Talha M. Khan

A Universal Method to Produce Low–Work Function Electrodes for Organic Electronics

A Sturdy Electrode Coating To operate efficiently, organic devices—such as light-emitting diodes—require electrodes that emit or take up electrons at low applied voltages (that is, have low work functions). Often these electrodes are metals, such as calcium, that are not stable in air or water vapor and have to be protected from environmental damage. Zhou et al. (p. 327; see the Perspective by Helander) report that a coating polymer containing aliphatic amine groups can lower the work functions of various types of electrodes by up to 1.7 electron volts and can be used in a variety of devices. Air-stable, physisorbed polymers containing aliphatic amine groups can improve the efficiency of organic electronic devices. Organic and printed electronics technologies require conductors with a work function that is sufficiently low to facilitate the transport of electrons in and out of various optoelectronic devices. We show that surface modifiers based on polymers containing simple aliphatic amine groups substantially reduce the work function of conductors including metals, transparent conductive metal oxides, conducting polymers, and graphene. The reduction arises from physisorption of the neutral polymer, which turns the modified conductors into efficient electron-selective electrodes in organic optoelectronic devices. These polymer surface modifiers are processed in air from solution, providing an appealing alternative to chemically reactive low–work function metals. Their use can pave the way to simplified manufacturing of low-cost and large-area organic electronic technologies.

Recyclable organic solar cells on cellulose nanocrystal substrates

Solar energy is potentially the largest source of renewable energy at our disposal, but significant advances are required to make photovoltaic technologies economically viable and, from a life-cycle perspective, environmentally friendly, and consequently scalable. Cellulose nanomaterials are emerging high-value nanoparticles extracted from plants that are abundant, renewable, and sustainable. Here, we report on the first demonstration of efficient polymer solar cells fabricated on optically transparent cellulose nanocrystal (CNC) substrates. The solar cells fabricated on the CNC substrates display good rectification in the dark and reach a power conversion efficiency of 2.7%. In addition, we demonstrate that these solar cells can be easily separated and recycled into their major components using low-energy processes at room temperature, opening the door for a truly recyclable solar cell technology. Efficient and easily recyclable organic solar cells on CNC substrates are expected to be an attractive technology for sustainable, scalable, and environmentally-friendly energy production.

High performance polymeric charge recombination layer for organic tandem solar cells

We report on inverted polymer tandem solar cells wherein the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), modified at one interface with ethoxylated polyethylenimine (PEIE), acts as an efficient charge recombination layer. This recombination layer shows very low optical absorption, high electrical conductivity, and a large work function contrast of 1.3 eV between its top and bottom interfaces. Its use yields tandem cells in which the open-circuit voltage is the sum of that of individual cells. The fill factor of tandem cells connected in series is found to be larger than that of single-junction cells. Its simple polymeric composition and its unprecedented performance make it a promising component for emerging organic photovoltaic technologies.

All-plastic solar cells with a high photovoltaic dynamic range

We report on semitransparent air-processed all-plastic solar cells, fabricated from vacuum-free processes, comprising two polymer electrodes, a polymeric work-function modification layer and a polymer:fullerene photoactive layer. The active layer and the top PEDOT:PSS electrode were prepared by sequential film-transfer lamination on polyethylenimine-modified PEDOT:PSS bottom electrodes. The transferring of films offers ease of layer patterning and the misalignment of defects in the different layers resulting from the additive film transfer lamination process yields high shunt resistance values of 108 ohm cm2. Consequently, all-plastic solar cells fabricated with this process exhibit very low reverse bias dark current and can operate in the photovoltaic quadrant with light irradiance varying over five orders of magnitude. The analysis of the values of the open-circuit voltage as a function of light irradiance over that wide dynamic range points toward an ideality factor of n = 1.82 and a reverse saturation current density of 6.2 × 10−11 A cm−2 for solar cells with an active layer comprised of a blend of poly(3-hexylthiophene) and an indene fullerene bis-adduct.

Organic Photovoltaic Cells with Stable Top Metal Electrodes Modified with Polyethylenimine

Efficient organic photovoltaic cells (OPV) often contain highly reactive low-work-function calcium electron-collecting electrodes. In this work, efficient OPV are demonstrated in which calcium electrodes were avoided by depositing a thin layer of the amine-containing nonconjugated polymer, polyethylenimine (PEIE), between the photoactive organic semiconductor layer and stable metal electrodes such as aluminum, silver, or gold. Devices with structure ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/poly(3-hexylthiophene):indene-C60-bis-adduct (P3HT:ICBA)/PEIE/Al demonstrated overall photovoltaic device performance comparable to devices containing calcium electron-collecting electrodes, ITO/PEDOT:PSS/P3HT:ICBA/Ca/Al, with open-circuit voltage of 775±6 mV, short-circuit current density of 9.1±0.5 mA cm(-2), fill factor of 0.65±0.01, and power conversion efficiency of 4.6±0.3%, averaged over 5 devices at 1 sun.

A Study on Reducing Contact Resistance in Solution-Processed Organic Field-Effect Transistors

We report on the reduction of contact resistance in solution-processed TIPS-pentacene (6,13-bis(triisopropylsilylethynyl)pentacene) and PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) top-gate bottom-contact organic field-effect transistors (OFETs) by using different contact-modification strategies. The study compares the contact resistance values in devices that comprise Au source/drain electrodes either treated with 2,3,4,5,6-pentafluorothiophenol (PFBT), or modified with an evaporated thin layer of the metal-organic molecular dopant molybdenum tris-[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd)3), or modified with a thin layer of the oxide MoO3. An improved performance is observed in devices modified with Mo(tfd)3 or MoO3 as compared to devices in which Au electrodes are modified with PFBT. We discuss the origin of the decrease in contact resistance in terms of increase of the work function of the modified Au electrodes, Fermi-level pinning effects, and decrease of bulk resistance by electrically doping the organic semiconductor films in the vicinity of the source/drain electrodes.

Organometallic Dimers: Application to Work-Function Reduction of Conducting Oxides

The dimers of pentamethyliridocene and ruthenium pentamethylcyclopentadienyl mesitylene, (IrCp*Cp)2 and (RuCp*mes)2, respectively, are shown here to be effective solution-processable reagents for lowering the work functions of electrode materials; this approach is compared to the use of solution-deposited films of ethoxylated poly(ethylenimine) (PEIE). The work functions of indium tin oxide (ITO), zinc oxide, and gold electrodes can be reduced to 3.3-3.4 eV by immersion in a toluene solution of (IrCp*Cp)2; these values are similar to those that can be obtained by spin-coating a thin layer of PEIE onto the electrodes. The work-function reductions achieved using (IrCp*Cp)2 are primarily attributable to the interface dipoles associated with the formation of submonolayers of IrCp*Cp(+) cations on negatively charged substrates, which in turn result from redox reactions between the dimer and the electrode. The electrical properties of C60 diodes with dimer-modified ITO cathodes are similar to those of analogous devices with PEIE-modified ITO cathodes.

Near room-temperature direct encapsulation of organic photovoltaics by plasma-based deposition techniques

Plasma-assisted atomic layer deposition (ALD) is used for the deposition of environmental barriers directly onto organic photovoltaic devices (OPVs) at near room temperature (30 °C). To study the effect of the ALD process on the organic materials forming the device, the precursor diffusion and intermixing at the interface during the growth of different plasma-assisted ALD inorganic barriers (i.e. Al2O3 and TiO2) onto the organic photoactive layer (P3HT:ICBA) was investigated. Depth profile x-ray photoelectron spectroscopy was used to analyze the composition of the organic/inorganic interface to investigate the infiltration of the plasma-assisted ALD precursors into the photoactive layer as a function of the precursor dimension, the process temperature, and organic layer morphology. The free volume in the photoactive layer accessible to the ALD precursor was characterized by means of ellipsometric porosimetry (EP) and spectroscopic ellipsometry as a function of temperature. The organic layer is shown to exhibit free volume broadening at high temperatures, increasing the infiltration depth of the ALD precursor into the photoactive layer. Furthermore, based on previous investigations, the intrinsic permeation properties of the inorganic layers deposited by plasma-assisted ALD were predicted from the nano-porosity content as measured by EP and found to be in the 10−6 gm−2 d−1 range. Insight from our studies was used to design and fabricate multilayer barriers synthesized at near-room temperature by plasma-assisted ALD in combination with plasma-enhanced CVD onto organic photovoltaic (OPVs) devices. Encapsulated OPVs displayed shelf-lifetimes up to 1400 h at ambient conditions.

Recent advances in organic photodiodes (Conference Presentation)

Although the detection of photons is ubiquitous, man-made photon detectors still limits the effectiveness of applications such as light/laser detection, photography, astronomy, quantum information science, medical imaging, microscopy, communications, and others. The performance of the technologically most advanced detectors based on CMOS semiconductor technology has improved during the last decades but at the detriment of increased complexity, higher cost, limited portability and compactness, and limited area. On the other hand, nature has produced a relatively simple detector with remarkable properties: the human eye. The exploration of new paradigms in photon detection using new material platforms might therefore provide a path to further challenge the frontiers of applications enabled by light. In this talk, we will report on the realization of solution-processed organic semiconductor visible spectrum photodetectors with a high specific detectivity above 1014 Jones, at least an order of magnitude larger than values found in photodiodes based on silicon. These detectors demonstrate a sub-pA current under reverse bias in the dark, making them suitable for detecting very low levels of light. The small dark current under reverse bias allows the characterization of these devices over 9 orders of magnitude of increasing light irradiance. The detectors are based on the device structure: tin-doped indium oxide / ethoxylated polyethylenimine / poly(3-hexylthiophene) : indene C60 bisadduct / molybdenum oxide / silver and present a path toward fabrication on flexible substrates. We will show that these detectors can operate over a large dynamic range in the self-powered photovoltaic mode where the light produces a photovoltage that can be measured directly without any external bias source. We believe that large-area flexible photodetectors with detectivity values comparable to or better than those displayed by silicon-based photodiodes will enable a wide variety of applications from the detection of radiation to non-planar imaging arrays.

Organic field-effect transistor circuits with electrode interconnections using reverse stamping

We discuss a non-vacuum low-cost reverse stamping method for the realization of circuits based on top-gate organic field-effect transistors (OFETs) with a bi-layer gate dielectric. This method allows for patterning of high-k inorganic dielectric films produced by atomic layer deposition and consequently of the bilayer gate dielectric layers used in our top-gate OFETs. We demonstrate the fabrication and operation of logic inverters and ring oscillators following this approach.