Key Ionic Electrolytes for Highly Self‐Stable Light‐Emitting Electrochemical Cells Based on Ir(III) Complexes

Light-emitting electrochemical cells (LEECs) are a promising low-cost option for display and solid-state lighting. In these devices, the interplay of mobile ions, electrons, and holes makes for rich physics that can be leveraged for high performance. One example of this interplay is in the formation and radiative decay of excitons-bound electron and hole pairs. Considerations from exciton binding and Langevin recombination suggest that a low dielectric constant (ϵ) would enhance emission. However, emission is also enhanced by the product of the bulk hole and electron concentrations, which in LEECs are enhanced by the motion of small mobile ions yielding high dielectric constants. These competing effects make it difficult to predict whether active layers with low or high dielectric constants will optimize device performance. Here, the effect of varying the dielectric constant on the performance of LEEC devices from ionic transition-metal complexes was studied by systematically exchanging the negative counterions paired with an iridium complex emitter. Electrochemical impedance spectroscopy, constant voltage and constant current device studies, and drift-diffusion simulations were performed. The results clarify the competing effects of Langevin bimolecular recombination and ion-assisted injection processes occurring in LEECs.

Organic light emitting diodes (OLED) have been greatly investigated for application in flat panel display and light source. A different type of OLED is light emitting electrochemical cell (LEC), which consists of luminescent chromophore films with solid electrolyte such as ionic ruthenium complex film. Driving process of LEC is different from that of OLED. That is, upon applied voltage, the electric double layer is formed at the interface between the anode or cathode and ionic luminescent film and hole and electron are injected from both electrodes into the luminescent film and then light is emitted by charge recombination. Thus, LEC has attractive features which are single-layer device and no requirement to use low work function metal as a cathode. However, LEC has some drawback which is ill charge-injection balance between hole and electron caused by the difference in ion size between large ruthenium complex cation and small counter anion. To improve the charge-injection balance, incorporation of small cation into ionic luminescent layer will be expected. In this study, current efficiency for LEC was improved by introduction of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as additive electrolyte into the ruthenium complex film of LEC. LEC was prepared by spin-coating tris(2,2’-bipyridyl) ruthenium(II) complex TFSI2 (Ru(bpy)3(TFSI)2) and poly(methyl methacrylate) (PMMA) matrix in acetonitrile solution with LiTFSI solid electrolyte on ITO anodes. And then silver was vacuum-deposited onto the resulting ruthenium complex film with solid electrolyte on ITO anodes. The luminescent property of LEC was performed by applying constant current. The standard LEC without LiTFSI was not emitted and the lower voltage than 1 V was observed in the constant current of smaller than 1.5 mA whereas it was emitted and the voltage of around 2.5 V was observed in the constant current of larger than 1.5 mA. These results indicate that the only hole injection occurs and the electron injection does not occur until the applied current over 1.5 mA. It’s due to the thicker electric double layer of ruthenium complex at the cathode of LEC. As introduction of LiTFSI into the ionic luminescent layer, the emission starts at the smaller applied current with increasing amount of LiTFSI. The maximum current efficiency becomes 3.0 cd/A in the LEC containing 3 wt% LiTFSI. However, the addition of more than 3 wt% LiTFSI into LEC makes LEC performance worse because the distance between ruthenium complex become wide and the electron hopping rate becomes slow. Finally, addition of 10 wt% LiTFSI makes crystalize ionic luminescent layer and it does not function as LEC. Therefore, we found that the introduction of 3 wt% LiTFSI to LEC was the optimum condition.

Two blue‐emitting cationic iridium complexes with 2‐(1H‐pyrazol‐1‐yl)pyridine (pzpy) as the ancillary ligands, namely, [Ir(ppy)2(pzpy)]PF6 and [Ir(dfppy)2(pzpy)]PF6 (ppy is 2‐phenylpyridine, dfppy is 2‐(2,4‐difluorophenyl) pyridine, and PF6− is hexafluorophosphate), have been prepared, and their photophysical and electrochemical properties have been investigated. In CH3CN solutions, [Ir(ppy)2(pzpy)]PF6 emits blue‐green light (475 nm), which is blue‐shifted by more than 100 nm with respect to the typical cationic iridium complex [Ir(ppy)2(dtb‐bpy)]PF6 (dtb‐bpy is 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine); [Ir(dfppy)2(pzpy)]PF6 with fluorine‐substituted cyclometalated ligands shows further blue‐shifted light emission (451 nm). Quantum chemical calculations reveal that the emissions are mainly from the ligand‐centered 3π–π* states of the cyclometalated ligands (ppy or dfppy). Light‐emitting electrochemical cells (LECs) based on [Ir(ppy)2(pzpy)]PF6 gave green‐blue electroluminescence (486 nm) and had a relatively high efficiency of 4.3 cd A−1 when an ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate was added into the light‐emitting layer. LECs based on [Ir(dfppy)2(pzpy)]PF6 gave blue electroluminescence (460 nm) with CIE (Commission Internationale de L'Eclairage) coordinates of (0.20, 0.28), which is the bluest light emission for iTMCs‐based LECs reported so far. Our work suggests that using diimine ancillary ligands involving electron‐donating nitrogen atoms (like pzpy) is an efficient strategy to turn the light emission of cationic iridium complexes to the blue region.

Light-emitting electrochemical cells with ionic transition metal complexes (iTMCs) comprising the active layer have great potential for lighting applications, but to date high luminance and fast turn on times have been challenging to attain without significant loss of lifetime. Here, we demonstrate iridium iTMC devices with high luminances of 3000–5000 cd/m2, reduced turn on times, and long lifetimes through incorporation of ionic additives. Furthermore, we show additional reduction of turn on time to seconds through heat processing. We rationalize these results as the enhancement of carrier injection through improved double-layer formation at the electrodes.

The synthesis, photophysical/electrochemical characterization, and implementation in light‐emitting electrochemical cells (LECs) of three novel red‐emitting heteroleptic [Cu(N^N)(P^P)]PF6 complexes are reported. The complex design consists in combining i) the bridged di(pyrazin‐2‐yl)sulfane N^N ligand with expanded π‐conjugation and electro‐withdrawing 4‐(trifluoromethyl)pyrimidine moieties and ii) the [(diphenylphosphino)phenyl] ether (DPEphos) P^P ligand. The effect of the N^N ligand substitution on the photophysical, electrochemical, ion conductivity, and morphological features in their respective powders and thin films is thoughtfully rationalized. This is rounded by the trends noted in single‐layered red‐emitting LECs (λmax = 630–660 nm) featuring moderate performances with irradiances of around 60–90 µW cm−2 and total emitted energies in the range of 4–12 mJ. A further optimization using a multilayered architecture, in which hole injection/transport and exciton formation processes are decoupled, leads to a significant enhancement of the irradiance up to ≈150 µW cm−2 and total emitted energies of 91 mJ without affecting device chromaticity. Finally, the best red‐emitting complex in LECs is used to fabricate host:guest white devices, achieving luminances of 12 cd m−2 in concert with an excellent white color quality (x/y CIE color coordinates of 0.31/0.32; color rendering index of 90) stable over lifespan.

It has recently been demonstrated that light‐emitting electrochemical cells (LECs) can be designed to deliver strong emission with high efficiency when the charge transport is effectuated by a majority host and the emission is executed by a minority guest. A relevant question is then: should the guest be physically blended with or chemically incorporated into the host? A systematic study is presented that establishes that for near‐infrared‐(NIR‐) emitting LECs based on poly(indacenodithieno[3,2‐b]thiophene) (PIDTT) as the host and 4,7‐bis(4,4‐bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)benzo[c][1,2,5]‐thiadiazole (SBS) as the guest the chemical‐incorporation approach is preferable. The host‐to‐guest energy transfer in LEC devices is highly efficient at a low guest concentration of 0.5%, whereas guest aggregation and ion redistribution during device operation severly inhibits this transfer in the physical‐blend devices. The chemical‐incorporation approach also results in a redshifted emission with a somewhat lowered photoluminescence quantum yield, but the LEC performance is nevertheless very good. Specifically, an NIR‐LEC device comprising a guest‐dilute (0.5 molar%) PIDTT‐SBS copolymer delivers highly stabile operation at a high radiance of 263 µW cm−2 (peak wavelength = 725 nm) and with an external quantum efficiency of 0.214%, which is close to the theoretical limit for this particular emitter and device geometry.

We have prepared and characterized polymer light-emitting electrochemical cells (LECs) containing a binary mixture of the conjugated polymer poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylenevinylene] and the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate as the active material. We demonstrate, for the first time, that it is possible to turn on and attain light emission from LECs, with a mm-sized interelectrode gap separating two identical Au electrodes, at a low voltage of 3 V and at room temperature.

The simple device architecture as well as the solution-based processing makes light-emitting electrochemical cells (LECs) a promising device concept for large-area flexible lighting solutions. The lack of deep-blue emitters, which are, at the same time, efficient, bright, and long-term stable, complementary to the wide variety of yellow-orange-emitting LECs, hampers the creation of white LECs. We present a hybrid device concept for the realization of white light emission by combining blue colloidal quantum dots (QDs) and an Ir-based ionic transition-metal complex (iTMC) LEC in a new type of white QD-LEC hybrid device (QLEC). By careful arrangement of the active layers, we yield light emission from both the blue QDs and the yellow iTMC emitter already at voltages below 3 V. The QLEC devices show homogeneous white light emission with high color rendering index (up to 80), luminance levels above 850 cd m-2, and a maximum external quantum efficiency greater than 0.2%.

The characteristic doping process in polymer light‐emitting electrochemical cells (LECs) causes a tradeoff between luminescence intensity and efficiency. Experiments and numerical modeling on thin film polymer LECs show that, on the one hand, carrier injection and transport benefit from electrochemical doping, leading to increased electron‐hole recombination. On the other hand, the radiative recombination efficiency is reduced by exciton quenching by polarons involved in the doping. Consequently, the quasi‐steady‐state luminescent efficiency decreases with increasing ion concentration. The transient of the luminescent efficiency shows a characteristic roll‐off while the current continuously increases, attributed to ongoing electrochemical doping and the associated exciton quenching. Both effects can be modeled by exciton polaron‐quenching via diffusion‐assisted Förster resonance energy transfer. These results indicate that the tradeoff between efficiency and intensity is fundamental, suggesting that the application realm of future LECs should be sought in high‐brightness, low‐production cost devices, rather than in high‐efficiency devices.

Solid‐state light‐emitting electrochemical cells (LECs) using sustainable and eco‐friendly materials and affording high brightness, efficiency, and stability are highly desired. Here, intrinsically ionic, thermally activated delayed fluorescence (TADF) materials 1–3 for efficient, bright, and stable LECs are reported. 1–3 feature carbazole‐type donors and cationic triazine‐type acceptors, which are located ortho to each other on the phenyl linkers. Through‐space charge‐transfer (CT) dominates the CT transitions in 1–3. In doped and neat films, 1–3 show blue and green TADF emission, respectively, with reverse intersystem crossing rates at around 7.0 × 105 s−1. 1–3 possess excellent electrochemical stability (except for the oxidation of 1) and film‐forming abilities. LECs using neat films of 1–3 as the single active layers afford green electroluminescence with peak brightness/peak external quantum efficiency (EQE) of up to 572 cd m−2/6.8% under 4.0 V and peak brightness/peak EQE/half‐lifetime of up to 860 cd m−2/5.4%/48 h under 50 A m−2. A longer half‐lifetime of 218 h has further been achieved at 162 cd m−2 under 10 A m−2. The work reveals the bright prospect for the development of efficient, bright, and stable LECs with intrinsically‐ionic TADF materials.

An extended displacement current measurement (DCM) is performed to analyze the operation mechanisms of a poly(p‐phenylenevinylene) derivative (Super Yellow)‐based light‐emitting electrochemical cell (LEC). The characteristics of the actual current, displacement current, and electroluminescence (EL) intensity during the relaxation processes of electrochemical doping are simultaneously measured. The transient characteristics indicate correlations between the conductance, capacitance, and EL efficiency. The conductance and capacitance decrease with proceeding doping relaxation, whereas the EL efficiency increases. The EL efficiency is dominated by the electrochemical doping state, rather than the actual current density. Moreover, the EL efficiency deteriorates with increasing direct current (DC) voltage applied for electrochemical doping. Since the DCM reveals that the electrical properties of the device obey the trap charge limited current regime in the intrinsic region and are almost independent of the applied DC voltage, efficiency deterioration is not responsible for the intrinsic region but for the doped region. The results suggest that the self‐absorption in the doped region causes efficiency loss, otherwise the emitting zone is formed close to the doped region. The extended DCM enables us to comprehensively analyze the operation mechanisms of LECs on the basis of the simultaneous observations of electrical and luminous characteristics, including their transient changes.

A DFT/time‐dependent DFT (TD‐DFT) investigation was conducted on a series of cationic iridium(III) complexes with 2‐phenylpyridine (ppyn) derivatives and a diphosphane (PPn) ancillary ligand to shed light on the effects of stereoisomerism and ligand substituents on the photophysical properties. The geometries, electronic structures, lowest‐lying singlet–singlet absorptions, vertical singlet–triplet excitations, and triplet–singlet emissions of N,N‐cis‐[Ir(ppy0)2(PP)]+ (1), N,N‐trans‐[Ir(ppy0)2(PP)]+ (2) and their derivatives were investigated with DFT‐based approaches [ppy0 = 2‐phenylpyridine, PP = 1,2‐bis(diphenylphosphanyl)ethene]. The complex N,N‐trans‐[Ir(ppy2)2(PP2)]+ (3b) shows high quantum phosphorescence efficiency (ΦPL) of 91 %, whereas an extremely low ΦPL (<1 %) was observed for N,N‐trans‐[Ir(ppy4)2(PP1)]+ (2d). To clarify this behavior, the S1–Tn splitting energy (ΔE), the transition dipole moment (μ) upon the S0→S1 transition, and the energy gap between the triplet metal‐to‐ligand charge transfer (3MLCT) π–π* and triplet metal‐centered (3MC) d–d states (ΔEMC–MLCT) were calculated. A drastically small ΔE and large μ for 3b (<0.05 eV and 1.38 D, respectively), compared to those for 2d (>0.2 eV and 1.26 D, respectively), were found to be closely linked to the substituents on the ppyn ligands. The remarkably small ΔE and similar μ for N,N‐cis 1c (<0.05 eV and 1.41 D, respectively), compared to those for N,N‐trans 2c (>0.1 eV and 1.42 D, respectively), could be attributed to the effects of the trans–cis structural isomerism. On the basis of these parameters, the higher ΦPL of 3b with respect to that of 2d was explained, and 1c, 1d, 2b, and 2e were considered to have better physical properties than the experimentally synthesized complexes 2, 2d, and 3b. The newly designed 1c, 1d, 2b, and 2e are expected to be highly emissive in the blue‐green region for light‐emitting electrochemical cell (LEC) applications.

Using imidazole‐type ancillary ligands, a new class of cationic iridium complexes (1–6) is prepared, and photophysical and electrochemical studies and theoretical calculations are performed. Compared with the widely used bpy (2,2′‐bipyridine)‐type ancillary ligands, imidazole‐type ancillary ligands can be prepared and modified with ease, and are capable of blueshifting the emission spectra of cationic iridium complexes. By tuning the conjugation length of the ancillary ligands, blue‐green to red emitting cationic iridium complexes are obtained. Single‐layer light‐emitting electrochemical cells (LECs) based on cationic iridium complexes show blue‐green to red electroluminescence. High efficiencies of 8.4, 18.6, and 13.2 cd A−1 are achieved for the blue‐green‐emitting, yellow‐emitting, and orange‐emitting devices, respectively. By doping the red‐emitting complex into the blue‐green LEC, white LECs are realized, which give warm‐white light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.42, 0.44) and color‐rendering indexes (CRI) of up to 81. The peak external quantum efficiency, current efficiency, and power efficiency of the white LECs reach 5.2%, 11.2 cd A−1, and 10 lm W−1, respectively, which are the highest for white LECs reported so far, and indicate the great potential for the use of these cationic iridium complexes in white LECs.

Emerging organic light‐emitting devices, such as light‐emitting electrochemical cells (LECs), offer a multitude of advantages but currently suffer from that most efficient phosphorescent emitters are based on expensive and rare metals. Herein, it is demonstrated that a rare metal‐free salt, bis(benzyltriphenylphosphonium)tetrabromidomanganate(II) ([Ph3PBn]2[MnBr4]), can function as the phosphorescent emitter in an LEC, and that a careful device design results in the fact that such a rare metal‐free phosphorescent LEC delivers broadband white emission with a high color rendering index (CRI) of 89. It is further shown that broadband emission is effectuated by an electric‐field‐driven structural transformation of the original green‐light emitter structure into a red‐emitting structure.

Sandwich polymer light-emitting electrochemical cells (LECs) with low electrolyte loading have been investigated. The LECs can be turned on to emit light at low voltages by applying either a forward- or reverse-bias current. The reverse operation, however, displays significantly higher luminance, frozen-junction behavior, and voltage instability. Moreover, the LECs display de-coupled luminance decay and voltage drift. Under forward-current operation, the luminance decreases for most of the test duration, while the operating voltage remains nearly unchanged. Under reverse-current operation, the luminance remains constant for over 200 h while the operating voltage more than doubles. The highly asymmetric device characteristics between forward and reverse operation can be explained by the different doping profiles created when the initial charge injection barriers are different. Under forward-current operation, the LEC film is predominantly p-doped. This leads to heavy luminescence quenching but a stable operating voltage. Under reverse operation, a predominately n-doped film is responsible for the higher luminance, frozen-junction behavior, and voltage drift. The anomalous device characteristics offer additional insights into the complex operating mechanism of LECs and the behaviours of a doped luminescent polymer.