This document summarizes the history and development of atomic layer deposition (ALD) and its applications in catalysis. It discusses key milestones in ALD including early work in 1974 and patents in 1990. It also examines using ALD to engineer catalysts by depositing thin films on high surface area powders. Experimental results are presented on optimizing the location of zinc promoters deposited by ALD to improve methanol production from carbon dioxide hydrogenation.
4. Riikka Puurunen, Aalto University, 26.10.2022
What
is ALD?
Van Ommen, Goulas, Puurunen,
“Atomic layer deposition” in
Kirk-Othmer Encyclopedia of
Chemical Technology, 2021,
https://doi.org/10.1002/0471238
961.koe00059
Wikimedia Commons
Growth
per cycle
(GPC)
Based on
repeated self-
terminating
reactions
5. Riikka Puurunen, Aalto University, 26.10.2022
ALD: selected milestones
1974
Atomic layer epitaxy (ALE)
patent 1974-11-29
“framework hypothesis” →
1965 “molecular layering”
1965 1983
ALE-electroluminescent
display demonstrator
* 1990: International conference on atomic layer
epitaxy (knowledge of molecular layering)
1990 ALE
catalyst patent
1990-01-16
1990*
2018 Millennium
Technology Prize
Dr. Tuomo Suntola
2013****
2018
vph-ald.com
**** 2013 Virtual Project on the History of ALD
2007 ALD MOSFET
with “high-k” to
production, Intel
2001**
*** 2005 J. Appl. Phys.
Review (Puurunen)
** 2001: International conference series on “atomic
layer deposition”
2005***
Essays: on ALE:Chem. Vap. Deposition 20 (2014) 332-344.;
on ML: Chem. Vap. Deposition 21 (2015) 216-240.
6. Riikka Puurunen, Aalto University, 26.10.2022
Active ALD process development
2010
2022
Puurunen, J. App. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727
Miikkulainen, Leskelä, Ritala, Puurunen, J. Appl. Phys. 113 (2013) 021301. https://doi.org/10.1063/1.4757907
https://www.atomiclimits.com/alddatabase/, accessed 2022-10-19.
7. Riikka Puurunen, Aalto University, 26.10.2022
ALD for microelectronics &
heterogeneous catalysts: 3-D
~seconds
~minutes, hours
Area ~ 10-1 m2
Area ~ 103 m2
Conformal film?
e.g.
100 m2/g
Microelectronics: wafers
Catalysts: powders
Time
Amount
adsorbed ideal ALD
+ non-ideal
continuous
component
“fast”
“slow”
Uniformly distributed
species?
9. Riikka Puurunen, Aalto University, 26.10.2022
Case 2: CO2 hydrogenation to methanol
Effect of Zn promoter location (ALD)
Support - ZrO2
Cu/ZnO/Zr
ZnO/Cu/Zr
ZnO/Zr
Cu/Zr
ZnO/Cu/ZnO/Zr
ZnO (by ALD)
Cu (by impregnation)
Arandia et al., Appl. Catal. B, in press (2022), https://doi.org/10.1016/j.apcatb.2022.122046
0
2
4
6
8
10
12
1 2 3
CO
2
conversion,
%
a
Zr
Zn/Zr
Cu/Zr
Zn/Cu/Zr
Cu/Zn/Zr
Zn/Cu/Zn/Zr
450 K 500 K 550 K
No measured
activity
STY
methanol
0
100
200
300
425 450 475 500 525 550 575
c
0
1
2
3
4
425 450 475 500 525 550 575
b
b
450 K 500 K 550 K
STY
methanol
mmolCH3OH gCu
-1h-1
mmolCH3OH gcat
-1h-1
Conditions: 30 bar, H2/CO2/N2
(71/23/6, v/v/v); GHSV = 7500 h-1
0
100
200
300
425 450 475 500 525 550 575
c
0
1
2
3
4
425 450 475 500 525 550 575
b
b
450 K 500 K 550 K
STY
methanol
mmolCH3OH gCu
-1h-1
mmolCH3OH gcat
-1h-1
Space time yield
10. Riikka Puurunen, Aalto University, 26.10.2022
Future?
1. Contribute to by-catalysis-
enabled green transition
2. Increase fundamental
understanding of ALD
More openness in science and education
…
Note: More ALD
capacity needed!
11. Riikka Puurunen, Aalto University, 26.10.2022
Acknowledgements and credits
https://pxhere.
com/en/photo/
1488167, CC0
https://en.wikipedia.org/wiki/
J%C3%B6ns_Jacob_Berzel
ius#/media/File:J%C3%B6n
s_Jacob_Berzelius_x_Joha
n_Way.jpg, CC0
Millennium
Prize
Organization
2018
By Riikka Puurunen
and Tuomo Suntola
- Own work 2014,
CC BY-SA 4.0,
https://commons.wiki
media.org/w/index.p
hp?curid=74884900
By Riikka L.
Puurunen, J. Ruud
van Ommen,
Aristeidis Goulas -
Own work 2020, CC
BY 4.0,
https://commons.wiki
media.org/w/index.ph
p?curid=97744756
By Aristeidis Goulas, J.
Ruud van Ommen,
Riikka L. Puurunen -
Own work 2020, CC BY
4.0,
https://commons.wikim
edia.org/w/index.php?c
urid=97939221
0
2
4
6
8
10
12
1 2 3
CO
2
conversion,
%
a
Zr
Zn/Zr
Cu/Zr
Zn/Cu/Zr
Cu/Zn/Zr
Zn/Cu/Zn/Zr
450 K 500 K 550 K
No measured
activity
STY
methanol
Arandia et al.,
Appl. Catal. B, in
press (2022),
https://doi.org/10
.1016/j.apcatb.20
22.122046
CC BY 4.0
From Suntola’s
collections. Published
in: Puurunen, Chem.
Vap. Deposition 20
(2014) 332-344.
https://doi.org/10.100
2/cvde.201402012 (c)
Author, CC BY-NC 3.0
By J. Ruud van Ommen,
Fenne B.M. van
Ommen, Riikka L.
Puurunen - Own work
2020, CC BY 4.0,
https://commons.wikime
dia.org/w/index.php?curi
d=102275667
From
Puurunen’s
collections
Credit: Aitor Arandia
… and many illustrations by RLP (handmade & other)…
Aalto - Catalysis group
Photo: Matti Reinikainen, 2022
Funding:
Neste
Virtual Project on the History
of ALD logo by Riikka
Puurunen, 2013
Collaborators through years