掺杂PEDOT ∶PSS对聚合物太阳能电池性能影响的研究

研究了掺杂后poly(3,4-ethylene dioxythiophene):poly(styrenesulphonic acid)(PEDOT ∶PSS)电导率的变化以及掺杂PEDOT ∶PSS薄膜对聚合物太阳能电池器件性能的影响. 实验发现,向PEDOT ∶PSS中掺入极性溶剂二甲基亚砜(DMSO)明显提高了薄膜的电导率,掺杂后的电导率最大值达到1.25 S/cm,比未掺杂时提高了3个数量级. 将掺杂的PEDOT ∶PSS薄膜作为缓冲层应用于聚合物电池 (ITO/PEDOT ∶PSS/P3HT ∶PCBM/LiF/Al) 中,发现高电导率的PEDOT ∶PSS降低了器件的串联电阻,增加了器件的短路电流,从而提高了器件的性能. 最好的聚合物太阳能电池在100 mW/cm²的光照下,开路电压(V_oc)为0.63 V,短路电流密度(J_sc)为11.09 mA·cm^-2,填充因子(FF)为63.7%,能量转换效率(η)达到4.45%. 关键词： PEDOT ∶PSS 电导率 聚合物太阳能电池 能量转换效率     

Investigating the performance of P3HT:PCBM organic solar cells involving gamma-irradiated PEDOT:PSS layer

In this work, we investigated for the first time the characteristics of (poly (3-hexylthiopene) and [6, 6]-phenyl C61-butyric acid methyl ester) (P3HT:PCBM) blends-based organic solar cell with 1.25?mg/mL boric-acid (H₃BO₃)-doped poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layer which is irradiated under the 40 Gray (Gy) dose of gamma (γ) ray. Experimental results showed that the parameters of solar cell improved with exposure to low-dose gamma radiation. In particular, it has provided a significant improvement in short-circuit current density (J_sc) and power conversion efficiency (PCE). About 49% increase in PCE to 1.22% and 40% increase in J_sc to 6.28?mA/cm² was obtained between the bare device and the device containing irradiated PEDOT:PSS:H₃BO₃. Also, it was determined that the H₃BO₃-doped PEDOT:PSS is more stable to temperature. More importantly, solar cell containing gamma-irradiated PEDOT:PSS:H₃BO₃ showed best performance comparing to conventional PEDOT:PSS-based cell.     

Improvement in performance of organic light-emitting devices by inclusion of multi-wall carbon nanotubes

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was modified by different concentrations of multi-wall carbon nanotubes (MWNTs), and the nanocomposites of PEDOT:PSS and MWNTs were firstly used as hole-injection layer in fabrication of organic light-emitting devices (OLEDs) by using a double-layer structure with hole-injection layer of doped PEDOT:PSS and emitting/electron transport layer of tris(8-hydroxyquinolinato) aluminum (Alq₃). PEDOT:PSS solution doped with MWNTs was spin-coated on clean polyethylene terephthalate (PET) substrate with indium tin oxide (ITO). It was found that the electroluminescence (EL) intensity of the OLEDs were greatly improved by using PEDOT:PSS doped with MWNTs as hole-injection layer which might have resulted from the hole-injection ability improvement of the nanocomposites. Higher luminescence intensity and lower turn-on voltage were obtained by these devices and the luminance intensity obtained from the device with the hole-injection layer of PEDOT:PSS doped by 0.4 wt.% MWNTs was almost threefolds of that without doping.     

Metal-electrode-free inverted organic photovoltaics using electrospray-deposited PEDOT:PSS and spin-coated HAT-CN exciton blocking layer

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) films were fabricated using an electrospray deposition (ESD) method. The ESD PEDOT:PSS films exhibited higher PSS content on the surface than spin-coated PEDOT:PSS films, which results in a higher work function. Based on this result, metal-electrode-free inverted organic photovoltaics (OPVs) were fabricated. The ESD PEDOT:PSS was used as the top electrode on the poly(3-hexythiophene-2,5-diyl) (P3HT):[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) light-absorbing layer. The power conversion efficiency (PCE) of OPVs was significantly increased with the 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile layer. The improved PCE would be attributed to the suppression of exciton quenching at the P3HT:PCBM and PEDOT:PSS interface.     

Anionic nonconjugated polyelectrolyte as an anode interfacial layer for polymer solar cells

Since the most high-performing donor polymers in polymer solar cells (PSCs) possessed the deep highest occupied molecular orbital (HOMO) level, interfacial engineering on anode contact is becoming increasingly important. Herein, we demonstrated efficient PSCs using an anionic poly(styrene sulfonate) (PSS) as an anode interfacial layer (AIL). With the formation of the dipole layer, the effective work function (WF) of indium tin oxide (ITO) electrode is significantly increased from 4.8 to 5.3 eV, providing favorable energetic alignment to the quasi-Fermi level of various donor polymers. Moreover, by incorporating cationic polyelectrolytes as a cathode interfacial layer, a pair of electric dipole layers induces a strong built-in electric field across the photoactive layer to drive efficient sweep-out of photogenerated charges. Consequently, the device with PSS AIL exhibited high power conversion efficiencies of 9.2 and 14.8% in PTB7-Th:PC₇₁BM- and PM6:Y6-based PSCs, respectively, both of which are higher than those of the devices with PEDOT:PSS.     

阳极界面修饰对钙钛矿太阳能电池性能的影响

采用在聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸(Poly(3,4-ethylenedioxythiophene)∶Poly(styrenesulfonate),PEDOT∶PSS)阳极界面层上直接旋涂二甲基亚砜(Dimethyl Sulfoxide,DMSO)的方法,对PEDOT∶PSS薄膜进行修饰,以提高所制得的钙钛矿太阳能电池器件性能.在5000rpm转速条件下旋涂DMSO后,器件的能量转换效率达到11.43%,与PEDOT∶PSS阳极界面层未做任何修饰的器件相比,效率提高了29.15%.测试表征了修饰前后PEDOT∶PSS薄膜的透光性、表面形貌、电导率、器件的外量子效率曲线以及器件在光照和暗态下的J-V特性曲线,分析了器件性能提高的原因.结果表明:经过修饰的PEDOT∶PSS薄膜导电性显著增强,从而更加有利于器件阳极对空穴的抽取和收集;较未修饰时,器件的短路电流密度得到了大幅度提升,进而使得器件获得更高的能量转换效率.     

Pentacene as a hole transport material for high performance planar perovskite solar cells

A cost-effective and efficient organic semiconductor pentacene was developed as a hole transport layer (HTL) material to replace classical PEDOT:PSS for planar perovskite solar cells (PSCs). As expected, the pentacene based device exhibits power conversion efficiency (PCE) of 15.90% (J_sc of 19.44 mA/cm², V_oc of 1.07 V, and FF of 77%), comparable to the PEDOT:PSS based device (PCE of 15.65%, J_sc of 18.78 mA/cm², V_oc of 1.07 V, and FF of 77%) under the same experimental conditions. The excellent performance of vacuum deposited pentacene is mainly attributed to the high efficient charge extraction and transfer in device due to the high-quality perovskite film grown on the top of pentacene substrate and a favorable energy-level alignment together with a desired downward band bending formed at the perovskite/pentacene interface. Our research has confirmed that pentacene could be served as a promising HTL material to achieve effective and potentially economical planar type PSCs.     

Improving efficiency of inverted perovskite solar cells via ethanolamine-doped PEDOT:PSS as hole transport layer

In order to fabricate high-performance inverted perovskite solar cells (PeSCs), an appropriate hole transport layer (HTL) is essential since it will affect the hole extraction at perovskite/HTL interface and determine the crystallization quality of the subsequent perovskite films. Herein, a facile and simple method is developed by adding ethanolamine (ETA) into poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as HTL. The doping of a low-concentration ETA can efficiently modify the electrical properties of the PEDOT:PSS film and lower the highest occupied molecular orbital (HOMO) level, which is more suitable for the hole extraction from the perovskite to HTL. Besides, ETA-doped PEDOT:PSS will create a perovskite film with larger grain size and higher crystallinity. Hence, the results show that the open-circuit voltage of the device increases from 0.99 V to 1.06 V, and the corresponding power conversion efficiency (PCE) increases from 14.68% to 19.16%. The alkaline nature of ethanolamine greatly neutralizes the acidity of PEDOT:PSS, and plays a role in protecting the anode, leading the stability of the devices to be improved significantly. After being stored for 2000 h, the PCE of ETA-doped PEDOT:PSS devices can maintain 84.2% of the initial value, which is much higher than 67.1% of undoped devices.     

Effect of dye dopants in poly(methylphenyl silane) light-emitting devices

To investigate the inter-molecular energy transfer between polysilane and dye dopants, poly(methylphenylsilane)(PMPS) was used as a host material and perylene as the blue dopant. The structure of the devices is indium–tin oxide (ITO)/PEDOT:PSS(30 nm)/PMPS:perylene(dye dopant 0.1–1.0 mol%)(60 nm)/Alq₃(20 nm)/LiF(0.5 nm)/Al(100 nm). Poly(3,4-ethylenedioxythiophene) (PEDOT):poly(4-styrenesulfonate) (PSS) is used as a buffer layer, tris(8-hydroxyquinoline)aluminum (Alq₃) as hole transporting layer, LiF as hole injection layer. The device shows a luminance 810 cd/m² at current density of 28 mA/cm², luminous efficiency of 0.14 lm/W. The external quantum efficiency (EQE) is about 0.5% and EQE increased up to 0.52% by doping with single wall carbon nanotubes (SWNT) into the emissive layer. We found an efficient inter-molecular energy transfer from polysilane to dye dopants. Furthermore, using the polysilane and energy-matched dye dopants enable to fabricate the electroluminescence devices through wet processes.     

Highly-efficient solution-processed phosphorescent multi-layer organic light-emitting diodes investigated by electromodulation spectroscopy

We report on electromodulation (EM) spectroscopy studies of phosphorescent multi-layer organic light-emitting diodes (OLEDs) that are processed from solution. Compared to conventional single-layer OLEDs, they comprise an additional layer of a crosslinkable, oxetane-functionalized triphenylamine-dimer (XTPD) that is inserted between the PEDOT:PSS anode and the emissive layer. Devices with optimized stack architecture feature reduced operating voltages and reach a current efficiency approaching 40 cd/A—twice as much as the corresponding single-layer device. Using EM measurements, we quantify the electric field in the XTPD layer and the emissive layer of such a multi-layer OLED and also measure the average electric field in a single-layer reference device. By comparing the dependence of the internal field on the applied voltage for devices with and without the XTPD layer, we find that in the device containing the XTPD layer there is an increased accumulation of electrons at the anode side of the emissive layer. This accumulation enhances the recombination probability and supports the injection of holes into the emissive layer which explains the observed efficiency improvement and reduction in operating voltage compared to conventional single-layer OLEDs.     

利用Ag_2O/PEDOT:PSS复合缓冲层提高P3HT:PCBM聚合物太阳能电池器件性能的研究

利用Ag2O/PEDOT:PSS(聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸盐)作为复合阳极缓冲层,制备了P3HT:PCBM(聚(3-已基噻吩):富勒烯衍生物)聚合物太阳能电池器件,并通过改变氧化银插入层的厚度来分析复合缓冲层对器件性能的影响.实验发现,具有阳极缓冲层修饰的器件在退火处理后,光伏性能得到了改善.相比于单一PEDOT:PSS缓冲层的器件,Ag2O/PEDOT:PSS复合缓冲层可以增大器件的短路电流密度和外量子效率,使器件效率得到提高.分析表明,退火处理可以有效改善活性层的薄膜形貌,增加光的吸收和激子的解离,而较薄氧化银的引入,可以有效降低阳极处空穴的输运势垒,提高器件空穴收集效率,并能充当化学间隔层,提高器件光伏性能和稳定性.     

NiO透明导电薄膜的制备及在聚合物太阳能电池中的应用

采用磁控溅射法制备出透明导电氧化物NiO薄膜.椭偏(SE)测试表明NiO薄膜在可见光区域透光性良好,通过调节生长、退火温度可调控NiO的折射率.采用X射线衍射(XRD)、扫描电子显微镜(SEM)手段研究表明,通过退火、改变衬底温度等,可有效改变NiO薄膜的晶体结构以及表面形貌,实现对NiO导电性的调控. 采用优化后的NiO材料为阳极阻挡层制备出的聚合物太阳能电池器件的效率为2.26%,是同等条件下采用 PEDOT:PSS阻挡层的电池器件的3倍以上.     

体异质结有机太阳能电池性能提高的研究

制备了四种不同结构的有机太阳能电池器件,器件1 ITO/LiF/PEDOT∶PSS/MEH-PPV/C₆₀/Al、器件2 ITO/PEDOT∶PSS/MEH-PPV/C₆₀/Al、器件3 ITO/LiF/PEDOT∶PSS/MEH-PPV∶C₆₀/C₆₀/Al和器件4 ITO/PEDOT∶PSS/MEH-PPV∶C₆₀/C₆₀/Al。测量了它们的电流－电压特性,结果显示在ITO和PEDOT∶PSS之间插入一薄层LiF使得器件性能得到较大提高。其器件1的J_SC和FF比器件2的提高了74%和31%; 器件3的J_SC比器件4的提高了约40%。这主要是由于LiF层有效地抑制了空穴向阳极的传输,并且LiF层在ITO和PEDOT:PSS之间形成了良好的界面特性。因此,这种结构上的改进有效地提高了有机太阳能电池的性能。     

Increased work function in PEDOT:PSS film under ultraviolet irradiation

An increase of work function （0.3 eV） is achieved by irradiating poly（3,4-ethylenedioxythiophene）：poly（styrene sul- fonate） （PEDOT：PSS） film in vacuum with 254-nm ultraviolet （UV） light. The mechanism for such an improvement is investigated by photoelectron yield spectroscopy, X-ray photo electron energy spectrum, and field emission technique. Sur- face oxidation and composition change are found as the reasons for work function increase. The UV-treated PEDOT：PSS film is used as the hole injection layer in a hole-only device. Hole injection is improved by UV-treated PEDOT：PSS film without baring the enlargement of film resistance. Our result demonstrates that UV treatment is more suitable for modifying the injection barrier than UV ozone exposure.     

A comparative study on the performance of hybrid solar cells containing ZnSTe QDs in hole transporting layer and photoactive layer

In this paper, ZnSTe quantum dots-based hybrid solar cells (HSC) with two different device architectures have been investigated. The improved performance of the poly(3-hexylthiophene) (P3HT) and [6,6]phenyl C₇₁ butyric acid methyl ester (PC₇₁BM)-based bulk heterojunction (BHJ) solar cells by the incorporation of ZnSTe quantum dots (QDs) with an average size of 2.96 nm in PEDOT:PSS layer and active layer that have been demonstrated. Although the efficiency of both types of devices is almost the same, a close comparison reveals different reasons behind their improved performance. The device prepared with QDs in the HTL has shown reduced series resistance, increased shunt resistance, and improved mobility. On the other hand, QDs in the photoactive layer demonstrates increased photo-generation leading to improved efficiency.     

Effect of sorbitol doping in PEDOT:PSS on the electrical performance of organic photovoltaic devices

Organic photovoltaic cells have important advantages, such as low cost and mechanical flexibility. The conducting polymer poly(3,4 ethylenedioxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely used as an interfacial layer or a polymer electrode in polymer electronic devices, such as photovoltaic devices and light-emitting diodes. In this report, we discuss the direct current (DC) conductivity of PEDOT:PSS films containing various weight ratios of sorbitol dopant. The work function is shown to steadily decrease with increasing dopant content. With different dopant contents, illuminated current–voltage photovoltaic characteristics were observed. Ultraviolet photoelectron spectroscopy (UPS) analysis revealed that the work function of the PEDOT:PSS was affected by its sorbitol content. The morphologies of the doped PEDOT:PSS films were characterized by atomic force microscopy (AFM). For the device fabrication, we made organic photovoltaic cells by a spin-coating process and Al deposition by thermal evaporation. The sorbitol dopant is able to improve the efficiency of the device.     

Conducting polymer based hybrid structure as transparent and flexible field electron emitter

An efficient cathode material with high transparency (93%) based on conducting polymer poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and single wall carbon nanotubes (SWCNTs) has been developed for the fabrication of highly transparent and flexible field electron emitters (FEE). This kind of material showed superior field emission (FE) performance with very high current density (10^–3A/cm²) at very low electric field. The FE performance of the hybrid materials was dramatically improved compared to either SWCNTs and PEDOT:PSS. Thus the hybrid structures of conducting polymer and SWCNTs might be a good choice for use as a cathode material to enhance the FE performance and for potential application in future portable displays. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improving the performance of perovskite solar cells with glycerol-doped PEDOT:PSS buffer layer

In this paper, we investigate the effects of glycerol doping on transmittance, conductivity and surface morphology of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate))(PEDOT:PSS) and its influence on the performance of perovskite solar cells.. The conductivity of PEDOT:PSS is improved obviously by doping glycerol. The maximum of the conductivity is 0.89 S/cm when the doping concentration reaches 6 wt%, which increases about 127 times compared with undoped. The perovskite solar cells are fabricated with a configuration of indium tin oxide(ITO)/PEDOT:PSS/CH_3NH_3PbI_3/PC_(61)BM/Al, where PEDOT:PSS and PC_(61)BM are used as hole and electron transport layers, respectively. The results show an improvement of hole charge transport as well as an increase of short-circuit current density and a reduction of series resistance, owing to the higher conductivity of the doped PEDOT:PSS. Consequently, it improves the whole performance of perovskite solar cell. The power conversion efficiency(PCE) of the device is improved from 8.57% to 11.03% under AM 1.5 G(100 mW/cm~2 illumination) after the buffer layer has been modified.     

Electric-field induced ion-leveraged metal–insulator transition in conducting polymer-based field effect devices

The field effect devices prepared completely from conducting polymers, especially poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS), were studied. Normally in a conductive “on” state, the transistor-like device has a transition to a substantially less conductive “off” state at an applied positive gate voltage, typically ∼15–25 V. The current ratio I_off/I_on can exceed 10⁻⁴ at room temperature. We have found that the field effect is strongly temperature dependent and is substantially reduced upon decreasing the temperature by only a 10 °C. This loss of current reduction upon application of a gate voltage is not due to the temperature dependence of the electrical conductivity of polymers of which the devices are made. The temperature dependence of the dc conductivity of the PEDOT/PSS follows the variable range hopping law both before and after application of the gate voltage, though with an increased activation energy, T₀. We suggest that the conducting polymer is near the metal–insulator transition and that the field effect in the device is related to the electric field modulating this transition in the region underneath the gate electrode. The transition is controlled and leveraged by ion motion. The time dynamics of the current with the gate modulation strongly supports our conjecture. We demonstrate the generality of the phenomena by presenting similar results for devices fabricated from the conducting polypyrrole doped with Cl.     

On the spectral difference between electroluminescence and photoluminescence of Si nanocrystals: a mechanism study of electroluminescence

A highly dense and uniform layer of Au nanoparticles (NPs) on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film has been produced by the pulsed laser deposition (PLD) technique toward the production of an improved efficiency photovoltaic device. The advantage of PLD over other techniques is the easy and precise control of the Au NPs size and spatial distribution, without needing of further NP surface functionalization. The efficiency enhancement factor related to Au NPs doping has been evaluated in a solar cell based on poly-(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) diffused bilayer. The short-circuit current density, J _SC, increases by 18 % and the power conversion efficiency by 22 %, respectively, in comparison with an equivalent device without Au NPs. The optical and morphological properties of the Au NPs layer have been selected in order to evaluate the contribution of the surface plasmon resonance as enhancement factor of the solar cell efficiency, in a range size where light scattering is negligible.