Óhlaðin sameidabrot og hlutverk lágorkurafeinda í fjölsameinda efnahvörfum við hreinsun rafeindadrifinna útfellinga - verkefni lokið

Fréttatilkynning verkefnisstjóra

11.8.2022

Þar sem háorku geislar víxlverka við fastefni er óumflýjanlegt að rafeindir losni úr þeim sameindum sem mynda efnið. Þessar rafeindir eru mjög hvarfgjarnar og valda að öllu jöfnu skaða. Hinsvegar, þar sem hægt er að stýra þeim efnahvörfum sem þær valda, er einnig hægt að nýta þær til að drífa áfram efnahvörf sem hafa jákvæð áhrif. Þar sem örtæknimunstur eru mynduð með háorkuljósi eða háorkurafeindageislum er því mikilvægt að skilja og geta stjórnað slíkum hvörfum. Það sama á við í geislameðferð á krabbameini þar sem sérsniðnar sameindir eru notaðar til að auka þann skaða sem slík geislun veldur krabbameinsfrumum. Grunnurinn að því að nýta sér lágorku rafeindir í efnahvörfum, hvort sem það er í örtækni eða krabbameinsmeðferð, er að skilja hvörfin sem eiga sér stað og hvernig hægt er að stýra þeim með sem bestum hætti. Á því var megin áhersla þessa verkefnis. 
Verkefnið var tvíþætt. Annarsvegar var unnið að uppbyggingu tilraunasamstæðu til að rannsaka
myndun óhlaðinna sameindabrota í rafeindadrifnum efnahvörfum. Hinsvegar var unnið að
rannsóknum á rafeindadrifnum efnahvörfum á efnum í gasham og á yfirborðum fastefna. Það var gert, bæði með tilraunum og skammtafræðilegum reikningum. Áherslan var á efni sem mögulega nýtast í örtækniiðnaði og rannsóknir voru unnar í samvinnu við erlend fyrirtæki og háskóla þar sem áhersla er á slíkar rannsóknir. Einnig voru skoðaðar leiðir til að auka virkni efna sem notuð eru til örvunar geislameðferðar á krabbameini.

Niðurstöður verkefnisins hafa verið birtar í átta greinum í alþjóðlegum, ritrýndum vísindatímaritum, sem flest hafa háan áhrifastuðul og sjö greinar um niðurstöður verkefnisins eru í skrifum. Þær verða sendar út til birtingar á næstu mánuðum. Verkefnið er einnig stór hluti þriggja doktorsverkefna sem áætlað er að verði varin í júní, október og nóvember 2022.

English:

Where high energy radiation interacts with solid material, low energy electrons are released. These
are highly reactive and may cause molecular fragmentation and damage to the material. However,
when the reactivity and the reaction paths initiated can be controlled, such low energy electrons may be used to direct chemical reactions favourably. Thus, where high energy light or high energy electron irradiation is used in nanotechnology to write pattern or structures, it is important to understand and eventually control the reactivity of the low energy electrons generated. The same applies in radiotherapy where specific radiosensitizers are used to amplify radiation damage to cancer cells. To be able to take advantage of these low energy electrons, may that be in nanotechnology or in radiotherapy, it is essential to understand their reactivity and how that reactivity can be directed in a favourable way by tailoring molecules to the right response. This was the main topic of the current project.

The project was twofold. On the one hand it aimed at the design and construction of instrumentation to detect neutral fragments in electron induced molecular fragmentation. On the other hand, a number of studies on low energy electron induced fragmentation of a variety of target molecules were conducted. These studies were both experimental and theoretical and low energy electron interaction with these molecules was studied in the gas phase and at surfaces. The emphasis was on molecular entities relevant for nanofabrication, but studies relevant to the design of efficient radiosensitizers were also conducted. The studies were conducted in collaboration with industrial and academic partners from Germany, France, US and Portugal, that all focus on these topics. Through this project the fundament for experimental instrumentation for the detection of neutral fragments in electron-molecule interaction has been laid. This instrumentation is one of a kind and has the potential to deepen our understanding of these reactions for the benefit of industrial nanofabrication as well as for other sectors, where electron induced fragmentation plays a role. This project has further enabled experimental and theoretical studies relevant for current industrial application of nanofabrication techniques, and studies that have the potential to influence current approaches in the design of radiosensitizers for use in cancer therapy. The results of this project have been publisher in eight articles in peer reviewed scientific journals, most of which have high impact factors. Further seven articles are in preparation and will be submitted for publication within the next few months. This project also constitutes a significant part of three PhD theses that will be up for defence in June, October, and November this year.

Information on how the results will be applied
Through this project the fundament for experimental instrumentation for the detection of neutral
fragments in electron-molecule interactions has been laid. This instrumentation is one of a kind and has the potential to deepen our understanding of these reactions for the benefit of industrial
nanofabrication as well as other sectors where electron induced fragmentation plays a role. In the last quarter of this year the instrumental assembly will be revisited and assessed with respect to manpower and financing needed to finalize it. Reliable neutral fragment detection in electron induced fragmentation has not been realized to date. It is the Holy Grail in these studies and will have high scientific impact and deliver information with potential utilization in industrial applications. The eight papers already published, and the forthcoming seven papers are all relevant for applications, mainly in nanofabrication, but also in cancer therapy. As is always the case with fundamental research the actual impact of this work can only be judged in the years to come.

A list of the project’s outputs
A significant output of this project is the fundament for experimental instrumentation for the detection of neutral fragments in electron-molecule interactions as has been discussed here above. Furthermore, eight peer reviewed scientific publications have already resulted from this project as well as data which is being prepared for seven additional publications. This project has also contributed significantly to the completion of three PhD theses that will be defended this year.

Publications
ISI Journals, published
1. Dissociative ionization and electron beam induced deposition of tetrakis(dimethylamino)silane,
a precursor for silicon nitride deposition. Po-Yuan Shih*, Reza Tafrishi*, Maicol Cipriani,
Christian Felix Hermanns, Jens Oster, Armin Gölzhäuser, Klaus Edinger and Oddur Ingólfsson#,
Phys. Chem. Chem. Phys., 2022, 24, 9564-9575. DOI: https://doi.org/10.1039/D2CP00257D
*Equal contribution first authors, #Corresponding Author
-Open Access (Green)
2. HF Formation through Dissociative Electron Attachment -A Combined Experimental and
Theoretical Study on Pentafluorothiophenol and 2-Fluorothiophenol. Maicol Cipriani and Oddur
Ingólfsson#, Int. J. Mol. Sci. 2022, 23(5), 2430. DOI: https://doi.org/10.3390/ijms23052430
#Corresponding Author
-Open Access (Gold)
3. Low-energy electron interaction and focused electron beam-induced deposition of molybdenum
hexacarbonyl (Mo(CO)6), Po-Yuan Shih*, Maicol Cipriani*, Christian Felix Hermanns, Jens Oster,
Klaus Edinger, Armin Gölzhäuser and Oddur Ingólfsson#, Beilstein J. Nanotechnol. 2022, 13,
182–191. https://doi.org/10.3762/bjnano.13.13
*Equal contribution first authors, #Corresponding Author
-Open Access (Gold)
4. The Role of Low-Energy Electron Interactions in cis-Pt(CO)2Br2 Fragmentation. Maicol Cipriani,
Styrmir Svavarsson, Filipe Ferreira da Silva, Hang Lu, Lisa McElwee-White and Oddur Ingólfsson#,
Int. J. Mol. Sci. 2021, 22(16), 8984; https://doi.org/10.3390/ijms22168984
#Corresponding Author
-Open Access (Gold)
5. Relative cross sections and appearance energies in electron impact ionization and dissociation of mono-halogenated biphenyls. Maicol Cipriani, Ragnar Bjornsson, Michael Barclay, Andreas
Terfortd, Howard Fairbrother and Oddur Ingólfsson#, Int. J. Mass Spectrom., 459, 2021, 116452
https://doi.org/10.1016/j.ijms.2020.116452
#Corresponding Author
-Open Access (Green)
6. Dissociative ionization of the potential focused electron beam induced deposition precursor π-
allyl ruthenium(II) tricarbonyl bromide, a combined theoretical and experimental study. Maicol
Cipriani, Rachel M. Thorman, Christopher R. Brewer, Lisa McElwee-White and Oddur Ingólfsson#,
Eur. Phys. J. D, 2019, 73, 227. DOI: https://doi.org/10.1140/epjd/e2019-100151-9
#Corresponding Author
-Open Access (Green)
7. The role of the dihedral angle and excited cation states in ionization and dissociation of monohalogenated biphenyls; a combined experimental and theoretical coupled cluster study. Michael Barclay, Ragnar Bjornsson#, Maicol Cipriani, Andreas Terfort, D. Howard Fairbrother and Oddur Ingólfsson#, Phys. Chem. Chem. Phys., 2019, 21, 4556-4567, DOI
https://doi.org/10.1039/C8CP07785A
#Corresponding Authors
-Open Access (Green)
8. Electron-Induced Reactions of Ru(CO)4I2: Gas Phase, Surface, and Electron Beam-Induced
Deposition. Thorman, Rachel M.; Jensen, Pernille A.; Yu, Jo-Chi; Matsuda, Scott J.; McElweeWhite, Lisa; Ingolfsson, Oddur; Fairbrother, D. Howard#. J. Phys. Chem. C, 2020, 124 (19), 10593-
10604. DOI: 10.1021/acs.jpcc.0c01801
#Corresponding Authors
-Open Access (Green)

ISI Journals, to be submitted
1. HF and CO2 loss from pentafluorobenzoic acid upon Dissociative Electron Attachment. Maicol
Cipriani and Oddur Ingólfsson. Manuscript in final stage of preparation, target Journal; Journal of
Chemical Physics A.
2. Dissociative electron attachment and dissociative ionization of 2-(trifluoromethyl) acrylic acid
(TFMAA), a model compound for use in extreme ultraviolet lithography resists. Reza Tafrishi,
Daniela Torres-Diaz, Lionel Amiaud, Oddur Ingólfsson, Anne Lafosse. Manuscript in final stage of
preparation, target Journal; Journal of Chemical Physics A.
3. Electron induced reactions of 2-(trifluoromethyl) acrylic acid (TFMAA) monolayers on a gold
substrate, a model compound for use as extreme ultraviolet lithography resists. Reza Tafrishi,
Daniela Torres-Diaz, Lionel Amiaud, Oddur Ingólfsson, Anne Lafosse. Manuscript in final stage of
preparation, target Journal; ACS Nano.
4. Electron induced reactions of methyl acetate, a combined gas phase and surface study on a model compound for use in extreme ultraviolet lithography resists. Reza Tafrishi, Daniela Torres-Diaz, Lionel Amiaud, Oddur Ingólfsson, Anne Lafosse. Manuscript in initial stage of preparation, target Journal; Beilstein Journal of Nanotechnology.
5. Gas-phase and UHV surface science studies on Me3AuPMe3 , a FEBID precursor for gold deposition. Ali Kamali, Elif Bilgilisoy (equal contribution 1st authors), Thomas Gentner, Gerd Ballmann, Sjoerd harder, Hubertus Marbach, Oddur Ingólfsson. Manuscript in final stage of preparation to be submitted to ACS Nano within the next few weeks.
6. Gas-phase and UHV surface science studies on [ClAuMe2]2, a FEBID precursor for gold deposition. Elif Bilgilisoy, Ali Kamali (equal contribution 1st authors), Thomas Gentner, Gerd Ballmann, Sjoerd Harder, Oddur Ingólfsson, and Hubertus Marbach. Manuscript in preparation to be submitted to Nanomaterials within the next two months.
7. Dissociative ionization and dissociative electron attachment to CF3AuCNR, a potential precursor
for FEBID gold deposition. Ali Kamali, Will Carden, Lisa McElwee-White, Oddur Ingólfsson.
Manuscript in preparation to be submitted to The Journal of Chemical Physics A within the next
two months.

PhD Theses
1. PhD theses, Maicol Cipriani, Title: Low energy electron induced decomposition of model
compounds for nano-scale fabrication and for application in chemoradiotherapy. Status:
Submitted, defence date 16. June, 2022.
2. PhD theses, Ali Kamali, Title: Low energy electron induced dissociation of potential gold containing FEBID precursor molecules. Status: In preparation, tentative defence date October, 2022.
3. PhD theses, Resa Tafrishi, Title: Low energy electron induced dissociation of model compounds for extreme ultra violet lithography resist material . Status: In preparation, tentative defence date
November, 2022.

Conferences attended:
1. Elena training school 2018 - Amsterdam, Netherlands, Attendee(s): Maicol Cipriani
2. First Elena conference 2018 – Warsaw, Poland, Attendee(s): Pernille Jensen, Maicol Cipriani
3. PosMol 2019 – Belgrade, Serbia,Attendee(s): Pernille Jensen, Maicol Cipriani
4. Second Elena Conference 2019 – Brussels, Belgium,Attendee(s): Maicol Cipriani
-Two conferences are booked 2022, where results from this project will be presented will probably
be three.

Heiti verkefnis: Óhlaðin sameidabrot og hlutverk lágorkurafeinda í fjölsameinda
efnahvörfum við hreinsun rafeindadrifinna útfellinga / Neutral dissociation and low energy electron induced intermolecular reactions in focused electron beam induced deposition
Verkefnisstjóri: Oddur Ingólfsson, Háskóla Íslands
Tegund styrks: Verkefnisstyrkur
Styrktímabil: 2018-2020
Fjárhæð styrks: 55,911 millj. kr. alls
Tilvísunarnúmer Rannís: 185346