Enhancement in CO gas sensing properties of hydroxyapatite thick films: Effect of swift heavy ion irradiation

This paper investigates the effect of swift heavy ion (SHI) irradiation on surface morphology of Hydroxyapatite (HAp) thick films and modification in gas sensing characteristics. The HAp nanopowder is synthesized by wet chemical process and the thick films are prepared by screen printing technique. These films are irradiated with Ag⁷⁺ ions with energy of 100 MeV at different fluences ranging from 3 × 10¹⁰ to 3 × 10¹³ ions/cm². X-ray diffraction and atomic force microscopy tools are employed to examine the phase and surface modification in HAp thick films due to swift heavy ion irradiation. The ion irradiation study shows that crystallinity decreases and grain size changes with increase in ion fluence. A precise study on gas sensing is carried out to confirm operating temperature of HAp thick film sensor to detect CO gas. Saturation region of the film with increasing gas concentration and other parameters such as response and recovery time are also investigated from the point of view of using HAp films as a sensor device. SHI irradiated HAp thick film shows enhancement in the gas response and saturation limit for CO gas. Furthermore, the irradiated HAp film shows fast response and recovery time for CO gas. The study concludes that nanoceramic HAp thick film is an excellent CO gas sensor at an operating temperature of 195 °C.     

Enhancement of wettability and antibiotic loading/release of hydroxyapatite thin film modified by 100 MeV Ag ion irradiation

The effect of swift heavy 100 MeV Ag⁷⁺ ions irradiation was studied on hydroxyapatite (HAp) thin film prepared by pulsed laser deposition technique (PLD). The GIXRD analysis confirmed the absence of any phase in the HAp phase due to irradiation. In addition, there was a considerable decrease in crystallinity and crystallite size on irradiation. There was no significant variation in the stoichiometry of the irradiated films. Irradiation seemed to decrease the optical band gap energy of HAp thin films. The surface roughness, wettability and bioactivity were improved on irradiation of the samples. Amount of amoxicillin loading/release increased (10%) in ion beam irradiated (1 × 10¹² ions cm⁻²) sample. Irradiated sample showed fast rate of amoxicillin (AMX) release than the pristine. Bactericidal effect was found to increase on irradiation. Surface modified and antibiotics incorporated HAp coated titanium implants may be used to prevent post-surgical infections and to promote bone-bonding of orthopedic devices.     

Fabrication of resistive CO gas sensor based on SnO2 nanopowders via low frequency AC electrophoretic deposition

A resistive CO gas sensor has been fabricated using AC electrophoretic deposition (ACEPD) technique. SnO₂ thick films are deposited by applying low frequency (0.01–1,000 Hz) AC electric field to a stable suspension of SnO₂ nanoparticles in acetyl acetone. A carbon film base electrode is used as deposit substrate. Effect of CO gas exposure on conductivity of the SnO₂ film at 300 °C is investigated. Results show that the sensor is sensitive and its response is repeatable. This work shows that ACEPD can be used as an easy and cheap technique for fabrication of electronic devices such as ceramic gas sensors.     

Swift heavy ion irradiation effect on Cu-doped CdS nanocrystals embedded in PMMA

Semiconductor nanocrystals (NCs) have received much interest for their optical and electronic properties. When these NCs dispersed in polymer matrix, brightness of the light emission is enhanced due to their quantum dot size. The CdCuS NCs have been synthesized by chemical route method and then dispersed in PMMA matrix. These nanocomposite polymer films were irradiated by swift heavy ion (SHI) (100 MeV, Si⁺⁷ ions beam) at different fluences of 1 × 10¹⁰ and 1 × 10¹² ions/cm² and then compared their structural and optical properties by XRD, atomic force microscopy, photoluminescence, and UV-Vis spectroscopy before and after irradiation. The XRD spectra showed a broad hump around 2θ ≈ 11·83° due to amorphous PMMA and other peaks corresponding to hexagonal structure of CdS nanocrystals in PMMA matrix. The photoluminescence spectra shows a broad peak at 530 nm corresponding to green emission due to Cu impurities in CdS. The UV-Vis measurement showed red shift in optical absorption and bandgap changed from 4·38–3·60 eV as the irradiation fluency increased with respect to pristine CdCuS nanocomposite polymer film.     

Optical properties of swift ion beam irradiated CdTe thin films

This paper reports the effect of swift (80 MeV) oxygen (O⁺⁶) ion irradiation on the optical properties of CdTe thin films grown by conventional thermal evaporation on glass substrates. The films are found to be slightly Te-rich in composition and irradiation results no change in the elemental composition. The optical constants such as refractive index (n), absorption coefficient (α) and the optical band gap energy show significant variation in their values with increase in ion fluence. Upon irradiation the band gap energy decreased from a value of 1.53 eV to 1.46 eV whereas the refractive index (n) increased from 2.38 to 3.12 at λ = 850 nm. The photoluminescence spectrum shows high density of native defects whose density strongly depends on the ion fluence. Both analyses indicate considerable defect production after swift ion beam irradiation.     

Effect of swift heavy ion beam irradiation on Au–polyaniline composite films

In this paper, two-step electrochemical synthesis method is reported for the fabrication of Au–polyaniline (Au–PANI) composite film. Initially, PANI film was electrochemically synthesized by using chronopotentiometery with optimized process parameters on platinum electrode. The synthesized PANI film acts as working electrode for the decoration of Au particles on the surface of PANI film by using cyclovoltammetry (CV) technique. Later, these films were irradiated under high vacuum (∼5 × 10⁻⁶ Torr) at room temperature with 40 MeV C⁵⁺ ion beam at various fluences ranging from 1 × 10¹¹ to 1 × 10¹³ ions/cm². The Au–PANI composite films were characterized before and after irradiation by using micro-Raman, X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The characteristic peaks of the Raman spectrum of Au–PANI composite films were reduced after irradiation. XRD spectra exhibited the decrease in the peak intensity. Moreover, interchain distance, interplanar distance, micro strain, dislocation density and distortion parameters were calculated. The analysis revealed a significant variation in these parameters with an increase in the ion fluence, which is in line with the Raman analysis. SEM shows the formation of clusters with porous structure after irradiation.     

Effect of SHI irradiation on the morphology of SnO2 thin film prepared by reactive thermal evaporation

SnO₂ thin films prepared by reactive thermal evaporation on glass substrates were subjected to 120 MeV Ag⁹⁺ ion irradiation. The surface topography progression using the swift heavy ion irradiation was studied. It shows creation of unique surface morphologies and regular structures on the surface of the SnO₂ thin film at particular fluences. Field Emission Scanning electron microscopy (FE-SEM) and Atomic force microscopy (AFM) are used for investigating the effect of Ag ions at different fluences on the surface of SnO₂. The morphological changes suggest that ion assisted/induced diffusion process play a significant role in the evolution of nanostructures on SnO₂ surface. The roughness increases from 9.4 to 14.9 with fluence upto 1 × 10¹² ions/cm² and beyond this fluence, the roughness decreases. Ion-beam induced recrystallization at lower fluences and amorphization or disordering of crystals at higher fluences are understood based on the thermal spike model.     

Influence of crystallinity on CO gas sensing for TiO2 films

In the present research, carbon monoxide (CO) gas sensing response was studied for TiO₂ thick films calcined and sintered between 700 and 900 °C. Crystalline phase, crystallite size, surface area, particle size, and amorphous content were measured for the calcined powder. Crystallinity of the powder was found to affect sensing response significantly towards CO. Anatase phase of TiO₂ thick film was stable up to 900 °C however, as calcination temperature increased from 700 to 900 °C, surface area and amorphous phase content decreased. Films calcined and sintered at 700 °C showed a lower response towards CO than those calcined at 800 °C. Upon increasing the calcination temperature further, particle growth and reduced surface area hindered the sensing response. A calcination temperature of 800 °C was necessary to achieve sufficient order in the crystal structure leading to more efficient adsorption and desorption of oxygen ions on the surface of TiO₂.     

Selective detection of hydrogen sulfide using copper oxide-doped tin oxide based thick film sensor array

In this work, copper oxide-doped (1, 3 and 5 wt%) tin oxide powders have been synthesised by sol–gel method and thick film sensor array has been developed by screen printing technique for the detection of H₂S gas. Powder X-ray diffraction pattern shows that the tin oxide (SnO₂) doped with 3 wt% copper oxide (CuO) has smaller crystallite size in comparison to 0, 1 and 5 wt% CuO-doped SnO₂. Furthermore, field emission scanning electron microscopy manifests the formation of porous film consisting of loosely interconnected small crystallites. The effect of various amounts of CuO dopant has been studied on the sensing properties of sensor array with respect to hydrogen sulfide (H₂S) gas. It is found that the SnO₂ doped with 3 wt% CuO is extremely sensitive (82%) to H₂S gas at 150 °C, while it is almost insensitive to many other gases, i.e., hydrogen (H₂), carbon monoxide (CO), sulphur dioxide (SO₂) and liquefied petroleum gas (LPG). Moreover, at low concentration of gas, it shows fast recovery as compared to response time. Such high performance of 3 wt% CuO-doped SnO₂ thick film sensor is probably due to the diminishing of the p–n junction and the smallest crystallite size (11 nm) along with porous structure.     

The gas sensitivity of nano TiO2-SnO2 film doped with Cd(II) ion

The nanocomposite oxide (0.2TiO₂-0.8SnO₂) doped with Cd²⁺ powder have been prepared and characterized by XRD and their gas-sensing sensitivity were characterized using gas sensing measurement. Experimental results show that, bicomponent nano anatase TiO₂ and rutile SnO₂ particulate thick film doped with Cd²⁺ behaves with good sensitivity to formaldehyde gas of 200 ppm in the air, and the optimum sensing temperature was reduced from 360 °C to 320 °C compared with the undoped Cd²⁺ thick film. The gas sensing thick films doped with Cd²⁺ also show good selectivity to formaldehyde among benzene, toluene, xylene and ammonia as disturbed gas and could be effectively used as an indoor formaldehyde sensor.     

Effect of swift heavy ion irradiation on bare and coated ZnS quantum dots

The present study compares structural and optical modifications of bare and silica (SiO₂) coated ZnS quantum dots under swift heavy ion (SHI) irradiation. Bare and silica coated ZnS quantum dots were prepared following an inexpensive chemical route using polyvinyl alcohol (PVA) as the dielectric host matrix. X-ray diffraction (XRD) and transmission electron microscopy (TEM) study of the samples show the formation of almost spherical ZnS quantum dots. The UV-Vis absorption spectra reveal blue shift relative to bulk material in absorption energy while photoluminescence (PL) spectra suggests that surface state and near band edge emissions are dominating in case of bare and coated samples, respectively. Swift heavy ion irradiation of the samples was carried out with 160 MeV Ni¹²⁺ ion beam with fluences 10¹² to 10¹³ ions/cm². Size enhancement of bare quantum dots after irradiation has been indicated in XRD and TEM analysis of the samples which has also been supported by optical absorption spectra. However similar investigations on irradiated coated quantum dots revealed little change in quantum dot size and emission. The present study thus shows that the coated ZnS quantum dots are stable upon SHI irradiation compared to the bare one.     

Structural damage studies in conducting indium-tin oxide (ITO) thin films induced by Au swift heavy ions (SHI) irradiation

Spray pyrolysis deposited indium-tin oxide (ITO) thin films were fabricated and irradiated using Au⁸⁺ swift heavy ions (SHI) (100 MeV energy), at different fluency doses ranging between 1×10¹¹ ions/cm² and 1×10¹³ ions/cm². After irradiation, significant changes have been observed in surface morphology and crystallographic structure pertaining to increase in grain size, change in surface roughness, crystallographic disorders of large crystallites, and noticed a net decrease in optical transmittance and electrical resistivity of these films.     

Energetic ion irradiation induced crystallization of Ni–Mn–Sn ferromagnetic shape memory alloy thin film

The ion irradiation induced crystallization of Ni–Mn–Sn ferromagnetic shape memory alloy (FSMA) thin film is investigated. Thin films of Ni–Mn–Sn FSMA synthesized by DC magnetron sputtering on Si substrate at 200 °C are irradiated by a beam of 120 MeV Ag ions at different fluence varying from 1 × 10¹² to 6 × 10¹² ions/cm². X-ray diffraction pattern reveals that the pristine film grows in L2₁ cubic austenite phase with poor crystallinity and crystallinity of the film improves with increasing ion fluence, which is attributed to the strain relaxation by the energy deposited by incoming ions and promotes the grain growth. Grain growth is further confirmed by Atomic force microscopy. The temperature dependent magnetization measurements show improvement in the magnetic and shape memory properties of the films with increasing fluence, which is ascribed to the ordering of austenite phase. Nanoindentation measurements show that with increasing fluence of 120 MeV Ag ions, films exhibit a greater stiffness and smaller tendency towards plastic deformation.     

Influence of 150 MeV Ni swift heavy ion irradiation on CuFe2O4 thin films prepared by radio frequency magnetron sputtering: Modification on structure and surface morphology

The bulk copper ferrite nanomaterials are synthesized by co-precipitation technique. The vibrating sample magnetometer measurement for bulk CuFe₂O₄ reveals its unsaturated superparamagnetic behavior. The crystallites of the synthesized nanomaterial are in cubic form having an average size of ~ 100 Å and are used as target to prepare thin films of various thicknesses (600, 900 and 1100 nm) by radio frequency magnetron sputtering technique. X-ray peaks arise only when films are annealed at 1200 °C and also they are found to be in tetragonal structure. The magnetic characteristics of 900 nm unirradiated CuFe₂O₄ thin film exhibit superparamagnetic behavior and have an unsaturated magnetic moment at high field. Magnetic force microscopy images of unirradiated CuFe₂O₄ thin films confirm the soft nature of the magnetic materials. The 150 MeV Ni¹¹⁺ swift heavy ion irradiation on these thin films at the fluence of 1 × 10¹⁴ ions/cm² modifies the polycrystalline nature due to electron-phonon coupling. Atomic force microscopy image shows that the swift heavy ion irradiation induces agglomeration of particles in 600 and 900 nm thin films and increases rms surface roughness from 33.43 to 39.65 and 69.7 to 102.46 nm respectively. However, in 1100 nm film, holes are created and channel-like structures are observed along with a decrease in the rms surface roughness from 75.12 to 24.46 nm. Magnetic force microscopy images of 900 nm irradiated thin film explain the formation of domains on irradiation and are also supported by the ferromagnetic hysteresis observed using vibrating sample magnetometer.     

Synthesis, characterization and gas sensing property of hydroxyapatite ceramic

Hydroxyapatite (HAp) biomaterial ceramic was synthesized by three different processing routes viz. wet chemical process, microwave irradiation process, and hydrothermal technique. The synthesized ceramic powders were characterized by SEM, XRD, FTIR and XPS techniques. The dielectric measurements were carried out as a function of frequency at room temperature and the preliminary study on CO gas sensing property of hydroxyapatite was investigated. The XRD pattern of the hydroxyapatite biomaterial revealed that hydroxyapatite ceramic has hexagonal structure. The average crystallite size was found to be in the range 31–54 nm. Absorption bands corresponding to phosphate and hydroxyl functional groups, which are characteristic of hydroxyapatite, were confirmed by FTIR. The dielectric constant was found to vary in the range 9–13 at room temperature. Hydroxyapatite can be used as CO gas sensor at an optimum temperature near 125°C. X-ray photoelectron spectroscopic studies showed the Ca/P ratio of 1.63 for the HAp sample prepared by chemical process. The microwave irradiation technique yielded calcium rich HAp whereas calcium deficient HAp was obtained by hydrothermal method.     

Solid-state reaction synthesized Pd-doped tin oxide thick film sensor for detection of H2, CO, LPG and CH4

This paper deals with the synthesis of tin oxide (SnO₂) nano-powders by a solid-state reaction technique. The synthesized powders have been characterized by simultaneous thermo gravimetric and differential thermal analysis (TG–DTA) and X-ray diffraction (XRD) techniques. Suitable calcination temperature is established by XRD and TG–DTA analysis. Thick film sensors have been developed from as-prepared undoped and palladium (Pd) doped (0.5 and 1 wt%) SnO₂ powders using screen printing technology for the detection of various pollutant gases such as, hydrogen (H₂), carbon monoxide (CO), liquefied petroleum gas (LPG) and methane (CH₄). The surface of the thick film sensor has been characterized by field emission scanning electron microscopy (FESEM). The sensing characteristics of thick films have been studied from the aspect of crystallite size of sensing material and microstructure of the thick film surface. It is found that SnO₂ doped with 1 % Pd exhibits the maximum sensitivity (79 %) towards CO gas along with fast response/recovery time (80 s, 197 s) and almost insensitive for H₂, LPG and CH₄.     

Impact of various irradiation photon energies and gamma doses on the optical properties of ZnSe nanostructure thin film

ZnSe thin films were prepared by thermal evaporation technique under high vacuum (10⁻⁶ Torr) at 300 K and different film thickness. The structure of thin films was measured using grazing incident in-plane X-ray diffraction (GIIXD) and shows single phase zinc blende structure. The particle sizes of the deposited films were estimated for low film thickness by TEM and high film thickness by GIIXD. The particle size of ZnSe films was decreased from ~8.53 to 3.93 nm as film thickness lowered from 200 to 20 nm which ensures the nanocrystalline structure. The optical transmission (T) and reflection (R) in the wavelength range 190–2,500 nm for irradiated and unirradiated ZnSe thin films under investigation were measured. The effect of irradiation of different energies in range (0.1–1.25 MeV) from X-ray, ¹³⁷Cs and ⁶⁰Co irradiation sources were studied for ZnSe thin films of 100 and 200 nm thicknesses. The dependence of the absorption spectra and refractive index were investigated for different energies irradiation sources. The ZnSe films show direct allowed interband transition. The effect of particle size of nanocrystalline ZnSe thin films for unirradiated and irradiated by gamma (γ) doses from ¹³⁷Cs on the optical properties was studied. Both the optical energy bandwidth and absorption coefficient (α) were found to be (γ) dose dependent.     

A novel ozone detection at room temperature through UV-LED-assisted ZnO thick film sensors

In this work a novel ozone detection at room temperature (RT) has been investigated. Two functional materials, ZnO and (W_0.9Sn_0.1)O_3 − x (WS10) oxides, have been synthesized to prepare thick film gas sensors, both used in conventional heated mode as well as at RT assisted by UV irradiation. As a source of light, a light emitting diode (LED) of 400 nm peak wavelength was used. Under typical operating conditions of the UV-LED, the radiation flux density ? over the sensor was of about 5 · 10¹⁷ photons/cm². Powders and films have been characterized by means of TG-DTA, SEM, TEM and XRD. Finally, electrical measurements have been performed on sensing films with the aim to compare conductive properties, surface barrier heights and ozone sensing features with and without UV irradiation. Despite the fact that two types of conventional heated sensors offered quite similar results with respect to ozone sensing, it turned out that, at RT and with the assistance of UV light, ZnO behaved excellently fast detecting ozone at concentrations down to 10 ppb, while for WS10 under the same operating conditions an opposite result was observed, i.e. very low response and long response time.     

Room temperature H2S gas sensing characteristics of platinum (Pt) coated porous alumina (PoAl) thick films

The study reports H₂S gas sensing characteristics of platinum (Pt) coated porous alumina (PoAl) films. The porous alumina (PoAl) thick layers were formed in the dark on aluminum substrates using an electrochemical anodization method. Thin semitransparent platinum (Pt) films were deposited on PoAl samples using chemical bath deposition (CBD) method. The films were characterized using energy dispersive X-ray analysis (EDAX) and scanning electron microscopy (SEM). The thicknesses of coated and bare films were measured using ellipsometry. The sensing properties such as sensitivity factor (S.F.), response time, recovery time and repeatability were measured using a static gas sensing system for H₂S gas. The EDAX studies confirmed the purity of Pt–PoAl film and indicated the formation of pure platinum (Pt) phase. The ellipsometry studies revealed the thickness of PoAl layer of about 15–17 μm on aluminum substrates. The SEM studies demonstrated uniform distribution of spherical pores with a size between 0.250 and 0.500 μm for PoAl film and nearly spherical platinum particles with average particle size ∼100 nm for Pt–PoAl film. The gas-sensing properties of these samples were studied in a home-built static gas characterization system. The H₂S gas sensing properties of Pt–PoAl at 1000 ppm of H₂S gave maximum sensitivity factor (S.F.) = 1200. The response time and recovery time were found to be 2–3 min and ∼1 min respectively. Further, the measurement of H₂S gas sensing properties clearly indicated the repeatability of gas sensing response of Pt–PoAl film. The present study indicated the significant potential of Pt coated PoAl films for H₂S gas sensing applications in diverse areas.     

Swift heavy ion induced modifications in structural,optical & magnetic properties of pure and V doped ZnO films

The effect of swift heavy ion irradiation on structural, optical and magnetic properties of pure ZnO, Zn_0.95V_0.05O and Zn_0.90V_0.10O films prepared by RF sputtering are studied. X-ray diffraction (XRD) analysis reveals no significant change in the ZnO crystal structure except a small change in intensity and peak broadening on irradiation. Raman spectra reveal the degradation of crystalline quality upon ion irradiation. Atomic force microscopy (AFM) study shows the formation of smaller sized nanostructures on ion irradiation. Photoluminescence (PL) spectra of ZnO films reveal the increase of defects such as oxygen vacancy in the films upon ion irradiation. The irradiated V doped ZnO films exhibit room temperature ferromagnetic behaviour. An increase in oxygen vacancy on ion irradiation together with V ion concentration favours enhanced ferromagnetic behaviour in irradiated V doped ZnO films.