Photo-oxidation of polymers used in electroluminescent devices

Abstract Two electroluminescent polymers, poly(2,5-bis(cholestanoxy)-1,4-phenylene vinylene) (BCHA-PPV) and poly(3-octylthiophene) (P3OT), have been characterized on Au and Al substrates in terms of photo-oxidative stability after exposure to UV and visible irradiation from a Hg lamp. Thin polymer films were analyzed in situ using IR reflection absorption spectroscopy (IRRAS), and ex situ by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) IR spectroscopy. The oxidation of BCHA-PPV is quite extensive, resulting in the formation of an ester and volatile aldehyde species. Singlet oxygen, formed by energy transfer from the BCHA-PPV triplet state, appears responsible for at least one photo-oxidation pathway. BCHA-PPV triplet exciton states will also form during electroluminescent device operation (the singlet exciton state is responsible for luminescence in the film) resulting in the formation of reactive singlet oxygen. Thus, it appears that BCHA-PPV will slowly self-degrade in the presence of oxygen when used as the active layer in electroluminescent devices. P3OT shows no detectable oxidation during similar exposure.

[1]  R. Porter,et al.  Hydroperoxides from phenyl ring reactions of photo-oxidized polystyrene , 1988 .

[2]  D. Lin-Vien The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules , 1991 .

[3]  W. Richardson,et al.  Thermal decomposition of substituted 1,2-dioxetanes. Consideration of mechanism , 1972 .

[4]  D. Briggs,et al.  High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database , 1992 .

[5]  Miller,et al.  Defect quenching of conjugated polymer luminescence. , 1994, Physical review letters.

[6]  Walter J. Murphy,et al.  ADVANCES IN CHEMISTRY SERIES: Numbers 15 and 17 Demonstrate Rapidly Crowing Interest in Documentation; International Conference To Be Held in 1958 , 1956 .

[7]  R. Greenler Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques , 1966 .

[8]  A. Schaap,et al.  Mechanisms of photooxygenation. 2. Formation of 1,2-dioxetanes via 9,10-dicyanoanthracene-sensitized electron-transfer processes [14] , 1980 .

[9]  Manikandan Jayaraman,et al.  Design, synthesis, and control of conducting polymer architectures: structurally homogeneous poly(3-alkylthiophenes) , 1993 .

[10]  R. Caudano,et al.  The aluminum–polyimide interface: An electron‐induced vibrational spectroscopy approach , 1988 .

[11]  J. Bakker,et al.  Photoactivation of the nematicidal compound alpha-terthienyl from roots of marigolds (Tagetes species). A possible singlet oxygen role. , 1979, The Journal of biological chemistry.

[12]  D. Roberts CNDO/S calculations of the thermal dissociation of 1,2-dioxetan , 1974 .

[13]  S. Holdcroft A photochemical study of poly(3-hexylthiophene) , 1991 .

[14]  R. N. Marks,et al.  Light-emitting diodes based on conjugated polymers , 1990, Nature.

[15]  C. Foote,et al.  Electron-transfer photooxidation. 3. Detection of radical-ion intermediates in the cyanoaromatic-sensitized photooxidation of trans- and cis-stilbene , 1980 .

[16]  B. Rånby,et al.  Photodegradation, photo-oxidation, and photostabilization of polymers;: Principles and applications , 1975 .

[17]  S. Holdcroft,et al.  Mechanisms of photodegradation of poly(3-alkylthiophenes) in solution , 1993 .

[18]  A. J. Heeger,et al.  Improved efficiency in polymer light-emitting diodes using air-stable electrodes , 1993 .

[19]  C. Foote,et al.  Photosensitized oxygenation of alkenes and sulfides via a non-singlet-oxygen mechanism , 1977 .

[20]  J. Ferraro Low-frequency vibrations of inorganic and coordination compounds , 1971 .

[21]  R. H. Friend,et al.  Efficient light-emitting diodes based on polymers with high electron affinities , 1993, Nature.

[22]  R. N. Marks,et al.  Light-emitting diodes fabricated with conjugated polymers — recent progress , 1994 .

[23]  Donal D. C. Bradley,et al.  Conjugated polymer electroluminescence , 1993 .