Using pyridal[2,1,3]thiadiazole as an acceptor unit in a low band-gap copolymer for photovoltaic applications

In this report, we explore the optoelectronic properties of a low band-gap copolymer based on the alternation of electron rich (thiophene and thienothiophene units) and electron deficient units (pyridal[2,1,3]thiadiazole (Py)). Initial density functional theory calculations point out the interest of using the Py unit to optimize the polymer frontier orbital energy levels. A high molecular weight (M_n = 49 kg/mol) solution-processable copolymer, based on Py, thiophene and thienothiophene units, has been synthesized successfully. From cyclic-voltammetry and UV–visible absorption measurements a relatively deep HOMO level (−5.1 eV) and an optical band-gap (1.48 eV) have been estimated. Charge transport both in horizontal and vertical directions were extracted from field-effect transistors and space charge limited current diodes, respectively, and led to a relatively high in-plane hole mobility in pure polymer films (0.7 × 10⁻² cm² V⁻¹ s⁻¹). GIWAXS results showed almost identical in-plane lamellar morphologies, with similar average size and orientation of the polymer crystalline domains in both, pure polymer films and polymer:fullerene blends. Also, the gate-voltage dependence of the field-effect mobility revealed that the energy disorder in the polymer domains was not altered by the introduction of fullerenes. The nevertheless significantly higher out-of-plane hole mobility in blends, in comparison to pure polymer films, was attributed to the minor amorphous polymer phase, presumably localized close to the donor/acceptor interface, whose signature was observed by UV–vis absorption. Promising photovoltaic performances could be achieved in a standard device configuration. The corresponding power conversion efficiency of 4.5% is above the value achieved previously with a comparable polymer using benzo [2,1,3]thiadiazole instead of Py as acceptor unit.     

MoO3 as p-type dopant for Alq3-based p–i–n homojunction organic light-emitting diodes

Using high-work-function material MoO₃ as a p-type dopant, efficient single-layer hybrid organic light-emitting diodes (OLEDs) with the p–i–n homojunction structure are investigated. When MoO₃ and Cs₂CO₃ are doped into the conventional emitting/electron-transport material tris-(8-hydroxyquinoline) aluminum (Alq₃), respectively, a significant increase in p- and n-type conductivities is observed compared to that of intrinsic Alq₃ thin films. With optimal doping, the hole and electron mobilities in Alq₃:MoO₃ and Alq₃:Cs₂CO₃ films was estimated to be 9.76 × 10⁻⁶ and 1.26 × 10⁻⁴ cm²/V s, respectively, which is about one order of magnitude higher than that of the undoped device. The p–i–n OLEDs outperform undoped (i–i–i) and single-dopant (p–i–i and i–i–n) OLEDs; they have the lowest turn-on voltage (4.3 V at 1 cd/m²), highest maximum luminance (5860 cd/m² at 11.4 V), and highest luminous efficiency (2.53 cd/A at 100 mA/cm²). These values are better than those for bilayer heterojunction OLEDs using the same emitting layer. The increase in conductivity can be attributed to the charge transfer process between the Alq₃ host and the dopant. Due to the change of carrier concentration in the Alq₃ films, the Fermi level of Alq₃ is close to the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) energy levels upon p- and n-type doping, respectively, and the carrier injection efficiency can thus be enhanced because of the lower carrier injection barrier. The carriers move closer to the center energy levels of the HOMO or LUMO distributions, which increases the hopping rate for charge transport and results in an increase of charge carrier mobility. The electrons are the majority charge carriers, and both the holes and electrons can be dramatically injected in high numbers and then efficiently recombined in the p–i–n OLEDs. As a result, the improved conductivity characteristics as well as the appropriate energy levels of the doped layers result in improved electroluminescent performance of the p–i–n homojunction OLEDs.     

A study of charge transport in a novel electroluminescent poly(phenylene vinylene-co-fluorenylene vinylene) based π-conjugated polymer

The charge transport properties in a novel electroluminescent poly{[2-(4′,5′-bis(3″-methylbutoxy)-2′-p-methoxy-phenyl)phenyl-1,4-phenylene vinylene]-co-(9,9-dioctyl-2,7-fluorenylene vinylene)} (BPPPV-PF) have been studied using a time-of-flight (TOF) photoconductivity technique. The TOF transients for holes were recorded over a range of temperatures (207–300 K) and electric fields (1.5 × 10⁵–6.1 × 10⁵ V/cm). The hole transport in this polymer was weakly dispersive in nature with a mobility at 300 K of 5 × 10⁻⁵ cm²/V s at 2.5 × 10⁵ V/cm. This increased to 8.4 × 10⁻⁵ cm²/V s at 6.1 × 10⁵ V/cm. The temperature and field dependence of charge mobility has been analyzed using the disorder formalisms (Bässler’s Gaussian disorder model (GDM) and correlated disorder model (CDM)). The fit with Gaussian disorder (GDM) model yielded the mobility pre-factor μ_∞ = 1.2 × 10⁻³ cm²/V s, energetic disorder parameter σ = 82 meV and positional disorder parameter Σ = 1.73. The average inter-site separation (a = 7 Å) and the charge localization length (L = 3.6 Å) was estimated by assuming the CDM type charge transport. The microscopic charge transport parameters derived for this polymer are almost identical to the reported values for fully conjugated polymers with high chemical purity. The results presented indicate that the charge transport parameters can be controlled and optimized for organic optoelectronic applications.     

Development of a new diindenopyrazine–benzotriazole copolymer for multifunctional application in organic field-effect transistors,polymer solar cells and light-emitting diodes

A new donor–acceptor (D?A) copolymer (PIPY–DTBTA) containing 6,12-dihydro-diindeno[1,2-b;1′,2′-e]pyrazine donor and benzotriazole acceptor was synthesized and characterized for multifunctional applications in organic field-effect transistors (OFETs), polymer solar cells (PSCs) and polymer light-emitting diodes (PLEDs). The polymer exhibits high molecular weights, excellent film-forming ability, a deep HOMO energy level, and good solution processability. Solution-processed thin film OFETs based on this polymer revealed good p-type characteristic with a high hole mobility up to 0.0521 cm² V^?1 s^?1. Bulk-heterojunction PSCs comprising this polymer and PC₆₁BM gave a power conversion efficiency (PCE) of 0.77%. The single-layer PLEDs based on PIPY–DTBTA emitted a yellow–red light with a maximum brightness of 385 cd m^?2 at the turn-on voltage of 6 V.     

Solution processable quinoxaline based molecular materials for organic field effect transistors

Three new solution processable quinoxaline based donor–acceptor–donor (D–A–D) type molecules have been synthesized for application in field effect transistors. These molecules were characterized by UV–visible spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and cyclic voltammetry. DFT calculation gives deeper insight into the electronic structure of these molecules. The crystallinity and morphology features of thin film were investigated using X-ray diffraction. These molecules show liquid crystalline phase confirmed by DSC and optical polarizing microscopy. Investigation of their field effect transistor performance indicated that these molecules exhibited p-type mobility up to 9.7 × 10^?4 cm² V^?1 s^?1 and on/off ratio of 10⁴.     

A study on phase transformation of SnOx thin films prepared by reactive magnetron sputtering

In the paper, SnO_x thin films were deposited by reactive magnetron sputtering from a tin target in O₂ containing working gas. The evolution from Sn-containing SnO to tetravalent SnO₂ films was investigated. The films could be classified into three groups according to their optical band gaps, which are E_g<2.5 eV, E_g=3.0–3.3 eV and E_g>3.7 eV. The electric measurements show that high conductivity can be obtained much easier in SnO₂ than in SnO films. A high electron mobility of 15.7 cm² V⁻¹ s⁻¹, a carrier concentration of 1.43×10²⁰ cm⁻³ and a resistivity of 2.8×10⁻³ Ω cm have been achieved in amorphous SnO₂ films. Films with the optical band gap of 3.0–3.3 eV remain amorphous though the substrate temperature is as high as 300 °C, which implies that °btaining high mobility in p-type SnO is more challenging in contrast to n-type SnO₂ films.     

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.     

Charge conduction study of phosphorescent iridium compounds for organic light-emitting diodes application

The charge conduction properties of a series of iridium-based compounds for phosphorescent organic light-emitting diodes (OLEDs) have been investigated by thin-film transistor (TFT) technique. These compounds include four homoleptic compounds: Ir(ppy)₃, Ir(piq)₃, Ir(Tpa-py)₃, Ir(Cz-py)₃, and two heteroleptic compounds Ir(Cz-py)₂(acac) and FIrpic. Ir(ppy)₃, Ir(piq)₃ and FIrpic are commercially available compounds, while Ir(Tpa-py)₃, Ir(Cz-py)₃ and Ir(Cz-py)₂(acac) are specially designed to test their conductivities with respect to the commercial compounds. In neat films, with the exception of FIrpic, all Ir-compounds possess significant hole transporting capabilities, with hole mobilities in the range of about 5 × 10⁻⁶–2 × 10⁻⁵ cm² V⁻¹ s⁻¹. FIrpic, however, is non-conducting as revealed by TFT measurements. We further investigate how Ir-compounds modify carrier transport as dopants when they are doped into a phosphorescent host material CBP. The commercial compounds are chosen for the investigation. Small amounts of Ir(ppy)₃ and Ir(piq)₃ (<10%) behave as hole traps when they are doped into CBP. The hole conduction of the doped CBP films can be reduced by as much as 4 orders of magnitude. Percolating conduction of Ir-compounds occurs when the doping concentrations of the Ir-compounds exceed 10%, and the hole mobilities gradually increase as their values reach those of the neat Ir films. In contrast to Ir(ppy)₃ and Ir(piq)₃, FIrpic does not participate in hole conduction when it is doped into CBP. The hole mobility decreases monotonically as the concentration of FIrpic increases due to the increase of the average charge hopping distance in CBP.     

Effect of trap states on the electrical doping of organic semiconductors

We demonstrate that direct charge transfer (CT) from trap states of host molecules to the p-dopant molecules raises the doping effect of organic semiconductors (OS). Electrons of the trap states in 4,4′-N,N′-dicarbazolyl-biphenyl (CBP) (E_HOMO = 6.1 eV) are directly transferred to the p-dopant, 2,2′-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) (ELUMO = 5.4 eV). This doping process enhances the conductivity of doped OS by different ways from the ordinary doping mechanism of generating free hole carriers and filling trap states of doped OS. Trap density and trap energy are analysed by impedance spectroscopy and it is shown that the direct charge transfer from deep trap states of host to dopants enhances the hole mobility of doped OS and the I–V characteristics of hole only devices.     

Charge transport properties in liquid carbazole

The hole mobility in 9-(2-ethylhexyl)carbazole so-called liquid carbazole, in poly(N-vinylcarbazole) (PVK) and in their blends is determined by time-of-flight experiment using a phthalocyanine charge generation layer. With an applied electric field of 2.5 × 10⁵ V/cm, mobilities of 4 × 10⁻⁶ cm²/Vs and 6 × 10⁻⁷ cm²/Vs are measured in liquid carbazole and PVK, respectively. The enhancement of the charge carrier mobility in liquid carbazole is attributed to both a larger transfer integral and changes in the distribution of the excimer trapping sites. The results show the potential interest of liquid carbazole for electroactive applications in optoelectronics.     

Charge transport properties and microstructure of polythiophene/polyfluorene blends

We present a combined charge transport and X-ray diffraction study of blends based on regioregular poly(3-hexylthiophene) (P3HT) and the polyfluorene co-polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2′′-diyl) (F8TBT) that are used in efficient all-polymer solar cells. Hole mobility is observed to increase by nearly two orders of magnitude from less than 10^?7 cm² V^?1 s^?1 for as spin-coated blends to 6 × 10^?6 cm² V^?1 s^?1 for blends annealed at 453 K at a field of 2.7 × 10⁵ V/cm, but still significantly below the time-of-flight mobility of unblended P3HT of 1.7 × 10^?4 cm² V^?1 s^?1. The hole mobility of the blends also show a strong negative electric-field dependence, compared with a relatively flat electric-field dependence of unblended P3HT, suggestive of increased spatial disorder in the blends. X-ray diffraction measurements reveal that P3HT/F8TBT blends show a phase separation of the two components with a crystalline part attributed to P3HT and an amorphous part attributed to F8TBT. In as-spun and mildly annealed blends, the measured d-values and relative intensities of the 100, 200 and 300 P3HT peaks are noticeably different to unblended P3HT indicating an incorporation of F8TBT in P3HT crystallites that distorts the crystal structure. At higher anneal temperatures the blend d-values approach that of unblended P3HT suggesting a well separated blend with pure P3HT crystallites. P3HT crystallite size in the blend is also observed to increase with annealing from 3.3 to 6.1 nm, however similar changes in crystallite size are observed in unblended P3HT films with annealing. The lower mobility of P3HT/F8TBT blends is attributed not only to increased P3HT structural disorder in the blend, but also due to the blend morphology (increased spatial disorder). Changes in hole mobility with annealing are interpreted in terms of the need to form percolation networks of P3HT crystallites within an F8TBT matrix, with a possible contribution due to the intercalation of F8TBT in P3HT crystallites acting as defects in the as-prepared state.     

Properties of fluorine-doped SnO2 thin films by a green sol–gel method

Fluorine doped tin oxide (FTO) films were fabricated on a glass substrate by a green sol–gel dip-coating process. Non-toxic SnF₂ was used as fluorine source to replace toxic HF or NH₄F. Effect of SnF₂ content, 0–10 mol%, on structure, electrical resistivity, and optical transmittance of the films were investigated using X-ray diffraction, Hall effect measurements, and UV–vis spectra. Structural analysis revealed that the films are polycrystalline with a tetragonal crystal structure. Grain size varies from 43 to 21 nm with increasing fluorine concentration, which in fact critically impacts resultant electrical and optical properties. The 500 °C-annealed FTO film containing 6 mol% SnF₂ shows the lowest electrical resistivity 7.0×10⁻⁴ Ω cm, carrier concentration 1.1×10²¹ cm⁻³, Hall mobility 8.1 cm²V⁻¹ s⁻¹, optical transmittance 90.1% and optical band-gap 3.91 eV. The 6 mol% SnF₂ added film has the highest figure of merit 2.43×10⁻² Ω⁻¹ which is four times higher than that of un-doped FTO films. Because of the promising electrical and optical properties, F-doped thin films prepared by this green process are well-suited for use in all aspects of transparent conducting oxide.     

Dicyano-functionalized chlorophyll derivatives with ambipolar characteristic for organic photovoltaics

Two ambipolar chlorophyll derivatives, namely, 3²,3²-dicyano-pyropheophorbide-a (Chl-1) and methyl 13¹-deoxo-13¹-(dicyanomethylene) pyropheophorbide-a (Chl-2), were synthesized for use as either the electron acceptor or the electron donor in organic planar-heterojunction solar cells. Despite the higher electron mobilities of these chlorophyll derivatives compared with their hole mobilities, devices using them as the electron donor with fullerene C₇₀ give much better photovoltaic performance than when they are used as the electron acceptor with copper phthalocyanine. In these Chl-based solar cells, the energy gap between the LUMO levels of the donor and acceptor molecules substantially affects the charge separation and resultant photocurrent and photovoltaic performance. The highest solar energy-to-electricity conversion efficiency of up to 2.3% has been achieved using the Chl-2/C₇₀ solar cell, under AM1.5 solar illumination (100 mW/cm²) after thermal annealing of the device. It was also confirmed that the electron mobility of blend films containing Chls and fullerene derivative PC₇₀BM was determined not only by the electron mobility of PC₇₀BM but also by that of Chls.     

Development of transparent conducting copper and iron co-doped cadmium oxide films: Effect of annealing in hydrogen atmosphere

Hydrogenated (annealed in hydrogen atmosphere) cadmium oxide (CdO) thin films co-doped with iron (Fe) of different levels and fixed (2.5%) copper (Cu) amount were deposited on glass and silicon wafer substrates by thermal evaporation. The films were characterised with X-ray fluorescence, X-ray diffraction, optical spectroscopy, and dc-electrical measurements. The obtained results show important improvements in the conductivity, mobility, and carrier concentration compared to un-doped and non-hydrogenated CdO. Hydrogenated CdO doped with 2.5% Cu and 1.3% Fe improved the conductivity (2293.6 S/cm) by ~46 times, mobility (78.31 cm²/V s) by ~11 times, and carrier concentration (1.82×10²⁰ cm⁻³) by ~4 times. This suggests the possibility of using CdO:Cu:Fe–H as transparent-conducting-oxide and dilute-magnetic-semiconductor field of applications.     

Sulfur stoichiometry driven chalcopyrite and pyrite structure of spray pyrolyzed Cu-alloyed FeS2 thin films

We report on fabrication of Cu_xFe_1−xS₂ (CFS) thin films using chemical spray pyrolysis followed by post-sulfurization. Post-sulfurized CFS films were grown with compact and good crystalline texture. The sulfur stoichiometry in CFS films was found to be crucial for determination of its crystal structure. The sulfur deficient CFS films were driven to chalcopyrite CFS (CH-CFS) structure whereas the sulfur cured CFS films were grown with Cu-incorporated pyrite CFS (P-CFS) structure which was confirmed by X-ray diffraction and Raman spectroscopy analysis along with UV–vis spectroscopy measurement. Electrical characterizations of both types of CFS films revealed p-type conductivity with carrier concentration in the range of 10¹⁸–10²⁰ cm⁻³ and mobility of 0.5–9 cm² V⁻¹ s⁻¹. The band gaps of CFS films of CH-CFS structure (0.885–0.949 eV) were found to be less than that of P-CFS structure (0.966–1.156 eV), which indicates its potential application for thermoelectric and photovoltaic devices.     

Effects of Ga concentration on structural and electrical properties of screen printed-CIGS absorber layers on polyethylene terephthalate

Copper indium gallium diselenide (CIGS) films were deposited as an absorber layer on polyethylene terephthalate (PET) substrates by a screen printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. The melting point of PET substrate is 254.9 °C; the average transmission in the visible (400 nm–800 nm) for PET substrates is greater than 85%. Effects of Ga content of the CIGS absorber layer on structural and electrical properties of the CIGS films were studied. The lattice parameters, a and c for all CIGS films were decreased with increasing Ga content. At room temperature, Hall mobility and charge-carrier concentration of the CIGS films varies from 97.2 to 2.69 cm² V⁻¹ s⁻¹ and 9.98×10¹⁶ to 3.23×10¹⁸ cm⁻³, respectively.     

Organic photovoltaic cells with high open circuit voltages based on pentacene derivatives

Heterojunction organic photovoltaic devices were fabricated using C₆₀ as the electron acceptor and several pentacene derivatives with triisopropylsilylethynyl functional groups as the electron donor. The open circuit voltage (V_oc) of functionalized pentacene-based cells is significantly higher (0.57–0.90 V) than for cells based on unsubstituted pentacene (0.24 V), due to the higher oxidation potentials of these pentacene derivatives. The performance of pentacene derivative cells is limited by lower current densities than the reference pentacene/C₆₀ cell. The absorption spectra of films and solutions of pentacene derivatives closely resemble one another, leading us to conclude that these films are amorphous in nature. Weak intermolecular coupling in the derivative films results in lower charge mobility and shorter exciton diffusion lengths relative to pentacene.     

A facile chemical reduction approach for effectively tuning thermoelectric properties of PEDOT films

Poly(3,4-ethylenedioxythiophene)–tosylate–polyethylene glycol–polypropylene glycol–polyethylene glycol (PEDOT–Tos–PPP) films were prepared via a vapor phase polymerization (VPP) method. The films possess good electrical conductivity (1550 S cm⁻¹), low Seebeck coefficient (14.9 μV K⁻¹) and thermal conductivity (0.501 W m⁻¹ K⁻¹), and ZT ∼ 0.02 at room temperature (RT, 295 K). Then, the films were treated with NaBH₄/DMSO solutions of different NaBH₄ concentrations to adjust the redox level. After the NaBH₄/DMSO treatment (dedoping), the electrical conductivity of the films continuously decreased from 1550 to 5.7 S cm⁻¹, whereas the Seebeck coefficient steeply increased from 14.9 to 143.5 μV K⁻¹. A maximum power factor of 98.1 μW m⁻¹ K⁻² has been achieved at an optimum redox level. In addition, the thermal conductivity of the PEDOT–Tos–PPP films decrease from 0.501 to 0.451 W m⁻¹ K⁻¹ after treated with 0.04% NaBH₄/DMSO solution. A maximum ZT value of 0.064 has been achieved at RT. The electrical conductivity and thermal conductivity (Seebeck coefficient) of the untreated and 0.04% NaBH₄/DMSO treated PEDOT–Tos–PPP films decrease (increases) with increasing temperature from 295 to 385 K. And the power factor of the films monotonically increases with temperature. The ZT at 385 K of the 0.04% NaBH₄/DMSO treated film is 0.155.     

Improving solution-processed n-type organic field-effect transistors by transfer-printed metal/semiconductor and semiconductor/semiconductor heterojunctions

Solution-processed n-type organic field effect transistors (OFETs) are in need of proper metal contact for improving injection and mobility, as well as balanced hole mobility for building logic circuit units. We address the two distinct problems by a simple technique of transfer-printing. Transfer-printed Au contacts on a terrylene-based semiconductor (TDI) significantly reduced the inverse subthreshold slope by 5.6 V/dec and enhanced the linear mobility by over 5 times compared to evaporated Au contacts. Hence, devices with a high-work-function metal (Au) are comparable with those with low-work-function metals (Al and Ca), indicating a fundamental advantage of transfer-printed electrodes in electron injection. We also transfer-printed a poly(3-hexylthiophene) (P3HT) layer onto TDI to construct a double-channel ambipolar transistor by a solution process for the first time. The transistor exhibits balanced hole and electron mobility (3.0 × 10⁻³ and 2.8 × 10⁻³ cm² V⁻¹ s⁻¹) even in a coplanar structure with symmetric Au electrodes. The technique is especially useful for reaching intrinsic mobility of new materials, and enables significant enlargement of the material tanks for solution-processed functional heterojunction OFETs.     

Organic field-effect transistor and its photoresponse using a benzo[1,2-b:4,5-b′]difuran-based donor–acceptor conjugated polymer

Organic field-effect transistors (OFETs) were fabricated through a solution process with a donor–acceptor (D–A) conjugated polymer poly{4,8-bis(2′-ethylhexylthiophene)benzo [1,2-b;3,4-b′]difuran-alt-5,5-(4′,7′-di-2-thienyl-5′,6′-dioctyloxy-2′,1′,3′-benzothiadiazole)} (PBDFTDTBT) as the active layer, which is a highly efficient D–A conjugated polymer as a donor in polymer solar cells with a power conversion efficiency (PCE) over 6.0%. The OFET devices showed a hole mobility of 0.05 cm²/Vs and an on/off ratio of 4.6 × 10⁵. Those are one of the best performance parameters for OFETs based on D–A conjugated polymers including benzo[1,2-b:4,5-b′]dithiophene (BDT) or benzo[1,2-b:4,5-b′]difuran (BDF) unit. The photoresponse of OFETs was investigated by modulating light with various intensities. The devices produced a photosensitivity (I_light/I_dark) of 1.2 × 10⁵ and a photoresponsivity of 360 mA W⁻¹ under white light illumination. The drain current in saturation region increases gradually with increasing illumination intensity. The threshold voltage exhibited a positive shift from −15.6 V in darkness to 27.8 V under illumination, which can be attributed to the well-known photovoltaic effect resulting from the transport of photogenerated holes and trapping of photogenerated electrons near the source electrode in organic phototransistors. Meanwhile, the devices showed good stability and with no obvious degeneration for 3 months in air. The study suggests that D–A conjugated polymers including BDF unit can be potentially applied in OFETs and organic phototransistors in addition to highly efficient polymer solar cells.