A SIMPLE METHOD FOR THE INCORPORATION OF LOW MOLECULAR WEIGHT DYES IN ULTRATHIN FILMS

A simple method for the fabrication of ultrathin films containing low molecular weight dye material is introduced(post-adsorption technique). The chromophore used is 4-nitro-4'-decyloxy azobenzene quaternary ammonium salt (azo-10Q).In classical layer-by-layer (LBL) procedures, where the substrate is dipped alternately into the chromophore solution and thecomplementary polyelectrolyte, the chromophore tends to desorb from the film during subsequent immersion in thepolyanion solution, and there is little or no indication of multilayer growth. The extent of desorption depends somewhat onthe selection of polyelectrolyte, the ionic strength and the pH of solution. An alternative approach is to first prepareconventional LBL films from a pair of oppositely charged polyelectrolytes, and then to soak this film into the chromophoresolution, where adsorption by penetration into the LBL film may take place. In preliminary results, a linear dependence ofUV absorbance on layer number of LBL film thus prepared was found, demonstrating the apparent effectiveness of the post-adsorption technique for the preparation of azo-10Q-containing ultrathin films.

Preparation and Characterization of Polymeric PVDF/PDDA Ultrathin Films

A new method for the production of nanoscaled polymeric multilayer films of ferroelectric PVDF is presented.The ultrathin multilayer films of poly diallyldimethylammonium chloride (PDDA) and polyvinylidene fluoride (PVDF) have been prepared on fuzed quartz substrate by the layer-by-layer self-assembly (LbL-SA) method.The PDDA/PVDF multilayer films with the thickness of 30 nm to 150 nm have been characterized by quartz crystal microbalance (QCM) and infrared spectra (IR) The QCM reveals that the alternant ultrathin films of PVDF and PDDA are well order assembled.The electric property of the ultrathin PDDA/PVDF multilayer films at room temperature is investigated.Experimental results show that property of ultrathin films differed from that of the thick films.

Role of the Confined Geometry on the Crystallization of Poly(ethylene terephthlate) Ultrathin Films

The reflection-absorption infrared (RAIR) was employed to study the crystallization kinetic of poly (ethylene terephthalate) (PET) ultrathin films. During isothermal crystallization the thinner PET film shows a slower kinetic compared with the thicker film. Moreover, the final crystallinity of films with various thickness was found decrease with thickness. The result of fitting our data to Avrami equation showed that the Avrami exponents decrease with film thickness.

Manipulating magnetic anisotropies of Co/MgO(001) ultrathin films via oblique deposition

We present a systematic investigation of magnetic anisotropy induced by oblique deposition of Co thin films on MgO（001） substrates by molecular beam epitaxy at different deposition angles,i.e.,0？,30？,45？,60？,and 75？with respect to the surface normal.Low energy electron diffraction（LEED）,surface magneto–optical Kerr effect（SMOKE）,and anisotropic magnetoresistance（AMR） setups were employed to investigate the magnetic properties of cobalt films.The values of in-plane uniaxial magnetic anisotropy（UMA） constant Ku and four-fold magnetocrystalline anisotropy constant K1 were derived from magnetic torque curves on the base of AMR results.It was found that the value of Ku increases with increasing deposition angle with respect to the surface normal,while the value of K_1 remains almost constant for all the samples.Furthermore,by using MOKE results,the Ku values of the films deposited obliquely were also derived from the magnetization curves along hard axis.The results of AMR method were then compared with that of hard axis fitting method（coherent rotation） and found that both methods have almost identical values of UMA constant for each sample.

Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films

In this work,poly(3-hexylthiophene)(P3HT)ultrathin films(P3HT-T)were prepared by spin-coating a dilute P3HT solution(in a toluene:o-dichlorobenzene(Tol:ODCB)blend with a volume ratio of 80:20)with ultrasonication and the addition of the nucleating agent bicycle[2.2.1]heptane-2,3-dicarboxylic acid disodium salt(HPN-68L)on glass,Si wafers and indium tin oxide(ITO)substrates.The electrical and mechanical properties of the P3HT-T ultrathin films were investigated,and it was found that the conductivity and crack onset strain(COS)were simultaneously improved in comparison with those of the corresponding pristine P3HT film(P3HT-0,without ultrasonication and nucleating agent)on the same substrate,regardless of what substrate was used.Moreover,the conductivity of P3HT-T ultrathin films on different substrates was similar(varying from 3.7 S·cm^(-1)to 4.4 S·cm^(-1)),yet the COS increased from 97%to 138%by varying the substrate from a Si wafer to ITO.Combining grazing-incidence wide-angle X-ray diffraction(GIXRD),UV-visible(UV-Vis)spectroscopy and atomic force microscopy(AFM),we found that the solid order and crystallinity of the P3HT-T ultrathin film on the Si wafer are highest,followed by those on glass,and much lower on ITO.Finally,the surface energy and roughness of three substrates were investigated,and it was found that the polar component of the surface energyγp plays a critical role in determining the crystalline microstructures of P3HT ultrathin films on different substrates.Our work indicates that the P3HT ultrathin film can obviously improve the stretchability and simultaneously retain similar electrical performance when a suitable substrate is chosen.These findings offer a new direction for research on stretchable CP ultrathin films to facilitate future practical applications.

Clay-protein ultrathin films:Design and bio-catalytic performance study

In recent years, immense interest has been paid to the biomolecular architecture with the aim of protein assembly in two di- mensions on solid substrates, and the constructions of clay-protein ultrathin films （CPUFs） are particularly concerned. This paper gives an overview of the recent research concerning the protein molecules （lysozyme, papain, protamine, bovine serum albumin） immobilized on clay mineral （Na-saponite） platelets and assembled in monolayered or multilayered hybrid ultrafilms or nanofilms. Two techniques including alternate layer-by-layer （LbL） assembly and the Langmuir-Blodgett （LB） are de- scribed in detail. A variety of means, including UV-vis absorption, attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectroscopy, XRD, AFM and surface chemistry techniques, have been described for characterization of the films in terms of quantification of protein and clay. The result reveals that electrostatic interaction is a prominent but not the only driving force in CPUF construction. In the case of LB technique, we managed to manipulate the elementary clay mineral platelets （1.3 nm in thickness） and assemble proteins into CPUFs with the aid of surfactants, and the formation of CPUFs was monitored via surface pressure vs. time （a--t） kinetics curves and surface pressure vs. area （a--A） isotherms. The factors that in- fluence protein adsorption on the clay layer, such as surfactants, the concentration of clay, equilibrium time, categories of pro- tein, and injection methods, were investigated. The parameters such as protein amount （nS）, packing density （O）, and average surface area per molecule （.（2） of deposited CPUFs were measured via method of surface chemistry and spectroscopy. By comparing the results of surface chemistry with those of adsorption experiments, we demonstrate that the surface chemistry method is a useful tool in investigating CPUFs. We also found that the water soluble protein molecules could form protein-clay hybrid monolayer over the dilute clay dispersions without addition of surfactants, and CPUFs containing elementary clay sheets and protein with great homogeneity were easily prepared by controlling certain surface pressure. To investigate the bio-catalytic performance of the immobilized lysozyme in CPUFs, we deposited CPUFs onto a cover glass, and installed the cover glass in a flow cell-grown reactor for Comamonas testosteroni （WDL7-GFP） incubation. The results show that the pro- liferation of WDL7-GFP is greatly suppressed by lysozyme, which demonstrates that lysozyme still retains its bioactivity after it is immobilized in the CPUFs.

Modeling the defect distribution and degradation of CdTe ultrathin films

The defect distribution across an ultrathin film CdTe layer of a CdS/CdTe solar cell is modelled by solving the balance equation in steady state. The degradation of the device parameters due to the induced defects during ion implantation is considered where the degradation rate is accelerated if the defect distribution is considerable.The defect concentration is maximum at the surface of the CdTe layer where implantation is applied and it is minimum at the junction with the CdS layer. It shows that ultrathin devices degrade faster if the defect concentration is high at the junction rather than the back region（CdTe/Metal）. Since the front and back contacts of the device are close in ultrathin films and the electric field is strong to drive the defects into the junction, the p-doping process might be precisely controlled during ion implantation. The modeling results presented here are in agreement with the few available experimental reports in literature about the degradation and defect configuration of the ultrathin CdTe films.

Crystallization behaviors of ultrathin Al-doped HfO2 amorphous films grown by atomic layer deposition

In this work, ultrathin pure HfO_2 and Al-doped HfO_2films（about 4-nm thick） are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.

Magnetic anisotropy and magnetization reversal of ultrathin iron films with in-plane magnetization on Si（111） substrates

The magnetic anisotropy and magnetization reversal of single crystal Fe films with thickness of 45 monolayer （ML） grown on Si（111） have been investigated by ferromagnetic resonance （FMR） and vibrating sample magnetometer （VSM）. Owing to the significant modification of the energy surface in remanent state by slight misorientation from （111） plane and a uniaxial magnetic anisotropy, the azimuthal angular dependence of in-plane resonance field shows a six-fold symmetry with a weak uniaxial contribution, while the remanence of hysteresis loops displays a two-fold one. The competition between the first and second magnetoerystalline anisotropies may result in the switching of in-plane easy axis of the system. Combining the FMR and VSM measurements, the magnetization reversal mechanism has also been determined.

Formations and morphological stabilities of ultrathin CoSi_2 films

In this paper we investigate the formations and morphological stabilities of Co-silicide fihns using 1-8-nm thick Co layers sputter-deposited on silicon （100） substrates. These ultrathin Co-silicide films are formed via solid-state reaction of the deposited Co films with Si substrate at annealing temperatures from 450 ℃ to 850 ℃. For a Co layer with a thickness no larger than i nm, epitaxially aligned CoSi2 films readily grow on silicon （100） substrate and exhibit good morphological stabilities up to 600 ℃. For a Co layer thicker than 1 nm, polycrystalline CoSi and CoSi2 films are observed. The critical thickness below which epitaxially aligned CoSi2 film prevails is smaller than the reported critical thickness of the Ni layer for epitaxial alignment of NiSi2 on silicon （100） substrate. The larger lattice mismatch between the CoSi2 film and the silicon substrate is the root cause for the smaller critical thickness of the Co layer.

Surface plasmon-polaritons on ultrathin metal films

We discuss the surface plasmon-polaritons used for ultrathin metal films with the aid of linear response theory and make comparisons with the known result given by Economou E N. In this paper we consider transverse electromagnetic fields and assume that the electromagnetic field in the linear response formula is the induced field due to the current of the electrons. It satisfies the Maxwell equation and thus we replace the current （charge） term in the Maxwell equation with the linear response expectation value. Finally, taking the external field to be zero, we obtain the dispersion relation of the surface plasmons from the eigenvalue equation. In addition, the charge-density and current-density in the z direction on the surface of ultrathin metal films are also calculated. The results may be helpful to the fundamental understanding of the complex phenomenon of surface plasmon-polaritons.

Crystallization and Morphology of Autophobic Dewetted Poly（ε-caprolactone）-b-poly（L-lactide） Diblock Copolymer Ultrathin Films

We have investigated the crystallization and morphological behaviors of poly（ε-caprolactone）-b-poly（L-lactide） （PCL-b-PLLA） in its autophobic dewetted ultrathin films （-11 nm） using atomic force microscopy （AFM） and transmission electron microscopy （TEM）. The autophobic dewetting process creates a well defined film geometry containing an extremely thin wetting layer （-4.5 nm） with densely distributed micrometer droplets atop, which re- stricts the primary nucleation process to occurring only in the droplets. In addition to the normally encountered flat-on lamellae, the growth of edge-on lamellae in such a thin wetting layer has been observed on both of two crys- tallization paths. In thermal crystallization, flat-on lamellae are favored at small supercoolings while edge-on la- mellae appear at very large supercoolings both in the droplets and the wetting layer. For cold crystallization, the edge-on lamellae can form easily in the droplets and grow into the wetting layer even at very small supercoolings. These observations are explained on the basis that the nucleation and lamellar orientation are strongly affected by the film geometry, the crystallization paths, and the applied supercoolings.

Thickness-driven spin reorientation transition in ultrathin films

We review recent studies by different experimental means of ultrathin films,exhibiting thickness-driven spin reorientation transitions(SRTs).The stage is set by determining,via phenomenological thermodynamic description,of the relevant phase diagrams for the possible types of SRT with and without applied magnetic field.Suitable representation may be chosen such that best use is made of the linear character(under thickness variation) of the system's path in anisotropy space.The latter involves higher-order bulk and surface anisotropies in a substantial way.We examine sensitive experimental techniques for the detection and quantification of SRTs,such as hysteresis measurements with magneto-optical Kerr effect(MOKE),micromagnetic studies utilizing scanning electron microscopy with polarization analysis(SEMPA),photoemission electron microscopy(PEEM) and spin-polarized low-energy electron microscopy(SPLEEM) as well as ac magnetic susceptibility measurements via MOKE.Key issues are conclusively discussed including the identification of reliable experimental fingerprints about whether a given SRT proceeds via a phase of coexistence or via a cone(canted) phase.We demonstrate how the application of the general theoretical ideas to carefully designed measurements leads to the determination of the most important material parameters in any ultrathin-film SRT,namely,the surface(interface) magnetic anisotropy constants.The review concludes by our personal outline for future promising work on SRTs.

Size Effect of Electromagnetic Constitutive Characteristics of Ultrathin Al Films

The ultrathin aluminum films with thickness in the range of 2～60 nm have been deposited by dc magnetron sputtering apparatus. Reflectance and transmittance of the obtained samples were measured with a WFZ-900-D4 UV/VIS spectrophotometer. The optical constant (n, k) and permittivity (ε', ε') were determined by applying Newton-Simpson recurrent substitution method. The results indicate that the electromagnetic constitutive characteristic of ultrathin aluminum films is a function of thickness and has obvious size effect.

Fabrication of Layer-by-layer Films of Polyhedral Oligomeric Silsesquioxanes

Layer-by-layer (LBL) self-assembly method was used to fabricate siliceous ultrathin films by using polyhedral oligomeric silsesquioxanes as building blocks. Ammonium salt of octasilsesquioxane acid (OSi8) and poly(diallyldimethylammonium chloride) (PDDA) were alternately assembled onto CaF2 slide to form nanocomposite multilayers. Linear build-up of the LBL films was confirmed by UV-Vis spectroscopy. IR spectrum suggests existence of OSi8 and PDDA in the LBL films. Atomic force microscopic surface topography of the LBL films indicates the OSi8 covers the entire surface of the topmost layer and shows a granular morphology.

Investigation on interface of NiFeCr/NiFe/Ta films with high magnetic field sensitivity

NiFeCr/NiFe/Ta films with excellent performance were prepared by magnetron sputtering system.The anisotropic magetoresistance (AMR) value (ΔR/R) and magnetic filed sensitivity (Sv,Sv=[d(ΔR/R)/dH]max.) for the 12 nm NiFe film deposited on NiFeCr buffer layer were 3.66% and 1.42×10-4%·T-1,respectively.The higher Sv of the film is close to that of a spin valve (SV).The microstructure analysis shows that the NiFeCr buffer layer has adopted the same structure with the same interplanar distance as the NiFe layer,inducing a strong NiFe (111) texture,and that the NiFeCr/NiFe interface is quite smooth,leading to a high degree of specular reflection of conduction electrons.Both increase the ΔR and reduce the R in the film,which lead to the high ΔR/R.Clean substrate surfaces are critical for preparation of high performance NiFeCr/NiFe/Ta films,and sputter cleaning or pre-deposition of 5 nm amorphous Al2O3 layer in the deposition chamber can provide the re-quired clean substrate surfaces for the growth of the buffer layer.

Dispersion compensation for an ultrathin metal film using LCD-CCD system

A dispersion compensation method is introduced to correct the distorted image passing through an ultrathin metal film.An LCD-CCD system is modeled by the back propagation network and used to evaluate the transmittance of the ultrathin metal film.Training samples for the network come from 729 images captured by shooting test patches,in which the RGB values are uniformity distributed between 0 and 255.The RGB value of the original image that will be distorted by the dispersion is first transformed by mapping from the LCD to the CCD,multiplied by the inverse matrix of the transmittance matrix,and finally transformed by mapping from the CCD to the LCD,then the corrected image is obtained.In order to verify the effectiveness of the proposed method,ultrathin aluminum films with different thicknesses are evaporated on glass substrates and laid between the CCD and LCD.Experimental results show that the proposed method compensates for the dispersion successfully.

Highly crystalline,highly stable n-type ultrathin crystalline films enabled by solution blending strategy toward organic single-crystal electronics

The development of n-type semiconductor is still far behind that of p-type semiconductor on account of the challenges in enhancing carrier mobility and environmental stability.Herein,by blending with the polymers,n-type ultrathin crystalline thin film was successfully prepared by the method of meniscus-guided coating.Remarkably,the n-type crystalline films exhibit ultrathin thickness as low as 5 nm and excellent mobility of 1.58 cm^(2) V^(-1) s^(-1),which is outstanding in currently reported organic n-type transistors.Moreover,the PS layer provides a high-quality interface with ultralow defect which has strong resistance to external interference with excellent long-term stability,paving the way for the application of n-type transistors in logic circuits.

In-situ temperature-controllable grazing incidence X-ray scattering of semiconducting polymer thin films under stretching

The advancement in grazing incidence X-ray scattering(GIWAXS)techniques at synchrotron radiation facilities has significantly deepened our understanding of semiconducting polymers.However,investigation of ultrathin polymer films under tensile conditions poses challenge,primarily due to limitations associated with the lack of suitable sample preparation methods and new stretching devices.This study addresses these limitations by designing and developing an in-situ temperature-controllable stretching sample stage,which enables real-time structural measurements of ultrathin polymer films at Beijing Synchrotron Radiation Facility.In particular,we report,for the first time,in-situ GIWAXS results of representative semiconducting polymer thin films under variable-temperature stretching.This research has overcome the limitations imposed by sample constraints,thus facilitating the achievement of valuable insights into the behavior of ultrathin polymer films under tensile conditions.Distinct changes in the molecular ordering and packing within the polymer thin films as a result of increasing applied strain and temperature have been uncovered.This study promotes future developments in the field,thus enabling the design and optimization of intrinsically stretchable electronic devices and other technologically relevant applications.