Сенсибилизации фотоэффекта

Спектры поглощения раствора и твердой пленки ПВК практически воспроизводят спектр исходного мономера изопропилкарбазола (ИПК). В твердой фазе хромофорные группы полимера сохраняют индивидуальность, и поглощение осуществляется каждой группой как отдельной молекулой. Как показали исследования флуоресценции, в твердой фазе оказывается возможным образование эксимеров между различными частями одной и той же молекулы. Каждая молекула имеет множество хромофорных групп, и эксимерная флуоресценция полимера, в отличие от флуоресценции мономера, относительно независима от концентрации. Основное состояние, у эксимеров, отсутствует, что делает невозможным их прямое возбуждение при поглощении света. Наблюдение эксимерной флуоресценции у твердого ПВК и ее анализ приводит к выводу, что возбуждение эксимеров должно происходить в результате миграции синглетных экситонов вдоль полимерной цепи или с одной цепи на другую. Аморфная структура полимера неизбежно предопределяет прыжковый характер движения экситона. Оценка средней длины пробега синглетных экситонов в ПВК дает значение 4-8 нм. Вероятность передачи энергии между моно мерными звеньями одной цепи по крайней мере на порядок превышает вероятность такой передачи между различными молекулами полимера, а собственные подвижности экситонов в полимере и мономере одинаковы. Оптические свойства ПЭПК близки к свойствам ПВК, так как они обусловлены наличием того же карбазольного хромофора. Длинноволновые полосы поглощения ПЭПК находятся у 345,295 и 260 нм.
Фото чувствительность ПВК впервые исследовал Хегль. Он установил, что даже ничтожные следы донорно-акцепторных молекул оказывают разительное влияние на фото чувствительность полимера. В дальнейшем была четко установлена определяющая роль донорно-акцепторного взаимодействия на фотоэлектрические процессы.

 

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