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How to assess good candidate molecules for self-activated optical power limiting
Linköping University, Department of Physics, Chemistry and Biology. Linköping University, Faculty of Science & Engineering.
Norwegian Def Res Estab FFI, Norway; Norwegian Univ Sci and Technol NTNU, Norway.
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering. Norwegian Univ Sci and Technol NTNU, Norway.
Swedish Def Res Agcy, FOI, Linkoping, Sweden.
2018 (English)In: Optical Engineering: The Journal of SPIE, ISSN 0091-3286, E-ISSN 1560-2303, Vol. 57, no 3, article id 030802Article in journal (Refereed) Published
Abstract [en]

Reverse saturable absorbers have shown great potential to attenuate laser radiation. Good candidate molecules and various particles have successfully been incorporated into different glass matrices, enabling the creation of self-activated filters against damaging laser radiation. Although the performance of such filters has been impressive, work is still ongoing to improve the performance in a wider range of wavelengths and pulse widths. The purpose of this tutorial is, from an optical engineering perspective, to give an understanding of the strengths and weaknesses of this class of smart materials, how relevant photophysical parameters are measured and influence system performance and comment on the pitfalls in experimental evaluation of materials. A numerical population model in combination with simple physical formulas is used to demonstrate system behavior from a performance standpoint. Geometrical reasoning shows the advantage of reverse saturable absorption over nonlinear scattering due to a fraction of scattered light being recollected by imaging system optics. The numerical population model illustrates the importance of the optical power limiting performance during the leading edge of a nanosecond pulse, which is most strongly influenced by changes in the two-photon absorption cross section and the triplet linear absorption cross section for a modeled Pt-acetylide. This tutorial not only targets optical engineers evaluating reverse saturable absorbing materials but also aims to assist researchers with a chemistry background working on optical power limiting materials. We also present photophysical data for a series of coumarins that can be useful for the determination of quantum yields and two-photon cross sections and show examples of characterization of molecules with excited triplet states. (c) 2018 Society of Photo-Optical Instrumentation Engineers (SPIE).

Place, publisher, year, edition, pages
SPIE-SOC PHOTO-OPTICAL INSTRUMENTATION ENGINEERS , 2018. Vol. 57, no 3, article id 030802
Keywords [en]
optical power limiting; reverse saturable absorption; photophysical parameters; measurement
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:liu:diva-147592DOI: 10.1117/1.OE.57.3.030802ISI: 000429265500002OAI: oai:DiVA.org:liu-147592DiVA, id: diva2:1201798
Note

Funding Agencies|Swedish Armed Forces

Available from: 2018-04-26 Created: 2018-04-26 Last updated: 2019-04-29
In thesis
1. 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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