An investigation into the effects of oxygen plasma discharge on tin-doped indium oxide thin films

The surfaces of tin-doped indium oxide (ITO) thin films for polymer light-emitting electrochemical cells (LECs) were modified by oxygen plasma discharge. The properties of the ITO surfaces were evaluated by means of the measurements of X-ray photoelectron spectroscopy (XPS), contact angle, surface free energy and polarity. The influence of surface properties of the ITO thin films on the performance of polymer LECs was investigated in terms of the turn-on voltage, injection current and luminance. When oxygen plasma discharge was employed to modify the ITO surfaces, the surface properties of ITO are optimized due to the improvement of surface stoichiometry and the enhancement of wettability. And the improved surface properties benefited from the oxygen plasma discharge is observed to decay with the time after the plasma discharge. The difference in chemical composition, surface free energy and polarity between the non-treated and treated ITO surfaces appears to become smaller with the increase of the time after plasma discharge. In addition, the electrical and optical performance of the devices is found to become worse with the increasing time after plasma discharge on ITO substrates. The results demonstrate that the device performance strongly depends on the ITO surface properties and the ITO/organic interface characteristics.     

ITO界面调制层对GZO电极LED器件性能的影响

采用磁控溅射制备GZO和具有ITO界面调控层的GZO(ITO/GZO)透明导电薄膜作为大功率LED的电流扩散层,对比研究界面调控层对LED器件性能的影响。研究结果表明,ITO/GZO薄膜的透过率在可见光区达80%以上,退火后的ITO/GZO薄膜有较低的电阻率(1.15×10^-3 Ω·cm)。ITO调控层的介入能够调制GZO表面粗糙度,有利于改善LED外量子效率,降低GZO/p-GaN界面的接触势垒,提高LED器件的光电性 能。通过ITO界面调控后,LED器件20 mA驱动电流下的工作电压从9.5 V降低为6.8 V,发光强度从245 mcd 升到297 mcd,提高了20%;驱动电流为35 mA时,其发光强度从340.5 mcd 升到511 mcd,提高了50%。     

Modification of the organic/La0.7Sr0.3MnO3 interface by in situ gas treatment

La_0.7Sr_0.3MnO₃ (LSMO) can act as a spin injection electrode in organic spin-valves and organic light-emitting devices. For the latter application, good control of the electronic structure of the organic/LSMO interface is a key issue to ensure sufficient current injection in the device. By exposing cleaned LSMO surfaces to activated oxygen and hydrogen, the work function of the samples can reach 5.15 and 4.3 eV, respectively, as shown by in situ photoemission measurements. The initial stage of formation of the organic/LSMO interface upon deposition of N,N′-bis-(1-naphyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) onto the oxygen-treated LSMO surface is examined. We find that the NPB molecules evenly cover the LSMO surface and that the interface barrier height is 0.8 eV, which is comparable to that at the NPB/indium tin oxide (ITO) interface with the ITO surface pretreated in situ by oxygen plasma.     

Advanced ion beam technology for versatile oxide thin film formation

Various oxide films, such as SnO₂, In₂O₃, Al₂O₃, SiO₂, ZnO, and Sn-doped In₂O₃ (ITO) have been deposited on glass and polymer substrates by advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry, crystallinity, and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. IBSD method has been carried out for understanding the growth mode of the films on glass and polymer substrate. Relationships between microstructure and electrical properties in ITO films on polymer and glass substrates were intensively investigated by changing ion energy, reactive gas environment, substrate temperature, etc. Smooth-surface ITO films (R_rms ⩽ 1 nm and R_p−v ⩽ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. In the case of Al₂O₃ and SiO₂ films, the oxygen and moisture barrier properties were also improved by IAR surface treatment. The experimental results of the oxide films prepared by the ion beam technologies and its applications will be represented in detail.     

Progress in Modification of Indium-Tin Oxide/Organic Interfaces for Organic Light-Emitting Diodes

The oxide/organic interfaces play crucial roles in the hole injection from the anode electrodes to the emitting organics in organic light-emitting diodes (OLEDs), and hence have strong impacts on the efficiencies and other properties of the devices. Indium-tin oxide (ITO) is currently the most popular anode material used in OLEDs due to several merits, such as good etch ability, good adherence, high transparency, low resistivity, and high work function. Interfacial engineering between the ITO electrode and the overlying organic layers is an important process to obtain the high performance of the diode devices. In this article, recent progress in modification of the ITO/organic interfaces is reviewed, as these interfaces are important to the development of the technologies aiming at improving the electroluminescence, and efficiencies as well as reducing the operation voltages of OLEDs. ITO/Organic interfacial properties can be controlled or modified by simply changing the surface properties of ITO using chemical or physical treatments, and by adding a buffer layer (e.g., metal, oxide, or organic thin films) between the ITO and hole transport or emitting organic layers. The literature data showed that the electroluminescence, efficiencies, and lifetimes of the OLEDs could be greatly increased and the operation voltage considerably decreased when the ITO/organic interfaces have been properly improved.     

Structural and electronic implications for carrier injection into organic semiconductors

We report on the structural and electronic interface formation between ITO (indium-tin-oxide) and prototypical organic small molecular semiconductors, i.e., CuPc (copper phthalocyanine) and α-NPD (N,N′-di(naphtalen-1-yl)-N,N′-diphenyl-benzidine). In particular, the effects of in situ oxygen plasma pretreatment of the ITO surface on interface properties are examined in detail: Organic layer-thickness dependent Kelvin probe measurements revealed a good alignment of the ITO work function and the highest occupied electronic level of the organic material in all samples. In contrast, the electrical properties of hole-only and bipolar organic diodes depend strongly on the treatment of ITO prior to organic deposition. This dependence is more pronounced for diodes made of polycrystalline CuPc than for those of amorphous α-NPD layers. X-ray diffraction and atomic force microscopic (AFM) investigations of CuPc nucleation and growth evidenced a more pronounced texture of the polycrystalline film structure on the ITO substrate that was oxygen plasma treated prior to organic layer deposition. These findings suggest that the anisotropic electrical properties of CuPc crystallites, and their orientation with respect to the substrate, strongly affect the charge carrier injection and transport properties at the anode interface.     

Improved electrical and optical properties of MEH-PPV light emitting diodes using Ba buffer layer and porphyrin

It has been found that insertion of a thin Ba buffer layer between the Al electrode and the MEH-PPV layer results in a significantly higher current density in ITO/MEH-PPV/Al polymer light-emitting diodes due to a reduction of the potential barrier at the cathode-polymer interface. The photoluminescence is found to increase with the addition of porphyrin-containing platinum as the central atom, showing that some of the triplet excitons decay radiatively as a result of mixing porphyrin.     

Mechanics of plasma exposed spin-on-glass (SOG) and polydimethyl siloxane (PDMS) surfaces and their impact on bond strength

Silicone polymer (PDMS), widely used for micro-fluidic and biosensor applications, possesses an extremely dynamic surface after it is subjected to an oxygen plasma treatment process. The surface becomes extremely hydrophilic immediately after oxygen plasma exposure by developing silanol bond (SiOH), which promotes its adhesion to some other surfaces like, silicon, silicon dioxide, glass, etc. Such a surface, if left in ambient dry air, shows a gradual recovery of hydrophobicity. We have found an identical behavior to occur to surfaces coated with a thin continuous film of SOG (methyl silsesquioxane). The chemistry induced by oxygen plasma treatment of a spin-on-glass (SOG) coated surface provides a much higher density of surface silanol groups in comparison to precleaned glass, silicon or silicon dioxide substrates thus providing a higher bond strength with polydimethyl siloxane (PDMS). The bonding protocol developed by using the spin coated and cured SOG intermediate layer provides an universal regime of multi level wafer bonding of PDMS to a variety of substrates. The paper describes a contact angle based estimation of bond strength for SOG and PDMS surfaces exposed to various combinations of plasma parameters. We have found that the highest bond strength condition is achieved if the contact angle on the SOG surface is less than 10°.     

Optical, electrical and photovoltaic properties of thermally annealed PPHT:DDE blend thin films

We have investigated the optical, electrical and photovoltaic properties of devices based on 1,2-diazoamino diphenyl ethane (DDE) and poly(3-phenyl hydrazone thiophene) (PPHT):DDE blend. It is observed from the J-V characteristics of the Al/DDE/ITO (ITO—indium tin oxide) device that the electron current injected from Al contact was shown to be space charge limited (SCL), indicating that Al forms nearly ohmic contact for electron injection into lowest unoccupied molecular orbital (LUMO) of DDE. The effect of thermal annealing and composition, on the optical, electrical and photovoltaic response of blend of PPHT and DDE sandwiched between a transparent ITO electrode and an Al back contact are investigated. The observed absorption quenching in the PPHT:DDE blend is attributed to the disordering of PPHT chains and charge transfer between PPHT and DDE as evidenced by FTIR spectra. The observed red shift in the absorption peak on thermal annealing is due to the improvement in the ordering and increases in conjugation length in PPHT. The observed dark current-voltage curves agree well with trap-controlled SCL transport theory. The photophysics of the blend material and influence of thermal annealing on the performance and morphology of these devices were discussed. Annealing process results in the formation of PPHT:DDE complex and increase in the ordering of polymer chain, that increases the incident photon to current efficiency (IPCE) and power conversion efficiency of the photovoltaic devices.     

Effect of atmospheric pressure dielectric barrier discharge air plasma on electrode surface

In order to study the influence of plasma on electrode, atmospheric pressure dielectric barrier discharge (DBD) air plasma is employed here to treat copper electrode surface. Plasma is generated between the parallel plate electrodes by means of high voltage produced by a high-frequency power supply with transformer. Electrode surface alterations induced by air plasma are investigated by using field emission scanning electron microscope (FE-SEM), X-ray energy dispersion spectroscopy (EDS) and contact angle measurement. The results show that DBD air plasma removes the organic contaminant on surface and causes electrode surface roughness, oxidization and nitridation. In addition, surface wettability is also improved, as concluded from contact angle measurements.     

掺杂DCJTB聚合物电化学池（LEC）的发光性质

通过在聚合物电化学池(LEC)发光器件的发光材料MEH-PPV中掺杂红光染料DCJTB,对LEC器件的发光性质进行研究。基于器件结构为ITO/MEH-PPV PEO LiCF3SO3/Al的薄膜LEC器件,其电致发光峰在570nm左右,通过在MEH-PPV与PEO的混合膜中掺杂不同比例的红光染料DCJTB,随着掺杂比例的增加,器件的发光峰由570nm向红光波段移动,通过控制DCJTB的掺杂比例制备了发光峰在570~650nm连续变化的LEC电致发光器件。对其分析认为从LEC主体发光聚合物MEH-PPV到染料DCJTB间发生了良好的能量传递。     

Angular-dependent photoemission studies of indium tin oxide surfaces

Indium tin oxide (ITO) surfaces were treated by solvent cleaning, by plasma of oxygen, argon, nitrogen and by argon ion (Ar⁺) sputtering. Angular-dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to determine the chemical composition, the chemical states and the work function after each treatment. It was found that oxygen plasma and nitrogen plasma chemically reacted with the ITO surfaces. Yet little etching of the surface can be observed after plasma treatments. Among all treatments, oxygen-plasma-treated ITO achieved the highest work function of 4.40 eV, whereas Ar⁺-sputtered ITO surface had the lowest work function of 3.90 eV. The stoichiometry of the ITO surface is shown to be the major controlling factor of the ITO work function. Received: 7 February 2000 / Accepted: 28 March 2000 / Published online: 13 September 2000     

Surface modification of a polyamide 6 film by He/CF4 plasma using atmospheric pressure plasma jet

Polyamide 6 (PA 6) films are treated with helium(He)/CF₄ plasma at atmospheric pressure. The samples are treated at different treatment times. The surface modification of the PA 6 films is evaluated by water contact angle, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The etching rate is used to study the etching effect of He/CF₄ plasma on the PA 6 films. The T-peel strengths of the control and plasma treated films are measured to show the surface adhesion properties of the films. As the treatment time increases, the etching rate decreases steadily, the contact angle decreases initially and then increases, while the T-peel strength increases first and then decreases. AFM analyses show that the surface roughness increases after the plasma treatment. XPS analyses reveal substantial incorporation of fluorine and/or oxygen atoms to the polymer chains on the film surfaces.     

高分子发光二极管载流子注入过程研究

采用交流阻抗谱，电容-电压，电容-频率等实验方法，研究了共轭高分子MEH-PPV(poly［2-methoxy，5-(2-ethylhexoxy)-1，4-phenylene vinylene］)发光二极管的载流子注入过程.对于结构为ITO/PEDOT/MEH-PPV/Ba/Al的发光器件，实验结果表明，电极界面是欧姆接触的，载流子的注入是非平衡的，器件薄膜中存在陷阱容易俘获注入电荷，形成空间电荷区，陷阱密度约为3.75×10¹⁶cm^-3. 关键词： 高分子发光二极管 交流阻抗谱 cole-cole图 载流子注入     

绝缘层LiF/Al电极对提高P-PPV发光器件发光性能的研究

为了提高聚合物电致发光器件中Ba（Ca）／Al阴极的稳定性,在该阴极与聚合物发光材料poly（2-（4-ethylexyl）phenyl-1,4-phenylene vinylene）（P-PPV）层之间插入一层7nm的LiF绝缘层,发光器件的发光性能在多项参数（发光器件的电压．电流特性、发光强度及外量子效率,以及电流效率等发光性能指标）上能够与工作性能优良但稳定性较差的Ba（Ca）／Al电极结构PLEDs器件的发光特性具有可比性。这对于研制高效率、高稳定的聚合物电致发光器件并最终将其用于商业目的,具有重大现实意义。     

纳米ZnO薄膜对有机电致发光器件性能的影响

由于有机电致发光器件(Organic light-emitting devices,OLEDs)的主动发光、高亮度等优点,在显示和照明领域有极大的应用前景。报道了纳米ZnO薄膜对这种发光器件性能的影响。在普通有机电致发光器件空穴传输层和发光层之间直接蒸镀一层纳米ZnO薄膜,当纳米ZnO薄膜的厚度为1nm时,器件的电流效率可达3.26cd/A,是没有纳米ZnO薄膜同类器件的1.24倍。适当厚度的纳米ZnO薄膜降低了发光层空穴的浓度,提高了电子和空穴的平衡,从而提高了器件的效率。     

ITO再生处理对有机电致发光器件特性的影响

分别采用Na OH和HCl溶液对废旧氧化铟锡(ITO)基板进行再生处理,用原子力显微镜(AFM)观测了处理后的ITO表面形貌,并基于再生处理过的ITO制备了有机电致发光器件(OLED),系统研究了器件的性能。结果表明,上述方法可以有效去除废旧ITO残留的铝电极并改变其表面的化学结构,提高了器件的特性,尤其以Na OH单次处理最为有效。以此制备的OLED器件电流效率达到12.08 cd/A,较之未回收利用的新ITO所制备的器件提高了14.7%;外量子效率达到5.23%,提高了11.7%。另外,经不同方法处理后,器件中生色团与生色团之间、生色团与助色团之间的空间位阻增大,器件发光光谱肩峰效应增强。     

Plasma treatment of ITO surfaces to improve luminescence characteristics of organic light-emitting devices with dopants

Indium-tin-oxide (ITO) surfaces were treated with O₂ and H₂ plasmas. The contact angle of water, X-ray photoelectron spectroscopy (XPS) spectra, and luminescence characteristics of organic light-emitting devices (OLEDs) fabricated on plasma-treated ITO surfaces using poly(N-vinylcarbazole) (PVK) films doped with 5,6,11,12-tetraphenylnaphthacene (rubrene) or Nile Red were investigated.Using O₂ plasma treatment, the contact angle was reduced from 35° to 13°. The luminance of OLEDs with rubrene was significantly improved. The luminous color of an OLED inserted poly (3,4-ethylenedioxythiophene)-polystyrene sulphonic acid (PEDOT-PSS) layer between Nile Red-doped PVK film and O₂-plasma-treated ITO surface turned white as the applied voltage increased.     

Uniformity analysis of dielectric barrier discharge (DBD) processed polyethylene terephthalate (PET) surface

A dielectric barrier discharge (DBD) plasma, operating in air at atmospheric pressure, has been used to induce changes in the surface properties of polyethylene terephthalate (PET) films. The effects that the key DBD operating parameters: discharge power, processing speed, processing duration, and electrode configurations, have on producing wettability changes in the PET surface region have been investigated. The approach taken involves the application of an Taguchi experimental design and robust analysis methodology. The various data sets obtained from these analyses have been used to studies the effect of the operating parameters on the surface uniformity and efficiency of the said treatment.In general, the results obtained indicate that DBD plasma processing is an effective method for the controlled surface modification of PET. Relatively short exposures to the atmospheric pressure discharge produces significant wettability changes at the polymer film surface, as indicted by pronounced reductions in the water contact angle measured. It was observed that the wettability of the resultant surface shows no significant differences in respect to orientation parallel (L-direction) or perpendicular (T-direction) to the electrode long axis. However, there was significant differences between the data obtained from these two orientations. Analysis of the role of each of the operating parameters concerned shows that they have a selective effectiveness with respect to resultant surface modification in terms of uniformity of modification and wettability. The number of treatment cycles and the electrode configuration used were found to have the most significant effects on the homogeneity of the resultant PET surface changes in L- and T-orientation, respectively. On the other hand, the applied power showed no significant role in this regard. The number of treatment cycles was found to be the dominant factor (at significance level of 0.05) in respect of water contact angle changes at the processed PET surface in both orientations. The driven metal electrodes (stainless steel or aluminium) were apparently superior to the driven dielectric electrode (ceramic or quartz) configurations. The grounded electrode in each case was a silicon rubber-covered aluminium plate (see later). The nature and scale of the surface changes that originate from the various processing conditions employed have been considered so as to determine the optimum treatment conditions in respect of processing outcomes, properties and any orientation dependence. Thus, it was revealed that higher processing speeds and longer processing durations are key for uniformity along the electrode axial orientation, while lower processing speeds and short exposure durations are key considerations, in the corresponding perpendicular orientation. In general, longer processing durations (low processing speeds and a high number of treatment cycles) and higher plasma powers induced greater changes in the surface wettability of the PET, as demonstrated by the observed water contact angles. This behaviour is taken to indicate that different combinations of DBD operating parameters and electrodes produce discharge conditions that can result in different plasma chemical processes in respect of uniformity, treatment efficiency and orientation dependence.     

Indium tin oxide surface treatments for improvement of organic light-emitting diode performance

We have systematically investigated the influence of UV ozone and acid (HCl) treatments (separate and combined) of the surface of indium tin oxide (ITO) on the ITO parameters and the performance of organic light-emitting diodes (OLEDs) fabricated on the treated substrates. The ITO substrates were characterized by Hall measurements, Seebeck coefficient measurements and surface-probe microscopy. After ITO characterization, two types of devices (ITO/NPB/rubrene/Alq₃/LiF/Al and ITO/TPD/rubrene/Alq₃/LiF/Al) were fabricated on the differently treated substrates. It was found that in both cases the optimal treatment was HCl followed by UV ozone, which resulted in the lowest turn-on voltage and the highest luminous efficiency. The maximum luminous efficiency in the ITO/NPB/rubrene/Alq₃/LiF/Al OLED with HCl followed by UV ozone treatment was 2.15 lm/W compared to 1.46 lm/W with UV ozone treatment only. PACS 81.65Cf; 85.60.Jb