Laser prepared organic heterostructures based on star-shaped arylenevinylene compounds

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV–Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.     

The effect of Ag intermediate layer on crystalline, optical and electrical properties of nano-structured thin film

ITO thin films and ITO/Ag/ITO multilayered films were prepared on glass substrate by reactive thermal evaporation technique without intentionally heating the substrate. After deposition the films were annealed in air at three different temperatures (300°C, 420°C and 540°C). The thickness of each layer in the ITO/Ag/ITO films was kept constant at 50 nm/10 nm/40 nm. The opto-electrical and structural properties of ITO/Ag/ITO multilayered films were compared with conventional ITO single-layer films. Although both films had identical thickness, 100 nm, the ITO/Ag/ITO films showed a lower resistivity. XRD spectra showed that Ag intermediate layer had a small effect on crystalline properties of ITO/Ag/ITO films.     

Dependence of intermediated noble metals on the optical and electrical properties of ITO/metal/ITO multilayers

Sn doped In₂O₃ (ITO) single layer and a sandwich structure of ITO/metal/ITO (IMI) multilayer films were deposited on a polycarbonate substrate using radio-frequency and direct-current magnetron sputtering process without substrate heating. The intermediated metal films in the IMI structure were Au and Cu films and the thickness of each layer in the IMI films was kept constant at 50 nm/10 nm/40 nm. In this study, the ITO/Au/ITO films show the lowest resistivity of 5.6 × 10⁻⁵ Ω cm.However the films show the lower optical transmission of 71% at 550 nm than that (81%) of as deposited ITO films. The ITO/Cu/ITO films show an optical transmittance of 54% and electrical resistivity of 1.5 × 10⁻⁴ Ω cm. Only the ITO/Au/ITO films showed the diffraction peaks in the XRD pattern. The figure of merit indicated that the ITO/Au/ITO films performed better in a transparent conducting electrode than in ITO single layer films and ITO/Cu/ITO films.     

Effect of tin-doped indium oxide film as capping layer on the agglomeration of copper film and the appearance of copper silicide

In this work, the effect of tin-doped indium oxide (ITO) film as capping layer on the agglomeration of copper film and the appearance of copper silicide was studied. Both samples of Cu 100 nm/ITO 10 nm/Si and ITO 20 nm/Cu 100 nm/ITO 10 nm/Si were prepared by sputtering deposition. After annealing in a rapid thermal annealing (RTA) furnace at various temperatures for 5 min in vacuum, the samples were characterized by four probe measurement for sheet resistance, X-ray diffraction (XRD) analysis for phase identification, scanning electron microscopy (SEM) for surface morphology and transmission electron microscopy (TEM) for microstructure.The results show that the sample with ITO capping layer is a good diffusion barrier between copper and silicon at least up to 750 °C, which is 100 °C higher than that of the sample without ITO capping layer. The failure temperature of the sample with ITO capping layer is about 800 °C, which is 100 °C higher than that of the sample without ITO capping layer. The ITO capping layer on Cu/ITO/Si can obstacle the agglomeration of copper film and the appearance of Cu₃Si phase.     

In_2O_3:Sn中间层改善B掺杂ZnO薄膜的性能及其应用研究

金属有机化学气相沉积(MOCVD)法生长的掺硼氧化锌(BZO)薄膜,具有天然的"类金字塔"绒面结构,作为硅基薄膜太阳电池的前电极具有良好的陷光效果.但直接获得的BZO薄膜表面形貌过于尖锐,影响后续硅基薄膜材料生长质量及太阳电池的光电转换效率.本文设计了以一层超薄In2O3:Sn(ITO)薄膜(～4 nm厚度)作为中间层的多层膜,并通过对顶层BZO薄膜的厚度调制,改善BZO薄膜的表面特性,薄膜结构为:glass/底层BZO/ITO/顶层BZO.合适厚度的顶层BZO薄膜有助于获得类似"菜花状"形貌特征,尖锐的表面趋于"柔和",而较厚的顶层BZO薄膜仍然保持"类金字塔状"结构."柔和"的BZO薄膜表面结构有助于提高后续生长薄膜电池的结晶质量.将获得的新型"三明治"结构多层膜应用于p-i-n型氢化微晶硅(μc-Si:H)薄膜太阳电池,相比传统的BZO薄膜,电池的量子效率QE在500—800 nm波长范围提高了～10%,并且电池的Jsc和Voc均有所提高.     

Preserving long-term emission stability of carbon nanotube field emitter using aluminum layer

Carbon nanotube (CNT) field emitter was fabricated, and then its emission stability was evaluated with three different anode structures; indium tin oxide (ITO)/glass, ZnS:Cu,Al(green phosphor)/ITO/glass, and Al/ZnS:Cu,Al/ITO/glass. It was found that the electron emission from CNTs to the phosphor layer degrades much faster than the emission to ITO layer does. The current decay time from 100 μA/cm² to 50 μA/cm² for ITO/glass and ZnS:Cu,Al/ITO/glass were 250 h and 20 h, respectively. Such rapid decay in emission current with the phosphor-coated anode was found to be attributed to the formation of Zn particles on CNTs during the field emission. However, the deposition of aluminum layer on the phosphor, in other words, using the anode structure of Al/ZnS:Cu,Al/ITO/glass recovered the stability that is comparable to that with an ITO/glass. The aluminum layer was found to efficiently prevent phosphor elements from being degassed, preserving the long-term emission stability of carbon nanotubes.     

MAPLE applications in studying organic thin films

Thin films of various organic materials have been created by the matrix assisted pulsed laser evaporation (MAPLE) technique. The principles, advantages, and difficulties of deposition are discussed. The focus is on target preparation, solvents, studied materials, and growth rate. Measured solvent transmissions and the results obtained are reported, and an overview of MAPLE applications is presented.     

Design challenges for matrix assisted pulsed laser evaporation and infrared resonant laser evaporation equipment

Since the development of the Matrix Assisted Pulsed Laser Evaporation (MAPLE) process by the Naval Research Laboratory (NRL) in the late 1990s, MAPLE has become an active area of research for the deposition of a variety of polymer, biological, and organic thin films. As is often the case with advancements in thin-film deposition techniques new technology sometimes evolves by making minor or major adjustments to existing deposition process equipment and techniques. This is usually the quickest and least expensive way to try out new ideas and to “push the envelope” in order to obtain new and unique scientific results as quickly as possible. This process of “tweaking” current equipment usually works to some degree, but once the new process is further refined overall designs for a new deposition tool based on the critical attributes of the new process typically help capitalize more fully on the all the salient features of the new and improved process. This certainly has been true for the MAPLE process.     

Electrical and optical properties of ITO and ITO/Cr-doped ITO films

In this paper we report on the effects of the insertion of Cr atoms on the electrical and optical properties of indium tin oxide (ITO) films to be used as electrodes in spin-polarized light-emitting devices. ITO films and ITO(80 nm)/Cr-doped ITO(20 nm) bilayers and Cr-doped ITO films with a thickness of 20 nm were grown by pulsed ArF excimer laser deposition. The optical, structural, morphological and electrical properties of ITO films and ITO/Cr-doped structures were characterized by UV–Visible transmission and reflection spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM) and Hall-effect analysis. For the different investigations, the samples were deposited on different substrates like silica and carbon coated Cu grids. ITO films with a thickness of 100 nm, a resistivity as low as ～4×10^?4 Ω?cm, an energy gap of ～4.3 eV and an atomic scale roughness were deposited at room temperature without any post-deposition process. The insertion of Cr into the ITO matrix in the upper 20 nm of the ITO matrix induced variations in the physical properties of the structure like an increase of average roughness (～0.4–0.5 nm) and resistivity (up to ～8×10^?4 Ω?cm). These variations were correlated to the microstructure of the Cr-doped ITO films with particular attention to the upper 20 nm.     

MAPLE activities and applications in gas sensors

During the last decade, many groups have grown thin films of various organic materials by the cryogenic Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique with a wide range of applications. This contribution is focused on the summary of our results with deposition and characterization of thin films of fibrinogen, pullulan derivates, azo-polyurethane, cryoglobulin, polyvinyl alcohol, and bovine serum albumin dissolved in physiological serum, dimethyl sulfoxide, sanguine plasma, phosphate buffer solution, H₂O, ethylene glycol, and tert-butanol. MAPLE films were characterized using FTIR, AFM, Raman scattering, and SEM. For deposition, a special hardware was developed including a unique liquid nitrogen cooled target holder. Overview of MAPLE thin film applications is given. We studied SnAcAc, InAcAc, SnO₂, porphyrins, and polypyrrole MAPLE fabricated films as small resistive gas sensors. Sensors were tested with ozone, nitrogen dioxide, hydrogen, and water vapor gases. In the last years, our focus was on the study of fibrinogen-based scaffolds for application in tissue engineering, wound healing, and also as a part of layers for medical devices.     

Deposition of antibacterial of poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride)) 20:80/gentamicin sulfate composite coatings by MAPLE

We report on thin film deposition of poly(1,3-bis-(p-carboxyphenoxy propane)-co-sebacic anhydride)) 20:80 thin films containing several gentamicin concentrations by matrix assisted pulsed laser evaporation (MAPLE). A pulsed KrF* excimer laser was used to deposit the polymer-drug composite thin films. Release of gentamicin from these MAPLE-deposited polymer conjugate structures was assessed. Fourier transform infrared spectroscopy was used to demonstrate that the functional groups of the MAPLE-transferred materials were not changed by the deposition process nor were new functional groups formed. Scanning electron microscopy confirmed that MAPLE may be used to fabricate thin films of good morphological quality. The activity of gentamicin-doped films against Escherichia coli and Staphylococcus aureus bacteria was demonstrated using disk diffusion and antibacterial drop test. Our studies indicate that deposition of polymer-drug composite thin films prepared by MAPLE is a suitable technique for performing controlled drug delivery. Antimicrobial thin film coatings have several medical applications, including use for indwelling catheters and implanted medical devices.     

Generation of surface features in films deposited by matrix-assisted pulsed laser evaporation: the effects of the stress confinement and droplet landing velocity

Coarse-grained molecular dynamics simulations are applied to investigate the origins of the surface features observed in films deposited by the Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. The formation of transient balloon-like structures with a polymer-rich surface layer enclosing matrix vapor, observed in earlier simulations of slow heating of polymer-matrix droplets, has been explored in this work at higher rates of thermal energy deposition. Tensile stresses generated in the regime of partial stress confinement are found to induce an internal boiling in the overheated droplets and associated generation of “molecular balloons” at thermal energy densities at which no homogeneous boiling takes place without the assistance of tensile stresses. Simulations of the dynamic processes occurring upon the collision of a polymer-matrix droplet with a substrate provide the molecular-level pictures of the droplet impact phenomenon and reveal the connections between the droplet landing velocity and the shapes of the polymer features observed in scanning electron microscopy images of films deposited in MAPLE experiments. The distinct types of surface features observed in MAPLE experiments, namely, wrinkled “deflated balloons,” localized arrangements of interconnected polymer filaments, and elongated “nanofibers,” are shown to emerge from different scenarios of droplet landing and/or disintegration observed in the simulations.     

Creation and Investigation of Organic Light-Emitting Structures Containing Arrays of Colloidal Quantum Dots

We have created organic electroluminescent structures—ITO/TPD/Alq3/Al and ITO/PEDOT:PSS/TPD/Alq3/Al—which are organic light-emitting diodes (OLEDs). Experiments on the incorporation of CdSe/ZnS colloidal quantum dots into the active layer of the structure have been performed. The parameters of the created structures have been determined using optical-spectroscopy methods. The appropriateness of using the method of high-speed vacuum thermal deposition as a main method for the deposition of structural layers has been demonstrated, and the possibility of accelerated formation of layers of the material without disturbing its chemical structure has been shown. By measuring the photoluminescence spectra at different points in samples, we have determined the quality of the obtained structures and plotted maps of the radiation power distribution of the material and of its thickness. Recommendations for the creation of upper contacts and other regions of light-emitting structures have been formulated. We have created organic structures with ITO/PEDOT:PSS/TPD/TPD + CQD’s CdSe/Alq3/Al colloidal quantum dots, in which electroluminescence of CdSe/ZnS quantum dots has been obtained for a wide range of applied voltages. It has been shown that the introduction of colloidal quantum dots into the structure leads to a significant modification of its electroluminescence spectrum.     

MAPLE deposition of methoxy Ge triphenylcorrole thin films

Methoxy Ge Triphenylcorrole [Ge(TPC)OCH₃] has been recently synthesized and deposited as thin film by the Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. In the last few years, corroles have been the object of an increasing number of studies and MAPLE technique seems to be a very promising deposition method for organic and polymeric films, producing good results for applications in chemical gas sensing layers production. In this work Ge(TPC)OCH₃ thin films were deposited by both spin coating and MAPLE techniques for comparison. The morphology of the films was investigated by Atomic Force Microscopy (AFM), while their optical properties were analyzed by photoluminescence (PL) and UV-vis absorption measurements and were compared with the ones of the starting solution. The film absorption spectrum presented the same peaks with the same relative intensities of that recorded in solution. The luminescence spectra were acquired periodically to evaluate the aging effects and no detectable variations were recorded over a period of 1 month.     

MAPLE-deposited polymer films for improved organic device performance

Matrix-assisted pulsed-laser evaporation (MAPLE) provides a mechanism for layer-by-layer growth to control the polymer–dielectric interface in organic metal–insulator–semiconductor (MIS) diodes and field-effect transistors (FETs). MAPLE-deposited copolymers of polyfluorene (PF) and polythiophene maintain their structural and optical properties, as determined by Raman spectroscopy, absorption, and photoluminescence. These films are further utilized in MIS and FET structures with SiO₂ and other polymer dielectrics. Since common polymer dielectrics prevent spin coating of solution processable polymers due to solubility effects, MAPLE is one of the only deposition techniques for investigating all polymer semiconductor-insulator interfaces. In this paper we present optical and electrical studies of MAPLE-deposited PF and polythiophene films in FETs and MIS structures. The FET carrier mobilities of these devices compare well with spin-coated devices. Capacitance–voltage and conductance–voltage from MIS structures with MAPLE-deposited PF copolymer films yield interface trap densities in the low 10¹² eV⁻¹ cm⁻² range.     

Graphene as interface modifier in ITO and ITO-Cr electrodes

We explore graphene as interface modifier for electrodes in optoelectronic organic devices by measuring the electrical properties of ITO/graphene and ITO/Cr/graphene. For this purpose, exfoliated graphene (EG) was electrochemically synthesized and deposited by spray-pyrolysis. The built-in voltage (Vbi) values were 450 mV for the ITO/CuPc/Al reference, 750 mV for ITO/Cr/graphene/CuPc/Al and 1000 mV for ITO/graphene/CuPc/Al device structures. From these results, we estimate the work functions as 3.20 eV, 3.45 eV and 4.75 eV for ITO/EG, ITO/Cr/EG and ITO. To understand how the work function changes, we carried out first-principles calculations based on density-functional theory (DFT) where Cr work function (~4.2 eV) is not modified by the deposition of pristine graphene; however there is a substantial increase (from 4.2 eV to 5.2 eV), upon deposition of graphene oxide (GO), resulting from a complete transfer of O atoms from the GO sheet to the Cr surface forming a thin layer of chromium oxide.     

在Pd/Cu(100)表面上外延的超薄Co膜的结构和磁性

利用脉冲激光溅射(PLD)和分子束外延(MBE)方法制备了超薄膜系统 Co/Pd/Cu(100).脉冲激 光溅射生长的单原子Pd层呈现了很好的二维生长模式.在这个Pd表面上，分子束外延生长的C o层直至12个原子层都表现了层-层生长模式.利用俄歇电子谱(AES)和低能电子衍射(LEED)研 究了该系统的表面结构.利用低温磁光克效应(MOKE)研究了系统的磁学性质.结构研究表明， Co层由于面内晶格失配应力而具有一个四方正交结构；与对比样品Co/Cu(100)的比较研究说 明Pd层的存在强烈地改善了Co膜的起始生长模式和结构.磁光克效应测量表明，Pd层的存在 改变了Co层的磁学性质. 关键词： 薄膜的磁性质 组织与形貌 界面磁性     

The Matrix-Assisted Pulsed Laser Evaporation (MAPLE) process: origins and future directions

This review discusses the origins and evolution of the MAPLE technique as it started as an alternative to spray coating of thin films for chemical vapor sensors. It describes its numerous applications for the deposition of thin films of polymeric, organic and biomaterials for various applications. This is followed by an overview of several new variations of the MAPLE technique. This review concludes with an outlook on the future of this highly versatile and successful vapor deposition process.     

Solvent-related effects in MAPLE mechanism

To study the role of the solvent and of the laser fluence in the matrix-assisted pulsed laser evaporation (MAPLE) process, we used a soft polymer (polydimethylsiloxane—PDMS) as “sensing surface” and toluene as solvent. Thin films of the PDMS polymer were placed in the position of the growing film, while a frozen toluene target was irradiated with an ArF laser at the conventional fluences used in MAPLE depositions (60–250 mJ/cm²). Apart the absence of solute, the MAPLE typical experimental conditions for the deposition of thin organic layers were tested. The effects on the PDMS films of the toluene target ablation, at different fluences, were studied using atomic force microscopy and contact angles measurements. The results were compared with the effects produced on similar PDMS films by four different treatments (exposure to a drop of the solvent, to saturated toluene vapors and to plasma sources of two different powers). From this comparative study, it appears that depending on the MAPLE experimental conditions: (1) the MAPLE process may be “semidry” rather than purely dry (namely the solvent is likely to be present in the deposition environment near the growing film), (2) the solvent, if sufficiently volatile, is in form of vapor molecules (neutral, ionized and probably dissociated) rather than in liquid phase near the substrate and (3) at relatively high laser fluences (>150 mJ/cm²), the formation of an intense plasma plume results which can damage/affect a soft substrate as well as a growing polymer film.     

Transparent conductive ITO/Ag/ITO multilayer electrodes deposited by sputtering at room temperature

ITO/Ag/ITO multilayers have been prepared onto conventional soda lime glass substrates by sputtering at room temperature. The optical and electrical characteristics of single layer and multilayer structures have been investigated as a function of the Ag and ITO film thicknesses. Transmittance and sheet resistance values are found mainly dependent on the Ag film thickness; whereas the wavelength range at which the maximum transmittance is achieved can be changed by adjusting the ITO films thickness. ITO/Ag/ITO electrodes with sheet resistance below 6 Ω/sq have been obtained for Ag film thickness above 10 nm and ITO layers thickness in the 30-50 nm range. These multilayers also show high transmittance in the visible spectral region, above 90% by discounting the glass substrate, with a maximum that is located at higher wavelengths for thicker ITO.