Single-molecule imaging of organic semiconductors: Toward nanoscale insights into photophysics and molecular packing

a b s t r a c t Photophysical properties of functionalized anthradithiophene (ADT) and pentacene (Pn) derivatives, as well as energy and charge transfer properties of donor-acceptor (D/A) pairs of these derivatives, are presented. The molecules studied were imaged on the single-molecule level in a polymeric and in a func- tionalized benzothiophene (BTBTB) crystalline host using room-temperature wide-field epifluorescence microscopy. The BTBTB host imposed orientational constraints on the guest molecules, depending on their functionalization. Flexibility of functionalization of both guest (ADT, Pn) and host (BTBTB) molecules can be used for systematic studies of nanoscale morphology and photophysics of D/A organic semiconductor bulk heterojunctions using single-molecule fluorescence microscopy.

[1]  J. Anthony.  Small-Molecule, Nonfullerene Acceptors for Polymer Bulk Heterojunction Organic Photovoltaics† , 2011 .

[2]  Christoph J. Brabec,et al.  Organic Ternary Solar Cells: A Review , 2013, Advanced materials.

[3]  John E. Anthony,et al.  Optical, photoluminescent, and photoconductive properties of functionalized anthradithiophene and benzothiophene derivatives , 2010, OPTO.

[4]  D. Ginger,et al.  Characterizing Morphology in Bulk Heterojunction Organic Photovoltaic Systems , 2010 .

[5]  W E Moerner,et al.  New directions in single-molecule imaging and analysis , 2007, Proceedings of the National Academy of Sciences.

[6]  J Enderlein,et al.  Theoretical study of detection of a dipole emitter through an objective with high numerical aperture. , 2000, Optics letters.

[7]  P. Barbara,et al.  Single-molecule spectroscopy of conjugated polymers. , 2005, Accounts of chemical research.

[8]  John E. Anthony,et al.  Energy Transfer and Exciplex Formation and Their Impact on Exciton and Charge Carrier Dynamics in Organic Films , 2011 .

[9]  M. J. Kendrick,et al.  Synthesis and charge transport studies of stable, soluble hexacenes. , 2012, Chemical communications.

[10]  Martin Baumgarten,et al.  Dithieno[2,3‐d;2′,3′‐d′]benzo[1,2‐b;4,5‐b′]dithiophene (DTBDT) as Semiconductor for High‐Performance, Solution‐Processed Organic Field‐Effect Transistors , 2009 .

[11]  T. Laurence,et al.  Polarization Spectroscopy of Single Fluorescent Molecules , 1999 .

[12]  Robert M Dickson,et al.  Three-dimensional single molecule rotational diffusion in glassy state polymer films. , 2002, Physical review letters.

[13]  Oksana Ostroverkhova,et al.  Handbook of organic materials for optical and (opto)electronic devices , 2013 .

[14]  Sankar Subramanian,et al.  Chromophore fluorination enhances crystallization and stability of soluble anthradithiophene semiconductors. , 2008, Journal of the American Chemical Society.

[15]  S. Krause,et al.  Efficient simultaneous fluorescence orientation, spectrum, and lifetime detection for single molecule dynamics. , 2012, The Journal of chemical physics.

[16]  B. Valeur,et al.  Molecular Fluorescence: Principles and Applications , 2001 .

[17]  M. Orrit,et al.  Single molecules detect ultra-slow oscillators in a molecular crystal excited by ac voltages , 2009 .

[18]  W E Moerner,et al.  Photophysical properties of acene DCDHF fluorophores: long-wavelength single-molecule emitters designed for cellular imaging. , 2007, The journal of physical chemistry. A.

[19]  M. Torres-Cisneros,et al.  Effect of PMMA impregnation on the fluorescence quantum yield of sol–gel glasses doped with quinine sulfate , 2001 .

[20]  John E. Anthony,et al.  Small-Molecule Bulk Heterojunctions: Distinguishing Between Effects of Energy Offsets and Molecular Packing on Optoelectronic Properties , 2013 .

[21]  John E. Anthony,et al.  Formation of the Donor–Acceptor Charge-Transfer Exciton and Its Contribution to Charge Photogeneration and Recombination in Small-Molecule Bulk Heterojunctions , 2012 .

[22]  Itaru Osaka,et al.  Thienoacene‐Based Organic Semiconductors , 2011, Advanced materials.

[23]  David Hofer,et al.  Aggregate formation and its effect on (opto)electronic properties of guest-host organic semiconductors , 2010 .

[24]  Alois Renn,et al.  Aligned terrylene molecules in a spin-coated ultrathin crystalline film of p-terphenyl , 2004 .

[25]  Michel Orrit,et al.  Single-molecule photophysics, from cryogenic to ambient conditions. , 2014, Chemical Society reviews.

[26]  John E. Anthony,et al.  Enhanced charge photogeneration promoted by crystallinity in small-molecule donor-acceptor bulk heterojunctions , 2014, Applied Physics Letters.

[27]  D. V. Vanden Bout,et al.  Unraveling the chromophoric disorder of poly(3-hexylthiophene) , 2013, Proceedings of the National Academy of Sciences.

[28]  Z. Bao,et al.  Correlating carrier type with frontier molecular orbital energy levels in organic thin film transistors of functionalized acene derivatives. , 2009, Journal of the American Chemical Society.

[29]  W. E. Moerner,et al.  Novel fluorophores for single-molecule imaging. , 2003 .

[30]  David Beljonne,et al.  Effect of fluorination on the electronic structure and optical excitations of pi-conjugated molecules. , 2007, The Journal of chemical physics.

[31]  F. Cichos,et al.  Blinking of single molecules in various environments , 2005 .

[32]  Paul F. Barbara,et al.  Detailed Investigation of Light Induced Charge Injection into a Single Conjugated Polymer Chain , 2008 .

[33]  John E. Anthony,et al.  High-mobility spin-cast organic thin film transistors , 2008 .

[34]  M. Halik,et al.  Interface engineering in high-performance low-voltage organic thin-film transistors based on 2,7-dialkyl-[1]benzothieno[3,2-b][1]benzothiophenes. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[35]  John E. Anthony,et al.  Optical, Fluorescent, and (Photo)conductive Properties of High-Performance Functionalized Pentacene and Anthradithiophene Derivatives , 2009 .

[36]  J. Fourkas,et al.  Rapid determination of the three-dimensional orientation of single molecules. , 2001, Optics letters.

[37]  H. Matsui,et al.  Inkjet printing of single-crystal films , 2011, Nature.

[38]  John E Anthony,et al.  Functionalized acenes and heteroacenes for organic electronics. , 2006, Chemical reviews.

[39]  Christopher R. Swartz,et al.  Synthesis and characterization of electron-deficient pentacenes. , 2005, Organic letters.

[40]  M. Orrit,et al.  Intermolecular intersystem crossing in single-molecule spectroscopy: Terrylene in anthracene crystal. , 2006, The Journal of chemical physics.

[41]  J. Hofkens,et al.  Fluorescence lifetimes and emission patterns probe the 3D orientation of the emitting chromophore in a multichromophoric system. , 2004, Journal of the American Chemical Society.

[42]  John E. Anthony,et al.  Contact-induced crystallinity for high-performance soluble acene-based transistors and circuits. , 2008, Nature materials.

[43]  J. Lupton,et al.  Single‐Molecule Spectroscopy for Plastic Electronics: Materials Analysis from the Bottom‐Up , 2010, Advanced materials.

[44]  J. Krajcovic,et al.  Spectral characteristics of bisthiophenes and terthiophenes linked with heterocyclic unit in solution and polymer matrix , 2001 .

[45]  W. Moerner,et al.  Experimental and theoretical investigations of environmentally sensitive single-molecule fluorophores , 2004, InternationalQuantum Electronics Conference, 2004. (IQEC)..

[46]  W. Moerner,et al.  Illuminating single molecules in condensed matter. , 1999, Science.

[47]  Kristin L. Wustholz,et al.  Applications of single-molecule microscopy to problems in dyed composite materials , 2008 .

[48]  John E. Anthony,et al.  Temperature dependence of exciton and charge carrier dynamics in organic thin films , 2011 .

[49]  John E. Anthony,et al.  Design of organic ternary blends and small-molecule bulk heterojunctions: photophysical considerations , 2015 .