Thin-film encapsulation of polymer-based bulk-heterojunction photovoltaic cells by atomic layer deposition

This study demonstrated thin-film encapsulation of bulk-heterojunction polymer photovoltaic cells, utilizing a process based on atomic layer deposition (ALD) that both prevented degradation caused by ambient gases and served as an annealing step that increased the initial efficiency of the cells. With the ALD temperature set at 140 °C and the total deposition time set at 1 h, the photovoltaic cells, based on blended poly-3-hexylthiophene (P3HT) and [6,6]-phenyl C₆₁ butyric acid methylester (PCBM), were optimally annealed during encapsulation, achieving a power conversion efficiency (PCE) of 3.66%. Encapsulating the cells with a 26 nm Al₂O₃/HfO₂ nanolaminated film overcoated with an epoxy resin protection layer enabled the cells to obtain an in-air degradation rate that was similar to cells that were stored in nominally O₂/H₂O-free atmosphere. The nanolaminated structure of the encapsulation film resolved the issue of hydrolysis-induced aging observed with Al₂O₃ films, owing to the hydrophobicity of the HfO₂ layers. Additionally, extended exposure of the ALD precursors during the ALD process significantly improved the coverage of the ALD films over the P3HT/PCBM active layer at the perimeter of the cells.     

OLED compatible water-based nanolaminate encapsulation systems using ozone based starting layer

Highly efficient nanolaminate diffusion barriers made of TiO₂/Al₂O₃ multilayers using low temperature atomic layer deposition optimized for organic light emitting diodes are presented. Water vapour transmission rates (WVTR) show values of the order of 10⁻³ g/m²/d at 38 °C, 90% RH on planarized PEN webs (pPEN) when ozone is used as the oxidizing precursor for Al₂O₃ deposition. OLED encapsulated with such diffusion barriers display few dark spots observed over 2000 h after deposition and for aging under ambient conditions. Diffusion barriers deposited using water as the oxidizing precursor for Al₂O₃ result in at least 10 times lower WVTR on pPEN webs (10⁻⁴ g/m²/d). However, these water based diffusion barriers are incompatible with OLEDs such that the latter show extensive black spot formation (areas of no visible luminescence) immediately after deposition. Finally through the growth of these initial black spots, more than 40% loss in initial luminescence occurs after merely 900 h of operation. In this report, we introduce a new methodology for OLED encapsulation using a two step process where 10 nm thick ozone Al₂O₃ based nanolaminate diffusion barrier is followed by a 90 nm thick water Al₂O₃ based diffusion barrier (keeping TiO₂ precursors always the same). With this novel diffusion barrier stack, no visible black spot growth is observed over 2000 continuous operation hours under ambient conditions. Simultaneously, high OLED luminescence representing 90% of the initial luminescence value, which is measured at t = 0 is maintained after 2000 h of operation. Low WVTR values in the 10⁻⁴ g/m²/d range on pPEN webs are consistently measured in these essentially water based barrier layers with only 10 nm thick starting ozone Al₂O₃ based nanolaminate diffusion barriers. The results reported here have implications on developing methodologies for ultra high performance, OLED compatible diffusion barriers by ALD.     

Atomic layer deposition of ZnO electron transporting layers directly onto the active layer of organic solar cells

Interlayers in organic solar cells (OSCs) are used to reduce energy barriers for charge injection/extraction, act as optical spacers, introduce carrier selectivity and increase organic/contact compatibility. To date, the most widely used inorganic interlayers are metal oxides such as TiO₂ and ZnO. However, these materials require harsh deposition conditions that could damage the organic active layers, and hence are generally used in inverted devices. Here we show, for the first time, that judicious selection of materials and processing conditions allow the use of an atomic layer deposition (ALD) system to deposit thin conformal ZnO interlayers on bulk heterojunctions (BHJs). ALD-ZnO interlayers were utilized as electron transporting layers (ETLs) in OSCs and compared to similar devices with solution deposited ZnO nanoparticle (np) ETLs. OSCs with ALD-ZnO ETLs exhibited higher photocurrent densities, J_sc, but lower open circuit voltages, V_oc. The low V_oc is associated with the presence of pinholes and an offset between the ALD-ZnO and PC₇₀BM electron conducting states. This offset results from traps and acceptor sites generated during the low temperature ALD process. To recover the V_oc we introduced a fluorinated phosphonic acid (PA) additive to the blend. We suggest that the additive migrates to the film surface, interacts with the ZnO to produce a denser layer and to passivate traps, effectively improving the device shunt resistance and energy level alignment and increasing V_oc. Overall, the devices with PA and ALD-ZnO ETLs possess significantly higher power conversion efficiencies (PCEs) than those with np-ZnO ETLs. For example, the champion ALD-ZnO device PCE is 3.5%, while that with np-ZnO is 2.75%.     

Improved photovoltaic characteristics of organic cells with heterointerface layer as a hole-extraction layer inserted between ITO anode and donor layer

We have fabricated an improved organic photovoltaic (OPV) cell in which organic heterointerface layer is inserted between indium-tin-oxide (ITO) anode and copper-phthalocyanine (CuPc) donor layer in the conventional OPV cell of ITO/CuPc/fullerene (C₆₀)/bathophenanthroline (Bphen)/Al to enhance the power conversion efficiency (PCE) and fill factor (FF). The inserted ITO-buffer layer consists of electron-transporting layer (ETL) and hole-transporting layer (HTL). We have changed the ETL and HTL materials variously and also changed their layer thickness variously. It is confirmed that ETL materials with higher LUMO level than the work function of ITO give low PCE and FF. All the double layer buffers give higher PCE than a single layer buffer of TAPC. The highest PCE of 1.67% and FF of 0.57% are obtained from an ITO buffer consisted of 3 nm thick ETL of hexadecafkluoro-copper-phthalocyanine (F₁₆CuPc) and 3 nm thick HTL of 1,1-bis-(4-methyl-phenyl)-aminophenylcyclohexane (TAPC). This PCE is 1.64 times higher than PCE of the cell without ITO buffer and 2.98 times higher than PCE of the cell with single layer ITO buffer of TAPC. PCE is found to increase with increasing energy difference (ΔE) between the HOMO level of HTL and LUMO level of F₁₆CuPc in a range of ΔE < 0.6 eV. From the ΔE dependence of PCE, it is suggested that electrons moved from ITO to the LUMO level of the electron-transporting F₁₆CuPc are recombined, at the F₁₆CuPc/HTL-interface, with holes transported from CuPc to the HOMO level of HTL in the double layer ITO buffer ETL, leading to efficient extraction of holes photo-generated in CuPc donor layer.     

Degradation of self-assembled monolayers in organic photovoltaic devices

Self-assembled monolayers (SAMs) based on n-octylphosphonic acid (C8PA) and 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA) were investigated for application as an anode buffer layer in C₆₀-based organic photovoltaic (OPV) devices. We found that the degradation of the OPV efficiency with respect to air exposure was significantly reduced with the perfluorinated PFOPA compared to the aliphatic C8PA. We attribute the OPV degradation to moisture diffusion from the top aluminum electrode and the lowering of the anode work function as a result of hydrolysis of the SAM buffer layer.     

Broad-band plasmonic Cu-Au bimetallic nanoparticles for organic bulk heterojunction solar cells

In this work, a facile preparation of Cu-Au bimetallic nanoparticles (NPs) with core-shell nanostructures is reported. Importantly, as-prepared Cu-Au NPs are highly stable, solution-processable and exhibit a broad localized surface plasmon resonance (LSPR) band at long wavelengths of 550–850 nm. Highly efficient plasmonic organic solar cells (OSCs) were fabricated by embedding Cu-Au NPs in an anodic poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer. The average power conversion efficiency (PCE) was enhanced from 3.21% to 3.63% for poly(3-hexylthiophene) (P3HT):phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) based devices, from 6.51% to 7.13% for poly[(ethylhexyl-thiophenyl)-benzodithiophene -(ethylhexyl)-thienothiophene](PTB7-th):PC₆₁BM based devices and from 7.53% to 8.48% for PTB7-th:PC₇₁BM based devices, corresponding to 9.5–13.4% PCE improvement. Such an improvement is very comparable to that (12.5%) obtained in those with plasmonic Au NPs but achieved at lower cost. This study thus demonstrates a novel and cost-effective approach to enhance the photovoltaic performance of OSCs, in combination with the broad-band plasmonic Cu-Au bimetallic nanostructures.     

Realization of solution processed multi-layer bulk heterojunction organic solar cells by electro-spray deposition

Electro-spray deposition (ESD) was applied to fabricate solution processed donor–acceptor bulk heterojunction organic photovoltaic devices with multi-layer structure. Solvent effect was observed when using different organic solvents. Power conversion efficiency (PCE) of the devices prepared from dichlorobenzene increased dramatically comparing to the ones from chloroform, owing to improved homogeneity of the films. ESD enabled us to fabricate solution processed multi-layer (donor/donor:acceptor/acceptor) devices with simple successive deposition steps. Energy Dispersive X-ray Reflectometry analysis confirmed distinct three layered structure of the active layers. Solar cell device parameters of the trilayer devices were compared to single layer devices and those of spin coated devices with the same donor:acceptor ratio and film thickness. Post-thermal treatment results showed that after annealing at 125 °C, trilayer devices exhibited best performance with the maximum PCE of 2.17%.     

Stable organic photovoltaic with PEDOT:PSS and MoOX mixture anode interfacial layer without encapsulation

Herein, we report about an efficient and stable organic photovoltaic that uses a poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) and molybdenum oxide (MoO_X) mixture for the anode interfacial layer, and that can reach 4.43% power conversion efficiency (PCE) under AM1.5 conditions. Utilizing PEDOT:PSS:MoO_X (1:1), the shelf lifetime of poly(3-hexylthiophene) (P3HT), and indene-C₆₀ bisadduct (ICBA)-based solar cells without encapsulation, can be realized with only a 25% deterioration after 672 h of storage in air. Furthermore, we compare the photovoltaic performance of the P3HT:ICBA-based organic photovoltaic with PEDOT:PSS, and PEDOT:PSS:MoO_X, in which PEDOT:PSS:MoO_X has outperformed the others. In addition, the water vapor transmission rate of PEDOT:PSS:MoO_X is 0.17 gm/(m² day), which is much less than that of PEDOT:PSS.     

Performance of ITO-free inverted organic bulk heterojunction photodetectors: Comparison with standard device architecture

We report on the fabrication of Indium Tin Oxide (ITO)-free inverted organic bulk heterojunction (BHJ) photodetectors of poly(3-hexylthiophene) (P3HT): 1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6) C61 (PCBM). The final inverted device structure is Cr/Al/Cr/P3HT:PCBM/poly-3,4-ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS)/Ag (Zimmermann et al., 2009) [1]. The device is top-absorbing with the light entering through the hole contact grid. We have fabricated standard devices with structure ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al in order to carry out a comparison study. Inverted photodetectors show slightly higher quantum efficiency and responsivity compared to standard devices. Frequency responses at different bias voltages were measured showing a maximum −3 dB cut-off frequency of 780 kHz and 700 kHz at −3 V for the standard and inverted structures respectively. Parameters extracted from the fit of a circuital model to the impedance spectroscopy measurements were used to estimate the photodiode cut-off frequency as function of bias.     

Efficient organic photovoltaics using solution-processed,annealing-free TiO2 nanocrystalline particles as an interface modification layer

A solution-processed, annealing-free TiO₂ nanocrystalline particles (TiO₂ NPs) as an interface modification layer was inserted in organic photovoltaics (OPVs), in which the widely used polymer poly (3-hexyl thiophene) (P3HT), a low band gap alkoxylphenyl substituted [1,2-b:4,5-b′] dithiophene-based polymer (PBDTPO-DTBO), and a soluble small molecule benzodithiophene derivative (TIBDT) were used as the donor material, respectively. The annealing-free TiO₂ NPs could be easily spin-coated upon the surface of organic active layers, and showed comparable properties to thermal-annealed ones. The power conversion efficiencies (PCEs) of OPV devices could be enhanced dramatically with inserting an annealing-free TiO₂ NPs layer. The PCEs of OPV devices based on P3HT:PC₆₁BM, PBDTPO-DTBO:PC₇₁BM and TIBDT:PC₆₁BM bulk heterojunctions were improved by 28%, 15% and 27%, respectively, with an annealing-free TiO₂ NPs layer, in which the highest PCE of 5.76% was achieved in PBDTPO-DTBO:PC₇₁BM OPVs. The solution-processed, annealing-free TiO₂ NPs thin films show great potential applications in the fabrication of large-area OPVs by printing or coating techniques on flexible polymer substrates. In particularly, it would promote to fabricate solution-processed, annealing-free OPV devices with suitable hole transport layer and organic/polymer active materials.     

Atomic layer deposited TiOx/AlOx nanolaminates as moisture barriers for organic devices

Atomic layer deposited nanolaminates of alternating AlO_x and TiO_x thin-films are investigated as moisture barriers for organic electronic devices. Direct encapsulation on organic light emitting diodes (OLEDs) is tested in aging experiments and compared to calcium corrosion tests of equivalent barrier films. This allows for a direct assessment of moisture barrier performance in simple as well as more complex systems. Thickness variations are performed for the nanolaminate single and total layer thickness, with an optimum single layer thickness of 1–2 nm observed. This correlates to the maximum number of dyads once completely closed single layers are produced. For large single layer thickness and low dyad count, strong lateral diffusion from the edges occurs in the OLEDs, which likely correlates to poor mechanical stability. At optimum single layer thickness, barriers remain mechanically and chemically stable up to 100 nm total thickness. OLEDs encapsulated with such nanolaminate barriers show no significant degradation after 2500 h of continuous aging.     

Enhanced storage/operation stability of small molecule organic photovoltaics using graphene oxide interfacial layer

Graphene and graphene oxide (GO) have been applied in flexible organic electronic devices with enhanced efficiency of polymeric photovoltaic (OPV) devices. In this work, we demonstrate that storage/operation stability of OPV can be substantially enhanced by spin-coating a GO buffer layer on ITO without any further treatment. With a 2 nm GO buffer layer, the power conversion efficiency (PCE) of a standard copper phthalocyanine (CuPc)/fullerene (C₆₀) based OPV device shows about 30% enhancement from 1.5% to 1.9%. More importantly, while the PCE of the standard device drop to 1/1000 of its original value after 60-days of operation-storage cycles; those of GO-buffered device maintained 84% of initial PCE even after 132-days. Atomic force microscopy studies show that CuPc forms larger crystallites on the GO-buffered ITO substrate leading to better optical absorption and thus photon utilization. Stability enhancement is attributed to the diffusion barrier of the GO layer which slow down diffusion of oxygen species from ITO to the active layers.     

Sub-nanometer atomic layer deposited Al2O3 barrier layer for improving stability of nonfullerene organic solar cells

Organic solar cells (OSCs) is a promising next-generation photovoltaic technology, however, the device stability remains to be the main barrier for its future commercialization. Herein, we reported the application of a sub-nanometer Al₂O₃ barrier layer in nonfullerene OSCs via atomic layer deposition (ALD), for the purpose of preventing metal ion diffusion from indium tin oxide (ITO) into the polymer layer caused by the corrosion of Poly(3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS). The thickness of the ALD-Al₂O₃ barrier layer was precisely optimized by controlling the number of ALD cycles (n) to achieve simultaneously good photoelectric properties and conformal coverage. An average power conversion efficiency (PCE) of 15.02% was demonstrated for the optimal OSCs with ALD-Al₂O₃ barrier layer. The above mentioned suppression of metal ion diffusion was experimentally confirmed by the cross sectional observations of transmission electron microscopy (TEM) and chemical mapping from energy-dispersive X-ray spectroscopy (EDX), resulting in a significantly improved operational stability with a device lifetime 3-times longer than that without ALD-Al₂O₃ barrier layer. Such ALD-assisted interface modification provides an effective approach to realize high-performance and stable OSCs.     

Ultraviolet-illuminated fluoropolymer indium–tin-oxide buffer layers for improved power conversion in organic photovoltaics

We demonstrate that the charge carrier extraction in double heterojunction organic photovoltaic(OPV) devices can be enhanced by inserting an UV-illuminated fluoropolymer polytetrafluoroethylene(PTFE) layer between indium–tin-oxide and the thermal evaporated copper–phthalocyanine(CuPc)/buckyball(C₆₀) organic active layers. In this work, we show that the anode work function influences the photocarrier collection characteristics, where the short-circuit current and open-circuit voltage increase from 1.6 to 4.8 mA/cm² and 0.41 to 0.48 V, respectively after the buffer layer insertion associated primary with the barrier decrease in the ITO/CuPc interface. This result shows the potential of UV-illuminated PTFE as a low-cost stable buffer layer for OPV devices.     

Hole extraction layer utilizing well defined graphene oxide with multiple functionalities for high-performance bulk heterojunction solar cells

A simple method for synthesizing a series of graphene oxide with precise oxidation (pr-GO) (mild oxidation, moderate oxidation and severe oxidation) by strictly controlling pre-oxidation steps, oxidant content and oxidation time has been successfully developed. The well defined pr-GO as hole extraction layer (HEL) presented multiple functionalities, like modulation of work function, enhanced interfacial dipole, and excellent film-forming properties, which had significantly improved the efficiency and stability of organic solar cells. The P3HT:PC₆₁BM system device based on pr-GO-3 HEL, which possessing well defined electronic structure and moderate oxidation, exhibited an improved 3.74% in power conversion efficiency and better air-stability compared to that of other pr-GOs and conventional PEDOT:PSS based devices. The well defined electronic structure pr-GO (i.e., suitable work function, larger interfacial dipole, and high repeatability) will provide better understanding in utilizing pr-GO film as HEL in future solar cell applications.     

Investigation of the s-shape caused by the hole selective layer in bulk heterojunction solar cells

A common failure mechanism of organic solar cells is the development of an s-shaped current voltage curve. Herein, we investigated the origin of this degradation mechanism by replacing the commonly used hole selective layer poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) with a co-evaporated layer of N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (TPD) and Dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HATCN). By varying the ratio of TPD to HATCN we are able to tune both the mobility and work function of the hole selective layer. Using a combination of field effect mobility measurements, Kelvin-Probe work function measurements, and numerical modeling we demonstrate that a degraded mobility of the hole selective layer leads to a buildup of charge within the device and reduction of fill factor.     

Room temperature solution-processed electron transport layer for organic solar cells

We present a new recipe for a solution-processed titanium oxide (TiO_x) based electron transport layer at room temperature. Due to its high chemical compatibility with all types of organic blends (semi-crystalline or amorphous) and it is good adhesion to both surfaces of glass/ITO substrate and the active layer (blend), the buffer layer is suitable for use in organic solar cell devices with conventional, inverted or multi-junction structures. The main goal of this recipe is producing with easiness an repeatable and stable precursor that will leads to titanium oxide buffer layer each time with the same quality. Since the processing of the titanium oxide layer itself does not require any initial or additional treatment before and after the coating, and can even be carried in air as well as under protective atmosphere, our room temperature solution-processed electron transport layer is highly versatile and very promising for cost effective mass production of organic solar cells.     

Gold nanorod enhanced organic photovoltaics: The importance of morphology effects

Organic photovoltaic devices with a 30% improvement in power conversion efficiency are achieved when gold nanorods (Au NR) are incorporated into the active bulk heterojunction (BHJ) layer. Detailed analysis of the system is provided through microscopy, device characterization, and spectroscopy, demonstrating that the enhancement effects are predominantly caused by induced morphology changes in the BHJ film rather than plasmonic effects. Wide angle X-ray diffraction provides evidence that the nanorods loaded into the BHJ film have an effect on polymer crystal orientation, leading to a systematic performance increase in the devices as a result of both internal and external efficiency improvements.     

Sub-100 nm ALD-assisted nanoimprint lithography for realizing vertical organic transistors with high ON/OFF ratio and high output current

We introduced a conformal atomic-layer-deposited aluminum oxide layer to cover the imprint mold to reduce the feature size and to strengthen the mold durability. A nano-hole array pattern with diameter down to 85 nm was successfully transferred to sample substrate to fabricate a vertical organic transistor. The Imprint vertical organic transistor exhibited high output current density as 4.35 cm²/V s and high ON/OFF current ratio as 11,000 at a low operation voltage as 1.5 V.