Focused soft X-ray beam induced deposition of metallic deposits from metal organic precursors is a promising novel technique for additive nanostructure fabrication. In the present work, the authors present a comparative study for deposition and in situ characterization of Co and Mn nanostructures in a scanning transmission x-ray microscope. The authors detect a significant selectivity of the deposition process with respect to the incident photon energy that arises from the enhanced x-ray absorption cross section of the precursor molecules for near-threshold excitation. This effect has been investigated for the L2,3-edges of the respective metal centers of two different precursor molecules as well as the N and O K-edges of the respective ligands. The authors find a photon-limited growth mode for deposition from cobalt tricarbonyl nitrosyl [Co(CO)3NO], while the process is precursor-limited for methylcyclopentadienyl manganese tricarbonyl [MeCpMn(CO)3] possibly due to a comparably low vapor pressure of the latter precursor.

1.
A.
Späth
,
F.
Tu
,
F.
Vollnhals
,
M.
Drost
,
S. K.
Calderón
,
B.
Watts
,
R. H.
Fink
, and
H.
Marbach
,
RSC Adv.
6
,
98344
(
2016
).
3.
J.
Wang
,
C.
Morin
,
L.
Li
,
A.
Hitchcock
,
A.
Scholl
, and
A.
Doran
,
J. Electron. Spectrosc. Relat. Phenom.
170
,
25
(
2009
).
4.
R.
Egerton
,
P.
Li
, and
M.
Malac
,
Micron
35
,
399
(
2004
).
5.
J.
Pablo-Navarro
,
C.
Magén
, and
J. M.
de Teresa
,
Nanotechnology
27
,
285302
(
2016
).
6.
R.
Córdoba
,
N.
Sharma
,
S.
Kölling
,
P. M.
Koenraad
, and
B.
Koopmans
,
Nanotechnology
27
,
355301
(
2016
).
7.
W.
van Dorp
,
Appl. Phys. A
117
,
1615
(
2014
).
8.
C.
Hagen
,
Appl. Phys. A
117
,
1599
(
2014
).
9.
I.
Utke
and
A.
Gölzhäuser
,
Angew. Chem. Int. Ed.
49
,
9328
(
2010
).
10.
A.
Botman
,
J.
Mulders
, and
C.
Hagen
,
Nanotechnology
20
,
372001
(
2009
).
11.
W.
Van Dorp
and
C.
Hagen
,
J. Appl. Phys.
104
,
081301
(
2008
).
12.
I.
Utke
,
P.
Hoffmann
, and
J.
Melngailis
,
J. Vac. Sci. Technol., B
26
,
1197
(
2008
).
13.
H.
Marbach
,
Appl. Phys. A
117
,
987
(
2014
).
14.
M. M.
Walz
,
M.
Schirmer
,
F.
Vollnhals
,
T.
Lukasczyk
,
H. P.
Steinrück
, and
H.
Marbach
,
Angew. Chem. Int. Ed.
49
,
4669
(
2010
).
15.
M. G.
Stanford
,
B. B.
Lewis
,
J. H.
Noh
,
J. D.
Fowlkes
,
N. A.
Roberts
,
H.
Plank
, and
P. D.
Rack
,
ACS Appl. Mater. Interfaces
6
,
21256
(
2014
).
16.
R.
Sachser
,
H.
Reith
,
D.
Huzel
,
M.
Winhold
, and
M.
Huth
,
ACS Appl. Mater. Interfaces
6
,
15868
(
2014
).
17.
S. G.
Rosenberg
,
M.
Barclay
, and
D. H.
Fairbrother
,
ACS Appl. Mater. Interfaces
6
,
8590
(
2014
).
18.
B.
Geier
 et al.,
J. Phys. Chem. C
118
,
14009
(
2014
).
19.
R.
Feder
,
E.
Spiller
, and
J.
Topalian
,
Polym. Eng. Sci.
17
,
385
(
1977
).
20.
D.
Spears
and
H. I.
Smith
,
Electron. Lett.
8
,
102
(
1972
).
21.
J. R.
Maldonado
and
M.
Peckerar
,
Microelectron. Eng.
161
,
87
(
2016
).
22.
A. F.
Leontowich
and
A. P.
Hitchcock
,
Appl. Phys. A
103
,
1
(
2011
).
23.
A. F.
Leontowich
,
A. P.
Hitchcock
,
B.
Watts
, and
J.
Raabe
,
Microelectron. Eng.
108
,
5
(
2013
).
24.
A.
Späth
,
B.
Watts
,
L. T.
Wasserthal
, and
R. H.
Fink
,
J. Synchrotron Radiat.
21
,
1153
(
2014
).
25.
J.
Wang
,
G. A.
Botton
,
M. M.
West
, and
A. P.
Hitchcock
,
J. Phys. Chem. B
113
,
1869
(
2009
).
26.
N.
Schmidt
,
A.
Scheurer
,
S.
Sperner
, and
R. H.
Fink
,
Z. Naturforsch. B
65
,
390
(
2010
).
27.
J.
Wang
,
H. D. H.
Stover
, and
A. P.
Hitchcock
,
J. Phys. Chem. C
111
,
16330
(
2007
).
28.
M.
Gentili
,
C.
Giovannella
, and
S.
Selci
,
Nanolithography: A Borderland Between STM, EB, IB, and X-ray Lithographies
(
Springer Science & Business Media
,
New York
,
2013
), Vol. 264.
29.
E.
Becker
,
W.
Ehrfeld
,
P.
Hagmann
,
A.
Maner
, and
D.
Münchmeyer
,
Microelectron. Eng.
4
,
35
(
1986
).
30.
W.
Chao
,
P.
Fischer
,
T.
Tyliszczak
,
S.
Rekawa
,
E.
Anderson
, and
P.
Naulleau
,
Opt. Express
20
,
9777
(
2012
).
31.
J.
Vila-Comamala
,
K.
Jefimovs
,
J.
Raabe
,
T.
Pilvi
,
R. H.
Fink
,
M.
Senoner
,
A.
Maaßdorf
,
M.
Ritala
, and
C.
David
,
Ultramicroscopy
109
,
1360
(
2009
).
32.
S.
Werner
,
S.
Rehbein
,
P.
Guttmann
, and
G.
Schneider
,
Nano Res.
7
,
528
(
2014
).
33.
I.
Mohacsi
,
I.
Vartiainen
,
M.
Guizar-Sicairos
,
P.
Karvinen
,
V. A.
Guzenko
,
E.
Müller
,
C. M.
Kewish
,
A.
Somogyi
, and
C.
David
,
Opt. Lett.
41
,
281
(
2016
).
34.
F.
Vollnhals
,
M.
Drost
,
F.
Tu
,
E.
Carrasco
,
A.
Späth
,
R. H.
Fink
,
H.-P.
Steinrück
, and
H.
Marbach
,
Beilstein J. Nanotechnol.
5
,
1175
(
2014
).
35.
F.
Tu
,
M.
Drost
,
F.
Vollnhals
,
A.
Späth
,
E.
Carrasco
,
R.
Fink
, and
H.
Marbach
,
Nanotechnology
27
,
355302
(
2016
).
36.
J.
Raabe
 et al.,
Rev. Sci. Instrum.
79
,
113704
(
2008
).
37.
T.
Huthwelker
,
V.
Zelenay
,
M.
Birrer
,
A.
Krepelova
,
J.
Raabe
,
G.
Tzvetkov
,
M. G.
Vernooij
, and
M.
Ammann
,
Rev. Sci. Instrum.
81
,
113706
(
2010
).
38.
H.
Ade
and
A. P.
Hitchcock
,
Polymer
49
,
643
(
2008
).
39.
E. M. G. B. L.
Henke
and
J. C.
Davis
,
At. Data Nucl. Data Tables
54
,
181
(
1993
).
40.
A. F. G.
Leontowich
,
A. P.
Hitchcock
,
T.
Tyliszczak
,
M.
Weigand
,
J.
Wang
, and
C.
Karunakaran
,
J. Synchrotron Radiat.
19
,
976
(
2012
).
41.
C. T.
Chantler
,
J. Phys. Chem. Ref. Data
24
,
71
(
1995
).
42.
A.
Saywell
 et al.,
Nat. Commun.
1
,
75
(
2010
).
43.
M.-M.
Walz
,
F.
Vollnhals
,
F.
Rietzler
,
M.
Schirmer
,
H.-P.
Steinrück
, and
H.
Marbach
,
Appl. Phys. Lett.
100
,
053118
(
2012
).
44.
H.
Sun
,
X.
Qin
, and
F.
Zaera
,
J. Phys. Chem. Lett.
3
,
2523
(
2012
).
45.
S.
Mehendale
,
J.
Mulders
, and
P.
Trompenaars
,
Nanotechnology
24
,
145303
(
2013
).
46.
A.
Botman
,
J.
Mulders
,
R.
Weemaes
, and
S.
Mentink
,
Nanotechnology
17
,
3779
(
2006
).
47.
P.
Salén
,
V.
Yatsyna
,
L.
Schio
,
R.
Feifel
,
R.
Richter
,
M.
Alagia
,
S.
Stranges
, and
V.
Zhaunerchyk
,
J. Chem. Phys.
144
,
244310
(
2016
).
48.
I.
Mohacsi
,
P.
Karvinen
,
I.
Vartiainen
,
V. A.
Guzenko
,
A.
Somogyi
,
C. M.
Kewish
,
P.
Mercere
, and
C.
David
,
J. Synchrotron Radiat.
21
,
497
(
2014
).
49.
See supplementary material at http://dx.doi.org/10.1116/1.4979274 for C K-edge NEXAFS spectra of the deposits presented in this work.

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