Warstwy Langmuira-Blodgett i ich wykorzystanie w elektronice molekularnej

• Autorzy: Chyla A.

Warianty tytułu

EN

Langmuir-Blodgett films and their application to molecular electronics

• Języki publikacji: PL

Abstrakty

PL

Omówiono metody wytwarzania oraz perspektywy zastosowania w elektronice molekularnej ultracienkich warstw złożonych z jednej lub kilku warstw monomolekularnych. Nawrót zainteresowania warstwami Langmuira-Blodgett (LB), zwłaszcza wśród badaczy zajmujących się nanotechnologią i inżynierią molekularną, tkwi w oferowanych przez technikę LB możliwościach operowania niewielkimi zbiorami cząsteczek o specyficznych, często zaprogramowanych właściwościach. W dwóch pierwszych rozdziałach monografii przedstawiono molekularny i termodynamiczny opis granicy faz oraz omówiono zagadnienia związane z napięciem powierzchniowym zarówno czystych cieczy jak i roztworów. Przedstawiono metody pomiaru napięcia powierzchniowego i szczegółowo omówiono stosowaną powszechnie w technice LB metodę płytki Wilhelmy'ego. Cząsteczki związku powierzchniowo czynnego zaadsorbowane na powierzchni cieczy tworzą powierzchniową warstwę Langmuira. Zmniejszenie powierzchni przypadającej na jedną cząsteczkę jest równoważne sprężaniu warstwy i prowadzi do gęściejszego upakowania cząsteczetc na powierzchni subfazy i przejścia warstwy w stan dwuwymiarowej cieczy. Dalsze sprężanie warstwy prowadzi do powstania stanu charakteryzującego się bardzo małą ściśliwością- dwuwymiarowego ciała stałego. Stan termodynamiczny oraz jakość otrzymanej warstwy określa izoterma sprężania, przedstawiająca zależność ciśnienia powierzchniowego od powierzchni przypadającej na pojedynczą cząsteczkę. Omówiono właściwości cząsteczek amfifilowych, tworzących warstwy Langmuira, oraz warunki laboratoryjne otrzymywania zarówno pojedynczych warstw LB, jak i układów wielowarstwowych. Przedstawiono zagadnienia związane z czystością materiałów i urządzeń, rozpościeraniem i sprężaniem monowarstwy oraz jej przenoszeniem na podłoża stałe. Na tle komercyjnych urządzeń do otrzymywania warstw, tzw. wanien LB, autor omawia wykonaną i oprogramowaną przez siebie i współpracowników wannę o stałym obwodzie, charakteryzującą się symetrycznym rozpływem materiału warstwy w trakcie badania izoterm sprężania oraz podczas nanoszenia warstwy na podłoże stałe. Opisano również wiele typów specyficznych cząsteczek oraz metody ich zastosowania do wytwarzania warstw LB o zaprojektowanych właściwościach. Opisane zagadnienia można zaliczyć do rozwijającej się intensywnie nauki o materiałach, której celem jest projektowanie cząsteczek o pożądanych właściwościach fizykochemicznych oraz weryfikacja właściwości zarówno samych cząsteczek, jak i ich zbiorów w postaci monomolekularnych warstw LB. Ważną rolę w projektowaniu cząsteczek odgrywają kwantowochemiczne badania modelowe. Badając izomeryzację cis-trans w azobenzenach, stwierdzono, że stosunkowo wysoka bariera rotacji wokół wiązania N=N w stanie gazowym znacznie obniża się po przyłączeniu protonu do jednego z atomów azotu wiązania azowego. Źródłem protonów w trakcie rozpościerania i nanoszenia warstw LB z subfazy wodnej są grupy karboksylowe używanych azobenzenów. Szczegółowe obliczenia barier reakcji izomeryzacji cis-trans w środowisku protycznym dla modelowych substancji - diazenu, dimetylodiazenu, azobenzenu (o ogólnym wzorze R1-NN-R2) oraz 4-fenyloazopirydyny pokazały, że geometrie stanu przejściowego zarówno formy neutralnej, jak i protonowanej są bardzo podobne, natomiast bariera izomeryzacji cis-trans po protonowaniu obniża się o wartość zależną od elektrofilowych właściwości podstawników i dodatnio naładowanych grup funkcyjnych, stabilizujących stan przejściowy. Podobny mechanizm może także występować w azobenzenach typu push-pull, używanych jako materiały w optyce nieliniowej. Opisano badania przemian strukturalnych zachodzących w warstwach LB i omówiono stabilność wytworzonych warstw, poddając szczegółowej analizie strukturę łańcuchów węglowodorowych na granicy faz gaz-ciecz oraz na podłożach stałych. Perspektywa zastosowania monomolekular-nych warstw LB i budowy układów wielowarstwowych z monowarstw nałożonych warstwa po warstwie wymusza potrzebę pomiaru ich rzeczywistej grubości, którą zazwyczaj określa się przez badanie stanu polaryzacji bądź intensywności spolaryzowanej liniowo fali świetlnej, odbitej od warstwy LB. Omówiono metody pomiarowe, których podstawę teoretyczną stanowi konwencjonalna teoria odbicia płaskiej fali elektromagnetycznej od ośrodka charakteryzującego się strukturą warstwową. Główne rozważania dotyczą metod stosowanych przez autora do wyznaczania zarówno grubości warstw, jak i ich parametrów optycznych, takich jak metoda różnicowego odbicia, zmodyfikowana metoda Laxhubera i metoda SPR. Końcową część monografii poświęcono zastosowaniu warstw LB w technice, a zwłaszcza w wielu dziedzinach elektroniki molekularnej. Opisano wiele urządzeń wykorzystujących zjawiska piezo- i piroelektryczne, nieliniowe zjawiska optyczne, efekt prostowniczy i polowy, zjawiska fotochromowe i elektrochromowe oraz elektroluminescencję. Omówiono zastosowanie warstw LB jako czynnych i biernych elementów czujników gazowych i chemicznych. Na tym tle przedstawiono udział autora w pracach związanych z badaniem i konstrukcją cienkowarstwowych czujników elektrochemicznych czujników SPR. Użycie pojedynczego czujnika gazowego, chemicznego lub biologicznego dostarcza w jednym pomiarze informacji w postaci jednej liczby, np. rezystancji lub spadku napięcia na rezystorze referencyjnym. Oznacza to, że w najlepszym razie możemy określić co najwyżej stężenie badanej substancji. Zastosowanie matrycy czujników pozwala rozróżnić wpływ kilku składników analitu i stanowi podstawę konstrukcji sieci neuronowej. Zaletą takiego rozwiązania jest powtarzalność wyników pomiaru oraz obiektywizm ekspertyz dokonywanych automatycznie przez sieć neuronową. Autor zbudował i przetestował miniaturową sieć neuronową, służącą do rozpoznawania składników mieszaniny alkohol etylowy-amoniak w powietrzu i pomiaru ich stężenia. Sieć stanowiły umieszczone w komorze mieszalnika gazów dwa konduktometryczne czujniki gazowe, w których warstwę LB składającą się z 3 lub 5 monowarstw mieszaniny 1:1 poli-(oktadecylo pirolu) i 4-f-butyloftalocyjaniny miedzi naniesiono na układ palczastych elektrod. Prąd płynący przez czujniki przy stałej różnicy potencjałów między elektrodami mierzono w funkcji stężenia gazu zarówno dla poszczególnych składników mieszaniny, jak i dla mieszanin gazów. Autor przedstawił swój udział w pracach nad zastosowaniem warstw Langmuira-Blodgett jako przykładów modelowych błon pseudobiologicznych. Techniką LB wytworzono podobne do biologicznych podwójne błony, otrzymane z klasycznych, długołańcuchowych cząsteczek kwasu eikozanowego oraz 22-trikozanowego z niewielką domieszką hek-satriakontanu. Warstwy podwójne były stabilne na powietrzu oraz hydrofilowe z obu stron i wytrzymywały do kilkudziesięciu zanurzeń i wynurzeń w trakcie pomiaru kąta zwilżania.

EN

Methods of fabricating and handling of Langmuir-Blodgett (LB) films as well as some perspectives of their application in the field of molecular electronics are presented. Within two introductory chapters the molecular and thermodynamic state of gas-liquid interface is described and methods of the surface tension measurements are also closed up. In particular, the Wilhelmy plate method is presented in details. Since LB films mostly consist amphiphilic molecules, particular attention is paid to the description of diverse molecules, those already used for LB films preparation as well as of novel ones, intentionally designed and functionalized to build up films of desired properties. The author gives some hints for quantum-chemical calculations concerning molecular engineering and shows his attainment on modification and manipulation of molecules to obtain LB films of expected properties. Structural changes and transitions occurring in LB films and problems related to film stability and real thicknesses of the films are widely described. Two methods of the thickness measurements were exploited: the modified Laxhuber method and the Surface Plasmon Resonance method. The latter one can be successfully used for determination of optical parameters of the film, particularly of environment depended parameters and therefore it can be used for construction of optical sensors. The author has also been involved in designing electrochemical gas and chemical sensors. He designed and built up a simple artificial neural network that can measure with a very high accuracy concentration of gases (ethanol and ammonia vapours) in mixtures. Finally, the author shows a possibility of building up some model, pseudo-biological membranes made of aliphatic acids mixed with long chain hydrocarbons.

Słowa kluczowe

PL

warstwy Langmuira-Blodgett; granica faz; napięcie powierzchniowe; związki powierzchniowo czynne; izoterma sprężania; ciśnienie powierzchniowe; technika LB

• Wydawca: Oficyna Wydawnicza Politechniki Wrocławskiej
• Czasopismo: Prace Naukowe Instytutu Chemii Fizycznej i Teoretycznej Politechniki Wrocławskiej. Monografie
• Rocznik: 2004
• Tom: nr 2
• Strony: 3--176
• Opis fizyczny: Bibliogr. 515 poz., tab., rys.

Twórcy

autor

Chyla A.

• Wydział Chemii Politechniki Wrocławskiej

• Instytut Chemii Fizycznej i Teoretycznej Politechniki Wrocławskiej, 50-370 Wrocław, Wybrzeże Wyspiańskiego 27.

Bibliografia

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