Photophysics, photochemistry, and optical properties of polyimides

Abstract This review discusses charge transfer (CT) interactions in wholly aromatic polyimides (PI). Discussion was extended to the influence of CT interactions on PI properties, i.e. photophysics, photochemistry, optical properties, and other properties. Section 2 deals with the electronic states and photophysics in PIs. Most of the experimental and theoretical data evidenced the presence of both intra- and interchain CT interactions in wholly aromatic PIs. A model compound approach made it possible to understand the detailed intramolecular photophysics including the intramolecular CT process. However, it is still a long way from obtaining quantitative information such as the concentration (population) and thermodynamic parameters of intermolecular CT complex (CTC) present in the PI solids. Wholly aromatic PIs show a broad/structureless fluorescence in a long-wavelength range, originating from intermolecular CTC. A few papers revealed that the CT fluorescence intensity increased corresponding to the degree of chain packing/staking. Thus, the CT fluorescence was applied to studies on local ordering and binary PI blend miscibility. In Section 3, the influence of CTC on photoconductivity, mechanical and other properties is discussed. Low molecular weight donor-loaded PI exhibited prominent photoconductivity enhancement. Transient absorption measurements revealed that the CTC formed between the added donor and the acceptor moiety in the PI chains is responsible for the photoinduced charge generation process. The donor-free PI film also showed a similar transient absorption spectrum to the donor-loaded PI film, suggesting that even wholly aromatic PI itself can form CTC. The CTC sites in PIs may act as physical crosslinks. But it is not yet clear how the thermal and mechanical properties (glass transition temperature, thermoplasticity or melt viscosity, modulus, etc.) of PI films are affected by CTC formation. A paper reported that CT-inhibited PIs, such as semi-aromatic PIs, tend to show a much higher voltage holding ratio, which is desirable for liquid crystal displays, than the corresponding wholly aromatic PIs. Section 4 reviews photosensitive PIs and their precursor systems. In this section, photochemistry in an intrinsically photosensitive polyimide containing a benzophenone unit and photodegradation in fluorine-containing PIs are also described. For benzophenone-containing PIs, the model compound approach was carried out to depict a detailed energy diagram including some photochemical kinetic parameters. The use of a series of model compounds elucidated a prominent conformation effect on the photoinduced hydrogen abstraction efficiency. The control of transparency and refractive indices and birefringence of PI films and molecular-design were focused in Section 5. This section also describes why the control of such optical properties has been demanding for practical applications. Finally, non-linear optical (NLO) properties of several PIs and their related systems, modified by attaching NLO chromophores, were reviewed.

[1]  D. L. Hammick,et al.  113. Interaction of Lewis acids with aromatic hydrocarbons and bases. Part XVI. The association of chloranil with methylbenzenes in cyclohexane , 1956 .

[2]  J. Brédas,et al.  Electronic structure of polyimide , 1987 .

[3]  Naoya Yoda,et al.  New Photosensitive High Temperature Polymers for Electronic Applications , 1984 .

[4]  I. Mita,et al.  Miscibility of polyimide/polyimide blends and charge-transfer fluorescence spectra , 1991 .

[5]  K. Horie,et al.  Synthesis and Chemically Amplified Photo-Cross-Linking Reaction of a Polyimide Containing an Epoxy Group , 1996 .

[6]  M. I. Bessonov,et al.  Polyamic Acids and Polyimides: Synthesis, Transformations, and Structure , 1993 .

[7]  M. Chowdhury.  ABSORPTION MAXIMA OF SOME MOLECULAR COMPLEXES , 1962 .

[8]  G. Price,et al.  Morphology of a phase-separated and a molecular composite PBT/ABPBI polymer blend , 1986 .

[9]  D. Y. Yoon,et al.  Molecular order in condensed states of semiflexible poly(amic acid) and polyimide , 1984 .

[10]  R. S. Mulliken.  Molecular Compounds and their Spectra. II , 1952 .

[11]  R. Yokota,et al.  Structure and Properties of Novel Asymmetric Biphenyl Type Polyimides. Homo- and Copolymers and Blends , 1999 .

[12]  K. Weiss,et al.  Photochemistry of charge-transfer systems. II. Complexes of pyromellitic dianhydride with polynuclear aromatic hydrocarbons , 1971 .

[13]  Toshihiko Matsumoto,et al.  Soluble Polyimides with Polyalicyclic Structure. 4. Colorless Polyimides from Bicyclo[2.2.1]heptane-2-endo,3-endo,5-exo,6-exo-tetracarboxylic 2,3:5,6-Dianhydride , 1995 .

[14]  Y. Tokita,et al.  Special Issue on Computational Polymer Science. I. Intramolecular Charge Transfer and Conformation of Polyimide Chains. Photophysical and Photochemical Processes in Model Compounds. , 1994 .

[15]  J. S. Patel,et al.  The mechanism of polymer alignment of liquid‐crystal materials , 1987 .

[16]  Norbert Adolph Lange,et al.  Handbook of chemistry , 1944 .

[17]  M. Ieda,et al.  Effect of Molecular Order on Photoconduction of Polyimide , 1984 .

[18]  Shinji Ando,et al.  Thin, flexible waveplate of fluorinated polyimide , 1993 .

[19]  Jung Y. Huang,et al.  Real-Time Poling Vapor Co-deposition of Dye-Doped Second-Order Nonlinear Optical Polymer Thin Films , 1997 .

[20]  Tsuguo Yamaoka,et al.  Fluorine-containing photoreactive polyimide. 6. Synthesis and properties of a novel photoreactive polyimide based on photo-induced acidolysis and the kinetics for its acidolysis , 1990 .

[21]  R. S. Mulliken.  MOLECULAR COMPOUNDS AND THEIR SPECTRA. 3. THE INTERACTION OF ELECTRON DONORS AND ACCEPTORS , 1952 .

[22]  R. Nagarajan,et al.  Photodegradation of polyimides. 6. Effect of donor-acceptor groups on the photooxidative stability of polyimides and model compounds , 1994 .

[23]  F. Nakanishi,et al.  Aliphatic poly(amido acids) and polyimides with cyclobutane ring in the main chain , 1973 .

[24]  M. I. Bessonov,et al.  Polyimides : thermally stable polymers , 1987 .

[25]  S. Kobayashi,et al.  Relationship between Pretilt Angles of Liquid Crystals and Surface Energies of Polyimides Containing Fluorine Atoms , 1995 .

[26]  P. Gardner,et al.  α- AND β-VERBESINOL. SESQUITERPENE ALCOHOLS OF THE cis-DECALIN SERIES , 1961 .

[27]  N. Kinjo,et al.  Re-examination of the relationship between packing coefficient and thermal expansion coefficient for aromatic polyimides , 1987 .

[28]  R. Siegoczyński,et al.  Radiative and radiationless processes in charge-transfer complexes , 1969 .

[29]  P. Pillai,et al.  Field dependence of photoconduction in Kapton polyimide film , 1979 .

[30]  J. P. Lafemina,et al.  Electronic structure and ultraviolet absorption spectrum of polyimide , 1989 .

[31]  T. Fukuda,et al.  Synthesis and properties of a second-order nonlinear optical side-chain polyimide , 1999 .

[32]  E. Lippert.  N. Mataga und T. Kubota: Molecular Interactions and Electronic Spectra. Marcel Dekker, Inc., New York 1970, 504 Seiten. Preis: $28.50 , 1971 .

[33]  Romeo B. Wagner,et al.  Synthetic organic chemistry , 1953 .

[34]  T. Moore,et al.  Photodriven charge separation in a carotenoporphyrin–quinone triad , 1984, Nature.

[35]  W. Person,et al.  Molecular Interactions and Electronic Spectra , 1970 .

[36]  C. R. Goldschmidt,et al.  Photoionization of charge-transfer systems. Pyromellitic dianhydride-mesitylene complex , 1969 .

[37]  H. Ogawa,et al.  Electrophotographic and structural studies on novel photoconductive polyimide films , 1991 .

[38]  K. Horie,et al.  Photoconductivity of a polyimide with an alicyclic diamine: Charge carrier photogeneration in the mixed layer packing arrangement , 1998 .

[39]  J. Tanaka,et al.  Phosphorescence of the Charge‐Transfer Triplet States of Some Molecular Complexes , 1967 .

[40]  E. Wachsman,et al.  Effect of cure history on the morphology of polyimide: Fluorescence spectroscopy as a method for determining the degree of cure , 1988 .

[41]  V. Lee,et al.  Synthesis and nonlinear optical properties of donor-acceptor substituted triaryl azole derivatives , 1993 .

[42]  S. Ando,et al.  Coloration of Aromatic Polyimides and Electronic Properties of Their Source Materials , 1997 .

[43]  Toshihiko Matsumoto,et al.  Soluble Polyimides with Polyalicyclic Structure.3. Polyimides from (4arH,8acH)-Decahydro-1t,4t:5c,8c-dimethanonaphthalene- 2t,3t,6c,7c-tetracarboxylic 2,3:6,7-Dianhydride , 1994 .

[44]  Tohru Matsuura,et al.  Low loss, heat-resistant optical waveguides using new fluorinated polyimides , 1993 .

[45]  J. Mcgrath,et al.  Polyimides : materials, chemistry, and characterization : proceedings of the Third International Conference on Polyimides, Ellenville, New York, November 2-4, 1988 , 1989 .

[46]  Juan C. Scaiano,et al.  The mechanism of photocure of inherently photosensitive polyimides containing a benzophenone group , 1989 .

[47]  K. Horie,et al.  Diffusion-Controlled Reactions in Polymer Systems , 1987 .

[48]  S. Freilich.  Photoconductivity of donor-loaded polyimides , 1987 .

[49]  Toshihiko Matsumoto,et al.  Soluble polyimides with polyalicyclic structure. 2. Polyimides from bicyclo[2.2.1]heptane-2-exo-3-exo-5-exo-6-exo-tetracarboxylic 2,3:5,6-dianhydride , 1993 .

[50]  J. Hedrick,et al.  Structures and dielectric properties of thin polyimide films with nano‐foam morphology , 1996 .

[51]  K. Horie,et al.  Photo-cross-linking reaction of benzophenone-containing polyimide and its model compounds , 1991 .

[52]  J. Scaiano,et al.  Photochemistry of a benzophenone-containing bisimide: a model for inherently photosensitive polyimides , 1988 .

[53]  J. P. Lafemina,et al.  Emission mechanism in polyimide , 1990 .

[54]  Wataru Sakai,et al.  Nonlinear optical (NLO) polymers. 3. NLO polyimide with dipole moments aligned transverse to the imide linkage , 1998 .

[55]  K. Horie,et al.  Photoconductivity of a Polyimide with an Alicyclic Diamine Doped with N,N,N′N′-Tetramethyl-p-phenylenediamine , 1997 .

[56]  Kang-Wook Lee,et al.  Microscopic Molecular Reorientation of Alignment Layer Polymer Surfaces Induced by Rubbing and Its Effects on LC Pretilt Angles , 1996 .

[57]  H. Hoegl.  On Photoelectric Effects in Polymers and Their Sensitization by Dopants1 , 1965 .

[58]  K. Horie,et al.  Absorption, Fluorescence, and Thermal Properties of Transparent Polyimides Based on Cyclobutanetetracarboxylic Dianhydride , 1998 .

[59]  Tsuneo Mitsuyu,et al.  Optical poling and its application in optical storage of a polyimide film with high glass transition temperature , 1998 .

[60]  Luping Yu,et al.  Design and Synthesis of Functionalized Polyimides for Second-Order Nonlinear Optics , 1994 .

[61]  A. Knoesen,et al.  Influence of the polymer structure on the achievement of polar orientation in high glass transition temperature nonlinear optical polyimides by photo-assisted poling , 1998 .

[62]  T. Matsuo,et al.  A Study of the Charge-Transfer Complexes. I. The Interaction of Pyromellitic Dianhydride with Polymethylbenzenes , 1965 .

[63]  I. Mita,et al.  Charge‐Transfer emission spectra of aromatic polyimides , 1989 .

[64]  Philippe Pretre,et al.  Relaxation Processes in Nonlinear Optical Polyimide Side-Chain Polymers , 1996 .

[65]  M. Jurich,et al.  Exceptionally Thermally Stable Polyimides for Second-Order Nonlinear Optical Applications , 1995, Science.

[66]  S. Ando,et al.  Perfluorinated polyimide synthesis , 1992 .

[67]  T. L. Clair,et al.  Solid‐State 13C‐NMR spectral evidence for charge transfer complex formation in aromatic diimides and dianhydrides , 1992 .

[68]  D. Rehm,et al.  Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer , 1970 .

[69]  M. Kakihana,et al.  Materials Research Society Symposium - Proceedings , 2000 .

[70]  K. Horie,et al.  Photophysical processes in aromatic polyimides. Studies with model compounds , 1993 .

[71]  Kazuyuki Horie,et al.  Third-order nonlinear optical properties of aromatic polyisoimides , 2000 .

[72]  I. Mita,et al.  Molecular aggregation and fluorescence spectra of aromatic polyimides , 1989 .

[73]  K. Horie,et al.  Polyimides with alicyclic diamines. II. Hydrogen abstraction and photocrosslinking reactions of benzophenone-type polyimides , 1994 .

[74]  G. Maier.  Polymers for microelectronics , 2001 .

[75]  M. Barmentlo,et al.  Effect of rubbing on the molecular orientation within polyimide orienting layers of liquid‐crystal displays , 1993 .

[76]  L. Hornak.  Polymers for lightwave and integrated optics : technology and applications , 1992 .

[77]  G. Tesoro,et al.  On the crosslinking mechanism of benzophenone-containing polyimides , 1988 .

[78]  M. Ieda,et al.  Photogeneration of Charge Carriers in Polyimide Films , 1983 .

[79]  Y. Shirota,et al.  Photoelectrical conversion of p-n heterojunction devices using thin films of titanyl phthalocyanine and a perylene pigment , 1996 .

[80]  W. W. Wright,et al.  A study of some properties of aromatic imides , 1971 .

[81]  Tohru Matsuura,et al.  Heat-resistant singlemode optical waveguides using fluorinated polyimides , 1993 .

[82]  Kenneth D. Singer,et al.  Polymers for second-order nonlinear optics , 1995 .

[83]  Samant,et al.  X-PEEM Study on Surface Orientation of Stylized and Rubbed Polyimides. , 1998, Macromolecules.

[84]  G. Oster,et al.  Ultraviolet induced crosslinking and grafting of solid high polymers , 1959 .

[85]  J. A. Logan,et al.  Near-surface alignment of polymers in rubbed films , 1995, Nature.

[86]  N. Turro.  Modern Molecular Photochemistry , 1978 .

[87]  Brédas,et al.  Electronic structure of polyimide and related monomers: Theory and experiment. , 1990, Physical review. B, Condensed matter.

[88]  S. Kuroda,et al.  Degradation of aromatic polymers: Part IV—Effect of temperature and light intensity on the photodegradation of polyethersulfone , 1990 .

[89]  J. Moore,et al.  An intrinsically photosensitive polyimide , 1989 .

[90]  S. Mazur,et al.  Electrochemistry of Aromatic Polyimides , 1987 .

[91]  C. Rao.  Ultraviolet and Visible Spectroscopy , 1967 .

[92]  K. L. Mittal,et al.  Polyimides: Fundamentals and Applications , 1996 .

[93]  C. David,et al.  Statistical theories of main chain scission and crosslinking of polymers—application to the photolysis and radiolysis of polystyrene studied by gel permeation chromatography , 1978 .

[94]  W. D. Phillips,et al.  Cyanocarbon Chemistry. II.1 Spectroscopic Studies of the Molecular Complexes of Tetracyanoethylene , 1958 .

[95]  T. Yamaoka,et al.  Fluorine-containing photoreactive polyimide. 7. Photochemical reaction of pendant 1,2-naphthoquinone diazide moieties in novel photoreactive polyimides , 1990 .

[96]  T. Kozawa,et al.  Transient Absorption Spectra of Photoconductive Polyimides and Their Model Compound by Picosecond Pulse Radiolysis , 1997 .

[97]  Joseph A. Castellano,et al.  Surface Anchoring of Liquid Crystal Molecules on Various Substrates , 1983 .

[98]  M. Ree,et al.  Miscibility behavior and reequilibration of binary poly(amic acid) mixtures , 1991 .

[99]  W. Volksen,et al.  Effects of chemical structure and precursor on optical properties, thermo-mechanical properties, and molecular orientation and order of thin films of stiff aromatic polyimides , 1994 .

[100]  C. Hoyle,et al.  Photodegradation of polyimides. I. A spectral, viscometric, chromatographic, and weight loss investigation of polyimides based on a hexafluorinated dianhydride , 1991 .

[101]  Y. M. Cai,et al.  Dispersion of second‐order optical properties of new high thermal stability guest chromophores , 1993 .

[102]  K. L. Mittal,et al.  Polyimides : synthesis, characterization, and applications , 1984 .

[103]  W. Price.  The effect of alkyl substitution on the spectra and ionization potentials of some fundamental chromophores. , 1947, Chemical reviews.

[104]  M. Ieda,et al.  Photoconduction in Polyimide (Kapton H) , 1982 .

[105]  K. Kao,et al.  Ultraviolet absorption and photoconduction spectra of polyimide films fabricated at various curing temperatures , 1993 .

[106]  Stephen Z. D. Cheng,et al.  Nonlinear-Optical Studies of a Fluorinated Poled Polyimide Guest-Host System , 1994 .

[107]  R. Cotter,et al.  Charge-transfer complexing in polymer mixtures. IV. Acceptor polymers from nitrophthalic acids and their mixtures with donor polymers from aryliminodiethanols , 1970 .

[108]  Luping Yu,et al.  Novel aromatic polyimides for nonlinear optics , 1995 .

[109]  E. Pitts,et al.  A Photographic Theory of Crosslinking Resists , 1981 .

[110]  J. Ishii,et al.  Unique fluorescence behavior of perylenetetracarboxydiimides in polyimide systems , 1998 .

[111]  V. Wintgens,et al.  Spectroscopic properties of aromatic dicarboximides. Part 2.—Substituent effect on the photophysical properties of N-phenyl-1,2-naphthalimide , 1994 .

[112]  C. A. Parker,et al.  Fluorescence of charge transfer complexes in solution , 1967 .

[113]  K. Watanabe.  Ionization Potentials of Some Molecules , 1957 .

[114]  R. Reisfeld,et al.  The perylene derivative BASF-241 solution as a new tunable dye laser in the visible , 1990 .

[115]  G. Smets,et al.  Photochemical reactions on polymers , 1984 .

[116]  V. Percec,et al.  Interchain electron donor-acceptor complexes: a model to study polymer-polymer miscibility? , 1986 .

[117]  Hiroshi Fujiwara,et al.  p‐i‐n like behavior in three‐layered organic solar cells having a co‐deposited interlayer of pigments , 1992 .

[118]  T. Yamaoka,et al.  A new positive‐type photoreactive polyimide precursor using 1,4‐dihydropyridine derivative , 1992 .

[119]  W. R. Remington.  The Effects of Steric Inhibition of Resonance on Ultraviolet Absorption Spectra1 , 1945 .

[120]  T. Russell,et al.  A small‐angle X‐ray scattering study of an aromatic polyimide , 1984 .

[121]  R. Penwell,et al.  Poly(N‐vinylcarbazole): A selective review of its polymerization, structure, properties, and electrical characteristics , 1978 .

[122]  T. Matsuura,et al.  Polyimide derived from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. 1. Synthesis and characterization of polyimides prepared with 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or pyromellitic dianhydride , 1991 .

[123]  D. W. Berreman,et al.  Solid Surface Shape and the Alignment of an Adjacent Nematic Liquid Crystal , 1972 .

[124]  Willi Volksen,et al.  Light-induced orientation in a high glass transition temperature polyimide with polar azo dyes in the side chain , 1996 .

[125]  Tohru Matsuura,et al.  Polyimides derived from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. 3. Property control for polymer blends and copolymerization of fluorinated polyimides , 1993 .

[126]  Toshihiko Matsumoto,et al.  Soluble and Colorless Polyimides from Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3:5,6-Dianhydrides1 , 1997 .

[127]  B. Zysset,et al.  Modified polyimide side-chain polymers for electrooptics , 1994 .

[128]  T. Yamashita,et al.  Photosensitive Polyimides: Fundamentals and Applications , 1995 .

[129]  I. Mita,et al.  Isothermal Imidization of an Aromatic Polyimide Precursor Studied by Fluorescence Spectroscopy , 1990 .

[130]  J. Koenig,et al.  Spectroscopic Studies of Poly[N,N'-bis(phenoxyphenyl)pyromellitimide]. 1. Structures of the Polyimide and Three Model Compounds , 1980 .

[131]  T. Matsuo.  A Study of the Charge-Transfer Complexes. II. The Complexes of Pyromellitic Dianhydride with Polycyclic Aromatic Compounds , 1965 .

[132]  J. Kendrick,et al.  Single-crystal x-ray studies of aromatic oligomers: conformation and packing in isomeric pyromellitimide-ether-sulfones , 1991 .

[133]  G. Kavarnos,et al.  Fundamentals of Photoinduced Electron Transfer , 1993 .

[134]  M. Takayanagi,et al.  Polymer composites of rigid and flexible molecules: System of wholly aromatic and aliphatic polyamides , 1980 .

[135]  C. Hoyle,et al.  Photodegradation of polyimides. II. Thermal property changes of polyimides based on a hexafluorinated dianhydride , 1991 .

[136]  Joel H. Hildebrand,et al.  A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons , 1949 .

[137]  H. M. Rosenberg,et al.  π-Complex Fluorescence. I. Room-Temperature Solution Studies of the Pyromellitic Dianhydride-Methylbenzene Complexes , 1966 .

[138]  G. F. Lipscomb,et al.  Thermal stability of electro‐optic response in poled polyimide systems , 1991 .

[139]  N. Mataga,et al.  Picosecond dynamics of photochemical electron transfer in porphyrin-quinone intramolecular exciplex systems , 1984 .

[140]  K. Horie,et al.  In-Plane Orientation in Poly(amic acid)s during Thermal Imidization , 1999 .

[141]  J. Ishii,et al.  Polyimide/Polyimide Blend Miscibility Probed by Perylenetetracarboxydiimide Fluorescence , 1999 .

[142]  S. Ando,et al.  Polyimides Derived from 2,2'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl. 4. Optical Properties of Fluorinated Polyimides for Optoelectronic Components , 1994 .

[143]  J. Verhoeven,et al.  Pronounced solvatochromism of charge-transfer complexes in strongly hydrogen bonding solvents , 1975 .

[144]  Thomas F. Deutsch,et al.  Time-resolved UV absorption of polyimide , 1991 .

[145]  R. Nagarajan,et al.  Photodegradation of Polyimides .5. An Explanation of the Rapid Photolytic Decomposition of a Selected Polyimide via Anhydride Formation , 1992 .

[146]  Y. Shindo,et al.  Spontaneous Molecular Orientation of Polyimides Induced by Thermal Imidization. 2. In-Plane Orientation , 1996 .

[147]  Kenneth D. Singer,et al.  Crosslinked polyimide electro‐optic materials , 1995 .

[148]  H. Philipp,et al.  Optical absorption of some polymers in the region 240-170 nm , 1986 .