Relationship between crystal morphology and photoluminescence in polynanocrystalline lead sulfide thin films

Thin films of lead sulfide (PbS) nanoparticles were grown on corning glass and Si(1 0 0) substrates by polyethylene glycol-assisted chemical bath deposition (CBD) method. This paper compares the morphology and the luminescence properties (PL) of the deposited thin films in the presence (or absence) of PEG300 and investigates the effect of deposition temperatures. Surface morphology and photoluminescence properties of samples were analyzed. The PL data show a blue-shift from the normal emission at ∼2900 nm in PbS bulk to ∼360 nm in nanoparticles of PbS thin films. Furthermore, the PL emission of the films obtained without the addition of PEG300 (type 1) was slightly shifted from that of the films obtained in presence of PEG300 (type 2) from ∼360 to ∼470 nm. The blue-shifting of the emission wavelengths from 2900 to ∼360 or 470 nm is attributed to quantum confinement of charge carriers in the restricted volume of nanoparticles, while the shift between the two types of PbS nanoparticles thin films is speculated to be due to an increase in the defect concentration. The blue-shift increased with increase of the deposition temperature, which suggests that there has been a relative depletion in particle sizes during the CBD of the films at higher temperatures. The PbS nanocrystalline thin films obtained in the presence of PEG300 at 60 °C exhibit a high blue luminescence.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Synthesis, characterization and optical properties of multipod ZnO whiskers

Multipod ZnO whiskers were synthesized successfully by two steps: pulsed laser deposition (PLD) and thermal evaporation process. First, a thin layer of Zn films were deposited on Si(1 1 1) substrates by PLD. Then the whiskers grew on Zn-coated Si(1 1 1) substrate by the simple thermal evaporation oxidation of the metallic zinc powder at 900 °C in the air without any catalysts or additives. The pre-deposited Zn films by PLD on the substrate can promote the growth of ZnO multipod whiskers effectively. The as-synthesized ZnO whiskers were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results revealed that the whiskers are highly crystalline with the wurtzite hexagonal structure. Room temperature photoluminescence (PL) spectrum of the whiskers shows a UV emission peak at ∼393 nm and a broad green emission peak at ∼517 nm, which was assigned to the near band-edge emission and the deep-level emission, respectively.     

Ex situ synthesis and optical properties of ZnO-PbS nanocomposites

Zinc oxide (ZnO) and lead sulphide (PbS) nanoparticles separately synthesized by a precipitation method were combined by an ex situ route to prepare ZnO-PbS nanocomposites with different molar ratios of ZnO and PbS. The structure and morphology of the ZnO, PbS and ZnO-PbS samples were analyzed with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A UV-vis spectrophotometer was used to collect the absorption and 325 nm He-Cd and 488 nm Ar lasers were used to collect the photoluminescence data from the samples. ZnO nanoparticles showed a broad and stable emission peak at ∼570 nm, while a strongly quantum confined emission from PbS nanoparticles was detected at ∼1344-1486 nm. The ZnO-PbS nanocomposites exhibited dual emission in the visible and near-infrared (NIR) regions that is associated with defects and recombination of excitonic centres in the ZnO and PbS nanoparticles, respectively. The PL intensity of the visible emission from the ZnO-PbS nanocomposite was shown to increase when the ZnO to PbS molar ratio was 5:1 and the emission was almost quenched at molar ratios of 1:1 and 1:5. For different molar ratios of ZnO to PbS, the PL intensity of the NIR emission from the ZnO-PbS nanocomposites was more intense than that of PbS nanoparticles.     

Tailoring the photoluminescence of PbS-nanoparticles layers deposited by means of the pulsed laser ablation technique

In this article, we report on the room-temperature pulsed laser deposition (PLD) of lead sulfide (PbS) nanoparticles (NPs) layers onto various substrates. It is particularly shown that the average size of PbS NPs can be controlled by varying the number of laser ablation pulses. The pulsed laser deposited PbS NPs are found to be of high-crystalline quality and their photoluminescence (PL) to blue shift significantly from 1420 to 880 nm, as their average diameter is decreased from 8.5 to 2.5 nm, thereby confirming the quantum size effect. The latitude of our PLD process is shown to permit the achievement of multilayered PbS-NPs structures of which the overall PL emission spectrum can be tailored through the appropriate stack of individual PbS-NPs layers.     

Structural and optical properties of YSZ thin films grown by PLD technique

We report on the structural and optical properties of yttria stabilized zirconia (YSZ) thin films grown by pulsed laser deposition (PLD) technique and in situ crystallized at different substrate temperatures (T_s = 400 °C, 500 °C and 600 °C). Yttria-stabilized zirconia target of ∼1 in. diameter (∼95% density) was fabricated by solid state reaction method for thin film deposition by PLD. The YSZ thin films were grown on an optically polished quartz substrates and the deposition time was 30 min for all the films. XRD analysis shows cubic crystalline phase of YSZ films with preferred orientation along 〈1 1 1〉. The surface roughness was determined by AFM for the films deposited at different substrate temperatures. The nano-sized surface roughness is found to increase with the increase of deposition temperatures. For the optical analysis, a UV-vis-NIR spectrophotometer was used and the optical band gap of ∼5.7 eV was calculated from transmittance curves.     

Quenching of surface traps in Mn doped ZnO thin films for enhanced optical transparency

The structural and photoluminescence analyses were performed on un-doped and Mn doped ZnO thin films grown on Si (1 0 0) substrate by pulsed laser deposition (PLD) and annealed at different post-deposition temperatures (500-800 °C). X-ray diffraction (XRD), employed to study the structural properties, showed an improved crystallinity at elevated temperatures with a consistent decrease in the lattice parameter ‘c’. The peak broadening in XRD spectra and the presence of Mn 2p3/2 peak at ∼640 eV in X-ray Photoelectron Spectroscopic (XPS) spectra of the doped thin films confirmed the successful incorporation of Mn in ZnO host matrix. Extended near band edge emission (NBE) spectra indicated the reduction in the concentration of the intrinsic surface traps in comparison to the doped ones resulting in improved optical transparency. Reduced deep level emission (DLE) spectra in doped thin films with declined PL ratio validated the quenching of the intrinsic surface traps thereby improving the optical transparency and the band gap, essential for optoelectronic and spintronic applications. Furthermore, the formation and uniform distribution of nano-sized grains with improved surface features of Mn-doped ZnO thin films were observed in Field Emission Scanning Electron Microscopy (FESEM) images.     

Preparation and properties of nanocrystalline powders in (Y1−xCex)3Al5O12 system

Nano-sized cerium-doped yttrium aluminum garnet (YAG:Ce) phosphors were synthesized via a simple sol-gel process using metal nitrate precursors. The prepared phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy, respectively. Pure cubic garnet phase was formed at temperatures ∼900 ^οC. The particle sizes of as-prepared powders were mostly in the range of 17-27 nm. The crystalline YAG:Ce showed broad emission peaks in the range of 400-700 nm and maximum intensities at 500 and 520 nm. It is found also that the emission intensity decreased with increasing Ce doping concentration from 0.1 to 1.5 at%. With increasing Ce doping concentration, the PL intensity was shifted towards shorter wavelengths.     

Studies on CdTe films deposited by pulsed laser deposition technique

Polycrystalline cadmium telluride films were successfully deposited on glass substrates by ablating a CdTe target by pulsed Nd–YAG laser. Microstructural studies indicated an increase in the average crystallite size from 15 nm to ∼50 nm with the increase in substrate temperature during deposition. The films deposited here were slightly tellurium rich. X-ray diffraction pattern indicated that the films deposited at 300 K had wurtzite structure while those deposited above 573 K were predominantly of zinc blende structure. Residual strain in the films deposited at 300 K was quite low as compared to those deposited at higher temperatures. PL spectra of all the CdTe films were dominated by a strong peak at ∼921 nm (∼1.347 eV) followed by a low intensity peak at ∼863 nm (∼1.438 eV). Characteristics Raman peaks for CdTe indicated a peak at ∼120 cm⁻¹ followed by peaks located at ∼140 cm⁻¹ and 160 cm⁻¹.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).     

Photoluminescence spectroscopy study on tris(8-hydroxyquinoline) aluminum film

In situ photoluminescence spectroscopy (PL) measurements of tris(8-hydroxyquinoline) aluminum (Alq₃) film were carried out. Upon deposition of Alq₃ on the glass substrate, the PL intensity changes dramatically, while the peak position of Alq₃ emission shows a sharp red-shift from 524 nm at the initial deposition of Alq₃, and tends to a saturation value of 536 nm for the film thickness range from 2 to 500 nm. This red-shift is associated with the change from the 2D to 3D exciton state with increasing Alq₃ film thickness. Temperature dependent PL spectra of Alq₃ films showed, besides the changes in the PL intensity, clearly a blue-shift of Alq₃ emission about 9 nm for the film annealing up to 150 °C, while no any shift of Alq₃ emission was observed for the film annealing below 130 °C. Both changes in PL intensity, and especially in the peak position of Alq₃ emission were attributed to crystallization (thermal) effect of Alq₃ film upon annealing.     

Size-dependent photoluminescent properties of uncapped CdS particles prepared by acoustic wave and microwave method

CdS particles with crystallite size of 5-12 nm have been prepared via acoustic wave stimulated (sonochemical) route and microwave initiated combustion method. X-ray line broadening and transmission electron microscopy (TEM) suggest that sonochemical powders are more amorphous (5-10 nm) compared to microwave-synthesized sulphides (10-15 nm). The photoluminescent (PL) properties of powders with size <10 nm show a clearly blue shifted, resolved emission with full-width at half-maxima (FWHM) ∼100 nm, while powders with size >15 nm show dominant blue to green narrow emission with FWHM ∼60 nm. The mechanistic details of the synthetic route appear to affect the morphology and consequently the PL properties to a significant extent.     

Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb sol gel derived phosphor

Terbium (1 mol%) doped ZnO-SiO₂ binary system was prepared by a sol-gel process. Nanoscopic effects of ZnO on the photoluminescence (PL) and the cathodoluminescence (CL) properties were studied. Defects emission from ZnO nanoparticles was measured at 560 nm and the line emission from Tb³⁺ ions in SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺ with a major peak at 542 nm was measured. The PL excitation wavelength for 542 nm Tb³⁺ emission was measured at ∼320 nm in both SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺. The CL data showed quenched luminescence of the ZnO nanoparticles at 560 nm from a composite of ZnO-SiO₂:Tb³⁺ and a subsequent increase in 542 nm emission from the Tb³⁺ ions. This suggests that energy was transferred from the ZnO nanoparticles to enhance the green emission of the Tb³⁺ ions. The PL and CL properties of ZnO-SiO₂:Tb³⁺ binary system and possible mechanism for energy transfer from the ZnO nanoparticles to Tb³⁺ ions are discussed.     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Fluorescence properties of Ag nanoparticles in water, methanol and hexane

Ag nanoparticles, synthesized employing the electro-exploding wire technique, are reported. Absorption in the UV-visible region by these particles is characterized by the features reported in the literature, namely, a possible plasmon peak at ∼404 nm. For Ag nanoparticles dispersed in water, photo-excitation in the ranges 210-235 and 255-280 nm produces similar fluorescence emission at ∼300 nm, whose corresponding resonant absorption takes place at 215 and 270 nm in the excitation spectra. Further, we study the effect of the surrounding medium (solvent effect) on fluorescence from these nanoparticles by comparing fluorescence emission in methanol and hexane for photo-excitation in the same range. Compared to water, fluorescence emission in methanol is observed red-shifted at ∼310 nm, which further red-shifts to ∼325 nm in hexane. The corresponding resonant absorptions in methanol are at 225 and 275 nm. Consequence of this red-shift in a less polar solvent is discussed.     

Preparation and optical properties of UV dye DMT-doped silica films

UV dye DMT-doped silica films were prepared by sol-gel process with dioxane as the cosolvent. Luminescence quenching was not observed even if the DMT concentration in the visibly transparent silica film is as high as 1.26×10⁻² M. The emission peaks centered at ∼375 nm for the films show red-shift of 35-45 nm, comparing with that of the cyclohexane solution of DMT. The fluorescence quantum efficiency of the films centered at ∼590 nm are larger than those at ∼375 nm.     

Structural and morphological study of ZnO thin films electrodeposited on n-type silicon

In this work, we report on the electrodeposition of ZnO thin films on n-Si (1 0 0) and glass substrates. The influence of the deposition time on the morphology of ZnO thin films was investigated. The ZnO thin films were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDS) and scanning electron microscopy (SEM). The results show a variation of ZnO texture from main (0 0 2) at 10 min to totally (1 0 1) at 15 min deposition time. The photoluminescence (PL) studies show that both UV (∼382 nm) and blue (∼432 nm) luminescences are the main emissions for the electrodeposited ZnO films. In addition, the film grown at 15 min indicates an evident decrease of the yellow-green (∼520 nm) emission band comparing with that of 10 min. Finally, transmittance spectra show a high transmission value up to 85% in the visible wavelength range. Such results would be very interesting for solar cells applications.     

Atomic force microscopic characterization of films grown by inverse pulsed laser deposition

Carbon nitride films have been deposited by KrF excimer laser ablation of a rotating graphite target in 5 Pa nitrogen ambient in an inverse pulsed laser deposition configuration, where the backward motion of the ablated species is utilised for film growth on substrates lying in the target plane. Topometric AFM scans of the films, exhibiting elliptical thickness distribution, have been recorded along the axes of symmetry of the deposition area. High resolution AFM scans revealed the existence of disk-like, or somewhat elongated rice-like features of 5-10 nm average thickness and ∼100 nm largest dimension, densely packed over the whole, approximately 14 × 10 cm² deposition area. The RMS roughness of the film decreased from 9 nm near to the laser spot down to 2 nm in the outer regions. Even the highest RMS value obtained for IPLD films was less than half of the typical, 25 nm roughness measured on simultaneously deposited PLD films.