Organic Light‐Emitting Transistors Containing a Laterally Arranged Heterojunction

An approach to produce organic light‐emitting transistors (OLETs) containing a laterally arranged heterojunction structure, which minimizes exciton quenching at the metal electrodes, is described. This device configuration provides an organic light‐emitting diode (OLED) structure where the anode (source) electrode, hole‐transport material (field‐effect material), light‐emitting material, and cathode (drain) electrode are laterally arranged, thus offering a chance to control the electroluminescent intensity by changing the gate bias. Pentacene and tris(8‐quinolinolato)aluminum (Alq₃) are employed as the field‐effect and light‐emitting materials, respectively. The laterally arranged heterojunction structures are achieved by successively inclined deposition of the field‐effect and light‐emitting materials. After deposition of pentacene, a narrow gap of about 10–20 nm between the drain electrode and pentacene was obtained, thereby creating an opportunity to fabricate a laterally arranged heterojunction. In the OLETs, unsymmetrical source and drain electrodes, that is, Au and LiF/Al ones, are used to ensure efficient injection of holes and electrons. Visible‐light emission from OLETs is observed under ambient atmosphere. This result is ascribed to efficient carrier injection and transport, formation of a heterojunction, as well as good luminescence from the organic emissive layer. The device structure serves as an excellent model system for OLETs and demonstrates a general concept of adjusting the charge‐carrier injection and transport, as well as the electroluminescent properties, by forming laterally arranged heterojunctions.     

Versatile,Benzimidazole/Amine‐Based Ambipolar Compounds for Electroluminescent Applications: Single‐Layer,Blue, Fluorescent OLEDs,Hosts for Single‐Layer,Phosphorescent OLEDs

A series of compounds containing arylamine and 1,2‐diphenyl‐1H‐benz[d]imidazole moieties are developed as ambipolar, blue‐emitting materials with tunable blue‐emitting wavelengths, tunable ambipolar carrier‐transport properties and tunable triplet energy gaps. These compounds possess several novel properties: (1) they emit in the blue region with high quantum yields; (2) they have high morphological stability and thermal stability; (3) they are capable of ambipolar carrier transport; (4) they possess tunable triplet energy gaps, suitable as hosts for yellow‐orange to green phosphors. The electron and hole mobilities of these compounds lie in the range of 0.68–144 × 10^?6 and 0.34–147 × 10^?6 cm² V^?1 s^?1, respectively. High‐performance, single‐layer, blue‐emitting, fluorescent organic light‐emitting diodes (OLEDs) are achieved with these ambipolar materials. High‐performance, single‐layer, phosphorescent OLEDs with yellow‐orange to green emission are also been demonstrated using these ambipolar materials, which have different triplet energy gaps as the host for yellow‐orange‐emitting to green‐emitting iridium complexes. When these ambipolar, blue‐emitting materials are lightly doped with a yellow‐orange‐emitting iridium complex, white organic light‐emitting diodes (WOLEDs) can be achieved, as well by the use of the incomplete energy transfer between the host and the dopant.     

The Role of Transition Metal Oxides in Charge‐Generation Layers for Stacked Organic Light‐Emitting Diodes

The mechanism of charge generation in transition metal oxide (TMO)‐based charge‐generation layers (CGL) used in stacked organic light‐emitting diodes (OLEDs) is reported upon. An interconnecting unit between two vertically stacked OLEDs, consisting of an abrupt heterointerface between a Cs₂CO₃‐doped 4,7‐diphenyl‐1,10‐phenanthroline layer and a WO₃ film is investigated. Minimum thicknesses are determined for these layers to allow for simultaneous operation of both sub‐OLEDs in the stacked device. Luminance–current density–voltage measurements, angular dependent spectral emission characteristics, and optical device simulations lead to minimum thicknesses of the n‐type doped layer and the TMO layer of 5 and 2.5 nm, respectively. Using data on interface energetic determined by ultraviolet photoelectron and inverse photoemission spectroscopy, it is shown that the actual charge generation occurs between the WO₃ layer and its neighboring hole‐transport material, 4,4',4”‐tris(N‐carbazolyl)‐triphenyl amine. The role of the adjacent n‐type doped electron transport layer is only to facilitate electron injection from the TMO into the adjacent sub‐OLED.     

Study of Configuration Differentia and Highly Efficient,Deep‐Blue,Organic Light‐Emitting Diodes Based on Novel Naphtho[1,2‐d]imidazole Derivatives

Two novel naphtho[1,2‐d]imidazole derivatives are developed as deep‐blue, light‐emitting materials for organic light‐emitting diodes (OLEDs). The 1H‐naphtho[1,2‐d]imidazole based compounds exhibit a significantly superior performance than the 3H‐naphtho[1,2‐d]imidazole analogues in the single‐layer devices. This is because they have a much higher capacity for direct electron‐injection from the cathode compared to their isomeric counterparts resulting in a ground‐breaking EQE (external quantum efficiency) of 4.37% and a low turn‐on voltage of 2.7 V, and this is hitherto the best performance for a non‐doped single‐layer fluorescent OLED. Multi‐layer devices consisting of both hole‐ and electron‐transporting layers, result in identically excellent performances with EQE values of 4.12–6.08% and deep‐blue light emission (Commission Internationale de l'Eclairage (CIE) y values of 0.077–0.115) is obtained for both isomers due to the improved carrier injection and confinement within the emissive layer. In addition, they showed a significantly better blue‐color purity than analogous molecules based on benzimidazole or phenanthro[9,10‐d]imidazole segments.     

Anthracene‐Containing Binaphthol Chromophores for Light‐Emitting Diode (LED) Fabrication

Non‐crystalline anthracene‐containing binaphthol chromophores were synthesized, characterized, and used in the fabrication of organic light‐emitting diodes (OLEDs). Specifically, the target molecules were 2,2′‐dihexyloxy‐1,1′‐binaphthol‐6,6′‐bisanthracene ( BA1 ) and 2,2′‐dimethoxyy‐1,1′‐binaphthol‐6,6′‐bisanthracene ( BA2 ). Molecules BA1 and BA2 provide amorphous solids, as determined by their glass‐transition temperature (T_g) measured by differential scanning calorimetry (DSC). Efficient multilayer OLEDs containing BA1 and BA2 were fabricated by evaporation techniques. Differences in the electroluminescence frequencies of these devices suggests that the degree of alkoxide substitution controls the mobility within the binaphthol material, and therefore the recombination region in the device. Compound BA2 can also be used to dope CBP ((4,4′‐bis(carbazol‐9‐yl)biphenyl)) in the fabrication of highly efficient OLEDs.     

Enhanced Hole Injection into Amorphous Hole‐Transport Layers of Organic Light‐Emitting Diodes Using Controlled p‐Type Doping

We demonstrate enhanced hole injection and lowered driving voltage in vacuum‐deposited organic light‐emitting diodes (OLEDs) with a hole‐transport layer using the starburst amine 4,4′,4″‐tris(N,N‐diphenyl‐amino)triphenylamine (TDATA) p‐doped with a very strong acceptor, tetrafluoro‐tetracyano‐quinodimethane (F₄‐TCNQ) by controlled coevaporation. The doping leads to high conductivity of doped TDATA layers and a high density of equilibrium charge carriers, which facilitates hole injection and transport. Moreover, multilayer OLEDs consisting of double hole‐transport layers of thick p‐doped TDATA and a thin triphenyl‐diamine (TPD) interlayer exhibit very low operating voltages.     

Electric‐Field‐Assisted Charge Generation and Separation Process in Transition Metal Oxide‐Based Interconnectors for Tandem Organic Light‐Emitting Diodes

The charge generation and separation process in transition metal oxide (TMO)‐based interconnectors for tandem organic light‐emitting diodes (OLEDs) is explored using data on electrical and spectral emission properties, interface energetics, and capacitance characteristics. The TMO‐based interconnector is composed of MoO₃ and cesium azide (CsN₃)‐doped 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) layers, where CsN₃ is employed to replace the reactive metals as an n‐dopant due to its air stability and low deposition temperature. Experimental evidences identify that spontaneous electron transfer occurs in a vacuum‐deposited MoO₃ layer from various defect states to the conduction band via thermal diffusion. The external electric‐field induces the charge separation through tunneling of generated electrons and holes from MoO₃ into the neighboring CsN₃‐doped BPhen and hole‐transporting layers, respectively. Moreover, the impacts of constituent materials on the functional effectiveness of TMO‐based interconnectors and their influences on carrier recombination processes for light emission have also been addressed.     

Reduction of Tungsten Oxide: A Path Towards Dual Functionality Utilization for Efficient Anode and Cathode Interfacial Layers in Organic Light‐Emitting Diodes

Here, we report on the dual functionality of tungsten oxide for application as an efficient electron and hole injection/transport layer in organic light‐emitting diodes (OLEDs). We demonstrate hybrid polymer light‐emitting diodes (Hy‐PLEDs), based on a polyfluorene copolymer, by inserting a very thin layer of a partially reduced tungsten oxide, WO_2.5, at the polymer/Al cathode interface to serve as an electron injection and transport layer. Significantly improved current densities, luminances, and luminous efficiencies were achieved, primarily as a result of improved electron injection at the interface with Al and transport to the lowest unoccupied molecular orbital (LUMO) of the polymer, with a corresponding lowering of the device driving voltage. Using a combination of optical absorption, ultraviolet spectoscopy, X‐ray photoelectron spectroscopy, and photovoltaic open circuit voltage measurements, we demonstrate that partial reduction of the WO₃ to WO_2.5 results in the appearance of new gap states just below the conduction band edge in the previously forbidden gap. The new gap states are proposed to act as a reservoir of donor electrons for enhanced injection and transport to the polymer LUMO and decrease the effective cathode workfunction. Moreover, when a thin tungsten oxide film in its fully oxidized state (WO₃) is inserted at the ITO anode/polymer interface, further improvement in device characteristics was achieved. Since both fully oxidized and partially reduced tungsten oxide layers can be deposited in the same chamber with well controlled morphology, this work paves the way for the facile fabrication of efficient and stable Hy‐OLEDs with excellent reproducibility.     

Mechanistic Study on High Efficiency Deep Blue AIE‐Based Organic Light‐Emitting Diodes by Magneto‐Electroluminescence

Aggregation‐induced emission (AIE) materials are highly attractive because of their excellent properties of high efficiency emission in nondoped organic light‐emitting diodes (OLEDs). Therefore, a deep understanding of the working mechanisms, further improving the electroluminescence (EL) efficiency of the resulting AIE‐based OLEDs, is necessary. Herein, the conversion process from higher energy triplet state (T₂) to the lowest singlet state (SS₁) is found in OLEDs based on a blue AIE material, 4′‐(4‐(diphenylamino)phenyl)‐5′‐phenyl‐[1,1′:2′,1′′‐terphenyl]‐4‐carbonitrile (TPB‐AC), obviously relating to the device efficiency, by magneto‐EL (MEL) measurements. A special line shape with rise at low field and reduction at high field is observed. The phenomenon is further clarified by theoretical calculations, temperature‐dependent MELs, and transient photoluminescence emission properties. On the basis of the T₂‐S₁ conversion process, the EL performances of the blue OLEDs based on TPB‐AC are further enhanced by introducing a phosphorescence doping emitter in the emitting layer, which effectively regulates the excitons on TPB‐AC molecules. The maximum external quantum efficiency (EQE) reaches 7.93% and the EQE keeps 7.57% at the luminance of 1000 cd m^?2. This work establishes a physical insight for designing high‐performance AIE materials and devices in the future.     

Highly Efficient p‐i‐n and Tandem Organic Light‐Emitting Devices Using an Air‐Stable and Low‐Temperature‐Evaporable Metal Azide as an n‐Dopant

Cesium azide (CsN₃) is employed as a novel n‐dopant because of its air stability and low deposition temperature. CsN₃ is easily co‐deposited with the electron transporting materials in an organic molecular beam deposition chamber so that it works well as an n‐dopant in the electron transport layer because its evaporation temperature is similar to that of common organic materials. The driving voltage of the p‐i‐n device with the CsN₃‐doped n‐type layer and a MoO₃‐doped p‐type layer is greatly reduced, and this device exhibits a very high power efficiency (57 lm W^?1). Additionally, an n‐doping mechanism study reveals that CsN₃ was decomposed into Cs and N₂ during the evaporation. The charge injection mechanism was investigated using transient electroluminescence and capacitance–voltage measurements. A very highly efficient tandem organic light‐emitting diodes (OLED; 84 cd A^?1) is also created using an n–p junction that is composed of the CsN₃‐doped n‐type organic layer/MoO₃ p‐type inorganic layer as the interconnecting unit. This work demonstrates that an air‐stable and low‐temperature‐evaporable inorganic n‐dopant can very effectively enhance the device performance in p‐i‐n and tandem OLEDs, as well as simplify the material handling for the vacuum deposition process.     

Extremely Low‐Threshold Amplified Spontaneous Emission of 9,9′‐Spirobifluorene Derivatives and Electroluminescence from Field‐Effect Transistor Structure

By doping 2,7‐bis[4‐(N‐carbazole)phenylvinyl]‐9,9′‐spirobifluorene (spiro‐SBCz) into a wide energy gap 4,4′‐bis(9‐carbazole)‐2,2′‐biphenyl (CBP) host, we demonstrate an extremely low ASE threshold of E_th = (0.11 ± 0.05) μJ cm^–2 (220 W cm^–2) which is the lowest ASE threshold ever reported. In addition, we confirmed that the spiro‐SBCz thin film functions as an active light emitting layer in organic light‐emitting diode (OLED) and a field‐effect transistor (FET). In particular, we succeeded to obtain linear electroluminescence in the FET structure which will be useful for future organic laser diodes.     

Light Out‐Coupling Efficiencies of Organic Light‐Emitting Diode Structures and the Effect of Photoluminescence Quantum Yield

Results obtained from modeling the light out‐coupling efficiency of an organic light‐emitting diode (OLED) structure containing the recently developed first‐generation fac‐tris(2‐phenylpyridine) iridium‐cored dendrimer (Ir‐G1) as the emissive organic layer are reported. Comparison of the results obtained for this material with those of corresponding structures based upon small‐molecule and polymer emissive materials is made. The calculations of out‐coupling efficiency performed here take account of many factors, including the photoluminescence quantum yield (PLQY) of the emissive materials. Further, how each material system might perform with regard to out‐coupling efficiency when a range of possible PLQYs are considered is shown. The calculations show that the very high efficiency of dendrimer‐based OLEDs can be attributed primarily to their high PLQY.     

Blue‐Light‐Emitting Oligoquinolines: Synthesis,Properties, and High‐Efficiency Blue‐Light‐Emitting Diodes

The synthesis, photophysics, cyclic voltammetry, and highly efficient blue electroluminescence of a series of four new n‐type conjugated oligomers, 6,6′‐bis(2,4‐diphenylquinoline) (B1PPQ), 6,6′‐bis(2‐(4‐tert‐butylphenyl)‐4‐phenylquinoline) (BtBPQ), 6,6′‐bis(2‐p‐biphenyl)‐4‐phenylquinoline) (B2PPQ), and 6,6′‐bis((3,5‐diphenylbenzene)‐4‐phenylquinoline) (BDBPQ) is reported. The oligoquinolines have high glass‐transition temperatures (T_g ≥ 133 °C), reversible electrochemical reduction, and high electron affinities (2.68–2.81 eV). They emit blue photoluminescence with 0.73–0.94 quantum yields and 1.06–1.42 ns lifetimes in chloroform solutions. High‐performance organic light‐emitting diodes (OLEDs) with excellent blue chromaticity coordinates are achieved from all the oligoquinolines. OLEDs based on B2PPQ as the blue emitter give the best performance with a high brightness (19 740 cd m^–2 at 8.0 V), high efficiency (7.12 cd A^–1 and 6.56 % external quantum efficiency at 1175 cd m^–2), and excellent blue color purity as judged by the Commission Internationale de L'Eclairage (CIE) coordinates (x = 0.15,y = 0.16). These results represent the best efficiency of blue OLEDs from neat fluorescent organic emitters reported to date. These results demonstrate the potential of oligoquinolines as emitters and electron‐transport materials for developing high‐performance blue OLEDs.     

The Photophysical Properties of Dipyrenylbenzenes and Their Application as Exceedingly Efficient Blue Emitters for Electroluminescent Devices

Three blue‐light emitting dipyrenylbenzene derivatives, 1‐(4‐(1‐pyrenyl)phenyl)pyrene (PPP), 1‐(2,5‐dimethoxy‐4‐(1‐pyrenyl)phenyl)pyrene (DOPPP), and 1‐(2,5‐dimethyl‐4‐(1‐pyrenyl)phenyl)pyrene (DMPPP), have been prepared by the Suzuki coupling reaction of aryl dibromides with pyreneboronic acid in high yields. These compounds exhibit high glass‐transition temperatures of 97–137 °C and good film‐forming ability. As revealed from single‐crystal X‐ray analysis, these dipyrenylbenzenes adopt a twisted conformation with inter‐ring torsion angles of 44.5°–63.2° in the solid state. The twisted structure is responsible for the low degree of aggregation in the thin films that leads to fluorescence emission of the neat films at 446–463 nm, which is shorter than that of the typical pyrene excimer emission. The low degree of aggregation is also conducive for the observed high fluorescence quantum yields of 63–75%. In organic light‐emitting diode (OLED) applications, these dipyrenylbenzenes can be used as either the charge transporter or host emitter. The non‐doped blue OLEDs that employ these compounds as the emissive layer can achieve a very high external quantum efficiency (η_ext) of 4.3–5.2%. In particular, the most efficient DMPPP‐based device can reach a maximum η_ext of 5.2% and a very high luminescence of 40 400 cd m^–2 in the deep‐blue region with Commission Internationale d'Énclairage (CIE) coordinates of (0.15, 0.11).     

Integration of a Rib Waveguide Distributed Feedback Structure into a Light‐Emitting Polymer Field‐Effect Transistor

Ambipolar light‐emitting organic field‐effect transistors (LEFETs) possess the ability to efficiently emit light due to charge recombination in the channel. Since the emission can be made to occur far from the metal electrodes, the LEFET structure has been proposed as a potential architecture for electrically pumped organic lasers. Here, a rib waveguide distributed feedback structure consisting of tantalum pentoxide (Ta₂O₅) integrated within the channel of a top gate/bottom contact LEFET based on poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) is demonstrated. The emitted light is coupled efficiently into the resonant mode of the DFB waveguide when the recombination zone of the LEFET is placed directly above the waveguide ridge. This architecture provides strong mode confinement in two dimensions. Mode simulations are used to optimize the dielectric thickness and gate electrode material. It is shown that electrode absorption losses within the device can be eliminated and that the lasing threshold for optical pumping of the LEFET structure with all electrodes (4.5 µJ cm^?2) is as low as that of reference devices without electrodes. These results enable quantitative judgement of the prospects for realizing an electrically pumped organic laser based on ambipolar LEFETs. The proposed device provides a powerful, low‐loss architecture for integrating high‐performance ambipolar organic semiconductor materials into electrically pumped lasing structures.     

Highly Efficient Non‐Doped Blue Organic Light‐Emitting Diodes Based on Fluorene Derivatives with High Thermal Stability

A new series of blue‐light‐emitting fluorene derivatives have been synthesized and characterized. The fluorene derivatives have high fluorescence yields, good thermal stability, and high glass‐transition temperatures in the range 145–193 °C. Organic light‐emitting diodes (OLEDs) fabricated using the fluorene derivatives as the host emitter show high efficiency (up to 5.3 cd A^–1 and 3.0 lm W^–1) and bright blue‐light emission (Commission Internationale de L'Eclairage (CIE) coordinates of x = 0.16, y = 0.22). The performance of the non‐doped fluorene‐based devices is among the best fluorescent blue‐light‐emitting OLEDs. The good performance of the present blue OLEDs is considered to derive from: 1) appropriate energy levels of the fluorene derivatives for good carrier injection; 2) good carrier‐transporting properties; and 3) high fluorescence efficiency of the fluorene derivatives. These merits are discussed in terms of the molecular structures.     

Hole Injection in a Model Fluorene–Triarylamine Copolymer

Recent developments in synthesis and purification have yielded conjugated polymers with hole mobilities exceeding 0.01 cm² V^?1 s^?1. Essential to harvesting the potential of these materials in organic light emitting diodes (OLEDs) is the identification of suitable ohmic contacts. Using a model fluorene copolymer that shows high‐mobility, non‐dispersive hole transport, it is demonstrated that electrodes commonly used as anodes in OLEDs are very poor hole injectors. Injection from Au and indium tin oxide anodes is limited by energy barriers of 0.75 and 0.65 eV, respectively, and the injected current is found to be temperature independent—a prediction that was not reproduced by the leading injection model for disordered organic semiconductors. Injection from a poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) anode, on the other hand, is found to become less efficient with electric field, a behavior which is currently not understood. In thinner poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐(4,4′‐(N‐(4‐sec‐butyl))diphenylamine)] films, which are of relevance to OLEDs, ohmic losses on the PEDOT:PSS layer are found to limit the flow of current. These results illustrate the opportunity to further improve the performance of OLEDs as well as the challenge posed by high mobility conjugated polymers for the design of hole injection layers.     

The Quest for High‐Performance Host Materials for Electrophosphorescent Blue Dopants

We report a systematic comparison study of 3,5‐di(N‐carbazolyl)tetraphenylsilane (SimCP) and N,N′‐dicarbazolyl‐3,5‐benzene (mCP), which are used as the host materials for phosphorescent blue dopants in organic light‐emitting diodes (OLEDs). On the basis of photoexcitation emission spectroscopy, thermal stability analysis, photoelectron analysis, charge transport measurements, and molecular dynamics (MD) simulations, we conclude that the non‐π‐conjugated meta‐substituted triphenylsilyl moiety of SimCP exerts a unique hindering effect on the molecular packing characteristics in the condensed phase. The chemical origin of the superior performance of SimCP over mCP is revealed, and is expected to be helpful for the molecular design of effective host materials for enhancing the performance of blue phosphorescent OLEDs.     

Creation of Bifunctional Materials: Improve Electron‐Transporting Ability of Light Emitters Based on AIE‐Active 2,3,4,5‐Tetraphenylsiloles

2,3,4,5‐Tetraphenylsiloles are excellent solid‐state light emitters featured aggregation‐induced emission (AIE) characteristics, but those that can efficiently function as both light‐emitting and electron‐transporting layers in one organic light‐emitting diode (OLED) are much rare. To address this issue, herein, three tailored n‐type light emitters comprised of 2,3,4,5‐tetraphenylsilole and dimesitylboryl functional groups are designed and synthesized. The new siloles are fully characterized by standard spectroscopic and crystallographic methods with satisfactory results. Their thermal stabilities, electronic structures, photophysical properties, electrochemical behaviors and applications in OLEDs are investigated. These new siloles exhibit AIE characteristics with high emission efficiencies in solid films, and possess lower LUMO energy levels than their parents, 2,3,4,5‐tetraphenylsiloles. The double‐layer OLEDs [ITO/NPB (60 nm)/silole (60 nm)/LiF (1 nm)/Al (100 nm)] fabricated by adopting the new siloles as both light emitter and electron transporter afford excellent performances, with high electroluminescence efficiencies up to 13.9 cd A^–1, 4.35% and 11.6 lm W^–1, which are increased greatly relative to those attained from the triple‐layer devices with an additional electron‐transporting layer. These results demonstrate effective access to n‐type solid‐state emissive materials with practical utility.     

Cover Picture: Low‐Work‐Function Surface Formed by Solution‐Processed and Thermally Deposited Nanoscale Layers of Cesium Carbonate (Adv. Funct. Mater. 12/2007)

The cover shows the structure of an efficient polymer light emitting diode (PLED) and its energy diagram at the interface between aluminum (Al) and a Cs₂CO₃ interfacial layer. It reveals the origin of enhanced electron injection from the Al electrode due to the low work function of a thermally evaporated Cs₂CO₃ layer, as reported on p. 1966 by Jinsong Huang, Zhen Xu, and Yang Yang. Pictures of the white‐ and red‐emitting PLEDs are also shown. Nanostructured layers of Cs₂CO₃ are shown to function very effectively as cathodes in organic electronic devices because of their good electron‐injection capabilities. Here, we report a comprehensive study of the origin of the low work function of nanostructured layers of Cs₂CO₃ prepared by solution deposition and thermal evaporation. The nanoscale Cs₂CO₃ layers are probed by various characterization methods including current–voltage (I–V) measurements, photovoltaic studies, X‐ray photoelectron spectroscopy (XPS), UV photoelectron spectroscopy (UPS), and impedance spectroscopy. It is found that thermally evaporated Cs₂CO₃ decomposes into CsO₂ and cesium suboxides. The cesium suboxides dope CsO₂, yielding a heavily doped n‐type semiconductor with an intrinsically low work function. As a result, devices fabricated using thermally evaporated Cs₂CO₃ are relatively insensitive to the choice of the cathode metal. The reaction of thermally evaporated Cs₂CO₃ with Al can further reduce the work function to 2.1 eV by forming an Al–O–Cs complex. Solution‐processed Cs₂CO₃ also reduces the work function of Au substrates from 5.1 to 3.5 eV. However, devices prepared using solution‐processed Cs₂CO₃ exhibit high efficiency only if a reactive metal such as Al or Ca is used as the cathode metal. A strong chemical reaction occurs between spin‐coated Cs₂CO₃ and thermally evaporated Al. An Al–O—Cs complex is formed as a result of this chemical reaction at the interface, and this layer significantly reduces the work function of the cathode. Finally, impedance spectroscopy results prove that this layer is highly conductive.