡♥ ❞r✐❡❞ ❛♥❞ ♣❧❛s♠❛ ❝❧❡❛♥❡❞ ✐♥ ❛✐r ❢♦r ✺ ♠✐♥ ❜❡❢♦r❡ ❞❡♣♦s✐t✐♥❣ s✐❧❛♥❡ ✉s✐♥❣ t❤❡ s❛♠❡ ♣r♦❝❡❞✉r❡ ❛s t❤❡ ✢❛t ❛❧✉♠✐♥✉♠ ♣❧❛t❡s✳

❆❝❦♥♦✇❧❡❞❣❡♠❡♥t ❚❤❡ ❛✉t❤♦rs t❤❛♥❦ ❑❋❯P▼ ✭❑✐♥❣ ❋❛❤❞ ❯♥✐✈❡rs✐t② ♦❢ P❡tr♦❧❡✉♠ ❛♥❞ ▼✐♥❡r❛❧s✮ ❛♥❞ t❤❡ ❖✣❝❡ ♦❢ ◆❛✈❛❧ ❘❡s❡❛r❝❤ ✭❖◆❘✮ ❢♦r t❤❡✐r ✜♥❛♥❝✐❛❧ s✉♣♣♦rt✳ ❚❤❡ ❛✉t❤♦rs ❛❧s♦ t❤❛♥❦ t❤❡ st❛✛ ❛t ▼❚▲ ✭▼✐❝r♦s②st❡♠s ❚❡❝❤♥♦❧♦❣② ▲❛❜♦r❛t♦r✐❡s✱ ▼■❚✮ ❢♦r t❤❡✐r ✐♥♣✉t ✐♥ s✐❧✐❝♦♥ ♣✐❧❧❛r ❢❛❜r✐❝❛t✐♦♥✱ t❤❡ ❵P❤♦t♦✈♦❧t❛✐❝s ❘❡s❡❛r❝❤ ▲❛❜♦r❛t♦r②✬ ✭Pr♦❢✳ ❚♦♥✐♦ ❇♦✉♥❛ss✐s✐✮ ❢♦r t❤❡ ❧❛s❡r s❝r✐❜✐♥❣ ❢❛❝✐❧✐t②✱ ❛♥❞ ❉r✳ ❙✐❞❞❛rt❤ ❙r✐♥✐✈❛s❛♥ ❢♦r t❤❡ ✐♥s✐❣❤t❢✉❧ ❞✐s❝✉ss✐♦♥s✳

❙✉♣♣♦rt✐♥❣ ■♥❢♦r♠❛t✐♦♥ ❆✈❛✐❧❛❜❧❡ • ❙✉♣♣❧❡♠❡♥t❛r② ■♥❢♦r♠❛t✐♦♥ ✿ ❋✐❧❡ ❝♦♥t❛✐♥s ✜❣✉r❡s ♦♥ ♣❧❛str♦♥ ✐♠❛❣✐♥❣✱ ❡①tr❛ ♠✐❝r♦✲ ❣r❛♣❤s ♦❢ s✉r❢❛❝❡s ❛♥❞ ❛ t❛❜❧❡ ♦❢ ❞✐♠❡♥s✐♦♥s ♦❢ ❛❧❧ t❤❡ s✐❧✐❝♦♥ t❡①t✉r❡s ✉s❡❞✳

• ❱✐❞❡♦ ❙✶✿ ❱✐❞❡♦ ♦❢ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ ❛ ❙✐❧✐❝♦♥ ♣✐❧❧❛r ❛rr❛②✳ ✷✷

ACS Paragon Plus Environment

Page 22 of 35

Page 23 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

• ❱✐❞❡♦ ❙✷✿ ❱✐❞❡♦ ♦❢ ♣❧❛str♦♥ r❡❝♦✈❡r② ♦♥ ❛ ❛❧✉♠✐♥✉♠ ❧❛s❡r t❡①t✉r❡❞ s✉r❢❛❝❡✳ • ❱✐❞❡♦ ❙✸✿ ❱✐❞❡♦ ♦❢ ❛ ❞r❛❣ r❡❞✉❝t✐♦♥ ❡①♣❡r✐♠❡♥t ✐♥ t❤❡ ❚❛②❧♦r✲❈♦✉tt❡ ❝❡❧❧✱ ✇✐t❤ ❛ ❝❧✐♣ ♦❢ t❤❡ ♣❛rt✐❛❧❧② r❡❝♦✈❡r❡❞ ♣❧❛str♦♥ ✈✐s✐❜❧❡ ❛❢t❡r t❤❡ ❡①♣❡r✐♠❡♥t✳

❘❡❢❡r❡♥❝❡s ✭✶✮ ❉r❡❧✐❝❤✱ ❏✳❀ ▼❛r♠✉r✱ ❆✳ P❤②s✐❝s ❛♥❞ ❆♣♣❧✐❝❛t✐♦♥s ♦❢ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❛♥❞ ❙✉♣❡r❤②✲ ❞r♦♣❤✐❧✐❝ ❙✉r❢❛❝❡s ❛♥❞ ❈♦❛t✐♥❣s✳ ❙✉r❢❛❝❡ ■♥♥♦✈❛t✐♦♥s ✷✵✶✹✱ ✷✱ ✷✶✶✕✷✷✼✳ ✭✷✮ P❛r❦✱ ❑✳ ❈✳❀ ❈❤❤❛tr❡✱ ❙✳ ❙✳❀ ❙r✐♥✐✈❛s❛♥✱ ❙✳❀ ❈♦❤❡♥✱ ❘✳ ❊✳❀ ▼❝❑✐♥❧❡②✱ ●✳ ❍✳ ❖♣t✐♠❛❧ ❉❡s✐❣♥ ♦❢ P❡r♠❡❛❜❧❡ ❋✐❜❡r ◆❡t✇♦r❦ ❙tr✉❝t✉r❡s ❢♦r ❋♦❣ ❍❛r✈❡st✐♥❣✳ ▲❛♥❣♠✉✐r ✷✵✶✸✱ ✷✾✱ ✶✸✷✻✾✕✶✸✷✼✼✳ ✭✸✮ ❇❡♥❣❛❧✉r✉ ❙✉❜r❛♠❛♥②❛♠✱ ❙✳❀ ❑♦♥❞r❛s❤♦✈✱ ❱✳❀ ❘ü❤❡✱ ❏✳❀ ❱❛r❛♥❛s✐✱ ❑✳ ❑✳ ▲♦✇ ■❝❡ ❆❞❤❡✲ s✐♦♥ ♦♥ ◆❛♥♦✲❚❡①t✉r❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s ✉♥❞❡r ❙✉♣❡rs❛t✉r❛t❡❞ ❈♦♥❞✐t✐♦♥s✳

❆❈❙ ❆♣♣❧✐❡❞ ▼❛t❡r✐❛❧s ❛♥❞ ■♥t❡r❢❛❝❡s ✷✵✶✻✱ ✽✱ ✶✷✺✽✸✕✶✷✺✽✼✳ ✭✹✮ ❆r♥♦tt✱ ❏✳❀ ❲✉✱ ❆✳ ❍✳ ❋✳❀ ❱✉❝❦♦✱ ▼✳ ❏✳❀ ▲❛♠❜✱ ❘✳ ◆✳ ▼❛r✐♥❡ ❆♥t✐❢♦✉❧✐♥❣ ❢r♦♠ ❚❤✐♥ ❆✐r✳ ❇✐♦❢♦✉❧✐♥❣ ✷✵✶✹✱ ✸✵✱ ✶✵✹✺✕✶✵✺✹✳ ✭✺✮ ❋❡♥❣✱ ❳✳ ❏✳❀ ❏✐❛♥❣✱ ▲✳ ❉❡s✐❣♥ ❛♥❞ ❈r❡❛t✐♦♥ ♦❢ ❙✉♣❡r✇❡tt✐♥❣✴❆♥t✐✇❡tt✐♥❣ ❙✉r❢❛❝❡s✳ ❆❞✲

✈❛♥❝❡❞ ▼❛t❡r✐❛❧s ✷✵✵✻✱ ✶✽✱ ✸✵✻✸✕✸✵✼✽✳ ✭✻✮ ❇✉tt✱ ❍✳ ❏✳❀ ❙❡♠♣r❡❜♦♥✱ ❈✳❀ P❛♣❛❞♦♣♦✉❧♦s✱ P✳❀ ❱♦❧❧♠❡r✱ ❉✳❀ ❇r✐♥❦♠❛♥♥✱ ▼✳❀ ❈✐❝✲ ❝♦tt✐✱ ▼✳ ❉❡s✐❣♥ Pr✐♥❝✐♣❧❡s ❢♦r ❙✉♣❡r❛♠♣❤✐♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ❙♦❢t ▼❛tt❡r ✷✵✶✸✱ ✾✱ ✹✶✽✕ ✹✷✽✳ ✭✼✮ ❲♦♥❣✱ ❚✳ ❙✳❀ ❙✉♥✱ ❚✳❀ ❋❡♥❣✱ ▲✳❀ ❆✐③❡♥❜❡r❣✱ ❏✳ ■♥t❡r❢❛❝✐❛❧ ▼❛t❡r✐❛❧s ✇✐t❤ ❙♣❡❝✐❛❧ ❲❡tt❛✲ ❜✐❧✐t②✳ ▼❘❙ ❇✉❧❧❡t✐♥ ✷✵✶✸✱ ✸✽✱ ✸✻✻✕✸✼✶✳ ✭✽✮ ❈❛ss✐❡✱ ❆✳ ❇✳ ❉✳❀ ❇❛①t❡r✱ ❙✳ ❲❡tt❛❜✐❧✐t② ♦❢ P♦r♦✉s ❙✉r❢❛❝❡s✳ ❚r❛♥s❛❝t✐♦♥s ♦❢ t❤❡ ❋❛r❛❞❛②

❙♦❝✐❡t② ✶✾✹✹✱ ✹✵✱ ✺✹✻✕✺✺✶✳ ✷✸

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

✭✾✮ ❚✐❛♥✱ ❨✳❀ ❙✉✱ ❇✳❀ ❏✐❛♥❣✱ ▲✳ ■♥t❡r❢❛❝✐❛❧ ▼❛t❡r✐❛❧ ❙②st❡♠ ❊①❤✐❜✐t✐♥❣ ❙✉♣❡r✇❡tt❛❜✐❧✐t②✳

❆❞✈❛♥❝❡❞ ▼❛t❡r✐❛❧s ✷✵✶✹✱ ✷✻✱ ✻✽✼✷✕✻✽✾✼✳ ✭✶✵✮ ●❡♦r❣❡✱ ❏✳ ❊✳❀ ❈❤✐❞❛♥❣✐❧✱ ❙✳❀ ●❡♦r❣❡✱ ❙✳ ❉✳ ❘❡❝❡♥t Pr♦❣r❡ss ✐♥ ❋❛❜r✐❝❛t✐♥❣ ❙✉♣❡r❛❡r♦✲ ♣❤♦❜✐❝ ❛♥❞ ❙✉♣❡r❛❡r♦♣❤✐❧✐❝ ❙✉r❢❛❝❡s✳ ❆❞✈❛♥❝❡❞ ▼❛t❡r✐❛❧s ■♥t❡r❢❛❝❡s ✷✵✶✼✱ ✹✱ ✶✻✵✶✵✽✽✳ ✭✶✶✮ ❚❤♦r♣❡✱ ❲✳ ❍✳ P❧❛str♦♥ ❘❡s♣✐r❛t✐♦♥ ✐♥ ❆q✉❛t✐❝ ■♥s❡❝ts✳ ❇✐♦❧♦❣✐❝❛❧ ❘❡✈✐❡✇s ✶✾✺✵✱ ✷✺✱ ✸✹✹✕✸✾✵✳ ✭✶✷✮ ❋❧②♥♥✱ ▼✳ ❘✳❀ ❇✉s❤✱ ❏✳ ❲✳ ▼✳ ❯♥❞❡r✇❛t❡r ❇r❡❛t❤✐♥❣✿ t❤❡ ▼❡❝❤❛♥✐❝s ♦❢ P❧❛str♦♥ ❘❡s✲ ♣✐r❛t✐♦♥✳ ❏♦✉r♥❛❧ ♦❢ ❋❧✉✐❞ ▼❡❝❤❛♥✐❝s ✷✵✵✽✱ ✻✵✽✱ ✷✼✺✕✷✾✻✳ ✭✶✸✮ ❇❛rt❤❧♦tt✱ ❲✳❀ ❙❝❤✐♠♠❡❧✱ ❚✳❀ ❲✐❡rs❝❤✱ ❙✳❀ ❑♦❝❤✱ ❑✳❀ ❇r❡❞❡✱ ▼✳❀ ❇❛r❝③❡✇s❦✐✱ ▼✳❀ ❲❛❧✲ ❤❡✐♠✱ ❙✳❀ ❲❡✐s✱ ❆✳❀ ❑❛❧t❡♥♠❛✐❡r✱ ❆✳❀ ▲❡❞❡r✱ ❆✳❀ ❇♦❤♥✱ ❍✳ ❋✳ ❚❤❡ ❙❛❧✈✐♥✐❛ P❛r❛❞♦①✿ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s ✇✐t❤ ❍②❞r♦♣❤✐❧✐❝ P✐♥s ❢♦r ❆✐r ❘❡t❡♥t✐♦♥ ✉♥❞❡r ❲❛t❡r✳ ❆❞✲

✈❛♥❝❡❞ ▼❛t❡r✐❛❧s ✷✵✶✵✱ ✷✷✱ ✷✸✷✺✕✷✸✷✽✳ ✭✶✹✮ ❲❛♥❣✱ P✳❀ ◗✐✉✱ ❘✳❀ ❩❤❛♥❣✱ ❉✳❀ ▲✐♥✱ ❩✳❀ ❍♦✉✱ ❇✳ ❋❛❜r✐❝❛t❡❞ ❙✉♣❡r✲❍②❞r♦♣❤♦❜✐❝ ❋✐❧♠ ✇✐t❤ P♦t❡♥t✐♦st❛t✐❝ ❊❧❡❝tr♦❧②s✐s ▼❡t❤♦❞ ♦♥ ❈♦♣♣❡r ❢♦r ❈♦rr♦s✐♦♥ Pr♦t❡❝t✐♦♥✳ ❊❧❡❝tr♦❝❤✐♠✐❝❛

❆❝t❛ ✷✵✶✵✱ ✺✻✱ ✺✶✼✕✺✷✷✳ ✭✶✺✮ ❘♦t❤st❡✐♥✱ ❏✳ P✳ ❙❧✐♣ ♦♥ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ❆♥♥✉❛❧ ❘❡✈✐❡✇ ♦❢ ❋❧✉✐❞ ▼❡❝❤❛♥✐❝s

✷✵✶✵✱ ✹✷✱ ✽✾✕✶✵✾✳ ✭✶✻✮ ❙r✐♥✐✈❛s❛♥✱ ❙✳❀ ❑❧❡✐♥❣❛rt♥❡r✱ ❏✳ ❆✳❀ ●✐❧❜❡rt✱ ❏✳ ❇✳❀ ❈♦❤❡♥✱ ❘✳ ❊✳❀ ▼✐❧♥❡✱ ❆✳ ❏✳ ❇✳❀ ▼❝❑✐♥✲ ❧❡②✱ ●✳ ❍✳ ❙✉st❛✐♥❛❜❧❡ ❉r❛❣ ❘❡❞✉❝t✐♦♥ ✐♥ ❚✉r❜✉❧❡♥t ❚❛②❧♦r✲❈♦✉❡tt❡ ❋❧♦✇s ❜② ❉❡♣♦s✐t✐♥❣ ❙♣r❛②❛❜❧❡ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇ ▲❡tt❡rs ✷✵✶✺✱ ✶✶✹✱ ✵✶✹✺✵✶✳ ✭✶✼✮ ❇♦❜❥✐✱ ▼✳ ❙✳❀ ❑✉♠❛r✱ ❙✳ ❱✳❀ ❆st❤❛♥❛✱ ❆✳❀ ●♦✈❛r❞❤❛♥✱ ❘✳ ◆✳ ❯♥❞❡r✇❛t❡r ❙✉st❛✐♥❛❜✐❧✐t② ♦❢ t❤❡ ✧❈❛ss✐❡✧ ❙t❛t❡ ♦❢ ❲❡tt✐♥❣✳ ▲❛♥❣♠✉✐r ✷✵✵✾✱ ✷✺✱ ✶✷✶✷✵✕✶✷✶✷✻✳ ✭✶✽✮ ❙❛♠❛❤❛✱ ▼✳ ❆✳❀ ❚❛❢r❡s❤✐✱ ❍✳ ❱✳❀ ●❛❞✲❡❧ ❍❛❦✱ ▼✳ ■♥✢✉❡♥❝❡ ♦❢ ❋❧♦✇ ♦♥ ▲♦♥❣❡✈✐t② ♦❢ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❈♦❛t✐♥❣s✳ ▲❛♥❣♠✉✐r ✷✵✶✷✱ ✷✽✱ ✾✼✺✾✕✾✼✻✻✳ ✷✹

ACS Paragon Plus Environment

Page 24 of 35

Page 25 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

✭✶✾✮ ❇♦❝q✉❡t✱ ▲✳❀ ▲❛✉❣❛✱ ❊✳ ❆ ❙♠♦♦t❤ ❋✉t✉r❡❄ ◆❛t✉r❡ ▼❛t❡r✐❛❧s ✷✵✶✶✱ ✶✵✱ ✸✸✹✕✸✸✼✳ ✭✷✵✮ ●♦✈❛r❞❤❛♥✱ ❘✳ ◆✳❀ ❙r✐♥✐✈❛s✱ ●✳ ❙✳❀ ❆st❤❛♥❛✱ ❆✳❀ ❇♦❜❥✐✱ ▼✳ ❙✳ ❚✐♠❡ ❉❡♣❡♥❞❡♥❝❡ ♦❢ ❊✛❡❝t✐✈❡ ❙❧✐♣ ♦♥ ❚❡①t✉r❡❞ ❍②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ P❤②s✐❝s ♦❢ ❋❧✉✐❞s ✷✵✵✾✱ ✷✶✱ ✵✺✷✵✵✶✳ ✭✷✶✮ ▲②✉✱ ❙✳❀ ◆❣✉②❡♥✱ ❉✳ ❈✳❀ ❑✐♠✱ ❉✳❀ ❍✇❛♥❣✱ ❲✳❀ ❨♦♦♥✱ ❇✳ ❊①♣❡r✐♠❡♥t❛❧ ❉r❛❣ ❘❡❞✉❝✲ t✐♦♥ ❙t✉❞② ♦❢ ❙✉♣❡r✲❍②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡ ✇✐t❤ ❉✉❛❧✲❙❝❛❧❡ ❙tr✉❝t✉r❡s✳ ❆♣♣❧✐❡❞ ❙✉r❢❛❝❡

❙❝✐❡♥❝❡ ✷✵✶✸✱ ✷✽✻✱ ✷✵✻✕✷✶✶✳ ✭✷✷✮ ❲❡♥③❡❧✱ ❘✳ ◆✳ ❘❡s✐st❛♥❝❡ ♦❢ ❙♦❧✐❞ ❙✉r❢❛❝❡s t♦ ❲❡tt✐♥❣ ❜② ❲❛t❡r✳ ■♥❞✉str✐❛❧ ✫ ❊♥❣✐✲

♥❡❡r✐♥❣ ❈❤❡♠✐str② ✶✾✸✻✱ ✷✽✱ ✾✽✽✕✾✾✹✳ ✭✷✸✮ ❱r❛♥❝❦❡♥✱ ❘✳ ❏✳❀ ❑✉s✉♠❛❛t♠❛❥❛✱ ❍✳❀ ❍❡r♠❛♥s✱ ❑✳❀ Pr❡♥❡♥✱ ❆✳ ▼✳❀ P✐❡rr❡✲▲♦✉✐s✱ ❖✳❀ ❇❛st✐❛❛♥s❡♥✱ ❈✳ ❲✳ ▼✳❀ ❇r♦❡r✱ ❉✳ ❏✳ ❋✉❧❧② ❘❡✈❡rs✐❜❧❡ ❚r❛♥s✐t✐♦♥ ❢r♦♠ ❲❡♥③❡❧ t♦ ❈❛ss✐❡✲ ❇❛①t❡r ❙t❛t❡s ♦♥ ❈♦rr✉❣❛t❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ▲❛♥❣♠✉✐r ✷✵✶✵✱ ✷✻✱ ✸✸✸✺✕ ✸✸✹✶✳ ✭✷✹✮ ▼❛♥✉❦②❛♥✱ ●✳❀ ❖❤✱ ❏✳ ▼✳❀ ❱❛♥ ❉❡♥ ❊♥❞❡✱ ❉✳❀ ▲❛♠♠❡rt✐♥❦✱ ❘✳ ●✳ ❍✳❀ ▼✉❣❡❧❡✱ ❋✳ ❊❧❡❝tr✐❝❛❧ ❙✇✐t❝❤✐♥❣ ♦❢ ❲❡tt✐♥❣ ❙t❛t❡s ♦♥ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✿ ❆ ❘♦✉t❡ ❚♦✇❛r❞s ❘❡✈❡rs✐❜❧❡ ❈❛ss✐❡✲t♦✲❲❡♥③❡❧ ❚r❛♥s✐t✐♦♥s✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇ ▲❡tt❡rs ✷✵✶✶✱ ✶✵✻✱ ✵✶✹✺✵✶✳ ✭✷✺✮ ❑r✉♣❡♥❦✐♥✱ ❚✳ ◆✳❀ ❚❛②❧♦r✱ ❏✳ ❆✳❀ ❲❛♥❣✱ ❊✳ ◆✳❀ ❑♦❧♦❞♥❡r✱ P✳❀ ❍♦❞❡s✱ ▼✳❀ ❙❛❧❛♠♦♥✱ ❚✳ ❘✳ ❘❡✈❡rs✐❜❧❡ ❲❡tt✐♥❣✲❉❡✇❡tt✐♥❣ ❚r❛♥s✐t✐♦♥s ♦♥ ❊❧❡❝tr✐❝❛❧❧② ❚✉♥❛❜❧❡ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ◆❛♥♦str✉❝t✉r❡❞ ❙✉r❢❛❝❡s✳ ▲❛♥❣♠✉✐r ✷✵✵✼✱ ✷✸✱ ✾✶✷✽✕✾✶✸✸✳ ✭✷✻✮ ▲✐✱ ❨✳❀ ◗✉éré✱ ❉✳❀ ▲✈✱ ❈✳❀ ❩❤❡♥❣✱ ◗✳ ▼♦♥♦st❛❜❧❡ ❙✉♣❡rr❡♣❡❧❧❡♥t ▼❛t❡r✐❛❧s✳ Pr♦❝❡❡❞✐♥❣s

♦❢ t❤❡ ◆❛t✐♦♥❛❧ ❆❝❛❞❡♠② ♦❢ ❙❝✐❡♥❝❡s ✷✵✶✼✱ ✶✶✹✱ ✸✸✽✼✕✸✸✾✷✳ ✭✷✼✮ ❇♦r❡②❦♦✱ ❏✳ ❇✳❀ ❈❤❡♥✱ ❈✳ ❍✳ ❘❡st♦r✐♥❣ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝✐t② ♦❢ ▲♦t✉s ▲❡❛✈❡s ✇✐t❤ ❱✐❜r❛t✐♦♥✲■♥❞✉❝❡❞ ❉❡✇❡tt✐♥❣✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇ ▲❡tt❡rs ✷✵✵✾✱ ✶✵✸✱ ✶✼✹✺✵✷✳ ✭✷✽✮ ❙t❛♠❛t♦♣♦✉❧♦s✱ ❈✳❀ ❙❝❤✉t③✐✉s✱ ❚✳ ▼✳❀ ❑ö♣♣❧✱ ❈✳ ❏✳❀ ❊❧ ❍❛②❡❦✱ ◆✳❀ ▼❛✐tr❛✱ ❚✳❀ ❍❡♠r❧❡✱ ❏✳❀

✷✺

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

P♦✉❧✐❦❛❦♦s✱ ❉✳ ❖♥ t❤❡ ❙❤❡❞❞✐♥❣ ♦❢ ■♠♣❛❧❡❞ ❉r♦♣❧❡ts✿ ❚❤❡ ❘♦❧❡ ♦❢ ❚r❛♥s✐❡♥t ■♥t❡r✈❡♥✐♥❣ ▲❛②❡rs✳ ❙❝✐❡♥t✐✜❝ ❘❡♣♦rts ✷✵✶✻✱ ✻✱ ✶✽✽✼✺✳ ✭✷✾✮ ▲❡❡✱ ❈✳❀ ❑✐♠✱ ❈✳✲❏✳ ❯♥❞❡r✇❛t❡r ❘❡st♦r❛t✐♦♥ ❛♥❞ ❘❡t❡♥t✐♦♥ ♦❢ ●❛s❡s ♦♥ ❙✉♣❡r❤②❞r♦♣❤♦✲ ❜✐❝ ❙✉r❢❛❝❡s ❢♦r ❉r❛❣ ❘❡❞✉❝t✐♦♥✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇ ▲❡tt❡rs ✷✵✶✶✱ ✶✵✻✱ ✵✶✹✺✵✷✳ ✭✸✵✮ ▲❧♦②❞✱ ❇✳ P✳❀ ❇❛rt❧❡tt✱ P✳ ◆✳❀ ❲♦♦❞✱ ❘✳ ❏✳ ❑✳ ❆❝t✐✈❡ ●❛s ❘❡♣❧❡♥✐s❤♠❡♥t ❛♥❞ ❙❡♥s✐♥❣ ♦❢ t❤❡ ❲❡tt✐♥❣ ❙t❛t❡ ✐♥ ❛ ❙✉❜♠❡r❣❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡✳ ❙♦❢t ▼❛tt❡r ✷✵✶✼✱ ✶✸✱ ✶✹✶✸✕✶✹✶✾✳ ✭✸✶✮ ▲❡❡✱ ❏✳❀ ❨♦♥❣✱ ❑✳ ❈♦♠❜✐♥✐♥❣ t❤❡ ▲♦t✉s ▲❡❛❢ ❊✛❡❝t ✇✐t❤ ❆rt✐✜❝✐❛❧ P❤♦t♦s②♥t❤❡s✐s✿ ❘❡✲ ❣❡♥❡r❛t✐♦♥ ♦❢ ❯♥❞❡r✇❛t❡r ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝✐t② ♦❢ ❍✐❡r❛r❝❤✐❝❛❧ ❩♥❖✴❙✐ ❙✉r❢❛❝❡s ❜② ❙♦✲ ❧❛r ❲❛t❡r ❙♣❧✐tt✐♥❣✳ ◆P● ❆s✐❛ ▼❛t❡r✐❛❧s ✷✵✶✺✱ ✼✱ ❡✷✵✶✳ ✭✸✷✮ ❱❛❦❛r❡❧s❦✐✱ ■✳ ❯✳❀ P❛t❛♥❦❛r✱ ◆✳ ❆✳❀ ▼❛rst♦♥✱ ❏✳ ❖✳❀ ❈❤❛♥✱ ❉✳ ❨✳❀ ❚❤♦r♦❞❞s❡♥✱ ❙✳ ❚✳ ❙t❛✲ ❜✐❧✐③❛t✐♦♥ ♦❢ ▲❡✐❞❡♥❢r♦st ❱❛♣♦✉r ▲❛②❡r ❜② ❚❡①t✉r❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ◆❛t✉r❡

✷✵✶✷✱ ✹✽✾✱ ✷✼✹✕✷✼✼✳ ✭✸✸✮ ❙❛r❛♥❛❞❤✐✱ ❉✳❀ ❈❤❡♥✱ ❉✳❀ ❑❧❡✐♥❣❛rt♥❡r✱ ❏✳ ❆✳❀ ❙r✐♥✐✈❛s❛♥✱ ❙✳❀ ❈♦❤❡♥✱ ❘✳ ❊✳❀ ▼❝❑✐♥✲ ❧❡②✱ ●✳ ❍✳ ❙✉st❛✐♥❡❞ ❉r❛❣ ❘❡❞✉❝t✐♦♥ ✐♥ ❛ ❚✉r❜✉❧❡♥t ❋❧♦✇ ✉s✐♥❣ ❛ ▲♦✇✲❚❡♠♣❡r❛t✉r❡ ▲❡✐❞❡♥❢r♦st ❙✉r❢❛❝❡✳ ❙❝✐❡♥❝❡ ❆❞✈❛♥❝❡s ✷✵✶✻✱ ✷✱ ❡✶✻✵✵✻✽✻✳ ✭✸✹✮ ❍♦❢✱ ❇✳ ❋❧✉✐❞ ❉②♥❛♠✐❝s✿ ❲❛t❡r ❋❧♦✇s ❖✉t ♦❢ ❚♦✉❝❤✳ ◆❛t✉r❡ ✷✵✶✼✱ ✺✹✶✱ ✶✻✶✕✶✻✷✳ ✭✸✺✮ ▲✐♥❣✱ ❍✳❀ ❙r✐♥✐✈❛s❛♥✱ ❙✳❀ ●♦❧♦✈✐♥✱ ❑✳❀ ▼❝❑✐♥❧❡②✱ ●✳ ❍✳❀ ❚✉t❡❥❛✱ ❆✳❀ ❑❛t③✱ ❏✳ ❍✐❣❤✲ ❘❡s♦❧✉t✐♦♥ ❱❡❧♦❝✐t② ▼❡❛s✉r❡♠❡♥t ✐♥ t❤❡ ■♥♥❡r P❛rt ♦❢ ❚✉r❜✉❧❡♥t ❇♦✉♥❞❛r② ▲❛②❡rs ♦✈❡r ❙✉♣❡r✲❍②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ❏♦✉r♥❛❧ ♦❢ ❋❧✉✐❞ ▼❡❝❤❛♥✐❝s ✷✵✶✻✱ ✽✵✶✱ ✻✼✵✕✼✵✸✳ ✭✸✻✮ ❱❡r❤♦✱ ❚✳❀ ❑♦r❤♦♥❡♥✱ ❏✳ ❚✳❀ ❙❛✐♥✐❡♠✐✱ ▲✳❀ ❏♦❦✐♥❡♥✱ ❱✳❀ ❇♦✇❡r✱ ❈✳❀ ❋r❛♥③❡✱ ❑✳❀ ❋r❛♥ss✐❧❛✱ ❙✳❀ ❆♥❞r❡✇✱ P✳❀ ■❦❦❛❧❛✱ ❖✳❀ ❘❛s✱ ❘✳ ❍✳ ❆✳ ❘❡✈❡rs✐❜❧❡ ❙✇✐t❝❤✐♥❣ ❇❡t✇❡❡♥ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙t❛t❡s ♦♥ ❛ ❍✐❡r❛r❝❤✐❝❛❧❧② ❙tr✉❝t✉r❡❞ ❙✉r❢❛❝❡✳ Pr♦❝❡❡❞✐♥❣s ♦❢ t❤❡

◆❛t✐♦♥❛❧ ❆❝❛❞❡♠② ♦❢ ❙❝✐❡♥❝❡s ✷✵✶✷✱ ✶✵✾✱ ✶✵✷✶✵✕✶✵✷✶✸✳ ✷✻

ACS Paragon Plus Environment

Page 26 of 35

Page 27 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

✭✸✼✮ ❋♦rs❜❡r❣✱ P✳❀ ◆✐❦♦❧❛❥❡✛✱ ❋✳❀ ❑❛r❧ss♦♥✱ ▼✳ ❈❛ss✐❡✲❲❡♥③❡❧ ❛♥❞ ❲❡♥③❡❧✲❈❛ss✐❡ ❚r❛♥s✐✲ t✐♦♥s ♦♥ ■♠♠❡rs❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s ✉♥❞❡r ❍②❞r♦st❛t✐❝ Pr❡ss✉r❡✳ ❙♦❢t ▼❛tt❡r

✷✵✶✶✱ ✼✱ ✶✵✹✕✶✵✾✳ ✭✸✽✮ ❉✉✱ P✳❀ ❲❡♥✱ ❏✳❀ ❩❤❛♥❣✱ ❩✳❀ ❙♦♥❣✱ ❉✳❀ ❖✉❛❤s✐♥❡✱ ❆✳❀ ❍✉✱ ❍✳ ▼❛✐♥t❡♥❛♥❝❡ ♦❢ ❆✐r ▲❛②❡r ❛♥❞ ❉r❛❣ ❘❡❞✉❝t✐♦♥ ♦♥ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡✳ ❖❝❡❛♥ ❊♥❣✐♥❡❡r✐♥❣ ✷✵✶✼✱ ✶✸✵✱ ✸✷✽✕ ✸✸✺✳ ✭✸✾✮ ❞❡ ▼❛❧❡♣r❛❞❡✱ ❍✳❀ ❈❧❛♥❡t✱ ❈✳❀ ◗✉éré✱ ❉✳ ❙♣r❡❛❞✐♥❣ ♦❢ ❇✉❜❜❧❡s ❛❢t❡r ❈♦♥t❛❝t✐♥❣ t❤❡ ▲♦✇❡r ❙✐❞❡ ♦❢ ❛♥ ❆❡r♦♣❤✐❧✐❝ ❙❧✐❞❡ ■♠♠❡rs❡❞ ✐♥ ❲❛t❡r✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇ ▲❡tt❡rs ✷✵✶✻✱

✶✶✼✱ ✵✾✹✺✵✶✳ ✭✹✵✮ ❉❛✈✐s✱ ❆✳ ▼✳❀ ▲❛✉❣❛✱ ❊✳ ●❡♦♠❡tr✐❝ ❚r❛♥s✐t✐♦♥ ✐♥ ❋r✐❝t✐♦♥ ❢♦r ❋❧♦✇ ♦✈❡r ❛ ❇✉❜❜❧❡ ▼❛t✲ tr❡ss✳ P❤②s✐❝s ♦❢ ❋❧✉✐❞s ✷✵✵✾✱ ✷✶✱ ✵✶✶✼✵✶✳ ✭✹✶✮ ▲✐♥❣✱ ❍✳❀ ❑❛t③✱ ❏✳❀ ❋✉✱ ▼✳❀ ❍✉❧t♠❛r❦✱ ▼✳ ❊✛❡❝t ♦❢ ❘❡②♥♦❧❞s ◆✉♠❜❡r ❛♥❞ ❙❛t✉r❛t✐♦♥ ▲❡✈❡❧ ♦♥ ●❛s ❉✐✛✉s✐♦♥ ■♥ ❛♥❞ ❖✉t ♦❢ ❛ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡✳ P❤②s✐❝❛❧ ❘❡✈✐❡✇

❋❧✉✐❞s ✷✵✶✼✱ ✷✱ ✶✷✹✵✵✺✳ ✭✹✷✮ ❱❛❦❛r❡❧s❦✐✱ ■✳ ❯✳❀ ❈❤❛♥✱ ❉✳ ❨✳ ❈✳❀ ▼❛rst♦♥✱ ❏✳ ❖✳❀ ❚❤♦r♦❞❞s❡♥✱ ❙✳ ❚✳ ❉②♥❛♠✐❝ ❆✐r ▲❛②❡r ♦♥ ❚❡①t✉r❡❞ ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ ▲❛♥❣♠✉✐r ✷✵✶✸✱ ✷✾✱ ✶✶✵✼✹✕✶✶✵✽✶✳ ✭✹✸✮ ▲✐♥✱ ❈✳ ❈✳❀ ❙♠✐t❤✱ ❋✳ ❘✳❀ ■❝❤✐❦❛✇❛✱ ◆✳❀ ❇❛❜❛✱ ❚✳❀ ■t♦✇✱ ▼✳ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❍②❞r♦✲ ❣❡♥ P❡r♦①✐❞❡ ✐♥ ❆q✉❡♦✉s ❙♦❧✉t✐♦♥s ❛t ❊❧❡✈❛t❡❞ ❚❡♠♣❡r❛t✉r❡s✳ ■♥t❡r♥❛t✐♦♥❛❧ ❏♦✉r♥❛❧ ♦❢

❈❤❡♠✐❝❛❧ ❑✐♥❡t✐❝s ✶✾✾✶✱ ✷✸✱ ✾✼✶✕✾✽✼✳ ✭✹✹✮ ▲♦❡✇✱ ❖✳ ❆ ◆❡✇ ❊♥③②♠❡ ♦❢ ●❡♥❡r❛❧ ❖❝❝✉r❡♥❝❡ ✐♥ ❖r❣❛♥✐s♠s✳ ❙❝✐❡♥❝❡ ✶✾✵✵✱ ✶✶✱ ✼✵✶✕ ✼✵✷✳ ✭✹✺✮ ▼❝❑❡❡✱ ❉✳ ❲✳ ❈❛t❛❧②t✐❝ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❍②❞r♦❣❡♥ P❡r♦①✐❞❡ ❜② ▼❡t❛❧s ❛♥❞ ❆❧❧♦②s ♦❢ t❤❡ P❧❛t✐♥✉♠ ●r♦✉♣✳ ❏♦✉r♥❛❧ ♦❢ ❈❛t❛❧②s✐s ✶✾✻✾✱ ✶✹✱ ✸✺✺✕✸✻✹✳

✷✼

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

✭✹✻✮ ▲✐❡❜❤❛❢s❦②✱ ❍✳ ❆✳ ❚❤❡ ❈❛t❛❧②t✐❝ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❍②❞r♦❣❡♥ P❡r♦①✐❞❡ ❇② t❤❡ ■♦❞✐♥❡✲ ■♦❞✐❞❡ ❈♦✉♣❧❡ ❆t ✷✺◦ ✳ ❏♦✉r♥❛❧ ♦❢ t❤❡ ❆♠❡r✐❝❛♥ ❈❤❡♠✐❝❛❧ ❙♦❝✐❡t② ✶✾✸✷✱ ✺✹✱ ✶✼✾✷✕✶✽✵✻✳ ✭✹✼✮ ❘♦②✱ ❈✳ ❇✳ ❈❛t❛❧②t✐❝ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦❢ ❍②❞r♦❣❡♥ P❡r♦①✐❞❡ ♦♥ s♦♠❡ ❖①✐❞❡ ❈❛t❛❧②sts✳

❏♦✉r♥❛❧ ♦❢ ❈❛t❛❧②s✐s ✶✾✻✽✱ ✶✷✱ ✶✷✾✕✶✸✸✳ ✭✹✽✮ ❙❡rr❛✲▼❛✐❛✱ ❘✳❀ ❇❡❧❧✐❡r✱ ▼✳❀ ❈❤❛st❦❛✱ ❙✳❀ ❚r❛♥❤✉✉✱ ❑✳❀ ❙✉❜♦✇♦✱ ❆✳❀ ❘✐♠st✐❞t✱ ❏✳ ❉✳❀ ❯s♦✈✱ P✳ ▼✳❀ ▼♦rr✐s✱ ❆✳ ❏✳❀ ▼✐❝❤❡❧✱ ❋✳ ▼✳ ▼❡❝❤❛♥✐s♠ ❛♥❞ ❑✐♥❡t✐❝s ♦❢ ❍②❞r♦❣❡♥ P❡r♦①✲ ✐❞❡ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦♥ P❧❛t✐♥✉♠ ◆❛♥♦❝❛t❛❧②sts✳ ❆❈❙ ❆♣♣❧✐❡❞ ▼❛t❡r✐❛❧s ❛♥❞ ■♥t❡r❢❛❝❡s

✷✵✶✽✱ ✶✵✱ ✷✶✷✷✹✕✷✶✷✸✹✳ ✭✹✾✮ ❉♦✱ ❙✳✲❍✳❀ ❇❛t❝❤❡❧♦r✱ ❇✳❀ ▲❡❡✱ ❍✳✲❦✳❀ ❑♦♥❣✱ ❙✳✲❤✳ ❍②❞r♦❣❡♥ P❡r♦①✐❞❡ ❉❡❝♦♠♣♦s✐t✐♦♥ ♦♥ ▼❛♥❣❛♥❡s❡ ❖①✐❞❡ ✭ P②r♦❧✉s✐t❡ ✮✿ ❑✐♥❡t✐❝s ✱ ■♥t❡r♠❡❞✐❛t❡s ✱ ❛♥❞ ▼❡❝❤❛♥✐s♠✳ ❈❤❡♠♦✲

s♣❤❡r❡ ✷✵✵✾✱ ✼✺✱ ✽✕✶✷✳ ✭✺✵✮ ❙❛♥❝❤❡③✱ ❙✳❀ ❙♦❧♦✈❡✈✱ ❆✳ ❆✳❀ ▼❡✐✱ ❨✳ ❋✳❀ ❙❝❤♠✐❞t✱ ❖✳ ●✳ ❉②♥❛♠✐❝s ♦❢ ❇✐♦❝❛t❛❧②t✐❝ ▼✐❝r♦❡♥❣✐♥❡s ▼❡❞✐❛t❡❞ ❜② ❱❛r✐❛❜❧❡ ❋r✐❝t✐♦♥ ❈♦♥tr♦❧✳ ❏♦✉r♥❛❧ ♦❢ ❆♠❡r✐❝❛♥ ❈❤❡♠✐❝❛❧

❙♦❝✐❡t② ✷✵✶✵✱ ✶✸✷✱ ✶✸✶✹✹✕✶✸✶✹✺✳ ✭✺✶✮ ❲❛♥❣✱ ❨✳❀ ❍❡r♥❛♥❞❡③✱ ❘✳ ▼✳❀ ❇❛rt❧❡tt✱ ❉✳ ❏✳❀ ❇✐♥❣❤❛♠✱ ❏✳ ▼✳❀ ❑❧✐♥❡✱ ❚✳ ❘✳❀ ❙❡♥✱ ❆✳❀ ▼❛❧❧♦✉❦✱ ❚✳ ❊✳ ❇✐♣♦❧❛r ❊❧❡❝tr♦❝❤❡♠✐❝❛❧ ▼❡❝❤❛♥✐s♠ ❢♦r t❤❡ Pr♦♣✉❧s✐♦♥ ♦❢ ❈❛t❛❧②t✐❝ ◆❛♥♦♠♦t♦rs ✐♥ ❍②❞r♦❣❡♥ P❡r♦①✐❞❡ ❙♦❧✉t✐♦♥s✳ ▲❛♥❣♠✉✐r ✷✵✵✻✱ ✷✷✱ ✶✵✹✺✶✕✶✵✹✺✻✳ ✭✺✷✮ ❏♦♥❡s✱ P✳ ❘✳❀ ❍❛♦✱ ❳✳❀ ❈r✉③✲❈❤✉✱ ❊✳ ❘✳❀ ❘②❦❛❝③❡✇s❦✐✱ ❑✳❀ ◆❛♥❞②✱ ❑✳❀ ❙❝❤✉t③✐✉s✱ ❚✳ ▼✳❀ ❱❛r❛♥❛s✐✱ ❑✳ ❑✳❀ ▼❡❣❛r✐❞✐s✱ ❈✳ ▼✳❀ ❲❛❧t❤❡r✱ ❏✳ ❍✳❀ ❑♦✉♠♦✉ts❛❦♦s✱ P✳❀ ❊s♣✐♥♦s❛✱ ❍✳ ❉✳❀ P❛t❛♥❦❛r✱ ◆✳ ❆✳ ❙✉st❛✐♥✐♥❣ ❉r② ❙✉r❢❛❝❡s ✉♥❞❡r ❲❛t❡r✳ ❙❝✐❡♥t✐✜❝ ❘❡♣♦rts ✷✵✶✺✱ ✺✱ ✶✷✸✶✶✳ ✭✺✸✮ ▼❛r♠✉r✱ ❆✳ ❯♥❞❡r✇❛t❡r ❙✉♣❡r❤②❞r♦♣❤♦❜✐❝✐t②✿ ❚❤❡♦r❡t✐❝❛❧ ❋❡❛s✐❜✐❧✐t②✳ ▲❛♥❣♠✉✐r ✷✵✵✻✱

✷✷✱ ✶✹✵✵✕✶✹✵✷✳

✷✽

ACS Paragon Plus Environment

Page 28 of 35

Page 29 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

✭✺✹✮ ●r♦ss♠❛♥♥✱ ❙✳❀ ▲♦❤s❡✱ ❉✳❀ ❙✉♥✱ ❈✳ ❍✐❣❤✲❘❡②♥♦❧❞s ◆✉♠❜❡r ❚❛②❧♦r✲❈♦✉❡tt❡ ❚✉r❜✉❧❡♥❝❡✳

❆♥♥✉❛❧ ❘❡✈✐❡✇ ♦❢ ❋❧✉✐❞ ▼❡❝❤❛♥✐❝s ✷✵✶✻✱ ✹✽✱ ✺✸✕✽✵✳ ✭✺✺✮ ❙❤✐✱ ❈✳❀ ❈✉✐✱ ❳✳❀ ❩❤❛♥❣✱ ❳✳❀ ❚❝❤♦✉❦♦✈✱ P✳❀ ▲✐✉✱ ◗✳❀ ❊♥❝✐♥❛s✱ ◆✳❀ P❛✈❡♥✱ ▼✳❀ ●❡②❡r✱ ❋✳❀ ❱♦❧❧♠❡r✱ ❉✳❀ ❳✉✱ ❩✳❀ ❇✉tt✱ ❍✳✲❏✳❀ ❩❡♥❣✱ ❍✳ ■♥t❡r❛❝t✐♦♥ ❜❡t✇❡❡♥ ❆✐r ❇✉❜❜❧❡s ❛♥❞ ❙✉♣❡r✲ ❤②❞r♦♣❤♦❜✐❝ ❙✉r❢❛❝❡s ✐♥ ❆q✉❡♦✉s ❙♦❧✉t✐♦♥s✳ ▲❛♥❣♠✉✐r ✷✵✶✺✱ ✸✶✱ ✼✸✶✼✕✼✸✷✼✳ ✭✺✻✮ ❇✐❝♦✱ ❏✳❀ ❚❤✐❡❧❡✱ ❯✳❀ ◗✉éré✱ ❉✳ ❲❡tt✐♥❣ ♦❢ ❚❡①t✉r❡❞ ❙✉r❢❛❝❡s✳ ❈♦❧❧♦✐❞s ❛♥❞ ❙✉r❢❛❝❡s ❆✿

P❤②s✐❝♦❝❤❡♠✐❝❛❧ ❛♥❞ ❊♥❣✐♥❡❡r✐♥❣ ❆s♣❡❝ts ✷✵✵✷✱ ✷✵✻✱ ✹✶✕✹✻✳ ✭✺✼✮ ❨♦✉♥❣✱ ❚✳ ■■■✳ ❆♥ ❊ss❛② ♦♥ t❤❡ ❈♦❤❡s✐♦♥ ♦❢ ❋❧✉✐❞s✳ P❤✐❧♦s♦♣❤✐❝❛❧ ❚r❛♥s❛❝t✐♦♥s ♦❢ t❤❡

❘♦②❛❧ ❙♦❝✐❡t② ♦❢ ▲♦♥❞♦♥ ✶✽✵✺✱ ✾✺✱ ✻✺✕✽✼✳ ✭✺✽✮ ❚✉t❡❥❛✱ ❆✳❀ ❈❤♦✐✱ ❲✳❀ ▼❛❜r②✱ ❏✳ ▼✳❀ ▼❝❑✐♥❧❡②✱ ●✳ ❍✳❀ ❈♦❤❡♥✱ ❘✳ ❊✳ ❘♦❜✉st ❖♠♥✐♣❤♦❜✐❝ ❙✉r❢❛❝❡s✳ Pr♦❝❡❡❞✐♥❣s ♦❢ t❤❡ ◆❛t✐♦♥❛❧ ❆❝❛❞❡♠② ♦❢ ❙❝✐❡♥❝❡s ✷✵✵✽✱ ✶✵✺✱ ✶✽✷✵✵✕✶✽✷✵✺✳ ✭✺✾✮ ❑✐♠✱ ❏✳ ●✳❀ ❈❤♦✐✱ ❍✳ ❏✳❀ P❛r❦✱ ❑✳ ❈✳❀ ❈♦❤❡♥✱ ❘✳ ❊✳❀ ▼❝❑✐♥❧❡②✱ ●✳ ❍✳❀ ❇❛r❜❛st❛t❤✐s✱ ●✳ ▼✉❧t✐❢✉♥❝t✐♦♥❛❧ ■♥✈❡rt❡❞ ◆❛♥♦❝♦♥❡ ❆rr❛②s ❢♦r ◆♦♥✲✇❡tt✐♥❣✱ ❙❡❧❢✲❈❧❡❛♥✐♥❣ ❚r❛♥s♣❛r❡♥t ❙✉r❢❛❝❡ ✇✐t❤ ❍✐❣❤ ▼❡❝❤❛♥✐❝❛❧ ❘♦❜✉st♥❡ss✳ ❙♠❛❧❧ ✷✵✶✹✱ ✶✵✱ ✷✹✽✼✕✷✹✾✹✳ ✭✻✵✮ ❇❛❜❛❦❤❛♥✐✱ ❇✳❀ ■✈❡②✱ ❉✳ ●✳ ❆♥♦❞✐❝ ❉❡♣♦s✐t✐♦♥ ♦❢ ▼❛♥❣❛♥❡s❡ ❖①✐❞❡ ❊❧❡❝tr♦❞❡s ✇✐t❤ ❘♦❞✲❧✐❦❡ ❙tr✉❝t✉r❡s ❢♦r ❆♣♣❧✐❝❛t✐♦♥ ❛s ❊❧❡❝tr♦❝❤❡♠✐❝❛❧ ❈❛♣❛❝✐t♦rs✳ ❏♦✉r♥❛❧ ♦❢ P♦✇❡r

❙♦✉r❝❡s ✷✵✶✵✱ ✶✾✺✱ ✷✶✶✵✕✷✶✶✼✳

✷✾

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 30 of 35

Page 31 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Schematic of an active superhydrophobic microtexture which generates gas on-demand upon addition of the reactant, hydrogen peroxide. 224x151mm (144 x 144 DPI)

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(a) Schematic of the thermodynamic states of gas bubbles spreading on textured surfaces. The stability of the states is dictated by both the microtexture and surface chemistry. The scale bar represents 0.5 mm; (b) Plot of the apparent contact angle of water (θ*w) on a textured surface (Wenzel roughness r = 2, solid fraction Φs = 0.4) versus Young's contact angle of water on a flat surface (θw). The theoretically predicted regime of stable underwater gas wetting or aerophilicity is also indicated by the shading in the plot. Plastron recovery is favored only in the region shaded in green. 249x146mm (144 x 144 DPI)

ACS Paragon Plus Environment

Page 32 of 35

Page 33 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(a) Micrograph of silicon texture with platinum coating on the sides and bottom of the texture, and Teflon coating on the entire texture (Si-Pt-Teflon); (b) Plastron recovery on Si-Pt-Teflon texture underwater at 4.5 wt.% H2O2; (c) Micrograph of laser textured aluminum pillars coated with MnO2 and Fluorosilane (Al-MnO2Fluorosilane); (d) Plastron recovery underwater on Al-MnO2-Fluorosilane texture at 1.5 wt.% H2O2. 259x120mm (144 x 144 DPI)

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Regime map for plastron reinflation experiments on Si-Pt-Teflon surfaces with varying texture parameters. The colors indicate whether plastron recovery was observed: plastron recovery (green) and blisters (red); The shape of the markers indicate the shape of the posts: cylindrical pillars (circles), square cylindrical pillars (square). The marker filling indicates whether the catalyst was deposited on the pillar tops: no catalyst on top (filled), catalyst on top (hollow). 175x134mm (144 x 144 DPI)

ACS Paragon Plus Environment

Page 34 of 35

Page 35 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(a) Micrograph of square pillars (width 100 µm, height 200 µm, and spacing 100 µm) machined on an aluminum rotor of radius Ri = 14 mm and coated with MnO2 and a fluorinated silane; (b) Drop of water (V = 12 µL)sitting on the hydrophobized machined rotor used for plastron recovery (θadv = 159±2; θrec = 109±5); (c) Schematic of the Taylor-Couette cell used for drag reduction measurements with fluid port for H2O2 injection; (d) Unwrapped views of the cylindrical surface of the rotor before plastron failure, after plastron failure, and after partial plastron recovery. This image was produced by imaging the rotating rotor at constant speed, and stitching together vertical sections of the rotor captured across one entire rotation. (e) Plot of the average wall shear stress, ζw, experienced by the rotor in the Taylor-Couette cell at Re = 47,000 during the initial period of drag reduction (Cassie state), plastron failure (Wenzel state) and plastron recovery (partial Cassie) stages. 249x239mm (144 x 144 DPI)

ACS Paragon Plus Environment