Influence of aluminium electrode preparation on PCE values of polymeric solar cells based on P3HT and PCBM

The main goal of the paper was investigation of influence of aluminum electrode preparation via thermal evaporation (TE) and the magnetron sputtering (MS) on power conversion efficiency (PCE) of polymeric solar cells. The photovoltaic properties of such three kinds devices based on poly(3-hexylthiophene-2,5-diyl) (P3HT) as ITO/P3HT/Al, ITO/P3HT:PCBM (1:1, w/w)/Al and ITO/PEDOT:PSS/P3HT:PCBM (1:1, w/w)/Al were investigated. For the constructed devices impedance spectroscopy were analyzed. For devices lack of PEDOT:PSS layer or lack of PCBM, photovoltaic parameters were very low and similar to the parameters obtained for device with Al electrode prepared by magnetron sputtering. The devices comprising PEDOT:PSS with P3HT:PCBM showed the best photovoltaic parameters such as a V_OC of 0.60 V, J_SC of 4.61 mA/cm², FF of 0.21, and PCE of 5.7 × 10^?1%.     

超薄PCBM层提高有机太阳电池效率

为研究超薄PCBM层对有机太阳电池的影响,制备了含和不含超薄PCBM层的两种不同结构的体相异质结太阳电池,电池结构分别为:ITO/PEDOT:PSS/P3HT+PCBM/PCBM/AI,ITO/PEDOT:PSS/P3HT+PCBM/Al.测试结果表明:所制备电池的开路电压分别为0.599 2V和0.572 7 V,能量转换效率分别为2.24％、1.21％,超薄PCBM层起到了电子传输的作用.     

采用空穴阻挡层提高有机太阳电池效率的研究

为研究BCP对有机太阳电池的影响,制备了含BCP层的体相异质结电池,器件结构为:ITO/PEDOT:PSS/P3HT+PCBM/BCP/LiF/Al。结果表明:BCP层起到了空穴阻挡和电子传输的作用,器件性能随着BCP层厚度的不同而变化,当BCP厚度为6nm时,其性能最好。     

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.     

Moderately reduced graphene oxide/PEDOT:PSS as hole transport layer to fabricate efficient perovskite hybrid solar cells

Graphene oxide (GO) with single layer was moderately reduced at 200 °C for 4 h under N₂. Then the moderately reduced graphene oxide (rGO) water solution was employed as an additive to tune the properties of conventional poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) solution. It's found that the incorporation of rGO into PEDOT:PSS nearly did not change its transparency, hydrophilic property, or the surface roughness. So, the rGO/PEDOT:PSS composite was used as a hole transport layer (HTL) to fabricate perovskite solar cells (PSCs). As a result, PSCs with rGO/PEDOT:PSS as HTL exhibit improved power conversion efficiency than that of PSCs with PEDOT:PSS as HTL. Our findings show that moderately reduced rGO/PEDOT:PSS could be an efficient HTL to improve power conversion efficiency of PSCs.     

An ammonia modified PEDOT: PSS for interfacial engineering in inverted planar perovskite solar cells

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) is one of the most widely used hole transport layers (HTL) in inverted perovskite solar cells (PSCs) due to its simple solution-processed ability, high transparency, and conductivity. However, PEDOT:PSS-based devices suffer a lower open-circuit voltage (V_oc) than devices with the conventional structure. To address this issue, we fabricated ammonia-modified PEDOT:PSS films by simply doping PEDOT:PSS solution with different ratio of ammonia. The acidity of PEDOT:PSS can be neutralized by the doped ammonia, which inhibits the ion-exchange reaction between PSS-H and CH₃NH₃I, thus retarding the reduction of the work function for PEDOT:PSS to some extent. As a result, a superior power conversion efficiency (PCE) of 15.5% was obtained for the device based on the ammonia-doped PEDOT:PSS HTL than that of the pristine PEDOT:PSS-based device. We ascribe the PCE enhancement to the increased V_oc and fill factor (FF), which is attributed not only to the better energy-level alignment between the ammonia-modified PEDOT:PSS film and perovskite layer but also to the increased grain size and crystallinity of perovskite film.     

Optical,electrical and mechanical properties of indium tin oxide on polyethylene terephthalate substrates: Application in bulk-heterojunction polymer solar cells

We investigated optical, electrical and mechanical properties of indium tin oxide (ITO) on flexible polyethylene terephthalate (PET) substrate, considering bulk-heterojunction (BHJ) polymer solar cells applications. Encapsulation of flexible solar cells with the architecture PET/ITO/PEDOT:PSS/P3HT:PCBM (or P3HT:PCBM:AZ-NDI-4)/Al was done by direct brush-painting with nail enamel. Active cell layer blends of [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with regioregular or regiorandom poly(3-hexylthiophene-2,5-diyl) (P3HT) were applied. Additionally for this role the mixture of regioregular P3HT:PCBM with naphthalene diimide–imine with four thiophene rings AZ-NDI-4 was tested. Obtained photovoltaic (PV) and optical (UV–vis) results of the flexible polymer solar cells were compared with the same architecture of devices on the glass/ITO substrate.     

Aging process of PEDOT:PSS dispersion and robust recovery of aged PEDOT:PSS as a hole transport layer for organic solar cells

Conducting p-type polymer of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely used for organic optoelectronics, particularly as a hole transport layer for organic solar cells. While the aged PEDOT:PSS dispersion impacts device performance, the aging of PEDOT:PSS dispersion have not been well investigated. Moreover, the recovery process of aged (two-year-old) PEDOT:PSS dispersion has not been demonstrated yet. Herein, it is found that aqueous PEDOT:PSS dispersion undergoes extensive phase separation during the aging process, resulting in both nanoscale and macroscale hydrophobic PEDOT-rich agglomerates. When the aged PEDOT:PSS thin film is integrated into P3HT:PCBM organic solar cells, the PEDOT-rich agglomerates trap the photogenerated holes at the PEDOT:PSS/P3HT interface, resulting in poor extraction efficiency in organic solar cells. To recover a hole transport functionality from aged PEDOT:PSS, three different solvents such as isopropyl alcohol (C₃H₇OH), ethanol (C₂H₅OH) and methanol (CH₃OH) are investigated. Among them, it is found that isopropyl alcohol (IPA) yielded very uniform PEDOT:PSS thin film layer. This is because hydrophobic functional groups of IPA solvent facilitated the preferential solvation of phase separated hydrophobic PEDOT-rich agglomerates. However, when non-optimal concentration of IPA solvents was added into the aged PEDOT:PSS dispersion, the size of PEDOT-rich agglomerates was adversely enlarged. When organic solar cells were fabricated using more than a two-year-old PEDOT:PSS that was treated with IPA solvent, the resulting device performance of organic solar cells was fully recovered and became comparable or better than that of organic solar cells fabricated with fresh PEDOT:PSS.     

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.     

Mitigating Detrimental Effect of Self-Doping Near the Anode in Highly Efficient Organic Solar Cells

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been one of the most established hole transport layers (HTL) in organic solar cells (OSCs) for several decades. However, the presence of PSS⁻ ions is known to deteriorate device performance via a number of mechanisms including diffusion to the HTL-active layer interface and unwanted local chemical reactions. In this study, it is shown that PSS⁻ ions can also result in local p-doping in the high efficiency donor:non-fullerene acceptor blends – resulting in photocurrent loss. To address these issues, a facile and effective approach is reported to improve the OSC performance through a two-component hole transport layer (HTL) consisting of a self-assembled monolayer of 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and PEDOT:PSS. The power conversion efficiency (PCE) of 17.1% using devices with PEDOT:PSS HTL improved to 17.7% when the PEDOT:PSS/2PACz two-component HTL is used. The improved performance is attributed to the overlaid 2PACz layer preventing the formation of an intermixed p-doped PSS⁻ ion rich region (≈5–10 nm) at the bulk heterojunction-HTL contact interface, resulting in decreased recombination losses and improved stability. Moreover, the 2PACz monolayer is also found to reduce electrical shunts that ultimately yield improved performance in large area devices with PCE enhanced from 12.3% to 13.3% in 1 cm² cells.     

Effects of exciton blocking layer and cathode electrode work function on the performance of polymer solar cells

In this study the effects of some important processing and post-processing treatments on the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester ([60]PCBM) solar cells were investigated. These parameters included the active layer film formation period, thermal annealing, electrical treatment, cathode work function modification, and exciton blocking layer type and thickness. Polymer bulk heterojunction solar cells having a glass/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM/(Ca or LiF)/Al structure were fabricated. The morphology of the active layer was investigated using atomic force microscopy. The results showed that the morphology state of the active layer exactly after spin coating process was very important parameter, which could dictate different responses of solar cells to a certain treatment. Using solvent additives to prolong the film formation period and storing in small dish could reach the morphology of the active layer near its best state in which there was no need to apply common post-treatment processes. A thickness at about 20 nm was required for Ca layer to effectively act as exciton blocking layer while LiF with 1 nm thickness worked better.     

Synthesis of polymers for hole and electron transport materials inorganic electroluminescent devices

Styrene-type polymers having tetraphenylbenzidine (TPD) or tetraphenylphenyldiaminobenzene unit (PDA) and a oxadiazole unit (PBD) on the side chain were prepared as hole and electron transport materials, respectively, of an electroluminescent (EL) device. The device structures employed were [indium-tin-oxide (ITO)/hole transport layer (HTL)/Al] (type I), or [ITO/hole transport layer (HTL)/electron transport layer (ETL)/Al] (type II). Type I devices provided current density higher than 100 mA/cm² but no luminescence was observed. Type II devices emitted luminescence of about 10 cd/m² at the current density of about 170 mA/cm². The emission maximums of these devices were 460 and 530 nm for the device using TPD and PDA, respectively     

Effects of tetramethylene sulfone solvent additives on conductivity of PEDOT:PSS film and performance of polymer photovoltaic cells

A solvent additive in PEDOT:PSS solution is one of many methods to improve the conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. We explore a new type of the solvent additive, namely tetramethylene sulfone (TMS), for the fabrication of the PEDOT:PSS conductive layer in the ITO/PEDOT:PSS/P3HT:PCBM/TiO_x/Al polymer photovoltaic cells, in comparison to a more common dimethyl sulfoxide (DMSO) solvent additive. At optimal conditions, the TMS additive at 10 wt.% has been found to enhance the conductivity of pristine PEDOT:PSS films from 0.04 S/cm up to approximately 189 S/cm, compared with the highest conductivity for the case of the DMSO additive at 15 wt.% of 117 S/cm. Possible mechanisms of this conductivity enhancement, relating to the polymer conformation and the film morphology, have been investigated by Raman spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy. The performance of the polymer photovoltaic cells fabricated with the solvent additives PEDOT:PSS films follows a similar trend to the conductivity of the films as a function of the additive concentration. The additives mainly lead to greater short circuit current density (J_sc) of the photovoltaic cells. The highest power conversion efficiency (PCE) of 2.24% of the device has been obtained with the 10 wt.% TMS additive of, compared to the PCE of 1.48% for the standard device without solvent additive.     

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.     

High-efficiency inverted polymer solar cells via dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer

Polymer solar cells (PSCs) are of great interest in the past decade owing to their potentially low-cost in the manufacturing by the solution-based roll to roll method. In this paper, a novel inverted device structure was introduced by inserting a high conductive PEDOT:PSS (hcPEDOT:PSS) layer between the Au nanoparticles (NPs)-embedded hole transport layer (PEDOT:PSS) and the top electrode layer. Power conversion efficiency (PCE) initially reached up to 4.51%, illustrating ∼10% higher compared with the device similarly enhanced by Au NPs plasmonics where only one PEDOT:PSS layer with the embedded Au NPs was used in single bulk heterojunction inverted PSCs based on the poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methylester (P3HT:PCBM). The PCE was further improved from 4.51% to 5.01% by adding the high-boiling point solvent of 1,8-diiodooctane (DD) into the active layer, presenting ∼20% enhancement in PCE through dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer. Morphologies of the active layers were characterised by SEM and AFM separately in the paper.     

High efficient ITO free inverted organic solar cells based on ultrathin Ca modified AZO cathode and their light soaking issue

Aluminum doped zinc oxide (AZO) was used to be the cathode instead of indium-tin-oxide (ITO) in the poly (3-hexylthiophene-2,5-diyl):[6,6]-phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM) based bulk heterojunction inverted organic solar cells (IOSCs). For the AZO only IOSC, the device shows a poor power conversion efficiency (PCE) of 1.34% and a light soaking issue related to the energy barrier at the AZO/P3HT:PCBM interface. When a 5 nm Ca modifying layer is inserted between AZO and P3HT:PCBM, the obtained AZO/Ca (5 nm) IOSC shows an increased PCE from 1.74% to 2.69% after 15 min illumination. It is thought that the increased photoconductivity of AZO/Ca (5 nm) film upon illumination and the enhanced electron transport across the AZO/Ca interface may be responsible for the light soaking issue. When an ultrathin Ca modifying layer of 1 nm is employed, a further improved PCE of 3.17% is obtained, and remarkably, no light soaking issue is observed in this case. However, this unexpected issue appears after the un-encapsulated AZO/Ca (1 nm) IOSC has been stored in air for several days, which may be due to the energy loss in the electron transport across the interface between partly oxidized Ca and AZO layers induced by the oxidization of Ca. Furthermore, the AZO/Ca (1 nm) IOSC has a comparable PCE to the referenced ITO/Ca (1 nm) IOSC and presents a better air-stability. It is thus concluded that the AZO cathode is a promising alternative of ITO to fabricate the high efficient and long-lifetime IOSCs.     

A Simple Cu(II) Polyelectrolyte as a Method to Increase the Work Function of Electrodes and Form Effective p-Type Contacts in Perovskite Solar Cells

One effective strategy to improve the performance of perovskite solar cells (PSCs) is to develop new hole transport layers (HTLs). In this work, a simple polyelectrolyte HTL, copper (II) poly(styrene sulfonate) (Cu:PSS), which comprises easily reduced Cu²⁺ counter-ions with an anionic PSS polyelectrolyte backbone is investigated. Photoelectron spectroscopy reveals an increase in the work function of the anode and upward band bending effect upon incorporation of Cu:PSS in PSC devices. Cu:PSS shows a synergistic effect when mixed with polyethylenedioxythiophene: polystyrenesulfonate (PEDOT:PSS) in various proportions and results in a decrease in the acidity of PEDOT:PSS as well as reduced hysteresis in completed devices. Cu:PSS functions effectively as a HTL in PSCs, with device parameters comparable to PEDOT:PSS, while mixtures of Cu:PSS with PEDOT:PSS shows greatly improved performance compared to PEDOT:PSS alone. Optimized devices incorporating Cu:PSS/PEDOT:PSS mixtures show an improvement in efficiency from 14.35 to 19.44% using a simple CH₃NH₃PbI₃ active layer in an inverted (P-I-N) geometry, which is one of the highest values yet reported for this type of device. It is expected that this type of HTL can be employed to create p-type contacts and improve performance in other types of semiconducting devices as well.     

Improving Performance and Stability of Flexible Planar‐Heterojunction Perovskite Solar Cells Using Polymeric Hole‐Transport Material

For realizing flexible perovskite solar cells (PSCs), it is important to develop low‐temperature processable interlayer materials with excellent charge transporting properties. Herein, a novel polymeric hole‐transport material based on 1,4‐bis(4‐sulfonatobutoxy)benzene and thiophene moieties (PhNa‐1T) and its application as a hole‐transport layer (HTL) material of high‐performance inverted‐type flexible PSCs are introduced. Compared with the conventionally used poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), the incorporation of PhNa‐1T into HTL of the PSC device is demonstrated to be more effective for improving charge extraction from the perovskite absorber to the HTL and suppressing charge recombination in the bulk perovskite and HTL/perovskite interface. As a result, the flexible PSC using PhNa‐1T achieves high photovoltaic performances with an impressive power conversion efficiency of 14.7%. This is, to the best of our knowledge, among the highest performances reported to date for inverted‐type flexible PSCs. Moreover, the PhNa‐1T‐based flexible PSC shows much improved stability under an ambient condition than PEDOT:PSS‐based PSC. It is believed that PhNa‐1T is a promising candidate as an HTL material for high‐performance flexible PSCs.     

Simple and Low-Cost Vanadyl Oxalate as Hole Transporting Layer Enables Efficient Organic Solar Cells

Organic solar cells (OSCs) with the conventional configuration usually use polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) as the hole-transporting layer (HTL); however, its acidity tends to affect the performance and long-term stability of the devices. Therefore, replacing PEDOT:PSS with other more stable HTLs is essential for realizing the practical applications of OSCs. To achieve this goal, a simple and low-cost vanadyl oxalate (VOC₂O₄) is identified as a HTL to facilitate high power conversion efficiencies (PCEs), good stability, and high thickness tolerance to be achieved in OSCs. The VOC₂O₄ thin film can be easily prepared by spin-coating from its aqueous solution onto ITO/glass substrate and thermally annealed at 100 °C to exhibit high transmittance, conductivity, and work function. It can be applied as a robust HTL with wide processing conditions, especially after being heated at 200 °C and treated with UV-ozone (UVO) to afford a very high PCE of 18.94% in OSCs. This value is among the highest PCEs obtained for binary OSCs. In addition, the derived OSCs exhibit high thickness tolerance and better stability than those based on PEDOT:PSS as HTL. These results reveal that VOC₂O₄ is an excellent HTL for OSCs, having great potential for large-area device applications.     

Hybrid photovoltaic structures based on amorphous silicon and P3HT:PCBM/PEDOT:PSS polymer semiconductors

Hybrid thin film photovoltaic structures, based on hydrogenated silicon (Si:H), organic poly(3-hexythiophene):methano-fullerenephenyl-C61-butyric-acid-methyl-ester (P3HT:PCBM) and poly(3,4ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films, have been fabricated. Organic semiconductor thin films were deposited by spin-coating technique and were exposed to radio frequency plasma enhanced chemical vapor deposition (RF PECVD) of Si:H films at deposition temperature T_d = 160 °C. Different types of structures have been investigated: H1) ITO/(p)SiC:H /P3HT:PCBM/(n) Si:H, H2) ITO/PEDOT:PSS/(i)Si:H/(n) Si:H and H3) ITO/PEDOT:PSS/P3HT:PCBM/(i)Si:H/(n)Si:H. Short circuit current density spectral response and current-voltage characteristics were measured for diagnostic of the photovoltaic performance. The current density spectral dependence of hybrid structures which contains organic layers showed improved response (50–80%) in high photon energy range (hν ≈ 3.1–3.5 eV) in comparison with Si:H reference structure. An adjustment in the absorbing layer thickness and in the contact material for ITO/PEDOT:PSS/(i)Si:H/(n)Si:H structure, resulted in a remarkably high short circuit current density (as large as 17.74 mA/cm²), an open circuit voltage of 640 mV and an efficiency of 3.75%.