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Efficient reverse saturable absorption of sol-gel hybrid plasmonic glasses
Linköping University, Department of Physics, Chemistry and Biology, Applied Optics. Linköping University, Faculty of Science & Engineering. Electrooptical Systems, Swedish Defence Research Agency (FOI), Linköping, Sweden.
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering. Department of Physics, Norwegian University of Science and Technology, Trondheim, Norway.
Laboratoire de Chimie, ENS de Lyon, Lyon, France.
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2017 (English)In: Optical materials (Amsterdam), ISSN 0925-3467, E-ISSN 1873-1252, Vol. 69, p. 134-140Article in journal (Refereed) Published
Abstract [en]

Monolithic silica sol-gel glasses doped with platinum(II) acetylide complexes possessing respectively four or six phenylacetylene units (PE2-CH2OH and PE3-CH2OH) in combination with various concentrations of spherical and bipyramidal gold nanoparticles (AuNPs) known to enhance non-linear optical absorption, were prepared and polished to high optical quality. The non-linear absorption of the glasses was measured and compared to glasses doped solely with AuNPs, a platinum(II) acetylide with shorter delocalized structure, or combinations of both. At 532 nm excitation wavelength the chromophore inhibited the non-linear scattering previously found for glasses only doped with AuNPs. The measured non-linear absorption was attributed to reverse saturable absorption from the chromophore, as previously reported for PE2-CH2OH/AuNP glasses. At 600 nm strong nonlinear absorption was observed for the PE3-CH2OH/AuNPs glasses, also attributed to reverse saturable absorption. But contrary to previous findings for PE2-CH2OH/AuNPs, no distinct enhancement of the non-linear absorption for PE3-CH2OH/AuNPs was observed. A numerical population model for PE3-CH2OH was used to give a qualitative explanation of this difference. A stronger linear absorption in PE3-CH2OH would cause the highly absorbing triplet state to populate quicker during the leading edge of the laser pulse and this would in turn reduce the influence from two-photon absorption enhancement from AuNPs.

Place, publisher, year, edition, pages
Amsterdam: Elsevier, 2017. Vol. 69, p. 134-140
National Category
Other Physics Topics
Identifiers
URN: urn:nbn:se:liu:diva-138093DOI: 10.1016/j.optmat.2017.04.024ISI: 000404305200018OAI: oai:DiVA.org:liu-138093DiVA, id: diva2:1106753
Note

Funding agencies: French CNRS; ENS Lyon; UCBL; Swedish Armed Forces

Available from: 2017-06-08 Created: 2017-06-08 Last updated: 2019-04-29Bibliographically approved
In thesis
1. Sol-Gel Glasses Doped with Pt-Acetylides and Gold Nanoparticles for Enhanced Optical Power Limiting
Open this publication in new window or tab >>Sol-Gel Glasses Doped with Pt-Acetylides and Gold Nanoparticles for Enhanced Optical Power Limiting
2017 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

High power laser pulses can be a threat to sensors, including the human eye. Traditionally this threat has been alleviated by colour filters that blocks radiation in chosen wavelength ranges. Colour filters’ main drawback is that they block radiation regardless of it being useful or damaging, information is removed for wavelengths at which the filter protect. Protecting the entire wavelength range of a sensor would block or strongly attenuate the radiation needed for the operation of the sensor.

Sol-gel glasses highly doped with Pt-Acetylide chromophores have previously shown high optical quality in combination with efficient optical power limiting through reverse saturable absorption1. These filters will transmit visible light unless the light fluence is above a certain threshold. A key design consideration of laser protection filters is linear absorption in relation to threshold level. By increasing chromophore concentration the threshold is lowered at the expense of higher linear absorption. This means that the user’s view is degraded through the filter.

Adding small amounts of gold nanoparticles to the glasses resulted in an increase in optical power limiting performance. The optimal concentration of gold nanoparticles corresponded to a mean particle distance of several micrometers. The work in this licentiate thesis is about the characterization and explanation of this effect.

The glasses investigated in this work were MTEOS Sol-Gel glasses doped with either only gold nanoparticles of varying shape and concentration, 50mM of PE2-CH2OH codoped with gold nanoparticles or 50mM of PE3-CH2OH codoped with gold nanoparticles. The glasses only doped with gold nanoparticles showed high optical power limiting performance at 532nm laser wavelength, but no optical power limiting at the fluences tested at 600nm. The PE2-CH2OH glasses codoped with gold nanoparticles showed an enhancement of optical power limiting at 600nm for the low gold nanoparticle concentration glasses. The enhancement was weakened or not present for higher concentrations. A similar enhancement above noise level for the PE3-CH2OH glasses was not found.

A population model is used to give a qualitative explanation of the findings. The improvement in optical power limiting performance for the PE2-CH2OH glasses is explained by the gold nanoparticles helping to more quickly populate the highly absorbing triplet state during the rising edge of the laser pulse by enhancing two-photon absorption. The lack of any marked enhancement for the PE3-CH2OH glasses is explained by the PE3-CH2OH chromophore already being of sufficiently high performance to quickly populate the highly absorbing triplet state during the rising edge of the laser pulse. Further work is necessary to validate this model against other chromophores and improving its quantitative predictive power.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2017
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1773
National Category
Atom and Molecular Physics and Optics Signal Processing Telecommunications
Identifiers
urn:nbn:se:liu:diva-135532 (URN)10.3384/lic.diva-135532 (DOI)9789176855454 (ISBN)
Presentation
2017-04-07, Planck, Fysikhuset, Campus Valla, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2017-03-16 Created: 2017-03-16 Last updated: 2019-10-12Bibliographically approved
2. Nonlinear materials for optical power limiting: characterization and modelling
Open this publication in new window or tab >>Nonlinear materials for optical power limiting: characterization and modelling
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

High power laser pulses can be a threat to optical sensors, including the human eye. Traditionally this threat has been alleviated by colour filters that block radiation in chosen wavelength ranges. Colour filters’ main drawback is that they block radiation regardless of it being useful or damaging, information is lost for wavelengths at which the filter is active. Protecting the entire wavelength range of a sensor would block or strongly attenuate the radiation needed for the operation of the sensor.

Sol-gel glasses highly doped with optically non-linear chromophores have previously shown high optical quality in combination with efficient optical power limiting (OPL) through reverse saturable absorption (RSA). These filters transmit visible light unless the light fluence is above a certain threshold. A key design consideration of laser protection filters is linear absorption in relation to the threshold level. A high linear absorption means that the user’s view is degraded by the filter.

To model the photokinetics of RSA chromophores, the five-level population model is widely used. It consists of three singlet and two triplet levels. Model parameters relevant for OPL performance include linear absorption cross-sections, two-photon absorption (2PA) cross-sections, lifetimes, quantum yields and inter-system-crossing (ISC) times. The dominant design paradigm is to have a highly absorbing and long-lived triplet state that is quickly populated by ISC during the beginning of a laser pulse.

To simultaneously achieve a lower threshold and linear absorption a vast number of materials for self-activated filters were evaluated, either as bulk glasses or solutions. An f/5 setup was used to evaluate their OPL performance while several photophysical measurements were performed to gain an understanding of system behaviour. The first three series of methyltriethoxysilane (MTEOS) Sol-Gel glasses were doped with gold nanoparticles either solely, or with one of two Pt-acetylide chromophores. One with shorter conjugated ligands, the second with similar but longer conjugated ligands. Finally, a series of multi-branched fluorene chromophores were evaluated in solution. Their central moiety was either an organic benzene unit or an ISC promoter in the form of para-dibromobenzene or a platinum(II)-alkynyl unit.

For the gold nanoparticle doped glasses, the lower performance Pt-acetylide with short ligands had its OPL threshold lowered at 600nm while the glasses doped with only gold nanoparticles showed no OPL at all. Secondly, the enhancement was most pronounced for very low gold nanoparticle concentrations. While gold nanoparticles alone showed good OPL performance at 532 nm, at this wavelength neither Pt-acetylide showed an obvious OPL enhancement beyond linear absorption losses from codoping with gold nanoparticles.

The improved OPL performance at 600 nm was attributed to stronger 2PA, by electric field enhancement from the gold nanoparticles. The lack of detectable OPL improvement for 532 nm and for the higher performance Pt-Acetylide chromophore with long ligands were qualitatively explained by a lower sensitivity to 2PA on system performance. A degraded performance from linear absorption by excess nanoparticles in front of the focus explained the weakening of the enhancement at higher gold nanoparticle concentrations.

All three fluorene chromophores, including the chromophore without a central ISC promoter, showed broadband OPL through the visible spectrum. The OPL performance of the two chromophores with ISC promoters was expected considering their transient absorption at microsecond time-scales. For the fluorene chromophore without an ISC-promoter, ultra-fast transient absorption was used to identify singlet excited state absorption as the source of the OPL performance.

Both of these series of experiments demonstrate how a simplistic view of simply increasing desired photophysical parameters, e.g. effective 2PA cross-section or ISC quantum yield, do not always result in a noticeable increase in system performance. By employing numerical population models it was possible to identify which parameters had the highest impact on OPL performance.

Abstract [sv]

Laserpulser med hög effekt kan vara ett hot mot optiska sensorer, inklusive det oskyddade ögat. Traditionellt har detta hot hanterats med färgfilter som stoppar strålning inom valda våglängdsband. Färgfilters huvudsakliga begränsning ligger i att de tar bort strålning oberoende av om den är användbar eller skadlig, att information försvinner för de våglängder filtret skyddar för. Skydd över hela det våglängdsband en sensor verkar i skulle stoppa eller kraftigt försvaga strålningen som sensorn behöver för att fungera.

Sol-gel glas högdopade med optiskt icke-linjära molekyler har tidigare visat hög optisk kvalité i kombination med en effektiv optisk effektbegränsning (OPL) via omvänd blekning (RSA). Dessa filter transmitterar synligt ljus så länge ljusets fluens (pulsenergi per area [J cm-2]) inte ligger över en viss begränsningsnivå. En nyckelfaktor i designen av laserskyddsfilter är linjärabsorption kontra begränsningsnivå. Genom att öka kromoforkoncentrationen så kan begränsningsnivån sänkas till kostnad av ökad linjärabsorption. Detta betyder dock att användarens omvärldsuppfattning genom filtret riskerar att minska.

För att modellera fotokinetiken av RSA-molekyler har femnivåpopulationsmodellen varit vida använd. Den består av tre singlet-nivåer och två tripletnivåer. Modellparametrar relevanta för OPL-prestanda innefattar kvantverkningsgrader, olika övergångars linjärabsorptionstvärsnitt, tvåfotonsabsorptionstvärsnitt och livstider samt halveringstider för överföring mellan singlet och triplettillstånd. Den dominanta designparadigmen är att ha ett hög- absorberande och långlivat tripletläge som snabbt populeras i början av en laserpuls.

För att samtidigt uppnå en lägre begränsningsnivå och lägre linjärabsorption utvärderades ett flertal självaktiverade filter, antingen i form av glas eller i vätskelösning. En f/5-uppställning användes för att utvärdera deras OPLprestanda medan en mängd fotofysiska mätningar utfördes för att få en förståelse för deras systembeteende. De tre första serierna av MTEOS Sol-Gel glas var dopade med guldnanopartiklar antingen enbart, eller med en av två Pt(II)-acetylidmolekyler. Den första hade kortare konjugerade ligandarmar, den andra var liknande men hade längre ligandarmar. Slutligen utvärderades en serie av flerarmade flourenmolekyler i vätskelösning. Deras centrala enhet bestod antingen av en organisk bensenring eller en ISC-gynnare i form av para-dibromobensen eller en Pt(II)-acetylidenhet.

Guldnanopartiklarna kunde förstärka OPL-prestandan för enbart den mindre effektiva korta Pt(II)-acetylidmolekylen på 600nm men ej 532nm. Filtren dopade med enbart guldnanopartiklar visade god prestanda på 532nm men ingen på 600nm. Alla tre fluorenmolekyler visade OPL genom det synliga spektrat, även den molekylen utan ISC-gynnare.

Både dessa serier experiment demonstrerar hur ett förenklat angreppsätt med att enbart öka eftertraktade fotofysiska parametrar, t.ex. effektivt 2PA-tvärsnitt eller ISC-kvantverkningsgrad, inte alltid resulterar i märkbart ökad systemprestanda. Genom att använda numeriska populationsmodeller visas hur det är möjligt att identifiera vilka parametrar som har den största inverkan på OPL-prestanda.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2019. p. 56
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1979
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:liu:diva-156612 (URN)10.3384/diss.diva-156612 (DOI)9789176851135 (ISBN)
Public defence
2019-05-10, Planck, Fysikhuset, Campus Valla, Linköping, 10:00 (English)
Opponent
Supervisors
Available from: 2019-04-29 Created: 2019-04-29 Last updated: 2019-05-13Bibliographically approved

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