Dibenzothiophene-S,S-dioxide based medium-band-gap polymers for efficient bulk heterojunction solar cells

Medium-band-gap polymers based on indacenodithiophene (IDT) and dibenzothiophene-S,S-dioxide (SO) derivatives, PIDT-SO and PIDT-DHTSO, were synthesized via a microwave assisted Stille polycondensation. The polymers have the maximum absorption ∼500 nm, high absorption coefficients above 0.6 × 10⁻² nm⁻¹, and medium band gaps of ∼2.2 eV. Their hole mobilities are around 2 × 10⁻⁴ cm² V⁻¹ s⁻¹ as measured by field effect transistors. The photovoltaic performances of the polymers were investigated on the inverted bulk heterojunction (BHJ) devices of ITO/PFN/PIDT-DHTSO:PC₇₁BM (1:3, w/w)/MoO₃/Al, and a power conversion efficiency (PCE) of 3.81% with an open-circuit voltage (V_oc) of 0.95 V, a short-circuit current (J_sc) of 8.20 mA cm⁻² and a fill factor (FF) of 48% were achieved. Those results indicated that dibenzothiophene-S,S-dioxide derivatives could be an excellent electron-deficient building block for medium-band-gap electron-donor polymers.     

Circuital modelling of S-shape removal in the current–voltage characteristic of TiOx inverted organic solar cells through white-light soaking

In this work light activation phenomenon in inverted bulk heterojunction (BHJ) organic solar cells (OSC) has been electrically modelled with a two-diode equivalent circuit. OSC are based on poly(3-hexylthiophene) (P3HT): 1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6) C61 (PCBM) with a titanium oxide (TiO_x) sublayer. Current–voltage (I–V) characteristics show a highly pronounced S-shape that is gradually removed during light activation process. The circuit used to model I–V curves includes two diodes in forward and reverse bias together with two parallel resistances, R_P1 and R_P2. The parallel of the reverse bias diode and its corresponding resistance R_P2 models the electrical behaviour of the TiO_x interlayer. This interlayer has been thermally treated at different temperatures, from 80 °C up to 180 °C, reducing the activation time from 400 s for unbaked devices down to 30 s for devices annealed at temperatures higher than 80 °C. The S-shape shown in the I–V characteristic is completely removed after a few minutes of white-light illumination. I–V curves recorded during the activation process have been fitted with the analytical solution of the two-diode circuit based on W-Lambert function. A decrease of the subcircuit 2 equivalent resistance has been found to be the cause of S-shape removal. This resistance diminishing is in good agreement with the increase of TiO_x conductance with baking temperature and white-light exposure time found by other authors.     

Solvent–vapor induced morphology reconstruction for efficient PCDTBT based polymer solar cells

This paper reports polymer solar cells with a 7% power conversion efficiency (PCE) based on bulk heterojunction (BHJ) composites of the alternating co-polymer, poly[N-9′′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT), and the fullerene derivative [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM). As confirmed by transmission electron microscopy, solvent–vapor annealing (SVA) of the thin (70 nm) BHJ photoactive layer by exposure to chloroform vapor, for a short period of time (30 s) after deposition, leads to reconstructed nanoscale morphology of donor/acceptor domains, well-dispersed fullerene phase and effective photo-absorption of BHJ. Consequently, SVA-reconstructed devices with a PCDTBT:PC₇₁BM blend ratio of 1:5 (wt%) exhibit ～50% improvement in PCE, with short-circuit current J_sc = 15.65 mA/cm², open-circuit voltage V_oc = 0.87 V, and PCE = 7.03%, in comparison to those of the 1:4 (wt%) blends with SVA treatment.     

Expanded graphite/pencil-lead as counter electrode for dye-sensitized solar cells

A kind of new carbon material - expanded graphite (EG) was prepared and then used with 5B pencil-lead as counter electrodes for the DSSCs. The EG/pencil-lead products were discussed following five different weight ratios of 1:0, 1:1, 1:2, 2:1, and 0:1. And flake graphite was employed for comparison. Commercial P25 TiO₂ adsorbing dye N719 was used as photoanode and ionic liquid was adopted as electrolyte to compose the cell. Using green light-emitting diode (525 nm, LED) as the light source, J-V curves were recorded using the Zahner Zennium CIMPS system based on an IM6x electrochemical workstation. When the mass ratio of the mixture was 1:1, the overall conversion efficiency of DSSCs reached to highest value 7.7% (J_sc = 0.441 mA cm⁻², V_oc = 683 mV, fill factor = 0.637) under green-light intensity.     

Efficient nondoped organic light-emitting diodes with Cu complex emitter

In Cu^I complex based organic light emitting diodes (OLEDs) a host matrix is traditionally thought to be required to achieve high efficiency. Herein, it is found that the device ITO/MoO₃ (1 nm)/4,4′-N,N′-dicarbazole-biphenyl (CBP, 35 nm)/[Cu(μ-I)dppb]₂ (dppb = 1,2-bis[diphenylphosphino]benzene, 20 nm)/1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi, 65 nm)/LiF (1 nm)/Al (100 nm) with a vacuum thermal evaporated nondoped Cu^I complex emissive layer (EML) showed external quantum efficiency and current efficiency of 8.0% and 24.3 cd/A at a brightness of 100 cd/m², respectively, which are comparable to the maximum efficiencies reported in an optimized doped OLED with the same emitter, higher efficiency than the OLED with a [Cu(μ-I)dppb]₂:CBP EML, and much higher efficiencies than the nondoped OLED with a bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)] EML. A series of reference films and single carrier devices were fabricated and studied to understand the difference between Cu^I and Ir^III complex based nondoped OLEDs.     

Photovoltaic properties of low band gap copolymers based on phenylenevinylene donor and cyanovinylene 4-nitrophenyl acceptor units

Two novel copolymers P1 and P2 having phenylenevinylene donor and cyanovinylene 4-nitrophenyl acceptor units, were synthesized by heck coupling and employed as electron donor along with PCBM or modified PCBM (F) as electron acceptor for the fabrication of bulk heterojunction (BHJ) photovoltaic devices. These copolymers P1 and P2 showed broad band absorption around 640-700 nm and optical band gap of 1.60 eV and 1.72 eV, respectively. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) estimated from cyclic voltammetry measurement reveals that these values are well suitable for the use of these copolymers as electron donor along with PCBM derivatives as electron acceptor for BHJ active layer. The suitable LUMO off set allows efficient photo-induced charge transfer at the donor/acceptor interfaces in the BHJ photovoltaic device and resulting power conversion efficiency (PCE) of 2.8% and 3.29% for P1 and P2, respectively, when PCBM is used as acceptor. This value has been improved up to 3.52% and 4.36% for the devices based on P1 and P2 when F is used as electron acceptor, instead of PCBM. We have also investigated the effect of solvent annealing on the photovoltaic performance of device based on P1: F and P2: F blends and found that the over all PCE of the devices is 4.36% and 4.88%, respectively. The increase in PCE is mainly due to the improvement in the J_sc, which is due to the increased charge transport in the annealed device as compared to as cast device.     

High mobility strained Si0.5Ge0.5/SSOI short channel field effect transistors with TiN/GdScO3 gate stack

Short channel p-type metal-oxide-semiconductor field effect transistors (MOSFETs) with GdScO₃ gate dielectric were fabricated on a quantum well strained Si/strained Si_0.5Ge_0.5/strained Si heterostructure on insulator. Amorphous GdScO₃ layers with a dielectric constant of 24 show small hysteresis and low density of interface states. All devices show good performance with a threshold voltage of 0.585 V, commonly used for the present technology nodes, and high I_on/I_off current ratios. We confirm experimentally the theoretical predictions that the drive current and the transconductance of the biaxially strained (1 0 0) devices are weakly dependent on the channel orientation. The transistor’s hole mobility, extracted using split C-V method on long channel devices, indicates an enhancement of 90% (compared to SiO₂/SOI transistors) at low effective field, with a peak value of 265 cm²/V s. The enhancement is however, only 40% at high electrical fields. We demonstrate that the combination of GdScO₃ dielectric and strained SiGe layer is a promising solution for gate-first high mobility short channel p-MOSFETs.     

High-power broad-area InGaNAs/GaAs quantum-well lasers in the 1200 nm range

High-power broad-area InGaNAs/GaAs quantum-well (QW) edge-emitting lasers on GaAs substrates in the 1200 nm range are reported. The epitaxial layers of the InGaNAs/GaAs QW laser wafers were grown on n⁺-GaAs substrates by using metal-organic chemical vapor deposition (MOCVD). The thickness of the InGaNAs/GaAs QW layers is 70 Å/1200 Å. The indium content (x) of the In_xGa_1−xN_yAs_1−y QW layers is estimated to be 0.35-0.36, while the nitrogen content (y) is estimated to be 0.006-0.009. More indium content (In) and nitrogen content (N) in the InGaNAs QW layer enables the laser emission up to 1300 nm range. The epitaxial layer quality, however, is limited by the strain in the grown layer. The devices were made with different ridge widths from 5 to 50 μm. A very low threshold current density (J_th) of 80 A/cm² has been obtained for the 50 μm × 500 μm LD. A number of InGaNAs/GaAs epi-wafers were made into broad-area LDs. A maximum output power of 95 mW was measured for the broad-area InGaNAs/GaAs QW LDs. The variations in the output powers of the broad-area LDs are mainly due to strain-induced defects the InGaNAs QW layers.     

Enhanced performance of dye-sensitized solar cells with novel 2,6-diphenyl-4H-pyranylidene dyes

Novel 2,6-diphenyl-4H-pyranylidene derivatives were designed and synthesized as dyes for dye-sensitized solar cells (DSSC). Dyes 2a, b with a phenyl substituent showed high DSSC energy conversion efficiencies of 5.3% (J_sc = 10.3 mA/cm², V_oc = 0.72 V, FF = 0.72) and 4.7% (J_sc = 8.9 mA/cm², V_oc = 0.73 V, FF = 0.72) at 100 mW/cm² under simulated AM 1.5 G solar light conditions. These values are twice better than that of dye 1 without the phenyl substituent under the same conditions. Both the photocurrent density (J_sc) and open circuit voltage (V_oc) of DSSCs based on dyes 2a, b are increased compared with 1. It can be attributed to their twisted structures, absorption abilities and proper energy levels. This result shows that the tetraphenylpyranylidene is a promising electron-donor unit for high-efficiency DSSCs.     

Novel brominated compounds using in binary additives based organic solar cells to achieve high efficiency over 10.3%

Solvent additives have been considered as a simple and efficient method to increase the performance of bulk-heterojunction (BHJ) organic solar cells, in which, the morphology of the active layer could obtain further improvements by using the binary solvent additives. In this paper, a series of brominated compounds, 1-Bromo-4-butylbenzene (Brbb), 1-Bromo-4-n-hexylbenzene (Brbh) and 1-Bromo-4-n-octylbenzene (Brbo), have been respectively incorporated with 1, 8-diiodooctane (DIO) and regarded as binary solvent additives to fabricate highly efficient bulk heterojunction (BHJ) organic solar cells (OSCs). Compared with the BHJ film based on single additive, the binary additives contained BHJ film shows increased optical absorption, efficient charge transport and better active layer morphology, leading to an enhancement of short-circuit current (J_SC) together with a higher achieved fill factor (FF). The conventional BHJ device using PTB7: PC₇₁BM or PTB7-th: PC₇₁BM with the binary solvent additives exhibit enhanced PCE of 8.13% and 10.31%, respectively, which is much higher than that of single additive based devices (7.04% for PTB7 and 8.73% for PTB7-th). The optimized performance of BHJ devices indicates that these brominated compounds are promising additives to improve device efficiency.     

Tandem small molecule organic photovoltaic cells with broad spectral response up to 1 μm and a high open-circuit voltage

We report a series-connected small molecule tandem photovoltaic cell utilizing two donors with complementary photovoltaic characteristics, lead phthalocyanine (PbPc) in the front subcell and boron subphthalocyanine chloride (SubPc) in the back subcell, to achieve both near infrared (NIR) response up to 1 μm and high open-circuit voltage (V_OC) of more than 1.5 V in the same device. We find that the C₆₀ layer thickness in the front subcell has a critical impact on the overall optical structure and photovoltaic performance of the tandem device. By combining transfer matrix calculations with subcell-selective spectral measurements, we are able to tune the optical field distribution inside the active layers and increase the photocurrent outputs from both subcells, leading to EQE > 30% over the wavelength range 400 nm < λ < 900 nm. This optimized tandem cell exhibits J_SC = (5.5 ± 0.1) mA/cm², fill factor = 0.54, V_OC = 1.53 V, and a power conversion efficiency of (4.5 ± 0.2)%.     

Microstructure and electric property of MgO/Fe/MgO tri-layer films forming a nano-granular system

For tunneling magnetoresistance (TMR) devices using ferromagnetic nano particle films, the size, dispersion and number of nano particles are important factors. Relating to this, single layered Fe films (thickness: t = 0.5 - 10.0 nm) sandwiched between two MgO (2 nm thick) layers were fabricated by molecular beam epitaxy. By depositing at T_s = RT (room temperature), the Fe layer had an isolated island structure for less than 1 nm thick. Correspondingly, the negative magnetoresistance effect was observed, which is characteristic of TMR. By increasing T_s, the resistivity and the magnetoresistance (MR) ratio was increased. In this study, it was found that the optimal parameters for the growth of nano particle MgO/Fe/MgO based films are t = 0.5 - 1.0 nm and T_s = RT − 120 °C.     

Improved self-gain in deep submicrometer strained silicon-germanium pMOSFETs with HfSiOx/TiSiN gate stacks

The self-gain of surface channel compressively strained SiGe pMOSFETs with HfSiO_x/TiSiN gate stacks is investigated for a range of gate lengths down to 55 nm. There is 125% and 700% enhancement in the self-gain of SiGe pMOSFETs compared with the Si control at 100 nm and 55 nm lithographic gate lengths, respectively. This improvement in the self-gain of the SiGe devices is due to 80% hole mobility enhancement compared with the Si control and improved electrostatic integrity in the SiGe devices due to less boron diffusion into the channel. At 55 nm gate length, the SiGe pMOSFETs show 50% less drain induced barrier lowering compared with the Si control devices. Electrical measurements show that the SiGe devices have larger effective channel lengths. It is shown that the enhancement in the self-gain of the SiGe devices compared with the Si control increases as the gate length is reduced thereby making SiGe pMOSFETs with HfSiO_x/TiSiN gate stacks an excellent candidate for analog/mixed-signal applications.     

Effect of a novel self-assembly based on coordination polymer with zinc porphyrin in supramolecular solar cells

Within this work, we firstly report the self-assemblies of zinc porphyrin coordination polymers (CPs) appended isonicotinic acid ligands by metal–ligand axial coordination approach immobilized on the nanostructured TiO₂ electrode surfaces in photoelectrochemical devices. Compared to the assemblies based on zinc porphyrins integrated isonicotinic acid ligands via metal–ligand axial coordination or metal–ligand edged binding approach, the CPs-based assemblies exhibit significantly improved photovoltaic performances. Especially, the assembly based on iminazole-substituted zinc porphyrin coordination polymer exhibits an excellent photovoltaic performance with a short circuit photocurrent density (J_sc) of 3.8 mA cm⁻², an open circuit voltage (V_oc) of 0.31 V, a fill factor (FF) of 0.67 and an overall conversion efficiency (η) of 0.48% under AM 1.5 conditions. The results serve as another good testing ground for the fabrication of supramolecular devices techniques in future.     

Structure difference of sorbitol derivatives influences the crystallization and performance of P3OT/PCBM organic photovoltaic solar cells

In this work, we compare the effects of sorbitol derivatives (1,3:2,4-dibenzylidene sorbitol (DBS), 1,3:2,4-di(p-methylbenzylidene) sorbitol (MDBS) and 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS)) on the performances of poly(3-octyl thiophene)/[6,6]-phenyl C₆₁-butyric acid methyl ester (P3OT/PCBM) bulk heterojunction (BHJ) organic photovoltaic (OPV) devices and explore the mechanism. Differential scanning calorimetry (DSC) and atomic force microscopy (AFM) measurements indicate that DBS, MDBS and DMDBS are nucleating agents of P3OT. DMDBS has the strongest molecular polarizability and exhibits the best propensity for self-assembly in 1,2-dichlorobenzene (ODCB). The strong π-π stacking of aromatic benzylidene group and the high density of the fibrillary aggregates supply more nucleation surfaces for P3OT, leading DMDBS has the highest nucleation efficiency (NE). Sorbitol derivatives accelerate the crystallization rate (G) of P3OT with the order as G_P3OT/DMDBS > G_P3OT/MDBS > G_P3OT/DBS > G_P3OT. The acceleration of the crystallization increases the number of tie molecules, causing the improvement of the connectivity between ordered regions, resulting dramatically increasing the carrier transport of P3OT. G_P3OT/DMDBS is highest, the connectivity between ordered regions is best in P3OT with DMDBS. UV–vis measurement indicates that the intra-chain order of P3OT reduces with the addition of sorbitol derivative, and the intra-chain order of P3OT with DMDBS is lowest. The P3OT/PCBM/sorbitol derivative BHJ OPV devices were fabricated and show that the short circuit current J_{SC P3OT/DMDBS} > J_{SC P3OT/MDBS} > J_{SC P3OT/DBS} > J_{SC P3OT}. It hints that the connectivity of tie molecules plays a significant role in defining semiconducting polymer transport characteristics, and is perhaps more important than molecular level interactions (inter- and intra-chain order) for efficient macroscopic charge carrier transport. Finally, it shows that adding sorbitol derivatives can improve the power conversion efficiency (PCE) of P3OT/PCBM BHJ OPV device, the best PCE as 1.77% is obtained in the P3OT/PCBM/DMDBS device.     

Efficient bulk heterojunction photovoltaic devices based on diketopyrrolopyrrole containing small molecule as donor and modified PCBM derivatives as electron acceptors

A new solution processable small molecule (DPP-CN) containing electron donor diketopyrrolopyrrole (DPP) core and cyanovinylene 4-nitrophenyl (CN) electron acceptor has synthesized for use as the donor material in the bulk heterojunction organic solar cells along with PCBM, modified PCBM i.e. F and A as electron acceptor. It showed a broad absorption in longer wavelength region having optical band gap around 1.64 eV. We have used PCBM, F and A as electron acceptor for the fabrication of bulk heterojunction photovoltaic devices. The power conversion efficiency (PCE) of the BHJ devices based on DPP-CN:PCBM, DPP-CN:F and DPP-CN:A blends cast from the THF solvent is 1.83%, 2.79% and 2.83%, respectively. The increase in the PCE based on F and A as electron acceptor is mainly due to the increase in both short circuit current (J_sc) and open circuit voltage (V_oc). The PCE value of the photovoltaic devices based on the blends DPP-CN:PCBM, DPP-CN:F and DDP-CN:A cast from the mixed solvents (DIO/THF) has been further improved up to 2.40%, 3.32% and 3.34%, respectively. This improvement is mainly due to the increased value of J_sc, which is attributed not only to the increase of crystallinity, but also to the morphological change in the film cast from mixed solvent. Finally, the device ITO/PEDOT:PSS/DPP-CN:A (DIO/THF cast)/TiO₂/Al device shows a PCE of 3.9%. The improved device performance could be attributed to the electron transporting and hole-blocking capabilities due to the introduced TiO₂ buffer layer.     

The structural and electrical properties of the SrTa2O6/In0.53Ga0.47As/InP system

The structural and electrical properties of SrTa₂O₆(SrTaO)/n-In_0.53GaAs_0.47(InGaAs)/InP structures where the SrTaO was grown by atomic vapor deposition, were investigated. Transmission electron microscopy revealed a uniform, amorphous SrTaO film having an atomically flat interface with the InGaAs substrate with a SrTaO film thickness of 11.2 nm. The amorphous SrTaO films (11.2 nm) exhibit a dielectric constant of ∼20, and a breakdown field of >8 MV/cm. A capacitance equivalent thickness of ∼1 nm is obtained for a SrTaO thickness of 3.4 nm, demonstrating the scaling potential of the SrTaO/InGaAs MOS system. Thinner SrTaO films (3.4 nm) exhibited increased non-uniformity in thickness. From the capacitance-voltage response of the SrTaO (3.4 nm)/n-InGaAs/InP structure, prior to any post deposition annealing, a peak interface state density of ∼2.3 × 10¹³ cm⁻² eV⁻¹ is obtained located at ∼0.28 eV (±0.05 eV) above the valence band energy (E_v) and the integrated interface state density in range E_v + 0.2 to E_v + 0.7 eV is 6.8 × 10¹² cm⁻². The peak energy position (0.28 ± 0.05 eV) and the energy distribution of the interface states are similar to other high-k layers on InGaAs, such as Al₂O₃ and LaAlO₃, providing further evidence that the interface defects in the high-k/InGaAs system are intrinsic defects related to the InGaAs surface.     

Al contacts to nanoroughened p-GaN

Nanoroughening of a p-GaN surface using nanoscale Ni islands as an etch mask was utilized to investigate the feasibility for the flip-chip configuration light-emitting diodes (LEDs) using an Al-based reflector. Improved ohmic characteristics were found for the nanoroughened sample. A specific contact resistivity of 8.9×10⁻² Ω cm² and a reflectance of 82% at 460 nm were measured for the nanoroughened Al contact. The Schottky barrier heights were decreased from 0.81 eV (I-V) and 0.84 eV (Norde) for the Al contact to 0.70 eV (I-V) and 0.69 eV (Norde) for the nanoroughened Al contact. The barrier height reduction may be attributed to enhanced tunneling and the increased contact area due to the nanoroughening. This work suggests that the ohmic contact characteristics and the light extraction efficiency may be improved further with a well-defined nanopatterned p-GaN layer.     

An oligothiophene dye with triphenylamine as side chains for efficient dye-sensitized solar cells

A novel oligothiophene-cyanoacrylic acid photosensitizer with two triphenylamine side chains (7T-2TPA) is designed and synthesized for dye-sensitized solar cells. 7T-2TPA exhibits broad (250-600 nm) and strong absorption (ε = 5.0 × 10⁴ L mol⁻¹ cm⁻¹ at 496 nm). The optical band gap (E_g) is estimated from the onset absorption edge to be 2.07 eV. The oxidation potential E_ox and reduction potential E_red vs NHE of the dye is 0.93 and −1.14 V, respectively. Dye-sensitized solar cell (DSSC) based on 7T-2TPA exhibits an open-circuit voltage (V_oc) of 724 mV, a short-circuit current density (J_sc) of 16.28 mA cm⁻², a fill factor (FF) of 0.684 and a power conversion efficiency of 8.06%. The efficiency of 8.06% is similar to that for widely used N719-based cell fabricated and measured under the same conditions.     

Resistive switching characteristics of ultra-thin TiOx

We investigated the resistive switching characteristics of Ir/TiO_x/TiN structure with 50 nm active area. We successfully formed ultra-thin (4 nm) TiO_x active layer using oxidation process of TiN BE, which was confirmed by X-ray Photoelectron Spectroscopy (XPS) depth profiling. Compared to large area device (50 μm), which shows only ohmic behavior, 250 and 50 nm devices show very stable resistive switching characteristics. Due to the formation and rupture of oxygen vacancies induced conductive filament at Ir and TiO_x interface, bipolar resistive switching was occurred. We obtained excellent switching endurance up to 10⁶ times with 100 ns pulse and negligible degradation of each resistance state at 85 °C up to 10⁴ s.