Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.     

Enhanced photovoltaic performance in inverted polymer solar cells using Li ion doped ZnO cathode buffer layer

We have proposed an approach to improve the photovoltaic performance of inverted polymer solar cells (i-PSC) using lithium ion doped ZnO (LiZnO) as cathode buffer layer (CBL). The LiZnO CBL was prepared using the diffusion technique, performed by inducing the Li ion of 8-hydroxyquinolatolithium (Liq) to diffuse into ZnO film through annealing the bi-layer ZnO/Liq film. Doping concentration of Li ion was controlled by using various thickness of Liq film and annealing temperature. Based on LiZnO CBL, the poly (3-hexylthiophene) [6,6]:-phenyl C61-butyric acid methyl ester (P3HT:PCBM) i-PSC device possessed a optimal power conversion efficiency (PCE) of 4.07%, which was 30% improved than that of the device with neat ZnO as CBL. The enhancement of the device performance could be attributed to the enhanced electron mobility and better band matching of the LiZnO CBL. Our finding indicates that the LiZnO film fabricated with relatively low temperature treatment has great potential for high-performance i-PSCs.     

Ga-doped ZnO as an electron transport layer for PffBT4T-2OD: PC70BM organic solar cells

Ga-doped ZnO(GZO) is investigated as an electron transport layer in organic solar cells based on a promising donor: acceptor system of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldode-cyl)-2,2′; 5′,2″; -5″,2‴-quaterthio-phen-5,5‴-diyl)] (PffBT4T-2OD):phenyl-C71-butyric acid methyl ester (PC₇₀BM). With the inverted geometry having a configuration of ITO/GZO (40 nm)/PffBT4T-2OD:PC₇₀BM (270 nm)/MoO₃ (20 nm)/Al (100 nm), maximum power conversion efficiency (PCE) of 9.74% has been achieved, while it is limited at 8.72% for devices with undoped ZnO. Our study based on the structural, morphological, compositional, and electrical characterizations indicate that suggests enhanced device performance of the GZO-based devices resulted mainly from the improved electrical properties of Ga-ZnO thin films as compared to undoped ZnO.     

TBP precursor agent passivated ZnO electron transport layer for highly efficient polymer solar cells

Defects passivation in electron transport layer (ETL) is a key issue to optimize the performance of polymer solar cells (PSCs). In this work, a novel strategy is developed to form defects passivated ZnO ETL by introducing 4-tert-butylpyridine (TBP) agent into precursor. While the power conversion efficiency (PCE) of the inverted PSCs based poly{4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno [3,4-b]thiophene-4,6-diyl}:[6,6]-phenyl C71-butyric acid methyl ester (PTB7:PC₇₁BM) with the pure ZnO ETL is 8.02%, that of the device with modified ZnO ETL is dramatically improved to 10.26%, with TBP accounting for ~28% efficiency improvement. Our study demonstrates that the precursor agent significantly affect the surface morphology and size of ZnO in ETL. Furthermore, it proves that the ZnO ETL with TBP (T-ZnO) is beneficial to polish interfacial contact between ETL and active layer and depress exciton quenching loss, resulting in enhanced exciton dissociation, efficient carrier collection and reduced charge recombination, thus improving the device performance. To verify the universality of T-ZnO ETL, the champion photovoltaic performance with a PCE of 11.74% (10% improvement) is obtained in the PBDB-T-2F:IT-4F based nonfullerene PSCs using T-ZnO as ETL. Our work developed a new, universal and facile strategy for designing highly efficient PSCs based on fullerene and nonfullerene blend systems.     

Performance enhancement in inverted polymer solar cells incorporating ultrathin Au and LiF modified ZnO electron transporting interlayer

The performance enhancement of inverted polymer solar cells (PSCs), based on the blend system of regioregular poly(3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methylester, due to incorporating ultrathin Au and LiF interlayer between the front transparent indium tin oxide and a ZnO electron transporting layer was analyzed. The results reveal that a 40% increase in PCE, e.g., from 2.62% to 3.67%, was observed for PSCs made with an optimal Au/LiF interlayer as compared to the one having a bare ZnO electron transporting layer. The presence of Au/LiF-modified ZnO interlayer between ITO and the organic layer helps to improve the charge collection. The absorption enhancement arising from the plasmon resonance of Au nanostructures also contributed to the improvement in PCE. It is shown that PSCs with LiF incorporated ZnO electron transporting layer allow improving cell lifetime, demonstrating <50% decrease in PCE compared to that of the ones with a bare ZnO interlayer after 240 day aging test for cells without encapsulation in air.     

Inverted-structure polymer solar cells fabricated by sequential spraying of electron-transport and photoactive layers

Inverted-structure polymer solar cells (I-PSCs) containing sequentially sprayed electron-transporting layers (ETLs) and photoactive layers were fabricated. Low-temperature sol–gel-derived ZnO thin films were used as the ETLs and films of a poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend were used as the photoactive layers. Nanoripples-containing ZnO ETLs could be successfully fabricated by controlling the spraying rate of the ZnO precursor solution and the subsequent annealing conditions. The P3HT/PCBM active layers sprayed on the ZnO ETLs were optimized using a unique solvent-assisted post-deposition treatment, namely, the sprayed solvent overlayer (SSO) treatment. The power conversion efficiency (PCE) of the I-PSCs based on the optimized ETLs and active layers was as high as 3.55%, which is comparable to that reported for I-PSCs fabricated using the conventional spin-coating method. The sprayed I-PSCs also exhibited high environmental stability, maintaining ∼80% of their PCE even after 40 days of aging in air under ambient conditions without encapsulation. The I-PSCs based on the P3HT/PCBM photoactive layers optimized using the SSO treatment displayed much higher stability than those based on photoactive layers optimized using a conventional thermal annealing treatment. This result indicated that the SSO treatment is a suitable post-deposition treatment method for improving the morphological stability of P3HT/PCBM active layers. Further, the fabrication technique investigated in this study is a high-throughput low-temperature one and is suitable for fabricating high-stability PSCs.     

Rubrene-based interfacial engineering toward enhanced performance in inverted polymer solar cells

Rubrene, an organic semiconductor having stable fused-ring molecular structure was used as a double interfacial layer in inverted organic solar cells. When a thin, 3 nm-thick layer of rubrene was introduced between a MoO₃-based hole-collecting layer and a bulk-heterojunction (BHJ) photo-active layer consisting of poly{4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl} (PTB7) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM), the power conversion efficiency was improved over 12% (from 7.2% to 8.1%). It was demonstrated that the insertion of thin rubrene layer showed suppressed exciton quenching and improved exciton dissociation, resulting in more efficient charge carrier collection and weaker charge recombination, thus improving the device performance.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

Improved performance of inverted polymer solar cells by utilizing alcohol-soluble oligofluorenes as efficient cathode interlayers

Two star-shaped oligofluorenes with hexakis(fluoren-2-yl)benzene as core are designed and synthesized, namely Tn0 and Tn1. Diethylamino groups are attached to the side chain of fluorene units of Tn0 and Tn1 and enable them alcohol solubility, additional hydrophobic nhexyl chains are grafted on the π-extended fluorene arms of Tn1. Power conversion efficiency (PCE) as high as 8.62% and 8.80% are achieved when utilizing Tn0 and Tn1 as cathode interlayers in inverted polymer solar cells, respectively. The work function of ITO effectively decreased by introducing interlayer, resulting in high Voc of the device, besides, the wetting properties of the interlayers can be tuned by modifying the oligofluorenes with π-extended structure, and the more hydrophobic interlayer will benefit the device performance with enhanced Jsc and FF.     

A new alcohol-soluble electron-transporting molecule for efficient inverted polymer solar cells

A new electron-transporting material 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPA) was synthesized by modifying a n-type small molecule bathocuproine (BCP). The introduced carboxyl groups make DPPA soluble in polar solvent and compatible with large-scale solution-processing techniques. The anchoring of carboxyl on ZnO (or ITO) substrates helps to form a DPPA electron transporting layer, building an improved interfacial contact between the substrate and active layer. Furthermore, the highest occupied molecular orbital level of DPPA shifts to ?6.45 eV, which is 0.38 eV deeper than that of BCP, suggesting enhanced hole-blocking. Inverted polymer solar cells using P3HT:PCBM blend as the active layer and DPPA modified ZnO as the electron transporting layer were fabricated. A power conversion efficiency (PCE) of 3.55% was obtained, which is about 10% higher than that of the conventional ZnO buffered devices (3.25%). The DPPA was also used to replace ZnO as the sole electron-extracting layer, resulting in an improved PCE of 3.46%, which indicates that DPPA-ETL/ITO forms a better cathode than conventional ZnO/ITO.     

Isopropanol-treated PEDOT:PSS as electron transport layer in polymer solar cells

Isopropanol (IPA)-treated poly(3,4-ethylenedioxithiophene):poly(styrene sulfonate) (PEDOT:PSS) was applied as a new electron transport layer (ETL) in P3HT:PCBM bulk heterojunction polymer solar cell (BHJ-PSC) devices for the first time, revealing the electron transport property of IPA-treated PEDOT:PSS in sharp contrast to the well known hole transport property of the untreated PEDOT:PSS. Under the optimized condition for incorporating PEDOT:PSS ETL, the power conversion efficiency (PCE) of the ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/IPA-treated PEDOT:PSS (ETL)/Al device (3.09%) is quite comparable to that of the reference ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/Al device without any ETL (3.06%), and an annealing treatment of PEDOT:PSS ETL at 120 °C for 10 min led to a PCE of 3.25%, which even slightly surpasses that of the reference device, revealing the electron transport property of IPA-treated PEDOT:PSS. The electron transport property of IPA-treated PEDOT:PSS is interpreted by the lowering of the work function of PEDOT:PSS upon IPA treatment and incorporation as ETL as probed by scanning Kelvin probe microscopy (SKPM).     

Acid-functionalized fullerenes used as interfacial layer materials in inverted polymer solar cells

Two types of carboxylic acid functionalized fullerence derivatives, 4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (p-EHO-PCBA) and bis-4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (bis-p-EHO-PCBA), were synthesized and investigated as an interfacial layer for inverted polymer solar cells (iPSCs). The –COOH groups on the PCBAs chemisorb to inorganic metal oxide (TiO_X), generating fullerene-based self-assembled monolayers (FSAMs). The devices with the mono- and bis-FSAMs exhibited substantially lower series resistance (R_S) values of 2.10 Ω cm² and 1.46 Ω cm², compared to that (4.15 Ω cm²) of the unmodified device. The TiO_X films modified with mono- and bis-FSAMs showed higher contact angles of 50° and 91°, respectively, than that of the pristine TiO_X film (33°). The increased contact angles were attributed to the enhanced hydrophobicity, improving the wetting properties with the organic photoactive layer. In addition, a comparison of device characteristics with electroactive FSAMs and non-electroactive benzoic acid SAMs clearly indicates that the FSAMs may suggest an additional pathway for photo-induced charge transfer and charge collection to ITO. After surface modification with FSAMs, the short-circuit current density (J_SC) and fill factor (FF) values increased substantially. The iPSCs based on poly(5,6-bis(octyloxy)-4-(thiophen-2-l)benzo[c][1,2,5]thiadiazole) (PTBT) and [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM) as an active layer showed remarkably improved power conversion efficiency up to 5.13% through incorporation of the FSAMs-based interfacial layer.     

Enhanced performance in inverted polymer solar cells via solution process: Morphology controlling of PEDOT:PSS as anode buffer layer by adding surfactants

Inverted polymer solar cells were fabricated by adding the amphiphilic surfactant ‘Surfynol 104 series’ to Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a anode buffer layer by solution process. With the introduction of Surfynol 104 series-added PEDOT:PSS, it was able to form a homogeneous film by adjusting the wettability of a hydrophobic poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) film. With decrease in series resistance (R_S) and increase in shunt resistance (R_SH), as a result, the short circuit current density (J_SC), open circuit voltage (V_OC) and fill factor (FF) of the optimized device were 10.2 mA/cm², 0.63 V and 61.3%, respectively, calculated the power conversion efficiency (PCE) was 4.0%. In addition, the air stability of the fabricated device was improved.     

Highly conductive Zinc-Tin-Oxide buffer layer for inverted polymer solar cells

Thin-films of Zinc Tin Oxide (ZTO) with an extremely high charge carrier mobility and superior optical transmittance are synthesized using a simple solution method. These ZTO films have been systematically studied for the application in inverted polymer solar cells (PSCs). The Hall effects measurements show that the charge mobility of the ZTO semiconductor is over 16.5 cm².V⁻¹.S⁻¹, which is the highest mobility value ever reported for oxide buffer made by using solution process. By applying the ZTO buffer layer in the inverted PSCs of P3HT:PC₆₁BM, the power conversion efficiency of the device is 30% higher than that of the devices made with other common buffer layers such as ZnO and TiO₂. Light intensity-dependent JV studies and PL measurements also indicate that ZTO buffer layer reduces surface recombination. This work demonstrates that the solution-synthesized ZTO is a promising new buffer layer with superior electron extraction capability for the solar cells.     

Potassium-neutralized perylene derivative (K4PTC) and rGO-K4PTC composite as effective and inexpensive electron transport layers for polymer solar cells

The polymer solar cell (PSC) with Ca/Al electrode always suffers from low stability mainly due to the incorporation of oxygen and moisture-sensitive Ca electron-transport interlayer (ETL). To alleviate this problem, air-stable alternatives to Ca ETL are highly desired. Herein, we report two solution-processable, air-stable, effective and inexpensive ETLs based on potassium-neutralized perylene tetracarboxylic derivative (K₄PTC) and its rGO composite (rGO-K₄PTC), respectively. These ETL materials were facilely prepared and characterized by means of UV-vis, FL, FTIR, XPS and UPS. Importantly, both ETLs exhibited a low work function (WF) of 4.0 eV, which well matches the LUMO level of fullerene acceptors and allows their use as ETL in PSCs. As a result, the P3HT and PTB7-th-based devices with respective ETL remarkably outperformed those without ETL yielding increases of ∼35% in power conversion efficiencies (PCEs), which indicates good electron-transporting capabilities of K₄PTC and rGO-K₄PTC interlayers. The high-performance PSCs with the ETL gave average PCEs of 6.17–6.18% (for PTB7-th:PC₆₁BM-based devices) and 7.26% (for PTB7-th:PC₇₁BM-based devices), respectively, fairly comparable to those of Ca/Al devices (6.50% and 7.50%). Furthermore, the rGO-K₄PTC device exhibited stability higher than that of the K₄PTC device probably due to the fact that the rGO-K₄PTC layer can provide more efficient protection for the active layer against degradation. Thus, rGO-K₄PTC layer might be more suitable for real applications as compared to the K₄PTC layer.     

High efficiency perovskite solar cells using a PCBM/ZnO double electron transport layer and a short air-aging step

Solution processed CH₃NH₃PbI_xCl_3–x based planar heterojunction perovskite solar cells with power conversion efficiency (PCE) above 14% are reported. The devices benefit from a phenyl-C₆₁-butyric acid methyl ester (PCBM)/ZnO double electron transport layer (ETL) as well as a short air-aging step. The role of the additional ZnO ETL is studied by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and secondary ions mass spectroscopy (SIMS). Apart from improving the energy level alignment, the ZnO layer blocks the reactions between the metal electrode and perovskite components, increasing the air stability of the device. A crucial step in our processing is a short air-aging step for the device, which significantly increases the device performance by reducing the recombination process. Since the ZnO nanoparticle layer requires no thermal annealing, the maximum temperature to fabricate the device can be kept below 100 °C, making this structure compatible with roll-to-roll processing on plastic films.     

Performance improvement of pentacene-doped P3HT:PCBM inverted polymer solar cells with AZO nanorod array passivated using photoelectrochemical technique

The pentacene-doped P3HT:PCBM inverted polymer solar cells (IPSCs) with Al-doped zinc oxide (AZO) nanorod array were fabricated. The AZO nanorod array could enhance the carrier collection and carrier extraction capability. The AZO nanorod array formed by the laser interference photolithography method and the wet etching process sequentially was used as the carrier collection and carrier transportation layers. The defects on the sidewall surface of the AZO nanorods were passivated by using the photoelectrochemical (PEC) method. It was demonstrated that the better performance of the IPSCs was obtained by PEC treatment. Compared with the IPSCs without PEC treatment, the short current density and power conversion efficiency of the IPSCs with PEC treatment for 60 s increased from 14.56 mA/cm² to 15.85 mA/cm² and 5.45% to 6.13%, respectively.     

Interfacial engineering of ZnO nanoarrays as electron transport layer for polymer solar cells

Highly uniform one-dimensional ZnO nanoarrays (ZnO NAs) fabricated by hydrothermal process were successfully explored as electron transport layer (ETL) for offering a direct and efficient path for electron transport in inverted polymer solar cells (PSCs). The inorganic CdS shell layer by in situ growth on the ZnO NAs surface was used to passivate and repair the surface defects of ZnO NAs. To further engineer the ZnO surface and improve the compatibility between ETL of inorganic ZnO/CdS core/shell and polymer blend contact junction, those organic molecules of 3,6,7,10,11-pentakis-(hexyloxy)-2-hydroxytriphenylene (TP-OH), 1-pyrenol (Py-OH) and 4′-(7-hydroxy-heptanoyl)-biphenyl-4-carbonitrile (BP-OH) were respectively spin-coated on the ZnO NAs/CdS surface to fabricate ETL based on ZnO/CdS/TP-OH NAs, ZnO/CdS/Py-OH NAs, ZnO/CdS/BP-OH NAs. The π–π interactions between the organic molecules and fullerene acceptors could lead to the well-organized distribution of active layer materials, which is in favor of the enhancement of electron selectivity and the reduction of recombination probability of electrons and holes. The incorporation of ZnO/CdS/Py-OH NAs as ETL into the inverted PSCs based on P3HT:PC₆₁BM resulted in a superior power conversion efficiency (PCE) of 4.2% with enhanced short circuit current (J_sc) and fill factor (FF), compared to 3.1% for bare ZnO NAs, due to the intermolecular close-stacking and relative stronger π–π interaction energy between Py-OH and fullerenes. In addition, the sensitized ZnO surface led to intimate interface between ETL and active layer, which would be in favor of increasing the stability of the device.     

Properties of inverted polymer solar cells based on novel small molecular electrolytes as the cathode buffer layer

Novel small-molecule electrolytes were designed and synthesized for use in the cathode interlayer in bulk-heterojunction polymer solar cells (PSCs). The synthesized materials consist of polar quaternary ammonium bromide with the addition of multiple hydroxyl groups, which are N,N,N,N,N,N-hexakis(2-hydroxyethyl)butane-1,4-diaminium bromide (C4) and N,N,N,N,N,N-hexakis(2-hydroxyethyl)hexane-1,6-diaminium bromide (C6). The materials generate a favorable interface dipole through the quaternary ammonium bromide. In addition, the multiple polar hydroxyl groups increased the interface dipole magnitude. The power conversion efficiency of the devices with the interlayer was up to 9.20% with a J_sc of 17.22 mA/cm², a V_oc of 0.75 V, and an FF of 71.3%. The PCE of devices with an interlayer show better long-term stability than a device without an interlayer. Our strategy shows that it is possible to enhance the efficiency of PSCs by simple approaches without complicated syntheses.