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Title: Measurement of Small Molecular Dopant F4TCNQ and C60F36 Diffusion in Organic Bilayer Architectures

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [1];  [2];  [1];  [3];  [1]
  1. Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering and Materials Science
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of Oxford (United Kingdom). Dept. of Physics

The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this paper, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C60F36) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics. With the use of absorbance spectroscopy, photoluminescence spectroscopy, neutron reflectometry, and near-edge X-ray absorption fine structure spectroscopy, we are able to obtain a comprehensive picture of the diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ spontaneously diffuses into the MeO-TPD material even at room temperature, while C60F36, a much bulkier molecule, is shown to have a substantially higher morphological stability. Finally, this study highlights that the differences in size/geometry and thermal properties of small molecular dopants can have a significant impact on their diffusion in organic device architectures.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, Davis, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC52-07NA27344; AC52-06NA25396; SC0010419
OSTI ID:
1438680
Report Number(s):
LLNL-JRNL-736459
Journal Information:
ACS Applied Materials and Interfaces, Vol. 7, Issue 51; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 71 works
Citation information provided by
Web of Science

References (52)

High-Performance Organic Field-Effect Transistors journal April 2009
Molecular Semiconductors in Organic Photovoltaic Cells journal November 2010
Aqueous Solution-Processed GeO 2 : An Anode Interfacial Layer for High Performance and Air-Stable Organic Solar Cells journal October 2013
Degradation Mechanism of Small Molecule-Based Organic Light-Emitting Devices journal March 1999
Efficiency and Air-Stability Improvement of Flexible Inverted Polymer Solar Cells Using ZnO/Poly(ethylene glycol) Hybrids as Cathode Buffer Layers journal June 2013
Stability of Polymer Solar Cells journal December 2011
Degradation and stability of polymer-based solar cells journal January 2012
Electron transporting semiconducting polymers in organic electronics journal January 2011
High-efficiency hole extraction/electron-blocking layer to replace poly(3,4-ethylenedioxythiophene)poly(styrene sulfonate) in bulk-heterojunction polymer solar cells journal January 2008
Low-voltage organic electroluminescent devices using pin structures journal January 2002
Doping of organic semiconductors journal December 2012
Fermi level shift and doping efficiency in p -doped small molecule organic semiconductors: A photoelectron spectroscopy and theoretical study journal July 2012
Enhanced Hole Injection into Amorphous Hole-Transport Layers of Organic Light-Emitting Diodes Using Controlled p-Type Doping journal August 2001
n-Doping of Organic Electronic Materials using Air-Stable Organometallics journal November 2011
Ultrastable and efficient red organic light emitting diodes with doped transport layers journal August 2006
p-type doping in organic light emitting diodes based on fluorinated C60 journal December 2008
Mechanistic Study on the Solution-Phase n-Doping of 1,3-Dimethyl-2-aryl-2,3-dihydro-1 H -benzoimidazole Derivatives journal September 2013
A novel p-dopant with low diffusion tendency and its application to organic light-emitting diodes journal April 2010
Quenching of excitons in doped disordered organic semiconductors journal November 2004
Polarons and bipolarons in doped polythiophene: A theoretical investigation journal August 1987
Bipolarons in poly(3-methylthiophene): Spectroscopic, magnetic, and electrochemical measurements journal November 1987
Lithium doping of semiconducting organic charge transport materials journal May 2001
Bright organic electroluminescent devices having a metal-doped electron-injecting layer journal November 1998
Controllable Molecular Doping and Charge Transport in Solution-Processed Polymer Semiconducting Layers journal June 2009
The chemical and structural origin of efficient p-type doping in P3HT journal May 2013
Introducing Solubility Control for Improved Organic P-Type Dopants journal August 2015
Organic light-emitting diodes using 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane as p-type dopant journal February 2009
Investigation of C 60 F 36 as low-volatility p -dopant in organic optoelectronic devices journal May 2011
Ground-State Interaction and Electrical Doping of Fluorinated C 60 in Conjugated Polymers journal November 2009
SPEAR — ToF neutron reflectometer at the Los Alamos Neutron Science Center journal November 2011
Co-refinement of multiple-contrast neutron/X-ray reflectivity data using MOTOFIT journal March 2006
Calibrated NEXAFS spectra of common conjugated polymers journal January 2011
The effect of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane charge transfer dopants on the conformation and aggregation of poly(3-hexylthiophene) journal January 2013
Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling journal June 2013
Effect of trap states on the electrical doping of organic semiconductors journal January 2014
Substituted Quinodimethans. II. Anion-radical Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan journal September 1962
Leuco Crystal Violet as a Dopant for n-Doping of Organic Thin Films of Fullerene C 60 journal November 2004
p-Doped p-phenylenediamine-substituted fluorenes for organic electroluminescent devices journal July 2009
2-(2-Methoxyphenyl)-1,3-dimethyl-1 H -benzoimidazol-3-ium Iodide as a New Air-Stable n-Type Dopant for Vacuum-Processed Organic Semiconductor Thin Films journal February 2012
An organic p-type dopant with high thermal stability for an organic semiconductor journal January 2008
Doped organic semiconductors: Physics and application in light emitting diodes journal September 2003
High-efficiency p-i-n organic light-emitting diodes with long lifetime journal January 2005
Controlling Electrical Properties of Conjugated Polymers via a Solution-Based p-Type Doping journal September 2008
Effect of Crystallization on the Electronic Energy Levels and Thin Film Morphology of P3HT:PCBM Blends journal April 2011
The Consequences of Interface Mixing on Organic Photovoltaic Device Characteristics journal March 2011
High work-function hole transport layers by self-assembly using a fluorinated additive journal January 2014
Intraphase Microstructure-Understanding the Impact on Organic Solar Cell Performance journal May 2013
DV-Xα calculation of electron energy-loss near edge-structures of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) journal April 2004
Electronic structure of C60F36 studied by quantum-chemical modeling of experimental photoemission and x-ray absorption spectra journal January 2009
Controlled p doping of the hole-transport molecular material N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine with tetrafluorotetracyanoquinodimethane journal July 2003
Highly Efficient Organic Devices Based on Electrically Doped Transport Layers journal April 2007
Photoelectron spectroscopy study of systematically varied doping concentrations in an organic semiconductor layer using a molecular p-dopant journal November 2009

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A Solvent‐Free Solution: Vacuum‐Deposited Organic Monolayers Modify Work Functions of Noble Metal Electrodes journal February 2019
Controlling Molecular Doping in Organic Semiconductors journal September 2017
Chemical and Morphological Control of Interfacial Self-Doping for Efficient Organic Electronics journal March 2018
Enhanced Charge Injection Properties of Organic Field-Effect Transistor by Molecular Implantation Doping journal January 2019
Trade-Off between Trap Filling, Trap Creation, and Charge Recombination Results in Performance Increase at Ultralow Doping Levels in Bulk Heterojunction Solar Cells journal August 2016
Solution-based electrical doping of semiconducting polymer films over a limited depth journal December 2016
Elementary steps in electrical doping of organic semiconductors journal March 2018
Uniform doping of graphene close to the Dirac point by polymer-assisted assembly of molecular dopants journal September 2018
Ground-state electron transfer in all-polymer donor–acceptor heterojunctions journal March 2020
Organic/Organic Heterointerface Engineering to Boost Carrier Injection in OLEDs journal February 2017
Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: effect of doping-induced aggregation on film morphology journal January 2016
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A photo-crosslinkable bis-triarylamine side-chain polymer as a hole-transport material for stable perovskite solar cells journal January 2020
Sequential molecular doping of non-fullerene organic solar cells without hole transport layers journal January 2020
Utilizing Diels–Alder “click” chemistry to functionalize the organic–organic interface of semiconducting polymers journal January 2020
Thermal stability and interlayer exchange processes in heterolayers of TiOPc and PTCDA on Ag(1 1 1) journal February 2019
Energy-level alignment at strongly coupled organic–metal interfaces journal March 2019
Morphology controls the thermoelectric power factor of a doped semiconducting polymer journal June 2017
Publisher Correction: Elementary steps in electrical doping of organic semiconductors journal June 2018