Taiho Park

A diketopyrrolopyrrole-containing hole transporting conjugated polymer for use in efficient stable organic–inorganic hybrid solar cells based on a perovskite

Poly[2,5-bis(2-decyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-(E)-1,2-di(2,2′-bithiophen-5-yl) ethene] (PDPPDBTE) was successfully incorporated as a p-type hole transporting material in solid-state organic–inorganic hybrid solar cells. The excellent optical and electrical properties of organo-lead halide perovskite (CH3NH3PbI3) nanocrystals used as light harvesters yielded a 9.2% power conversion efficiency (PCE) for the best-performing cell that exceeded the value (7.6%) obtained from the best hole conductor yet reported (2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9′-spirobifluorene, spiro-MeOTAD). The high PCE was attributed to the optimal oxidation potential (5.4 eV) and excellent charge carrier mobility of the polymer. The hydrophobicity of the polymer prevented water permeation into the porous perovskite heterojunction, and long-term aging tests over 1000 hours confirmed the enhanced stability of the PDPPDBTE-based cells.

Dopant-free polymeric hole transport materials for highly efficient and stable perovskite solar cells

We report a dopant-free polymeric hole transport material (HTM) that is based on benzo[1,2-b:4,5:b′]dithiophene and 2,1,3-benzothiadiazole, which results in highly efficient and stable perovskite solar cells (∼17.3% for over 1400 h at 75% humidity). The HTM comprises a random copolymer (RCP), which is characterized using UV-vis absorption spectroscopy, cyclic voltammetry, space-charge-limited current, and grazing-incidence wide-angle X-ray scattering. The RCP-based perovskite solar cell exhibits the highest efficiency (17.3%) in the absence of dopants [lithium bis(trifluoromethanesulfonyl)imide and tert-butylpyridine]. The observed efficiency is attributed to a deep HOMO energy level and high hole mobility. In addition, the long-term stability of the device is dramatically improved by avoiding deliquescent or hygroscopic dopants and by introducing a hydrophobic polymer layer. RCP devices maintain their initial efficiency for over 1400 h at 75% humidity, whereas devices made of HTMs with additives fail after 900 h.

Size-tunable mesoporous spherical TiO2 as a scattering overlayer in high-performance dye-sensitized solar cells

Size-tunable mesoporous spherical TiO2 (MS TiO2) with a surface area of ∼110 m2 g−1 have been prepared through combination of “dilute mixing”-driven hydrolysis of titanium(iv) tetraethoxide and solvothermal treatment. The hierarchically structured MS TiO2 are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen sorption analysis. Using three different MS TiO2 (587, 757, and 1554 nm in diameter) as a scattering overlayer on a transparent nanocrystalline TiO2 film, bi-layered dye-sensitized solar cells (DSCs) have been fabricated. Since the MS TiO2 particles are comprised of ∼10 nm nanocrystallites that cluster together to form large secondary spheres, they can function as light scatterers without sacrificing the surface area for dye-uptake. As a result, the present MS TiO2-based cells perform a noticeable improvement in the overall efficiency: maximum 9.37% versus 6.80% for the reference cell made of a TiO2 nanocrystalline film. This extraordinary result is attributed to the dual effects of enhanced dye loading and light scattering.

Well-Defined Nanostructured, Single-Crystalline TiO2 Electron Transport Layer for Efficient Planar Perovskite Solar Cells

An electron transporting layer (ETL) plays an important role in extracting electrons from a perovskite layer and blocking recombination between electrons in the fluorine-doped tin oxide (FTO) and holes in the perovskite layers, especially in planar perovskite solar cells. Dense TiO2 ETLs prepared by a solution-processed spin-coating method (S-TiO2) are mainly used in devices due to their ease of fabrication. Herein, we found that fatal morphological defects at the S-TiO2 interface due to a rough FTO surface, including an irregular film thickness, discontinuous areas, and poor physical contact between the S-TiO2 and the FTO layers, were inevitable and lowered the charge transport properties through the planar perovskite solar cells. The effects of the morphological defects were mitigated in this work using a TiO2 ETL produced from sputtering and anodization. This method produced a well-defined nanostructured TiO2 ETL with an excellent transmittance, single-crystalline properties, a uniform film thickness, a large effective area, and defect-free physical contact with a rough substrate that provided outstanding electron extraction and hole blocking in a planar perovskite solar cell. In planar perovskite devices, anodized TiO2 ETL (A-TiO2) increased the power conversion efficiency by 22% (from 12.5 to 15.2%), and the stabilized maximum power output efficiency increased by 44% (from 8.9 to 12.8%) compared with S-TiO2. This work highlights the importance of the ETL geometry for maximizing device performance and provides insights into achieving ideal ETL morphologies that remedy the drawbacks observed in conventional spin-coated ETLs.

High-Field-Effect Mobility of Low-Crystallinity Conjugated Polymers with Localized Aggregates.

Charge carriers typically move faster in crystalline regions than in amorphous regions in conjugated polymers because polymer chains adopt a regular arrangement resulting in a high degree of π-π stacking in crystalline regions. In contrast, the random polymer chain orientation in amorphous regions hinders connectivity between conjugated backbones; thus, it hinders charge carrier delocalization. Various studies have attempted to enhance charge carrier transport by increasing crystallinity. However, these approaches are inevitably limited by the semicrystalline nature of conjugated polymers. Moreover, high-crystallinity conjugated polymers have proven inadequate for soft electronics applications because of their poor mechanical resilience. Increasing the polymer chain connectivity by forming localized aggregates via π-orbital overlap among several conjugated backbones in amorphous regions provides a more effective approach to efficient charge carrier transport. A simple strategy relying on the density of random copolymer alkyl side chains was developed to generate these localized aggregates. In this strategy, steric hindrance caused by these side chains was modulated to change their density. Interestingly, a random polymer exhibiting low alkyl side chain density and crystallinity displayed greatly enhanced field-effect mobility (1.37 cm(2)/(V·s)) compared with highly crystalline poly(3-hexylthiophene).

Sulfur-incorporated carbon quantum dots with a strong long-wavelength absorption band

In this work, we synthesize sulfur-incorporated carbon quantum dots (S-CQDs) and report the effect of sulfur on their electronic structure. Sulfur provides the density of states or emissive trap states for photoexcited electrons, and hence improves absorbance and photoluminescence intensity in the long-wavelength (∼500 nm) regime. The formation of the emissive trap states in the band-gap is confirmed by time-resolved emission decay spectroscopy. It is revealed that the emissive trap states prolong the fluorescence lifetime of low energy (∼2.5 eV) photoexcited electrons. To explore further the change in the band-gap energy, we demonstrate charge transport in S-CQD films that serve as the channels of field-effect transistors (FETs). The turn-on voltage of the S-CQD-based FETs decreases with the increase of the sulfur concentration, which is consistent with the optical changes. Our results establish a technical basis to incorporate heterogeneous atoms into CQDs and examine the related changes made to their optoelectronic properties. This method would open up new prospects to control the band-gap energy of CQDs in mild conditions, and hence promote their applications in imaging agents and optoelectronic devices.

A novel quasi-solid state dye-sensitized solar cell fabricated using a multifunctional network polymer membrane electrolyte

A series of liquid junction dye-sensitized solar cells (DSCs) was fabricated based on polymer membrane-encapsulated dye-sensitized TiO2 nanoparticles, prepared using a surface-induced cross-linking polymerization reaction, to investigate the dependence of the solar cell performance on the encapsulating membrane layer thickness. The ion conductivity decreased as the membrane thickness increased; however, the long term-stability of the devices improved with increasing membrane thickness. Nanoparticles encapsulated in a thick membrane (ca. 37 nm), obtained using a 90 min polymerization time, exhibited excellent pore filling among TiO2 particles. This nanoparticle layer was used to fabricate a thin-layered, quasi-solid state DSC. The thick membrane prevented short-circuit paths from forming between the counter and the TiO2 electrode, thereby reducing the minimum necessary electrode separation distance. The quasi-solid state DSC yielded a high power conversion efficiency (7.6 → 8.1%) and excellent stability during heating at 65 °C over 30 days. These performance characteristics were superior to those obtained from a conventional DSC (7.5 → 3.5%) prepared using a TiO2 active layer with the same thickness. The reduced electrode separation distance shortened the charge transport pathways, which compensated for the reduced ion conductivity in the polymer gel electrolyte. Excellent pore filling on the TiO2 particles minimized the exposure of the dye to the liquid and reduced dye detachment.

Thermodynamic Control over the Competitive Anchoring of N719 Dye on Nanocrystalline TiO2 for Improving Photoinduced Electron Generation

TiO(2) electrodes, sensitized with the N719 dye at high immersion temperatures during the sensitization process, were found to have large fractions of weakly bound N719 on the electrode surface, which resulted in dye aggregation and decreased device longevity. These disadvantages were ameliorated using a low-temperature stearic acid (SA)-assisted anchoring method described here. The activation energy (ΔE(NS)(++)) and relative fraction of strongly bound N719 were twice as large as the respective values obtained without the use of SA. Slowing of adsorption, both by thermal means and through SA-mediated processes, effectively controlled the binding mode of N719 on the surface of TiO(2). The resulting sensitized electrodes displayed enhanced device longevity and improved generation of photoinduced electrons.

Green-Solvent-Processable, Dopant-Free Hole-Transporting Materials for Robust and Efficient Perovskite Solar Cells

In addition to having proper energy levels and high hole mobility (μh) without the use of dopants, hole-transporting materials (HTMs) used in n-i-p-type perovskite solar cells (PSCs) should be processed using green solvents to enable environmentally friendly device fabrication. Although many HTMs have been assessed, due to the limited solubility of HTMs in green solvents, no green-solvent-processable HTM has been reported to date. Here, we report on a green-solvent-processable HTM, an asymmetric D-A polymer (asy-PBTBDT) that exhibits superior solubility even in the green solvent, 2-methylanisole, which is a known food additive. The new HTM is well matched with perovskites in terms of energy levels and attains a high μh (1.13 × 10-3 cm2/(V s)) even without the use of dopants. Using the HTM, we produced robust PSCs with 18.3% efficiency (91% retention after 30 days without encapsulation under 50%-75% relative humidity) without dopants; with dopants (bis(trifluoromethanesulfonyl) imide and tert-butylpyridine, a 20.0% efficiency was achieved. Therefore, it is a first report for a green-solvent-processable hole-transporting polymer, exhibiting the highest efficiencies reported so far for n-i-p devices with and without the dopants.

Reduced charge recombination by the formation of an interlayer using a novel dendron coadsorbent in solid-state dye-sensitized solar cells

3,4,5-Tris(dodecyloxy)benzoic acid (DOBA) and the Z907 dye were coadsorbed to form a light-sensitizing monolayer in a solid-state dye-sensitized solar cell (sDSC). Coadsorption of DOBA which has three hydrocarbon chains permitted preparation of a denser monolayer of dyes and DOBA. This dense monolayer formed interlayer between TiO2 and Spiro-OMeTAD (hole conductor), effectively preventing charge recombination, while half of the photocurrent was dissipated via recombination reaction when Z907 solely anchored on the surface of TiO2. Moreover, the DOBA induced a lower population of density-of-state (DOS) in the surface of TiO2, shifting the position of the conduction band (CB) toward negative values. This resulted in higher open-circuit voltage (VOC) for the device made with Z907 and DOBA than that of the Z907-sensitized device. These surface properties were investigated using electrochemical impedance spectroscopy (EIS), intensity modulated photocurrent/photovoltage spectroscopy (IMPS and IMVS).