Radiation-induced change of polyimide properties under high-fluence and high ion current density implantation

Polyimide (PI) films were implanted with 40-keV Ar⁺ and 80-keV Ar²⁺ ions in a fluence range of 5.0×10¹⁴–1.5×10¹⁷ cm^-2 at ion-current densities of 1–16 A/cm². It is shown that the conductivity of the samples rises with the ion-current density at a fixed fluence. Electrophysical parameters of the polyimide change stepwise with the implantation fluence when it exceeds a certain value. The change of electrical parameters of the implanted PI correlates with that of the optical and paramagnetic characteristics. The phenomenon of complete volatilisation of argon implanted with an energy of 40 keV due to surface heating and disordering under the high-power beam is found. It is shown that the change of ion charge and energy at constant beam-power density causes only a quantitative change in the polymer characteristics. A model of PI alteration and carbonised phase formation, taking into account the action of the high-power ion beam and the peculiarities of PI chemical structure, is developed to explain the observed effects. Implantation at high ion-current density can be suggested as an efficient practical means to control polymer conductivity and other parameters. PACS 61.80.Jh; 61.82.Pv; 72.80.Le; 76.30.Pk; 78.30.Jw; 81.05.Lg     

Modification of the magnetic properties of polyimide films by cobalt ion implantation

The magnetic characteristics of polyimide films implanted with Co⁺ ions with an energy of 40 keV in the dose range D = 2.50 × 10¹⁶?1.25 × 10¹⁷ cm^?2 at ion current densities j = 4, 8, and 12 μA/cm² have been investigated. It has been shown that, at implantation doses of less than 5 × 10¹⁶ cm^?2, the superparamagnetic properties of modified samples are described by the Langevin equation. At higher doses, there is an intercluster interaction. It has been found that, with an increase in the ion current, the cluster size decreases. The sizes of the formed clusters are determined and vary in the range from 3.9 to 11.0 nm, depending on the implantation dose.     

The influence of argon ion bombardment on the electrical and optical properties of clean silicon surfaces

The effect of low energy noble gas ion bombardment on the electrical and optical properties of Si(211) surfaces has been investigated by surface conductivity and field effect measurements, ellipsometry and AES. With this combination of techniques, information is obtained concerning the electrical properties, the chemical composition and the damage of the surface layer. Upon ion bombardment in the energy range of 500–2000 eV, ellipsometry shows the formation of a damaged surface layer with optical properties close to those of an evaporated amorphous silicon film. In order to measure the conductivity changes as sensitive as possible, nearly intrinsic silicon crystals were used. For the clean, 5200 Ω cm Si(211) surface, bombarded only with a mass-analyzed argon ion beam, a small increase in conductivity is found to occur after a small ion dose (saturation after 5 × 10¹⁴ ions cm^?2 while after 5 × 10¹³ ions cm^?2 already half of the increase has occurred). The effect was found to be independent of ion energy between 500 and 2000 eV. As the field effect signal did not change after this treatment, it is concluded that the surface state density in the neighbourhood of the Fermi level shows a slight decrease.     

Ion synthesis of silver nanoparticles in viscous-fluid epoxy resin

A method is described for the ion synthesis of silver nanoparticles in epoxy resin that is in a viscousfluid state (viscosity 30 Pa s) during irradiation. The viscous-fluid or glassy polymer is implanted by 30-keV silver ions at a current density of 4 μA/cm² in the ion beam in the dose range 2.2 × 10¹⁶–7.5 × 10¹⁶ ions/cm². The epoxy layers thus synthesized contain silver nanoparticles, which are studied by transmission electron microscopy and optical absorption spectroscopy. The use of the viscous-fluid state increases the diffusion coefficient of the implanted impurity, which stimulates the nucleation and growth of nanoparticles at low implantation doses and allows a high factor of filling of the polymer with the metal to be achieved.     

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.     

Influence of high energy electron irradiation on the characteristics of polysilicon thin film transistors

The influence of high energy electron (23 MeV) irradiation on the electrical characteristics of p-channel polysilicon thin film transistors (PSTFTs) was studied. The channel 220 nm thick LPCVD (low pressure chemical vapor deposition) deposited polysilicon layer was phosphorus doped by ion implantation. A 45 nm thick, thermally grown, SiO2 layer served as gate dielectric. A self-alignment technology for boron doping of the source and drain regions was used. 200 nm thick polysilicon film was deposited as a gate electrode. The obtained p-channel PSTFTs were irradiated with different high energy electron doses. Leakage currents through the gate oxide and transfer characteristics of the transistors were measured. A software model describing the field enhancement and the non-uniform current distribution at textured polysilicon/oxide interface was developed. In order to assess the irradiation-stimulated changes of gate oxide parameters the gate oxide tunneling conduction and transistor characteristics were studied. At MeV dose of 6×10¹³ el/cm², a negligible degradation of the transistor properties was found. A significant deterioration of the electrical properties of PSTFTs at MeV irradiation dose of 3×10¹⁴ el/cm² was observed.     

Correlation of Electronic and Magnetic Properties of Thin Polymer Layers with Cobalt Nanoparticles

Nanoparticles (NPs) of cobalt are synthesized in shallow layers of polyimide using 40 keV implantation of Co⁺ ions with a few different fluences at various ion current densities. Nucleation of individual NPs at low fluencies and their percolation at high fluencies are crucial processes governing the electrical and magnetic properties of the metal/polymer nanocomposites that can be controlled by the implantation regimes. In particular, one can tune the magnetoresistance between negative and positive through appropriate choice of ion fluence and current density. The found non‐monotonous dependence of the magnetoresistance on the applied magnetic field allows suggestion of spin‐dependent domain wall scattering affecting the electron transport. The samples implanted with low fluencies demonstrate superparamagnetic behavior down to very low blocking temperatures. For high fluence (1.25 × 10¹⁷ cm⁻²) the transition to ferromagnetic ordering is observed that is related to the increased magnetic interaction of NPs.     

Spatial distribution of defects produced by boron ion implantation of silicon

A simple technique for the study of the spatial distribution of the damage produced by ion implantation of silicon has been developed. The damage depth distribution for 40 keV boron ions in silicon has been studied at irradiation doses from 7 × 10¹¹ to 3.9 × 10¹⁴ ions/cm² and the relative defect peak depth R _d/R _p = 0.85 determined. An increase of layer conductivity as the surface part of the implanted layer is removed has been revealed. This effect is caused by the presence of radiation defects in the surface region of the layer. The “electrical” cluster diameter is about 28 A and the overlapping cluster dose is close to 1 × 10¹³ ions/cm².     

Optical properties of metal nanoparticles synthesized in a polymer by ion implantation: A review

Polymer composite layers irradiated by 30-keV Ag⁺ ions with doses from 3.1×10¹⁵ to 7.5×10¹⁶ cm^?2 and an ion current of 4 µA/cm² are investigated. The composites were examined using Rutherford backscattering (RBS), transmission electron microscopy (TEM), and optical spectroscopy. As follows from electron microscopy and electron microdiffraction data, ion implantation is a promising tool for synthesizing silver nanoparticles in the surface region. The optical density spectra taken of these composites demonstrate that the silver nanoparticles exhibit unusually weak plasma resonance. The formation of silver nanoparticles in layers carbonized by ion implantation is considered. Based on the Mie theory, optical extinction spectra for silver particles in the polymer and carbon matrices are simulated and optical spectra for complex silver core-carbon sheath nanoparticles are calculated. The physics behind the experimental optical spectra of the composite is discussed.     

Changes in Structural and Optical Properties of Polycarbonate Induced by Ag+ Ion Implantation

Transparent polycarbonate samples were implanted with 1 MeV Ag⁺ ions to various doses ranging from 5 × 10¹⁴ to 3 × 10¹⁶ ions cm^?2 with a beam current density of 900 nA cm^?2. Modification in the structure of polycarbonate as a function of the implantation fluence was investigated using micro-Raman spectroscopy, glancing angle X-ray diffraction, and UV-Vis spectroscopy. Raman spectroscopy pointed toward the formation of graphite structures/clusters due to the ion implantation. UV-Vis absorption analysis suggests the formation of a carbonaceous layer and a drastic decrease in optical band gap from 4.12 eV to 0.50 eV at an implanted dose of 3 × 10¹⁶ ions cm^?2. The correlation between the decrease in band gap and the structural changes is discussed.     

Ion synthesis of copper nanoparticles in sapphire and their modification by high-power excimer laser pulses: A review

Composite layers made in sapphire by implantation of 40-keV Cu⁺ ions at a dose of 1 × 10¹⁷ cm⁻² and an ion beam current density varying from 2.5 to 10 μA/cm² are studied. It is shown that ion implantation makes it possible to synthesize a composite layer containing copper nanoparticles at the surface of the insulator. However, the nanoparticle size distribution in this layer is nonuniform. The composite layer is exposed to high-power excimer laser radiation with the aim of modifying the size and size distribution of the metal nanoparticles in it. The resulting structures are examined by Rutherford backscattering, optical reflection spectroscopy, and atomic force microscopy. It is found that the laser irradiation diminishes copper nanoparticles in the composite layer. Experimental data on laser modification may be explained by photofragmentation and/or melting of the nanoparticles in the sapphire matrix under the action of nanosecond laser pulses.     

磷离子注入速率对4H-SiC(0001)晶格恢复与电阻率降低的影响

高剂量的磷离子注入4H-SiC(0001)晶面，注入速率从1.0×1012到4.0×1012 P+ cm-2s-1变化，而注入剂量固定为2.0×1015 P+ cm-2。室温注入，1500oC的高温下退火。利用光荧光和拉曼谱分析注入产生的晶格损伤以及退火后的残余缺陷。通过霍耳测试来分析注入层的电学性质。基于上述测试结果，发现通过减小磷离子的注入速率，极大地减少了注入层的损伤及缺陷。考虑到室温注入以及相对较低的退火温度(1500 oC)，在注入速率为1.0×1012 P+ cm-2s-1及施主浓度下为4.4×1019 cm-3的条件下，获得了非常低的方块电阻106 Ω/sq。     

Ion bombardment induced decomposition of polyimide (PIQ) studied by X-ray Photoelectron Spectroscopy (XPS) and Direct Recoil (DR) spectrometry

Angular resolved X-ray photoelectron spectroscopy (XPS) and time-of-flight direct recoil (DR) spectrometry are used to characterize the surface changes in polyimide iso-indroquinazolinedione (PIQ®: Hitachi Chem. Co.) induced by 4 keV Ar⁺ bombardment. Deconvolution of the XPS data along with a stoichiometry of CH_{2.2 ± 0.2} as determined from DR intensities indicate the presence of an uppermost hydrocarbon layer on the initial surface. Upon Ar⁺ bombardment the H, N, and O concentrations decrease and the surface layer carbon concentration increases to > 94 at %. This carbonaceous layer exhibits C1s chemical shifts and line shapes that are similar to those of an ion bombarded graphite surface, along with an enhanced electrical conductivity.     

Photorefractive properties of ion-implanted waveguides in strontium barium niobate crystals

0.61 Ba_0.39Nb₂O₆, SBN61), either by proton or helium ion implantation. Proton-implanted samples show a large increase of dark conductivity that reduces or even prevents the recording of refractive index gratings. For waveguides formed by helium implantation this effect is absent, and they can be used for efficient holographic recording. Photorefractive properties of the waveguides are investigated by two-beam coupling. After implantation with 2.0 MeV He⁺ and doses of (0.5-5)×10¹⁵ cm^-2, the samples have to be polarized again, because heating or charge effects at the crystals surface during the implantation process decreases or even reverses the effective electrooptic coefficients in the waveguiding layer. For repoled samples, we find logarithmic gain coefficients of up to 45 cm^-1 with time constants for the build-up of the purely π/2-shifted refractive index grating of the order of 1 ms for the blue lines of an Ar⁺ laser. Photoconductivity depends nonlinearly on light intensity with an exponent x≈0.55. With increasing implanted helium dose, both electronic and nuclear damage of the waveguiding layer grows, and the photorefractive properties of the waveguides are considerably degraded. Received: 20 February 1997/Revised version: 1 May 1997     

Mixing of Au in Si induced by secondary and high-order recoil implantation

The mixing of Au in Si induced by secondary and high-order recoil implantation was investigated using 350 keV Ar⁺ and 350 keV Kr⁺ ions to fluences from 1?×?10¹⁶ to 3?×?10¹⁶ ions/cm² at room temperature. The thickness of the Au layer evaporated on Si substrate was ～2400 Å.The ranges of the Ar and Kr ions were chosen to be lower than the thickness of the Au layer in order to avoid the ballistic mixing produced by the primary knock-on atoms. Rutherford backscattering spectrometry (RBS) experiments were carried out to study the effects induced by Ar and Kr irradiation at the interface of Au–Si system. We observed that in the case of the irradiation with Ar⁺ ions, a broadening of the Au–Si interface occurred only at the fluence of 3?×?10¹⁶ Ar⁺/cm² and it is attributed to the surface roughening induced by ion bombardment. In contrast, the RBS analysis of a sample irradiated with 2?×?10¹⁶ Kr⁺/cm² clearly showed, in addition to the broadening effect, the formation of a mixed zone of Au and Si atoms at the interface. The mixing of Au in Si atoms can be explained by the secondary and high-order recoil implantation followed by subsequent collision cascades.     

Radiation damage of material surfaces under prolonged irradiation with He+ and Ar+ ions with broad energy spectra

The results of studying the redistribution of Be, Al, Ti, Fe, Cu, Zr, Mo, and W atoms incorporated in polycrystalline metal samples under irradiation with He⁺, (He⁺ + Ar⁺), and Ar⁺ ion beams with a broad energy spectrum and an average energy of 10 keV at irradiation doses of 1 × 10²¹ ion/cm² are studied. It is discovered that irradiation at doses exceeding 1 × 10¹⁹ ion/cm² results in local small-crystal formations being produced in a near-surface substrate layer. Their typical dimensions are less than 1–5 μm, and their the density is up to 1–100. They contain incorporated atoms and impurity atoms with a concentration of 0.1–10 at %. Subsequent irradiation at a dose of 1 × 10²⁰ ions/cm² or more leads to disappearance of these formations, mainly because of sputtering processes.     

Amorphous GaP produced by ion implantation

Two types of non-crystalline states (“disordered” and “amorphous”) of GaP were produced by using ion implantation and post annealing. A structural-phase-transition-like annealing behaviour from the “disordered” state to the “amorphous” state was observed.The ion dose dependence and the annealing behaviour of the atomic structure of GaP implanted with 200 keV ? N⁺ ions were studied by using electron diffraction, backscattering and volume change measurements. The electronic structure was also investigated by measuring optical absorption and electrical conductivity.The implanted layer gradually loses the crystalline order with the increase of the nitrogen dose.The optical absorption coefficient α and electric conductivity σ of GaP crystals implanted with 200 keV?N⁺ ions of 1 × 10¹⁶ cm^?2 were expressed as αhν = C(hν ? E₀)ⁿ and log $\text{σ = A ? BT}{}^{\mathrm{<mtext>-</mtext><mtext>1</mtext><mtext>4</mtext>}}$, respectively. Moreover, the volume of the implanted layer increased about three percent and the electron diffraction pattern was diffused halo whose intensity monotonically decreases along the radial direction. These results indicate that the as-implanted layer has neither a long range order nor a short range order (“disordered state”).In the sample implanted at 1 × 10¹⁶ cm^?2, a structural phase-transition-like annealing stage was observed at around 400°C. That is, the optical absorption coefficient α abruptly fell off from 6 × 10⁴ to 7 × 10³ cm^?1 and the volume of the implanted layer decreased about 2% within an increase of less than 10 degrees in the anneal temperature. Moreover, the short range order of the lattice structure appeared in the electron diffraction pattern. According to the backscattering experiment, the heavily implanted GaP was still in the non-crystalline state even after annealing.These facts lead us to believe that heavily implanted GaP, followed by annealing at around 400°C, is in the “amorphous” state, although as-implanted Gap is not in the “amorphous” state but in the “disordered” state.     

Enhancement in electrochemical properties of ionic liquid-based nanocomposite polymer electrolytes by 100 MeV Si9+ swift heavy ion irradiation

Swift heavy ion (SHI) irradiation has been used as a tool to enhance the electrochemical properties of ionic liquid-based nanocomposite polymer electrolytes dispersed with dedoped polyaniline (PAni) nanorods; 100 MeV Si⁹⁺ ions with four different fluences of 5?×?10¹⁰, 1?×?10¹¹, 5?×?10¹¹, and 1?×?10¹² ions cm^?2 have been used as SHI. XRD results depict that with increasing ion fluence, crystallinity decreases due to chain scission up to fluence of 5?×?10¹¹ ions cm^?2, and at higher fluence, crystallinity increases due to cross-linking of polymer chains. Ionic conductivity, electrochemical stability, and dielectric properties are enhanced with increasing ion fluence attaining maximum value at the fluence of 5?×?10¹¹ ions cm^?2 and subsequently decrease. Optimum ionic conductivity of 1.5?×?10^?2 S cm^?1 and electrochemical stability up to 6.3 V have been obtained at the fluence of 5?×?10¹¹ ions cm^?2. Ac conductivity studies show that ion conduction takes place through hopping of ions from one coordination site to the other. On SHI irradiation, amorphicity of the polymer matrix increases resulting in increased segmental motion which facilitates ion hopping leading to an increase in ionic conductivity. Thermogravimetric analysis (TGA) measurements show that SHI-irradiated nanocomposite polymer electrolytes are thermally stable up to 240–260 °C.     

Synthesis of periodic plasmonic microstructures with copper nanoparticles in silica glass by low-energy ion implantation

Ion implantation was used to locally modify the surface of silica glass to create periodic plasmonic microstructures with Cu nanoparticles. Nanoparticles were synthesized by Cu-ion irradiation of the silica glass at the ion energy of 40 keV, dose of 5×10¹⁶ ions/cm² and current density of 5 μA/cm². This procedure involves low-energy ion implantation into the glass through a mask placed at the surface. Formation of nanoparticles was observed by optical spectroscopy and atomic force microscopy. The presented results clearly demonstrate how the low-energy ions can be used for the fabrication of photonic microstructures on dielectric surfaces in a single-step process.     

Surface damage and topography of erbium metal films implanted with helium to high fluences

Topographical and expansion effects which occur as a result of implanting erbium thin films with helium up to fluences of 1.5 × 10¹⁸ He⁺/cm² are described. There exists an inverse relationship between critical dose and annealing temperature with respect to the formation of surface bubbles. Post implantation annealing at or below 400°C is found to strongly reduce implantation induced expansion for doses less than 3.5 × 10¹⁷ He⁺/cm², but is observed to result in increased expansion above this dose. At temperatures above 400°C, expansion is increased for all doses investigated. Details of bubble development in the implanted layer are discussed and the manner in which surface bubbles develop from enlarged subsurface bubbles is illustrated.