Synthesis and microstructure of metal oxide thin films containing metal nanoparticles by liquid phase deposition (LPD) method

Au nanoparticles dispersed SiO₂-TiO₂ composite films have been prepared by a novel wet process, Liquid Phase Deposition (LPD) method. The composite films were characterized by XRD, XPS, TEM, ICP, SEM and UV-VIS absorption spectroscopy. The results showed that the SiO₂-TiO₂ composite films containing Au^III and Au^I ionic species were co-deposited from a mixed solution of ammonium silicofluoride, ammonium hexafluorotitanate, boric acid and tetrachloroauric acid. The heat treatment induced the reduction of Au ions and formation of Au nanoparticles in the film. TEM observation revealed that the Au nanoparticles with 5-10 nm in diameter were found to be dispersed uniformly in the SiO₂-TiO₂ matrix. The optical absorption band due to the surface plasmon resonance of dispersed Au particles were observed at the wavelength of 550 nm and shifted toward longer wavelength with increasing heat treatment temperature. Received 28 November 2000     

Influence of argon ion bombardment on the formation of intermetallic compounds in the nickel-aluminum system

The formation of Ni _x Al _y intermetallic compounds in two-layer (Ni/Al) structures (nickel films deposited on aluminum substrates in vacuum) under bombardment by Ar⁺ ions has been studied experimentally. The method based on Rutherford backscattering of He⁺ ions is used to demonstrate that argon ion bombardment causes the formation of intermetallic compounds in the near-surface layer. The thickness of the intermetallic layer formed in the near-surface region substantially exceeds the projective ion path. The composition and thickness of the intermetallic layer depend mainly on the implantation dose and the substrate temperature, rather than on the ion current density. In the intermetallic layer, the content of nickel increases with increasing temperature. It has been established that, in the absence of bombardment, intermetallic phases are not observed at temperatures lower than T = 400°C and that, in the presence of bombardment, the Ni₃Al intermetallic layer arises at a temperature of 320°C.     

聚氨酯/硫化银纳米复合材料的合成及荧光传感性能

通过生物矿化合成了聚氨酯/Ag2S纳米复合薄膜．通过傅里叶变换红外光谱研究、扫描量热法(DSC)、扫描电镜等方法研究了硫化银纳米粒子对复合薄膜物理性质的影响．用DSC 测定了复合材料的热 稳定性．通过对纳米复合材料荧光性能的研究发现薄膜对Ni(II)的存在非常敏感,少量Ni(II)离子的存在使得荧光光谱强度迅速增加．可以预测此复合薄膜可被开发成水溶液中Ni(II)的传感器．     

On the nature of ion bombardment-induced phase transformations in films of transition metals

Abstract

Electron diffraction studies have been made of polycrystalline Ni films irradiated with well separated beams of ions of different nature, namely ions of inert (He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺) and reactive (N⁺ and O⁺) gases. The Ni films were prepared under vacuum conditions (P? 3·10^?6Pa during evaporation) preventing an appreciable contamination of the films with impurities. The samples were irradiated at T? 300 K with ion beams of energies from 10 to 100 keV in the dose range between 5·10¹⁶ cm^?2 and the value leading to sample destruction.

Irradiation with noble gas ions revealed no phase transitions in the Ni films. A similar result was obtained in irradiation of Fe and Cr films with He⁺ ions. The bombardment of Ni films with reactive gas ions does cause changes in the lattice structure of the samples under study, depending on the nature of the bombarding ions. The N⁺ ion bombardment gives rise to the hcp phase with the lattice parameters typical of the Ni₃N compound, and the O⁺ ion bombardment results in the fcc phase with the NiO-type parameter.

The conclusion is drawn on the chemical origin of the phase transformations in the Ni films under ion bombardment. The necessity of revising the concept about the polymorphous nature of phase transformations induced in the films of transition metals by ion bombardment is substantiated.     

Investigation of structure and magnetic characteristics of Ni-implanted AlGaN films

The structural, valence of elements and magnetic characteristics of Ni-implanted Al_0.5Ga_0.5N films, deposited on Al₂O₃ substrates by metalorganic chemical vapor deposition (MOCVD), were reported. Ni ions were implanted into Al_0.5Ga_0.5N films by Metal Vapor Arc (MEVVA) sources under the energy of 100 keV for 3 h. The films were annealed at 900 K in the furnace for the transference of Ni ions from interstitial sites to substitutional sites in AlGaN and activating the Ni³⁺ ions. Characterizations were carried out in situ using X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and Vibrating sample magnetometer (VSM), indicating that the films have wurtzite structure without forming a secondary phase after annealing. Ni ions were successfully implanted into substitutional sites of Al_0.5Ga_0.5N films and the chemical bonding states of Ni³⁺ is Ni–N. The apparent hysteresis loops prove the films exhibited ferromagnetism at 300 K. The room temperature (RT) M_s and H_c obtained were approximately 0.22 emu/g and 32.97 Oe, respectively. From the first-principles calculation, A total magnetic moment of 2.86 μB per supercell is calculated: the local magnetic moment of NiN₄ tetrahedron, 2.38 μB, makes the primary contribution. The doped Ni atom hybridizes with its four nearby N atoms in NiN₄ tetrahedron, then N atoms are spin polarized and couple with Ni atom with strong magnetization, which result in ferromagnetism. Therefore, the p-d exchange mechanism is responsible for ferromagnetism in Ni-doped AlGaN. It is expected that the room temperature ferromagnetic Ni-doped Al_0.5Ga_0.5N films can make it possible to the applications for the spin electric devices.     

Phase transformation in Ni–Mn–Sn ferromagnetic shape memory alloy thin films induced by dense ionization

The effects of 200 MeV Au ions irradiation on the structural and magnetic properties of Ni–Mn–Sn ferromagnetic shape memory alloy (FSMA) thin films have been systematically investigated. In order to understand the role of initial microstructure and phase of the film with respect to high energy irradiation, the two types of Ni–Mn–Sn FSMA films having different phases at room temperature were irradiated, one in martensite phase (Ni_58.9Mn_28.0Sn_13.1) and other in austenite phase (Ni₅₀Mn_35.6Sn_14.4). Transmission electron microscope (TEM) and scanning electron microscope (SEM) images along with the diffraction patterns of X-rays and electrons confirm that martensite phase transforms to austenite phase at a fluence of 6×10¹² ions/cm² and a complete amorphization occurs at a fluence of 3×10¹³ ions/cm², whereas ion irradiation has a minimal effect on the austenitic structure (Ni₅₀Mn_35.6Sn_14.4). Thermo-magnetic measurements also support the above mentioned behaviour of Ni–Mn–Sn FSMA films with increasing fluence of 200 MeV Au ions. The results are explained on the basis of thermal spike model considering the core and halo regions of ion tracks in FSMA materials.     

Direct production of carbon nanotubes decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Carbon nanotubes (CNTs) decorated with Cu₂O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 45 °C using the corrosive effect of H₂SO₄ which was added to solution. These nanoparticles provide the nucleation sites for CNT growth avoiding the need for a buffer layer. The surface morphology of the Ni catalyst films and CNT growth over this catalyst was studied by scanning electron microscopy (SEM). High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O₂ at atmospheric environment, during the CNTs growth, lead to the production of CNTs decorated with about 6 nm Cu₂O nanoparticles. We used SEM to study the surface characteristics of Ni catalyst films and characteristic of grown CNTs. Raman spectroscopy, transmission electron microscopy (TEM), electron diffraction (EDX), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) revealed the formation of CNTs. The selected area electron diffraction pattern, EDX, and XPS studies show that these CNTs were decorated with Cu₂O nanoparticles. This way of fabrication is the easiest and lowest cost method.     

Electrical characteristics of etched ion-tracks in polyimide filled with silver nanoparticles

Silicon ions, of energy 150?MeV and fluence ～10¹²?ions/cm², were used to register latent tracks in 40?µm thick polyimide samples. Different sizes of tracks were obtained by etching the ion irradiated polyimide samples, in chemical solutions, by varying the temperature and etching period. Silver nanoparticles were diffused into the etched tracks by immersing the polyimide samples in silver solution and then irradiating with 6.5?MeV electrons at different fluences varying from 1?×?10¹⁵ to 5?×?10¹⁵?cm^?2. Results of morphological and elemental analysis, carried out by Scanning Electron Microscopy and Energy Dispersive X-ray. Analysis revealed that the conical tracks could be fully filled with silver nanoparticles at electron fluence of 5?×?10¹⁵?cm^?2. The minimum d. c. resistance of an array of tracks, filled with silver nanoparticles and measured across the polyimide film, was orders of magnitude higher as compared to that of silver wires of equivalent sizes connected in parallel. In addition, these silver nanoparticles filled tracks exhibited rectifying I–V behavior and frequency dependent a. c. resistance, characteristic of metal–polymer nano-composites. Possible mechanisms have been discussed, which can justify the asymmetric current–voltage characteristics in such nano-composites.     

Ag implantation-induced modification of Ni–Ti shape memory alloy thin films

Nanocrystalline thin films of Ni–Ti shape memory alloy are deposited on an Si substrate by the DC-magnetron co-sputtering technique and 120?keV Ag ions are implanted at different fluences. The thickness and composition of the pristine films are determined by Rutherford Backscattering Spectrometry (RBS). X-Ray diffraction (XRD), atomic force microscopy (AFM) and four-point probe resistivity methods have been used to study the structural, morphological and electrical transport properties. XRD analysis has revealed the existence of martensitic and austenite phases in the pristine film and also evidenced the structural changes in Ag-implanted Ni–Ti films at different fluences. AFM studies have revealed that surface roughness and grain size of Ni–Ti films have decreased with an increase in ion fluence. The modifications in the mechanical behaviour of implanted Ni–Ti films w.r.t pristine film is determined by using a Nano-indentation tester at room temperature. Higher hardness and the ratio of higher hardness (H) to elastic modulus (E_r) are observed for the film implanted at an optimized fluence of 9?×?10¹⁵ ions/cm². This improvement in mechanical behaviour could be understood in terms of grain refinement and dislocation induced by the Ag ion implantation in the Ni–Ti thin films.     

Synthesis and characterization of β-Ni(OH)2 up grown nanoflakes by SILAR method

In this paper we report a “bottom up” approach to synthesize β-Ni(OH)₂ nanoflakes using novel successive ionic layer adsorption and reaction (SILAR) method. Ni(OH)₂ thin films have been deposited on glass substrate using aqueous alkaline nickel chloride as nickel ion source and double distilled water maintained at 353 K temperature as hydroxyl ion source. The structural, surface morphological, optical and electrical properties of films are examined. The nanocrystallinity and β-phase of Ni(OH)₂ are confirmed by X-ray diffraction and FT-IR studies. Scanning electron microscope study revealed microporous and random distribution of well up grown interlocked nanoflakes. Optical absorption studies show wide optical band gap of 3.26 eV for β-Ni(OH)₂. The electrical properties revealed that β-Ni(OH)₂ has negative temperature coefficient of resistance with p-type semiconducting behaviour. The electrochemical property studied by cyclic voltametry in 2 M KOH electrolyte solution revealed pseudo capacitive behaviour, when β-Ni(OH)₂ thin film employed as working electrode in three electrode electrochemical cell with platinum as counter electrode and saturated calomel as reference electrode. The specific capacitance of 350 F g⁻¹ is obtained with nanoflake like morphology.     

Formation of silver nanoclusters in transparent polyimides by Ag-K ion-exchange process

Silver nanoclusters embedded in two transparent fluorinated polyimides, 4,4'-hexafluoroisopropylidene diphthalic anhydride – 2,3,5,6-tetramethyl paraphenylene diamine (6FDA-DAD) and 3,3',4,4' – biphenyltetracarboxylic acid dianhydride – 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (BPDA-3F), have been produced by surface modification with KOH aqueous solution followed by K-assisted Ag doping and thermal reduction in hydrogen atmosphere. The reaction rate of the nucleophilic hydrolysis in KOH, studied by Fourier transform infrared spectroscopy (FT-IR) and Rutherford backscattering spectrometry (RBS), depends on the polyimide chemical structure. After ion-exchange in AgNO₃ solution and subsequent annealing, the polyimide structure recovery was monitored by FT-IR whereas the characteristic surface plasmon absorption band of silver nanoparticles was evidenced by optical absorption measurements. The structure of silver nanoclusters as related to size and size distribution in the different polyimide matrices was thoroughly investigated by Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The collected data evidenced a uniform distribution of Ag clusters of nanometric size after thermal treatment at 300 ^○C in both polyimides. For the same ion-exchange treatment parameters and annealing temperature, XRD analyses evidenced the presence of crystallites with similar sizes.     

FMR and TEM Studies of Co and Ni Nanoparticles Implanted in the SiO<Subscript>2</Subscript> Matrix

Fused silica plates have been implanted with 40 keV Co⁺ or Ni⁺ ions to high doses in the range of (0.25–1.0) × 10¹⁷ ions/cm², and magnetic properties of the implanted samples have been studied with ferromagnetic resonance (FMR) technique supplemented by transmission electron microscopy, electron diffraction and energy dispersive X-ray spectroscopy. The high-dose implantation with 3d-ions results in the formation of cobalt and nickel metal nanoparticles in the irradiated subsurface layer of the SiO₂ matrix. Co and Ni nanocrystals with hexagonal close packing and face-centered cubic structures have a spherical shape and the sizes of 4–5 nm (for cobalt) and 6–14 nm (for nickel) in diameter. Room-temperature FMR signals from ensembles of Co and Ni nanoparticles implanted in the SiO₂ matrix exhibit an out-of-plane uniaxial magnetic anisotropy that is typical for thin magnetic films. The dose and temperature dependences of FMR spectra have been analyzed using the Kittel formalism, and the effective magnetization and g-factor values have been obtained for Co- and Ni-implanted samples. Nonsymmetric FMR line shapes have been fitted by a sum of two symmetrical curves. The dependences of the magnetic parameters of each curve on the implantation dose and temperature are presented.     

射频溅射微晶NiOxHy膜电致变色性能及其机理研究

研究了射频溅射制备的NiO_x膜的电致变色性能,发现富氧非理想化学配比的NiO _x(x>1)膜具有变色活性,这种膜出现Ni³⁺和Ni²⁺的混 合价态,当H^＋注入并占据Ni空位时,导致Ni³⁺的t_2g 能级被填满,Ni³⁺被阴极还原为Ni²⁺引起光学透明,即为漂白态; 反之,H⁺被萃取出NiO 关键词： xH_y膜')" href="#">NiO_xH_y膜 电致变色     

Ion beam synthesis and investigation of nanocomposite multiferroics based on barium titanate with 3d metal nanoparticles

Samples of nanocomposite multiferroics have been synthesized by implantation of Co⁺, Fe⁺, and Ni⁺ ions with an energy of 40 keV into ferroelectric barium titanate plates to doses in the range (0.5–1.5) × 10¹⁷ ions/cm². It has been found that nanoparticles of metallic iron, cobalt, or nickel are formed in the barium titanate layer subjected to ion bombardment. With an increase in the implantation dose, the implanted samples sequentially exhibit superparamagnetic, soft magnetic, and, finally, strong ferromagnetic properties at room temperature. The average sizes of ion-synthesized 3d-metal nanoparticles vary in the range from 5 to 10 nm depending on the implantation dose. Investigation of the orientation dependence of the magnetic hysteresis loops has demonstrated that the samples show a uniaxial (“easy plane”) magnetic anisotropy typical of thin granular magnetic films. Ferromagnetic BaTiO₃: 3d metal samples are characterized by a significant shift of the ferromagnetic resonance signal in an external electric field, as well as by a large (in magnitude) magnetodielectric effect at room temperature. These results indicate that there is a strong magnetoelectric coupling between the ferroelectric barium titanate matrix and ion-synthesized nanoparticles of magnetic metals.     

The influence of low-temperature silver-ion exchange on the spectral-luminescent properties of fluorophosphate glasses doped with PbSe

Changes in the absorption and luminescence spectra of fluorophosphate glasses doped with PbSe caused by low-temperature Ag⁺–Na⁺ ion exchange are considered. It is found that the silver distribution gradient in a near-surface layer about 16 μm thick leads to two different processes of interaction between metal and semiconductor nanoparticles. PbSe molecular clusters and quantum dots more efficiently grow in deep layers with a low silver concentration. The near-surface glass layers with a high silver concentration exhibit formation of Ag metal nanoparticles, on the surface of which interaction with PbSe molecular clusters leads to the formation of Ag–Se–Pb bonds, which transform into Ag₂Se layers in the process of heat treatment. The appearance of the new phase is confirmed by X-ray diffraction.     

快重离子辐照聚酰亚胺潜径迹的电子能损效应

快重离子辐照聚合物材料时，由于密集电离激发在其路径上产生几纳米直径的潜径迹，径迹形貌受离子种类、离子能量等多种因素的影响.为了研究电子能损对径迹形成所起的作用，利用1.158GeV 的Fe⁵⁶离子和 1.755GeV Xe¹³⁶离子在室温真空环境下辐照叠层聚酰亚胺(PI)薄膜，结合傅里叶转换红外光谱(FTIR)分析技术对辐照引起的化学变化进行了测量.聚酰亚胺官能团的降解及炔基的生成是离子辐照聚合物的主要特征，在注量1×10¹¹到6×10¹²/cm²范围及较宽的电子能损(dE/dX)_e范围 (Fe⁵⁶ 离子：2.2 到 5.2 keV/nm， Xe¹³⁶ 离子：8.6 到 11.3 keV/nm)对官能团的断键率及炔基生成率进行了研究. 红外结果显示在实验涉及的能损范围都有炔基生成，应用径迹饱和模型对实验结果进行拟合，不同能损下的平均损伤径迹半径及炔基生成径迹半径被得到，通过热峰模型对实验结果拟合，给出了离子在聚酰亚胺中产生潜径迹的能损阈值，实验给出的径迹形貌的电子能损效应曲线与热峰模型预言走势基本一致. 关键词： 离子辐照 潜径迹 红外光谱 热峰模型     

Radiation-induced modification of reflection spectra beyond the ion path region in polyimide films

Modification of the surface layers of polyimide films under γ-radiation and implantation with 30–100 keV Ni, Mn, Ag, Co, Fe and B ions in the dose range of 10¹⁵–1.5 × 10¹⁷ cm^–2 are investigated by reflection spectra measurements. Ion implantation is shown to lead to the modification of reflection from the rear (unimplanted) polymer side. Depending on the kind of ion and implantation mode a strong increase in the integrated reflection coefficient in the polymer opacity range is observed, as well as growth of the reflection intensity of optical bands λ₁ = 254 and λ₂ = 311 nm and their shifts to the short-wavelength region. The change in the reflection coefficient far beyond the implanted region is caused by the radiation-induced transformation of the polymer supermolecular structure near the surface and the relaxation of mechanical stress formed during film production.     

The effect of high implant doses and high ion current densities on polyimide film properties

Ar⁺ and Ar²⁺ ions with energies of 40 and 80 keV are implanted into thin polyimide films. The implant doses and the ion current densities are varied in a wide range between 2.5×10¹⁴ and 1.5×10¹⁷ cm⁻² and between 1 and 16 μA/cm², respectively. The effect of the implantation parameters on the electrical, paramagnetic, and optical properties of the ion-modified near-surface polymer layer is studied. It is shown that the radiation-stimulated thermolysis of polyimide and its chemical constitution are responsible for a monotonic growth of the electrical conductivity of the layer with increasing ion current at a given implant dose. When the ion current density is fixed, the conductivity grows stepwise with implant dose, whereas the concentration of paramagnetic centers and the optical transmission of the modified layer decrease. The dependences observed are treated within a model of the structural reconfiguration of the polymer carbonized phase formed during the implantation.     

Mössbauer and magnetic studies on nanocrystalline NiFe2O4 particles prepared by ethylene glycol route

NiFe₂O₄ nanoparticles have been synthesized by co-precipitation method at 145°C in N₂ atmosphere using ethylene glycol as solvent and capping agent. This gives the promising synthesis route for nanoparticles at low temperature. The as-synthesized NiFe₂O₄ is subsequently heated at 400°C, 500°C, 700°C and 800°C. Crystallite size increases with the heat treatment temperature. The heat treatment temperature has direct effect on the electron paramagnetic resonance and intrinsic magnetic properties. The room temperature Mössbauer spectrum of the 800°C heated sample shows the two sextets pattern indicating that the sample is ferrimagnetic and Fe^3?+? ions occupy both tetrahedral and octahedral sites of spinel structure.