Coupled chemical reactions in dynamic nanometric confinement: V. The influence of Li+ and F− ions on etching of nuclear tracks in polymers

Etching of continuous nuclear tracks in thin polymer foils from both sides is known to lead to the formation of double-conical nanopores. In this work and related ones we try to find out how this etching kinetics is modified when materials are added which react with each other upon their contact towards some new product that influences the etching. For that purpose we have chosen here Li⁺ and F^? ions as the additions, which react with each other to form LiF precipitations. The coupled etching and precipitation kinetics is recorded by measuring the electrical current that is transmitted through the foils upon application of a low-frequency alternating sinusoidal voltage. Depending on the etchant concentrations, the etching temperature and the time of Li⁺ and F^? addition, different effects are found that range from (a) no alteration of the transmitted current at all, via (b) the emergence of an alternating current with a temperature-dependent amplitude, and (c) the complete vanishing of any transmitted current at all, towards (d) chaotic transmitted current histories with phases with strong current spike emission and (e) rather quiet phases, alternating with each other in a rather unsystematic way. The observed effects are ascribed to (a) the enhanced penetration efficiency of both the Li⁺ and F^? ions through the polymeric bulk and/or latent ion tracks after the removal of the polymer's protective surface layer by the etchant, (b) the high mobility of preferentially the F^? ions within the polymer, (c) the LiF precipitation within the polymer or on its surface upon encounter of Li⁺ and F^? ions, (d) the nanofluidic properties of narrow etched tracks covered with Li⁺ ions on the wall surfaces and F^? ions beyond, and/or (e) the formation of LiF membranes within the etched tracks.     

SHI induced nano track polymer filters and characterization

Swift heavy ion irradiation produces damage in polymers in the form of latent tracks. Latent tracks can be enlarged by etching it in a suitable etchant and thus nuclear track etch membrane can be formed for gas permeation / purification in particular for hydrogen where the molecular size is very small. By applying suitable and controlled etching conditions well defined tracks can be formed for specific applications of the membranes. After etching gas permeation method is used for characterizing the tracks. In the present work polycarbonate (PC) of various thickness were irradiated with energetic ion beam at Inter University Accelerator Centre (IUAC), New Delhi. Nuclear tracks were modified by etching the PC in 6N NaOH at 60 (±1) °C from both sides for different times to produce track etch membranes. At critical etch time the etched pits from both the sides meet a rapid increase in gas permeation was observed. Permeability of hydrogen and carbon dioxide has been measured in samples etched for different times. The latent tracks produced by SHI irradiation in the track etch membranes show enhancement of free volume of the polymer. Nano filters are separation devices for the mixture of gases, different ions in the solution and isotopes and isobars separations. The polymer thin films with controlled porosity finding it self as best choice. However, the permeability and selectivity of these polymer based membrane filters are very important at the nano scale separation. The Swift Heavy Ion (SHI) induced nuclear track etched polymeric films with controlled etching have been attempted and characterized as nano scale filters.      

Coupled chemical reactions in dynamic nanometric confinement: IV. Ion transmission spectrometric analysis of nanofluidic behavior and membrane formation during track etching in polymers

In recent papers, it was shown that coupled chemical-topological reactions (CCRs) with both NaOH etchant and silver salts, performed in thin swift-heavy ion-irradiated polymers under the application of a test voltage across the polymer foils, eventually gave rise to characteristic current/voltage features and Bode plots that were tentatively attributed to the formation of Ag₂O membranes within the etched tracks. The same was also found when replacing the silver ions by lithium ions, and adding fluoride ions to the NaOH etchant, to promote LiF membrane formation. Ion Transmission Spectrometry (ITS) enabled us to reconfirm the existence of these membranes beyond doubt. The membrane thickness was determined to be ～0.2–0.4?µm in the best cases.

ITS also revealed that hitherto membrane formation occurs only in ～1% of all tracks, or even less. The reason for this poor abundance seems to be that the decisive factor for membrane formation, which is the firm anchoring of the emerging solid Ag₂O or LiF reaction products on the etched track walls, was hitherto rarely fulfilled. We attribute this tentatively to the too high test voltage applied for controlling the CCR process that might hinder the product anchoring on the walls by promoting nanofluidic electromigration. Indeed, voltage reduction seems to improve the situation.     

Ion track etching revisited: II. Electronic properties of aged tracks in polymers

We compile here electronic ion track etching effects, such as capacitive-type currents, current spike emission, phase shift, rectification and background currents that eventually emerge upon application of sinusoidal alternating voltages across thin, aged swift heavy ion-irradiated polymer foils during etching. Both capacitive-type currents and current spike emission occur as long as obstacles still prevent a smooth continuous charge carrier passage across the foils. In the case of sufficiently high applied electric fields, these obstacles are overcome by spike emission. These effects vanish upon etchant breakthrough. Subsequent transmitted currents are usually of Ohmic type, but shortly after breakthrough (during the track’ core etching) often still exhibit deviations such as strong positive phase shifts. They stem from very slow charge carrier mobility across the etched ion tracks due to retarding trapping/detrapping processes. Upon etching the track’s penumbra, one occasionally observes a split-up into two transmitted current components, one with positive and another one with negative phase shifts. Usually, these phase shifts vanish when bulk etching starts. Current rectification upon track etching is a very frequent phenomenon. Rectification uses to inverse when core etching ends and penumbra etching begins. When the latter ends, rectification largely vanishes. Occasionally, some residual rectification remains which we attribute to the aged polymeric bulk itself. Last not least, we still consider background currents which often emerge transiently during track etching. We could assign them clearly to differences in the electrochemical potential of the liquids on both sides of the etched polymer foils. Transient relaxation effects during the track etching cause their eventually chaotic behaviour.     

Study of current drain during electrochemical etching of polycarbonate detectors

Polycarbonate (PC) detector is one of the common detectors for neutron and radon gas detection. Using this detector it is possible to measure the dose in mSv, by counting tracks/cm² on an etched surface. In this paper, a special procedure has been suggested to determine the dose based on current drain during the etching process. In these experiments the effects of voltage, frequency, effective etched area, PC detector's thickness, etched area (one side or two sides), etching solution temperature and dose absorbed by the PC foil have been studied.The results obtained show the current drain variation for a voltage of 200–1600 V, a frequency of 2–10 kHz, effective area with a diameter of 2–12 cm, PC thickness of 125–250–375– and a temperature of etching solution of 25–.Lexan PC foils were exposed to doses of of neutrons. The unexposed foils were considered as the background (BG) foils. Most of the experiments were performed at a voltage of 800 V, a frequency of 2 and 8 kHz, foil thickness of , diameter of effective etched area of foils of 2, 6 and 12 cm, temperatures of 25 and and the etching process from 0 up to overload stage. Overload stage occurs when the foil becomes so thin due to growth of the tracks that it leads to sparking between phase and null that makes a hole in the foil.Current drain curves versus the function of the etching time are absolutely different for various doses from zero (BG) to 10 rad (BG up to ). This is true especially for the time interval from 3 h of etching up to overload stage. In this way, it is possible to obtain a calibration of PC detector net current drain based on its absorbed dose.In this experiment, the number and diameter of tracks and their relation with drain current and PC foil residual thickness at overload stage have been studied.The same experiment has been performed for various concentrations of radon gas (Bq/m3) as well.     

Funnel-type etched ion tracks in polymers

It is shown that conical track etching is a much more complicated process than generally assumed. The choice of the corresponding parameters (i.e. the ratios of concentrations and diffusion coefficients of both etchant (e.g. NaOH) and stopping solutions (e.g. HCl) and the etching temperature) determines the ratio of polymer dissolution to etchant penetration. The latter value controls the counterplay of diffusion, etching, ionic conductivity, field emission and capacitive effects, which is decisive for both the final track shapes and their electronic properties. The stages of track evolution during etching under different conditions are outlined in detail. Both transparent conical nanopores and “funnel-type” tracks can be obtained, the latter consisting of a shorter cone and a residual latent track. Depending on the internal structure of that latent track segment, such funnel-type tracks either allow smooth transmission of the rectified currents or they emit unipolar current spikes. Not only the study of electronic properties of single ion tracks, but also of a multitude of tracks makes sense. Depending on the applied parameters, the individual track properties may either just add up, or new effects may be found that emerge from the interaction of the tracks among each other. This is preferentially the case for spike-emitting tracks, where effects such as phase-locked spike synchronization can be found as described by neural network theory.     

Electrical current pulsations through ion irradiated polymer foils in electrolytes

Funnel-type ion tracks were produced in thin polymer foils by swift heavy ion irradiation and subsequent treatment with both low concentration etchants and acids from two different sides. The funnel shapes consist of shallow etched cones and residual latent tracks and thus combine both their characteristic properties, rectification and current spike emission, in one track each. Arrays of spike-emitting tracks are known to exhibit phase-locked synchronous electrical pulsations in accordance with the neural network theory. These pulsations were studied here on arrays of funnel-type tracks for the first time. As expected, the results strongly depend on the track density. In foils with low track densities, synchronous oscillations are rare and rather unstable events, whereas foils with high track densities exhibit stable, strong and long-lasting pulsations. Insertion of 0.1 M KCl solution into tracks at low density improved the shape and regularity of the spuriously occurring spikes somewhat, as compared with water in these tracks.     

Morphologies of latent and etched heavy-ion tracks in {111} CaF2

Structure details of latent tracks created by U, Pb and Au ions (energies 6.9, 28.7 and 11.1?MeV/A, respectively) in {111} CaF₂ have been extracted by means of scanning force microscopy and transmission electron microscopy. The revealed structure has assisted in the interpretation of the etching behaviour of tracks created in {111} CaF₂ by 9.2?MeV/A Bi ions. In the latter experiments, irradiated fragments were immersed for short durations in a 3:1 10% HCl/96% H₂SO₄ solution and the morphology of the formed etch pits was derived by high-resolution scanning electron microscopy and scanning force microscopy. Three conclusions emerged. First, ion-induced surface hillocks exhibit no resistance against etchant attack. Second, the primary etching diameter of the track coincides with the nanometric width of the structurally altered track core. Third, the structure of the etch pits, 3-faced symmetric pyramidal depressions with {122} faces, indicates that etching across the track halo, a few tens of nanometers wide strained crystal, is dominated by surface energies of crystal faces.     

Electrolytes in etching of latent tracks of heavy ions in polyethylene terephthalate

Previously unknown features of etching of polyethylene terephthalate, latent tracks of multiply charged accelerated ions in it, and track membrane pore formation are considered. It was found that K ions (in the form of KCl salt) in a KOH solution enhance etching of both initial polyethylene terephthalate and tracks. Ba²⁺ ions enhancing etching of initial polymer significantly inhibit etching of tracks. It is assumed that etching inhibition is associated with Ba²⁺ ion adsorption on track active centers. The features detected are used to fabricate track membranes with thin selective layer.     

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.     

离子径迹模板法制备纳米线

重离子辐照的高分子有机膜,经过适当的处理,可以作为模板制备金属和可溶性盐纳米线,此方法称为离子径迹模板法。介绍了用电化学沉积方法和过饱和溶液法制备金属纳米线和可溶性盐纳米线的基本原理和制各实例,同时还展望了离子径迹模板法制备纳米线的一些可能的应用。The polymer foils irradiated by heavy ions can be used as temptates to prepai nanowires and some inorganic salt nanowires. It is called ＂ion-track template method＂. Compared to other templates, such as AAO template and porous silicon, etched ion-track template is more convenient and flexible. The density of the pores can be easily controlled by changing the ion fluences and the diameter of the pores can be altered through changing the etching condition. The pores of the etched ion-track template are well aligned. We present some examples of preparing metallic nanowires and inorganic salt wires by electrochemical deposition and by supersaturation solution method, respectively. We also introduce some applications of nanowires prepared with ion-track template method.     

Coordination chemistry and kinetics of preferential etching on surfaces of TiO2 (rutile)

Fused KHSO₄ can be used as both a polish and a preferential etchant for the {001} surfaces of rutile, depending on the temperature of the system. Polishing occurs at temperatures above 550°C. At temperatures below 550°C, three types of etch pit are observed, two well defined with regular shapes (sides parallel to the <110> and <100> and <130> directions, respectively) and one irregularly shaped. Photochemical deposition of silver [1] onto the crystal surface and subsequent removal (HNO₃) prior to etching causes the irregularly shaped pits to be etched more rapidly than in the case of a surface region that was not predeposited. A chemical reaction mechanism is presented to interpret the observed etching behavior. The crystal structure (i.e. the different ionic composition of different crystallographic planes) and surface chemistry of rutile are considered in the formulation of this mechanism. It is suggested that etchant molecules form surface complexes on the TiO₂ (after dehydration of surface OH groups) through coordination of Ti⁴⁺ via terminal and bridged out-of-plane O^2? positions. Evidence is presented to show that the etching rate-determining reaction is the dissolution of these soluble surface complexes. The observed photochemical effects are explained on the basis of the trapping of photogenerated holes or electrons at certain crystal defects.     

The statistical process of pore growth in multi pore foils

Using the electrolytical etching method the breakthrough-times (i.e. the time when the two etched cones from both sides of the detector contact) and the resulting track etching rates v_t of heavy ion tracks in 8 μm polycarbonate Makrofol KG have been measured. The samples were irradiated at the GSI, Darmstadt (Germany) with gold ions and different fluences at a specific energy of 11.6 MeV/u. All foils were etched in 6 n NaOH at room temperature. Fluctuations of breakthrough-times of single pore foils were analysed. Also the breakthrough-time of multi-pore-foils were measured. The dependence of the mean breakthrough-time on the ion fluence is dicussed. This dependence will be explained by the fluctuations of the breakthrough-time of the pores.     

A study of the basic properties of electrochemical track etching

The basic properties of the electrochemical track etching method proposed by Tommasino were studied for PC and PET foils irradiated with fission fragments and/or alpha-particles. Etching was performed in a specially designed double-wall vessel applying electric fields of different strengths and frequencies. The variation in the diameters of the discharge spots produced around the tracks of fission fragments entering PC and PET foils at right angles was systematically studied as a function of the strength and frequency of the electric field, etching time and etchant temperature. For alpha-tracks registered in PC foils the dependence of the discharge spot diameter on particle energy was also determined. It was found that the production of discharge spots started at a threshold field strength depending on the type of particle. The temperature dependence of the growing rate of discharge spots followed the Arrhenius law, but with a reduced activation energy as compared to that obtained for the chemical etching rate of the bulk material.     

微米/纳米相结合的三维金属铝图案

利用光刻，反应离子刻蚀以及电化学阳极氧化技术在铝基底上构建出了微米纳米相结合的三维金属铝图案。首先在铝片的表面形成一层具有图案的二氧化硅阻碍层，阳极氧化过程中，在二氧化硅阻碍层之下会形成侧向生长的倾斜孔道和残留的金属铝微结构。形成机制可阐述为：由于表面二氧化硅阻碍层的存在造成局域电场方向的偏折，影响到反应过程中离子的输运，从而导致侧向倾斜孔的形成，而在远离阻碍层的区域孔道则会正常垂直表面向下生长。这种垂直与侧向阳极腐蚀的同时进行导致在二氧化硅阻碍层之下形成了金属铝微结构。     

单锥形纳米孔的制备和离子传导特性研究

用荷能重离子径迹刻蚀的方法在高分子多聚物膜 (PET) 上制备出单锥形纳米孔. 刻蚀过程通过监测跨膜电流来控制, 最大刻蚀电流I_max不同, 得到的锥形孔小孔孔径也不同. 研究单锥形纳米孔在KCl 溶液中的I-V曲线发现, 单锥形纳米孔的离子传导呈现出不对称特性, 该现象称为整流效应, 整流系数γ大小随纳米小孔孔径大小和电解质溶液浓度而变化. 关键词： 径迹刻蚀 纳米孔 离子传导 整流系数     

抗金属污染的超绝缘材料研究

使用串列加速器产生的32S离子对不同厚度的聚碳酸酯、聚脂膜进行了不同密度的辐照，并在不同温度、不同碱度和不同蚀刻时间条件下，研究了蚀刻对孔形状、孔径以及膜表面损耗等的影响.通过表面金属镀膜的方式研究了该膜的抗金属污染的绝缘性能.结果显示，其抗金属污染的绝缘性能得到了大幅度提高.     

A new versatile electrochemical etching chamber (Vecec) system for multi-size and multi-shape detector processing

A new versatile electrochemical etching ECE chamber (VECE) system is introduced in which the effective electrochemically etched area can have variable sizes and/or shapes required using templet etching. The flat rubber washers act as templets and holders of the etchant, and control the size and shape of the effective etched area of the detector which can be of various shapes and sizes desired. The system was operated in two operation modes A and B in which the both sides and one side of the detector were etched respectively. Detectors with etched areas having diameters from 1 to 18 cm can have also been successfully etched by this system. Multi-chambers have been also designed using this principle for larger-scale multi-detector processing. The effects of etching area and time on the current through the detector have also been studied.     

Optimization of porous silicon preparation technology for SERS applications

A series of porous silicon samples prepared at different etching parameters, namely etchant composition, etching time and current density, was investigated as substrates for surface-enhanced Raman scattering (SERS). Silver nanostructures were deposited on porous silicon by immersion plating method and Rhodamine 6G was used as analyte. The relation between the etching parameters, morphology of porous silicon surface and its SERS efficiency after silver deposition is examined. We show that a high HF content in the etchant allows the formation of a film with close-packed silver nanocrystals, which possess strong surface enhancement properties.     

Effects of stirring on the bulk etch rate of CR-39 detector

It is well established that the bulk etch rates for solid state nuclear track detectors are affected by the concentration and the temperature of the etchant. Recently, we found that the bulk etch rate for the LR 115 detector to be affected by stirring during etching. In the present work, the effects of stirring on the bulk etch rate of the CR-39 detector is investigated. One set of sample was etched under continuous stirring by a magnetic stirrer at 70°C in a 6.25 N NaOH solution, while the other set of samples was etched without the magnetic stirrer. After etching, the bulk etch thickness was measured using Form Talysurf PGI (Taylor Hobson, Leicester, England). It was found that magnetic stirring did not affect the bulk etch of the CR-39 detector, which was in contrast to the results for the LR 115 detector.