Solution processable small molecules for organic light-emitting diodes

Pristine fullerenes mixed by vacuum-free solution process: Efficient electron transport layer for planar perovskite solar cells

Organic semiconductors devices, such as, organic solar cells (OSCs), organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs) have drawn increasing interest in recent decades. As organic materials are flexible, light weight, and potentially low-cost, organic semiconductor devices are considered to be an alternative to their inorganic counterparts. This dissertation will focus mainly on OSCs and OLEDs. As a clean and renewable energy source, the development of OSCs is very promising. Cells with 9.2% power conversion efficiency (PCE) were reported this year, compared to < 8% two years ago. OSCs belong to the so-called third generation solar cells and are still under development. While OLEDs are a more mature and better studied field, with commercial products already launched in the market, there are still several key issues: (1) the cost of OSCs/OLEDs is still high, largely due to the costly manufacturing processes; (2) the efficiency of OSCs/OLEDs needs to be improved; (3) the lifetime of OSCs/OLEDs is not sufficient compared to their inorganic counterparts; (4) the physics models of the behavior of the devices are not satisfactory. All these limitations invoke the demand for new organic materials, improved device architectures, low-cost fabrication methods, and better understanding of device physics. For OSCs, we attempted to improve the PCE by modifying the interlayer between active layer/metal. We found that ethylene glycol (EG) treated poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) improves hole collection at the metal/polymer interface, furthermore it also affects the growth of the poly(3- hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) blends, making the phase segregation more favorable for charge collection. We then studied organic/inorganic tandem cells. We also investigated the effect of a thin LiF layer on the hole-collection of copper phthalocyanine (CuPc)/C70-based small molecular OSCs. A thin LiF layer serves typically as the electron injection layer in OLEDs and electron collection interlayer in the OSCs. However, several reports showed that it can also assist in holeinjection in OLEDs. Here we first demonstrate that it assists hole-collection in OSCs, which is more obvious after air-plasma treatment, and explore this intriguing dual role. For OLEDs, we focus on solution processing methods to fabricate highly efficient phosphorescent OLEDs. First, we investigated OLEDs with a polymer host matrix, and enhanced charge injection by adding hole- and electron-transport materials into the system. We also applied a hole-blocking and electron-transport material to prevent luminescence quenching by the cathode. Finally, we substituted the polymer host by a small molecule, to achieve more efficient solution processed small molecular OLEDs (SMOLEDs); this approach is cost-effective in comparison to the more common vacuum thermal evaporation. All these studies help us to better understand the underlying relationship between the organic semiconductor materials and the OSCs and OLEDs’ performance and will subsequently assist in further enhancing the efficiencies of OSCs and OLEDs. With better efficiency and longer lifetime, the OSCs and OLEDs will be competitive with their inorganic counterparts.

In this paper, a blue fluorescent organic light-emitting diode (OLED) with a 1 cm2 emitting area was fabricated by a solution process. The ITO/spin MADN:13% UBD-07/TPBi/Al was used as the basic structure in which to add a hole-injection layer PEDOT:PSS and an electron-injection layer LiF, respectively. The device structure was optimized to obtain a longer lifetime. Firstly, the TPBi, which is an electron transport layer and a hole-blocking layer, was added to the structure to increase the electron transport rate. When the TPBi thickness was increased to 20 nm, the luminance was 221 cd/m2, and the efficiency was 0.52 cd/A at a voltage of 8 V. Since the addition of the hole-injection layer (HIL) increased the hole current but did not increase the electron current, the electron transport layer (ETL) Alq3 with the lowest unoccupied molecular orbital (LUMO) was added as stepped ETL to help the TPBi transport more electron current into the emitting layer. When the thickness of the TPBi/Alq3 was 10 nm/15 nm, the luminance reached 862 cd/m2, the efficiency was 1.29 cd/A, and the lifetime increased to 252 min. Subsequently, a hole-injection layer PEDOT:PSS with a thickness of 55 nm was added to make the ITO surface flatter and to reduce the probability of a short circuit caused by the spike effect. At this time, the luminance of 311 cd/m2, the efficiency of 0.64 cd/A, and the lifetime of 121 min were obtained. Following this, the thickness of the emitting layer was doubled to increase the recombination probability of the electrons and the holes. When the thickness of the emitting layer was 90 nm, and the thermal evaporation method was used, the efficiency was 3.23 cd/A at a voltage of 8V, and the lifetime was improved to 482 min. Furthermore, when the thickness of the hole-injection layer PEDOT:PSS was increased to 220 nm, the efficiency increased to 3.86 cd/A, and the lifetime was increased to 529 min. An infrared thermal image camera was employed to detect the temperature variation of the blue OLEDs. After the current was gradually increased, it was found that the heat accumulation of the device became more and more significant. When the driving current reached 50 mA, the device burnt out. It was found that the maximum temperature that the OLED device could withstand was approximately 58.83 degrees C at a current of 36.36 mA.

Solution processes have promising advantages of low manufacturing cost and large-scale production, potentially applied for the fabrication of organic and quantum dot light-emitting diodes (OLEDs and QLEDs). To meet the expected lifespan of OLEDs/QLEDs in practical display and lighting applications, tandem architecture by connecting multiple light-emitting units (LEUs) through a feasible intermediate connection layer (ICL) is preferred. However, the combination of tandem architecture with solution processes is still limited by the choices of obtainable ICLs due to the unsettled challenges, such as orthogonal solubility, surface wettability, interfacial corrosion, and charge injection. This review focuses on the recent progresses of solution-processed tandem OLEDs and tandem QLEDs, covers the design and fabrication of various ICLs by solution process, and provides suggestions on the future challenges of corresponding materials and devices, which are anticipated to stimulate the exploitation of the emerging light technologies.

Realizing External Quantum Efficiency over 25% with Low Efficiency Roll-Off in Polymer-Based Light-Emitting Diodes Synergistically Utilizing Intramolecular Sensitization and Bipolar Thermally Activated Delayed Fluorescence Monomer

Alkoxy-capped carbazole dendrimers as host materials for highly efficient narrowband electroluminescence by solution process

High-Efficiency Dual-Dopant Polymer Light-Emitting Diodes with Ultrafast Inter-fluorophore Energy Transfer

Work function tunning of lithium-doped vanadium oxide for functioning as hole injection layer in organic light-emitting diodes

Pi-conjugated polymer light emitting devices have the potential to be the next generation of solid state lighting. In order to achieve this goal, a low cost, efficient and large area production process is essential. Polymer based light emitting devices are generally deposited using techniques based on solution processing e.g.: spin coating, ink jet printing. These techniques are not well suited for cost-effective, high throughput, large area mass production of these organic devices. Ultrasonic spray deposition however, is a deposition technique that is fast, efficient and roll to roll compatible which can be easily scaled up for the production of large area polymer light emitting devices (PLEDs). This deposition technique has already successfully been employed to produce organic photovoltaic devices (OPV)¹. Recently the electron blocking layer PEDOT:PSS² and metal top contact³ have been successfully spray coated as part of the organic photovoltaic device stack. In this study, the effects of ultrasonic spray deposition of polymer light emitting devices are investigated. For the first time – to our knowledge -, spray coating of the active layer in PLED is demonstrated. Different solvents are tested to achieve the best possible spray-able dispersion. The active layer morphology is characterized and optimized to produce uniform films with optimal thickness. Furthermore these ultrasonic spray coated films are incorporated in the polymer light emitting device stack to investigate the device characteristics and efficiency. Our results show that after careful optimization of the active layer, ultrasonic spray coating is prime candidate as deposition technique for mass production of PLEDs.

The emission properties of polymer light-emitting diode (PLEDs), using blue emissive poly(9,9-dioctylfluorene) (PFO) and yellow-green emissive poly[9,9-dioctylfluorenyl-2,7-diyl)-co-1, 4-benzo-{2,1'-3}- thiadiazole)] (F8BT) fabricated by the spin-coating method, the toluene vapor method and the thermal printing method, were investigated. poly(2,7-(9,9-din-octylfluorene)-alt-(1,4-phenylene-( (4-sec-butylphenyl)imino)-1,4-phenylene)) (TFB) is useful for buffer layer and a dopant when we use the spin-coating method. When we use TFB as interlayer of PLED, TFB acts as exciton-blocking layer, thus prevents luminescence quenching. When we use TFB with 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole (PBD) as dopants of PFO, better current efficiency was achieved, compared to PFO only device. This result derives from these materials working as hole and electron transporting molecules. The blue and yellow-green PLEDs fabricated by the spincoating method showed maximum efficiencies of approximately 1.1 and 1cd/A, respectively. The device with bis[1-(9,9-dimethyl-9H-fluoren-2-yl)-isoquinoline](acetylacetonate)iridium(III) (Ir(fliq)2acac) doped in PFO showed red-emission and a maximum efficiency of approximately 1cd/A. Current efficiencies of PLEDs with the β phase of PFO fabricated by the thermal printing method and the toluene vapor method were found to have better emission efficiency than that with the amorphous phase of PFO by the spin-coating method. The EL spectra of PLEDs using PFO and PFO:F8BT fabricated by the thermal printing method were polarized. The transient characteristics of PLEDs using β phase of PFO were better than amorphous phase of that. It is expected to improve the characteristics of PLEDs by the optimization of the thermal printing method. We demonstrated improved light emission of PLEDs with the high-quality β phase by the thermal printing method.

Organic light emitting diodes (OLED) are developing rapidly and provide a huge market potential for signage, lighting and display applications. Cost efficient manufacturing of OLED components on different flexible substrates is under heavy investigation. In this paper focus is on polymer OLEDs and their non‐vacuum solution processing using roll‐to‐roll (R2R) printing techniques. In this paper VTT's R2R manufacturing process capabilities for printed OLED components are presented. Several demonstrator concepts based on printed OLED technology are introduced including; printed OLED elements 1) in a smart package, 2) a 7‐segment display integrated in a ID‐1 card, 3) an electronics voting card with OLED indicator and 4) a 35 cm 2 OLED lighting element printed on glass.

We fabricated the organic light-emitting diodes (OLEDs) with sensitizer by solution process. The addition of sensitizer into the emission layer improved the device efficiency. 4,4′-N,N′-dicarbazole-biphenyl (CBP), bis(2-phenylquinoline)iridium(III) (acetylacetonate) [Ir(pq)2(acac)], tris(2-phenylpyridine)iridium [Ir(ppy)3] were used as host, red emitting dopant, and sensitizer, respectively. The sensitizer leads to the cascade energy transfer from the host into the red emitting dopant. The doping concentration of sensitizer was varied as 0∼20 wt% and optimized. As a result, the device with 5% Ir(ppy)3 shows the luminous efficiency, power efficiency, and quantum efficiency of 5.1 cd/A, 4.0 lm/W, and 3.0%, respectively. These efficiencies are about 3 times as high as that of device without sensitizer.

This work demonstrates successful large area inkjet printing of a thermally activated delayed fluorescence (TADF) material as the emitting layer of organic light-emitting diodes (OLEDs). TADF materials enable efficient light emission without relying on heavy metals such as platinum or iridium. However, low-cost manufacturing of large-scale TADF OLEDs has been restricted due to their incompatibility with solution processing techniques. In this study, we develop ink formulation for a TADF material and show successful ink jet printing of intricate patterns over a large area (6400 mm2) without the use of any lithography. The stable ink is successfully achieved using a non-chlorinated binary solvent mixture for a solution processable TADF material, 3‐(9,9‐dimethylacridin‐10(9H)‐yl)‐9H‐xanthen‐9‐one dispersed in 4,4’-bis-(N-carbazolyl)-1,1’-biphenyl host. Using this ink, large area ink jet printed OLEDs with performance comparable to the control spin coated OLEDs are successfully achieved. In this work, we also show the impact of ink viscosity, density, and surface tension on the droplet formation and film quality as well as its potential for large-area roll-to-roll printing on a flexible substrate. The results represent a major step towards the use of TADF materials for large-area OLEDs without employing any lithography.

Constructing thermally activated delayed fluorescence dendrimers for solution processable blue OLEDs by molecular engineering of peripheral dendrons

In this work, a solution processed Al-In-O/InOx bilayer resistive switching random access memory (RRAM) is demonstrated at temperature as low as 180 °C. The memory cell exhibits remarkable forming free resistive switching characteristics with stable data retention and low set/reset voltages. More importantly, this solution processed bilayer shows stable memory properties under different bending angles on a flexible substrate. The resistive switching mechanism was systematically investigated. Compared to single layer devices, an Al-In-O mixing layer is induced by the solution process in the bilayer RRAM. The first principle calculation confirms that in the Al-In-O mixing layer, the formation energy of oxygen vacancies is significantly reduced compared with the AlOx layer. As a result, the formation of the oxygen vacancy based conductive filament is realized without the electroforming process. The RRAM fabricated by the printable solution process at low temperature shows great application potential in next generation wearable electronics.