D–A copolymer with high ambipolar mobilities based on dithienothiophene and diketopyrrolopyrrole for polymer solar cells and organic field-effect transistors

Donor–acceptor (D–A) type conjugated polymers have been developed to absorb longer wavelength light in polymer solar cells (PSCs) and to achieve a high charge carrier mobility in organic field-effect transistors (OFETs). PDTDP, containing dithienothiophene (DTT) as the electron donor and diketopyrrolopyrrole (DPP) as the electron acceptor, was synthesized by stille polycondensation in order to achieve the advantages of D–A type conjugated polymers. The polymer showed optical band gaps of 1.44 and 1.42 eV in solution and in film, respectively, and a HOMO level of 5.09 eV. PDTDP and PC₇₁BM blends with 1,8-diiodooctane (DIO) exhibited improved performance in PSCs with a power conversion efficiency (PCE) of 4.45% under AM 1.5G irradiation. By investigating transmission electron microscopy (TEM), atomic force microscopy (AFM), and the light intensity dependence of J_SC and V_OC, we conclude that DIO acts as a processing additive that helps to form a nanoscale phase separation between donor and acceptor, resulting in an enhancement of μ_h and μ_e, which affects the J_SC, EQE, and PCE of PSCs. The charge carrier mobilities of PDTDP in OFETs were also investigated at various annealing temperatures and the polymer exhibited the highest hole and electron mobilities of 2.53 cm² V⁻¹ s⁻¹ at 250 °C and 0.36 cm² V⁻¹ s⁻¹ at 310 °C, respectively. XRD and AFM results demonstrated that the thermal annealing temperature had a critical effect on the changes in the crystallinity and morphology of the polymer. The low-voltage device was fabricated using high-k dielectric, P(VDF-TrFE) and P(VDF-TrFE-CTFE), and the carrier mobility of PDTDP was reached 0.1 cm² V⁻¹ s⁻¹ at V_d = −5 V. PDTDP complementary inverters were fabricated, and the high ambipolar characteristics of the polymer resulted in an output voltage gain of more than 25.     

High open-circuit voltage polymer solar cells based on D–A copolymer of indacenodithiophene and fluorine-substituted benzotriazole

A medium band gap D–A copolymer of indacenodithiophene (IDT) and fluorinated dithienylbenzotriazole (FBTA), PIDT-FBTA, was synthesized for the application as donor material in polymer solar cells (PSCs). PIDT-FBTA showed deeper highest occupied molecular orbital (HOMO) energy level due to the strong electron-withdrawing difluorine substitution on benzotriazole acceptor unit in the D–A copolymer. The PSCs based on PIDT-FBTA:PC₇₀BM (1:3) exhibited a high V_oc of 0.90 V and a power conversion efficiency (PCE) of 3.62% under the illumination of AM 1.5G, 100 mW cm⁻². The device performance was further improved by methanol treatment with PCE increased to 4.90% and V_oc increased to 0.92 V.     

Realization of triplet–triplet annihilation in planar heterojunction exciplex-based organic light-emitting diodes

Triplet–triplet annihilation (TTA) for enhancement of luminous efficiency occurs with difficulty in exciplex-based organic light-emitting devices (OLEDs) because it is an interaction among several neighboring donor and acceptor molecules. However, TTA has been realized in our planar-heterojunction (PHJ) exciplex-based OLEDs by using a thin recombination zone to enhance the interfacial density of the triplet states. The TTA process, which is characterized by a high-field decrease (HFD) in the magneto-electroluminescence from the PHJ OLEDs, appears at approximately 150 K and becomes stronger with decreasing temperature. At a given temperature, the higher the injected current is, the stronger HFD is observed. Additionally, we find that TTA could even happens at room temperature with appropriate selection of the donor molecule, which may be attributed to the favorable electron-donating ability of the methoxy group (–OCH₃) in the donor molecule and the matched overlaps of the intermolecular conformation of the donor and the acceptor.     

Use of benzothiadiazole–triphenylamine amorphous polymer for reproducible performance of polymer–fullerene bulk-heterojunction solar cells

An amorphous polymer, poly(BTD-TPA), which consists of benzothiadiazole and triarylamine units, can be successfully utilized to fabricate bulk heterojunction (BHJ) organic photovoltaics (OPVs), and the OPV performance can be demonstrated to be independent of the casting solvent or thermal annealing temperature. The OPV based on poly(BTD-TPA):PC₇₀BM (1:4) that was fabricated using chloroform (boiling point of 61 °C) and annealed at 60 °C for 10 min exhibited a power conversion efficiency (PCE) of 2.81% under simulated solar irradiation through an air mass of 1.5 at 100 mW cm⁻². On the other hand, the OPV fabricated using o-dichlorobenzene (boiling point of 181 °C) and annealed at 110 °C for 10 min exhibited a PCE of 2.65%. Almost the same PCEs and incident photon to current conversion efficiencies (IPCEs) were obtained in both OPVs. The use of an amorphous film of poly(BTD-TPA) in the fabrication of OPVs offers great advantages over the use of a polycrystalline film of regioregular poly(3-hexylthiophene) (P3HT) in terms of high reproducibility of the OPV performance.     

Triarylphosphine oxide–phenanthroline molecular conjugate as a promising doped electron-transport layer for organic light-emitting diodes

Over the past three decades, transparent high electron mobility molecular materials have attracted intensive research efforts for organic light-emitting diodes as electron-transport layer for the sake of low working voltage, high power efficiency and operational stability. However, developing high-performing electron-transport materials presents a demanding challenge owing to difficulties in synthesis, purification and/or processing. In this contribution, we show that n-doping a simple and facilely available phenanthroline derivative, namely 3-(6-diphenylphosphinylnaphth-2-yl)-1,10-phenanthroline Phen-NaDPO with a high T_g of 116 °C, is capable of greatly increasing the electron conductivity up to 3.3 × 10⁻⁴ S m⁻¹. The characterization of the blue sky fluorescent and green phosphorescent OLEDs involving this doped electron-transport layer Phen-NaDPO:50% wt Cs₂CO₃ revealed comparable performances to the analogue BPhen (T_g ≈ 66 °C) OLEDs. For instance, the resulting sky blue fluorescent OLEDs provided ca. 15 cd/A, 13 lm/W @1000 cd m⁻² & t₉₅ ≈ 167 h @1000 cd m⁻². The present finding shows that the doped Phen-NaDPO may be a robust electron-transport material for optoelectronics.     

Highly efficient,orange–red organic light-emitting diodes using a series of green-emission iridium complexes as hosts

We investigated highly efficient phosphorescent organic light-emitting diodes (OLEDs) based on an orange–red emission iridium complex as the guest and five green emission iridium complexes as the host material, respectively. For comparison, a device using a common fluorescent host CBP (4,4′-bis(N-carbazolyl)-1,1′-biphenyl) has also been fabricated. Results show that the steric hindrance and exciton transporting property of the iridium complex host are found to be critical to this kind of doping system, a proper steric hindrance and improved exciton transporting ability result in reducing of triplet–triplet annihilation, thus improving of the device performance. In addition, all devices using iridium complexes as host have better performance than that of CBP, which arised from the fact that those green emission iridium complexes have a lower triplet excited energy befitting for energy confinement and a higher highest occupied molecular orbital (HOMO) level for hole injection.     

A host material with a small singlet–triplet exchange energy for phosphorescent organic light-emitting diodes: Guest,host, and exciplex emission

A host material containing a triazine core and three phenylcarbazole arms, called 2,4,6-tris(3-(carbazol-9-yl)phenyl)-triazine (TCPZ), was developed for phosphorescent organic light-emitting diodes (OLEDs). Ultra-low driving voltages were achieved by utilizing TCPZ as the host due to its decreased singlet–triplet exchange energy (ΔE_ST) and low-lying lowest unoccupied molecular orbital (LUMO) energy level. Interaction between the RGB triplet emitters and TCPZ were studied in both photoluminescent and electroluminescent processes. Transient photoluminescence (PL) measurement of the co-deposited film of fac-tris(2-phenylpyridine) iridium (Ir(PPy)₃):TCPZ exhibits a shoulder at 565 nm whose lifetime is about two times longer than that of the Ir(PPy)₃ triplet excitons and can be attributed to the triplet exciplex formed between Ir(PPy)₃ and TCPZ. Such exciplex was also found for the green phosphorescent OLED, giving the most efficient phosphorescent OLED with triplet exciplex emission hitherto. Different from the PL process, a broad featureless band with a maximum at 535 nm was found for the OLED based on an EML of iridium(III) bis(4,6-(di-fluorophenyl)pyridinato-N,C²′)picolinate (FIrpic):TCPZ, which can be attributed to the emission from the singlet excited state of TCPZ formed by direct hole-electron recombination. A multi-emitting-layer white OLED was also fabricated by utilizing FIrpic and tris(1-phenylisoquinolinolato-C²,N)iridium(III) (Ir(piq)₃) as the complementary triplet emitters and TCPZ as the host. Different from most of ever reported white OLEDs fabricated with blue/red complementary triplet emitters that exhibit color rendering index (CRI) lower than 70, a high CRI of 82 is achieved due to the combination of blue and red phosphorescence emissions from FIrpic and Ir(piq)₃, and the emerging green fluorescence emission from TCPZ.     

Studying singlet fission and triplet fusion by magneto-electroluminescence method in singlet–triplet energy-resonant organic light-emitting diodes

Organic light emitting diodes (OLEDs) utilizing a singlet–triplet energy-resonant (E_S ≈ 2E_T) layer (rubrene) were fabricated to investigate the singlet fission and triplet fusion by the magneto-electroluminescence (MEL) of device from R.T. to 20 K. A large positive MEL (23.5%) was obtained at R.T. due to magnetic-field-suppressed singlet fission. With decreasing temperatures, the MELs changed their signs both at low-field and high-field components because of a gradual decrease in singlet fission simultaneously followed by an increasing triplet fusion, leading to a negative MEL around −7.5% at 20 K. Moreover, transient electroluminescence and MELs from the control devices were used to further confirm the exciton fission and fusion processes in rubrene-based OLEDs. Our findings of MEL may provide a useful pathway to study the microscopic dynamics of excited states in organic optoelectronic devices.     

Intermolecular interactions in organic semiconductors based on annelated β-oligothiophenes and their effect on the performance of organic field-effect transistors

A series of derivatives based on annelated β-oligothiophenes were synthesized and characterized as active layer in organic field-effect transistors (OFETs). Highest field-effect mobility of 0.52 V^?1 s^?1 for 2,5-dibiphenyl-dithieno[2,3-b:3′,2′-d]thiophene (DBP-DTT), 2.2 cm² V^?1 s^?1 for 2,5-distyryl-dithieno[2,3-b:3′,2′-d]thiophene (DEP-DTT), and 0.16 cm² V^?1 s^?1 for 1,4-di[2-dithieno[2,3-b:3′,2′-d] thiophen-2-yl-vinyl]benzene (DDTT-EP) were obtained, while 2,5-diphenyl-dithieno [2,3-b:3′,2′-d]thiophene (DP-DTT) presents no field-effect behaviors. Their thermal, optical and electrochemical properties, topographical and X-ray diffraction patterns of films, and the single crystal structures were also investigated. With the end-capping groups changing in these materials, the intermolecular interactions could transform from S–S in DP-DTT to S–C in DBP-DTT, to S–π in DEP-DTT, and to the coexisting of S–S and S–π in DDTT-EP. According to the device performances and the results of transfer integral calculations, it was revealed that S–π intermolecular interaction benefits not only improving the mobility but also reducing the threshold voltage (V_T), while S–S intermolecular interaction is not favorable for promoting the mobility.     

MoO3–Au composite interfacial layer for high efficiency and air-stable organic solar cells

Efficient and stable polymer bulk-heterojunction solar cells based on regioregular poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₁BM) blend active layer have been fabricated with a MoO₃–Au co-evaporation composite film as the anode interfacial layer (AIL). The optical and electrical properties of the composite MoO₃–Au film can be tuned by altering the concentration of Au. A composite film with 30% (weight ratio) Au was used as the AIL and showed a better performance than both pure MoO₃ and PEDOT:PSS as AIL. The surface morphology of the MoO₃–Au composite film was investigated by atomic force microscopy (AFM) and showed that the originally rough ITO substrate became smooth after depositing the composite film, with the root mean square roughness (RMS) decreased from 4.08 nm to 1.81 nm. The smooth surface reduced the bias-dependent carrier recombination, resulting in a large shunt resistance and thus improving the fill factor and efficiency of the devices. Additionally, the air stability of devices with different AILs (MoO₃–Au composite, MoO₃ and PEDOT:PSS) were studied and it was found that the MoO₃–Au composite layer remarkably improved the stability of the solar cells with shelf life-time enhanced by more than 3 and 40 times compared with pure MoO₃ layer and PEDOT:PSS layer, respectively. We argue that the stability improvement might be related with the defect states in MoO₃ component.     

Regulating charges and excitons in simplified hybrid white organic light-emitting diodes: The key role of concentration in single dopant host–guest systems

A series of high-performance hybrid white organic light-emitting diodes (WOLEDs) with simplified structures are developed by systematically investigating the influence of dopant concentrations. An ultrahigh color rendering index of 88 and a peak forward-viewing power efficiency of 44.9 lm/W are achieved in the single-emitting-layer WOLED with a low concentration (0.1%) and a moderate concentration (1%), respectively. To investigate the effect of high concentration (4%), a dual-emitting-layer device is realized, achieving an efficiency of 15.8 lm/W (1000 cd/m²). Besides, the devices show extremely stable color with a Commission Internationale de L’Eclairage (CIEx, y) variation of Δ(x, y) ? (0.008, 0.008) during a large range of luminance. Furthermore, the origin of the color-stability and working mechanism of the devices are discussed, which can be attributed to the multifunctional dopant which reduces charge mobilities together with a suitable hole transport material which exhibits strong electron- and exciton-blocking ability.     

Synthesis of ZnO and Fe2O3 nanoparticles by sol–gel method and their application in dye-sensitized solar cells

ZnO and Fe₂O₃ nanoparticles have been formed in a silica matrix, through the sol–gel method and were used as a photoanode to fabricate dye-sensitized solar cells (DSCs). The obtained oxides were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscope and UV–visible absorption spectroscopy. The results indicate that ZnO and Fe₂O₃ prepared by this method may be used as photoanodes in photo-electro-chemical energy conversion systems. DSSCs have been built using eosin Y as photosensitizer and their photocurrent, open-circuit voltage, fill factor and efficiency have been measured under direct sunlight illumination (1000 Wcm^?2). A ZnO-film solar cell had the best performance with an open-circuit voltage of V_oc=0.7 V and short-circuit current density of I_sc=490 μA/cm². This was attributed to high optical gap energy and transparency of ZnO compared to Fe₂O₃. The effects of annealing temperature and concentration of Fe₂O₃ on conversion efficiency of the Fe₂O₃ based solar cell were also studied.     

Characterization of two new (A–π)2–D–A type dyes with different central D unit and their application for dye sensitized solar cells

We report the photophysical, electrochemical and theoretical properties of two dyes with same acceptor, π-linker and anchoring acceptor unit and different TPA (D1) and pyran (D2) donor central unit. The change in the central unit resulted in corresponding different photophysical and electrochemical properties. The dye sensitized solar cell fabricated using dye D1 showed the higher incident photon to current efficiency of 54%, a short circuit current (J_sc) of 11.86 mA/cm², an open circuit voltage of 0.64 V, and fill factor (FF) of 0.68, corresponding an overall power conversion efficiency of 5.16% which is higher than that for D2 based DSSCs (4.42%). The difference in the PCE of DSSCs based on D1 and D2 is partly, due to the smaller amount of dye loading, higher dark current and charge recombination rate of D1 based DSSC. The electrochemical spectra of DSSCs demonstrated longer electron life time and charge recombination resistance and small charge transport resistance for D1 sensitized DSSC, results the higher PCE.     

Role of the donor material and the donor–acceptor mixing ratio in increasing the efficiency of Schottky junction organic solar cells

Schottky junction organic solar cells (OSCs) employ a high work-function anode and an active layer comprised of fullerene and low concentrations of donor. In this study, the roles of the donor material and the donor–acceptor mixing ratio in Schottky junction OSCs are explored. The results show that the high short circuit current (J_sc) seen in Schottky junction OSCs at low donor concentrations arises primarily from photocurrent contributions from charge-transfer intermolecular states in C₆₀ aggregates. These aggregates absorb light at 400–600 nm and are thus well matched to the solar spectrum. The presence of the donor molecules is shown to be necessary for the dissociation of the C₆₀ aggregate excitons, which ultimately allows for enhanced photocurrents. The exciton dissociation process is governed primarily by the highest occupied molecular orbial (HOMO) energy level difference between the donor and C₆₀, and is only efficient when this difference is large enough for the energetically favorable transfer of holes from C₆₀ to the donor material. Increasing the donor concentration beyond a certain threshold hinders C₆₀ aggregate formation and thus removes its contribution to photocurrent completely. Furthermore, the V_oc is shown to be strongly influenced by the choice of donor material, indicating that it is not set by the Schottky junction barrier height as previously thought. In spite of this influence on V_oc, the choice of donor in the active layer does not appear to play a significant role in the extraction of holes from the Schottky junction organic solar cells. Optimized chlorine indium phthalocyanine (ClInPc) doped C₇₀ Schottky cells were fabricated to demonstrate a peak power conversion efficiency of 3.6%.     

Investigation of donor–acceptor copolymer films and their blends with fullerene in the active layers of bulk heterojunction solar cells by Raman microspectroscopy

Thin films made of three low-band gap donor–acceptor copolymers (CDTF, CDTDP and CDTDOP) composed of 4,6-bis(3′-dodecylthiophen-2′-yl)thieno[3,4-c][1,2,5]thiadiazole-5′,5′-diyl as an electron-acceptor structural unit and various electron-donor structural units, such as 9,9-bis(2-ethylhexyl)fluorene-2,7-diyl, 2,5-didodecyl-1,4-phenylene and 2,5-didodecyloxy-1,4-phenylene, respectively, and thin films of their blends with various ratios of a soluble fullerene derivative [6,6]-phenyl C₆₁-butyric acid methyl ester ([60]PCBM) as an active layer for bulk heterojunction solar cells were studied by means of UV–vis absorption spectroscopy and Raman microspectroscopy. The molecules of CDTDP and CDTDOP possess the same main chains; they differ in the side-chain oxygen only, which changes the donor strength of the donor units. UV–vis and Raman studies allow us to show differences in the hindering of molecule planarization and aggregation in the blends. Absorption of the polymer films covered the whole visible spectral region and extended up to near infrared for CDTDOP. The absorption behavior of the CDTDP blend films qualitatively differed from the absorption behavior of the blend films of CDTF or CDTDOP. The Raman measurements were performed at two different laser excitation wavelengths (633 and 785 nm), which enabled the photoluminescence of both components in the Raman spectra to be distinguished. The Raman study was performed in different parts of the films, including the separated areas. It was proven that the separated areas in the blend films had higher contents of [60]PCBM than the rest of the films.     

Zirconium oxide dielectric layer grown by a surface sol–gel method for low-voltage,hysteresis-free,and high-mobility polymer field effect transistors

A simple, facile surface sol–gel method is introduced for the fabrication of zirconium oxide films for use as a dielectric layer of a solution-processed polymer field effect transistor (PFET). High dielectric strength is demonstrated for a zirconium oxide layer under room-temperature fabrication conditions using a surface sol–gel method without any post-treatments, which are typically needed in general sol–gel methods. X-ray photoemission spectroscopy showed that the fabricated zirconium oxide layer consists of inorganic ZrO₂ and organic alkoxide groups, which can explain its marginal dielectric constant (∼9) and continuous film properties. In addition, by finishing the surface sol–gel synthesis at the stage of chemisorption, the hydrophobic nature of the final surface was retained, leading to a trap-free semiconductor/dielectric interface. As a result, the PFET made with a conventional polymeric semiconductor rendered nearly hysteresis-free and high mobility (0.3 cm²/V) characteristics at low voltage (<2 V).     

Effects of ultraviolet–ozone treatment on organic-stabilized ZnO nanoparticle-based electron transporting layers in inverted polymer solar cells

Electron transporting layers (ETLs) in inverted polymer solar cells (I-PSCs) were fabricated by spin coating a colloidal dispersion of ZnO nanoparticles (NPs), and the effects of ultraviolet–ozone (UVO) treatment on the ZnO NP ETLs were investigated. The brief UVO treatment (<5 min) could considerably improve the performance of the resulting I-PSCs (∼30% increase in power conversion efficiency); whereas, excessive UVO treatment (>10 min) caused significant degradation. The characterization of the ZnO ETLs as a function of the UVO treatment duration revealed that brief treatment can remove the residual organic stabilizer molecules on the surface of the ZnO films by UV induced decomposition mechanism. However, excessive treatment can generate additional defects on/within the ZnO films, which can induce charge recombination. This effect was further confirmed by the thermal treatment of the ZnO ETLs at a high temperature (280 °C) at which the organic surfactants could be removed. Flexible I-PSCs were also fabricated using indium doped tin oxide coated plastic substrates and the usefulness of the room temperature UVO treatment was further confirmed in view of its potential applicability in flexible devices.     

Analysis of quantum efficiency and optical enhancement in amorphous Si p–i–n solar cells

The effect of i-layer thickness, tin oxide texture, and back reflector (BR) on optical enhancement has been systematically studied in a series of 20 a-Si p–i–n solar cells. The internal quantum efficiency has been analyzed by a simple model based on the work of Schade and Smith. The enhancement of optical absorption is characterized by m, a wavelength-dependent fitting parameter representing the increase in optical pathlength relative to the i-layer thickness d. Solar cells with an Al BR have negligible optical enhancement, with m < 1.5, consistent with large parasitic absorption at the Al/Si interface as reported by others. Solar cells on highly textured SnO₂ with ZnO/Al or ZnO/Ag BR have peak values of m ∼ 3–4, with ZnO/Ag having slightly larger values than ZnO/Al. It was found that m has a strong dependence on the product αd, and that maximum values of m increase with reflectivity of the BR. It is shown that a major source of parasitic absorption loss at long wavelengths is light trapping in the textured SnO₂ front contact. Copyright © 2002 John Wiley & Sons, Ltd.     

A strategy to enhance both VOC and JSC of A–D–A type small molecules based on diketopyrrolopyrrole for high efficient organic solar cells

Four different diketopyrrolopyrrole (DPP)-based small molecules (SMs) with A–D–A type structure were synthesized, where electron-donating unit (D) was systematically varied with different electron-donating power (thiophene vs. phenylene; thienothiophene vs. naphthalene) and different molecular planarity (bithiophene vs. thienothiophene; and biphenylene vs. naphthalene). The small molecules with weak donating unit (phenylene or naphthalene) have deeper HOMO energy levels than those with strong donating unit (thiophene or thienothiophene), and thus exhibit higher V_OC. When the fused aromatic ring (thienothiophene or naphthalene) with planar molecular structure is introduced in SMs, the SMs exhibit high hole mobility and thus afford high J_SC. As a result, the introduction of naphthalene (weak donating power and planar structure) enhances both V_OC and J_SC, resulting in a promising power conversion efficiency of 4.4%. This result provides a valuable guideline for rational design of conjugated small molecules for high performance organic solar cells.