This work examines the possibility of real-time detecting of single nitro compounds microcrystals [cyclotrimethylenetrinitramine (RDX) and pentaerythritol tetranitrate (PETN)] with sizes of ∼130 to 600 μm by the terahertz (THz) imaging. A THz video camera based on a microbolometer matrix was used to record images in transmission and reflection optical schemes. A photoconductive antenna was used as a THz source. It was experimentally demonstrated that the spectral selectivity of identifying of nitro compounds microcrystals in the THz range strongly depends on their size, and the results of mathematical modeling based on the Mie scattering theory showed that this effect is due to the complex dependence of the extinction cross section of the microcrystals on their size. The results of the work can be used in the development of real-time THz visualization systems.
The THz reflection spectra of optically thin hexogen (RDX) samples were studied by terahertz imaging with spectral resolution. A photoconductive antenna excited by femtosecond laser radiation was used as a source of broadband THz radiation. The presence of a Fourier spectrometer (as well as band-pass THz filters) and a microbolometric THz video camera in the experimental setup made it possible to use the terahertz imaging method to study reflection spectra taking into account scattering in the range of 0.6 to 1 THz. The influence of the optical characteristics of the substrate on the THz reflection spectra was studied. In particular, the conditions for observing the effect of anomalous dispersion for RDX samples with different dispersion in the frequency region of the RDX absorption band 0.8 THz were studied. The obtained results demonstrate the application of the method of terahertz imaging with spectral resolution based on THz video camera for the identification of explosives with concentrations 0.75 to 50 mg / cm2 on various surfaces.
Currently, luminescent sensors for detecting vapors of nitroaromatic compounds and other explosives are being actively developed. In practice, the stability of the luminescence signal of the sensor is of great importance. In this work we study photostability of sensitive luminophore embedded in porous silicon microcavities under exciting at a wavelength of 450 nm. As the sensitive luminophore we used Poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMOPPV). It was found that the rate of photodegradation of MDMO-PPV luminescence depends nonlinearly on the intensity of the exciting radiation. Apparently, the observed effect is related to the limited rate of diffusion of oxygen molecules into the porous silicon. Additionally, similar studies were carried out for MDMO-PPV films on a glass substrate. It is shown that in this case the photostability of the luminophore decreases by several times. Based on the data obtained, the operating modes of the sensor element are analyzed.
We exploit micro-nano structuration to achieve multifunctional windows offering outstanding optical and fluidic properties to enhance the operation of surveillance or detection devices under rainy conditions. These windows are based on synthesis of an artificial index gradient for antireflection properties and improvement of their water repellency property thanks to their structuration at a subwavelength scale with controlled conical geometries. We demonstrate the realization of multifunctional germanium windows for LWIR camera, using two approaches: nanoimprint lithography, well-known for its very high resolution enabling applications from visible to thermal infrared domain, followed by etching techniques, and 3D direct laser writing based on Two-Photon Polymerization (TPP), which is of interest thanks to its ability to manufacture complex 3D structuration directly. Optical characterization shows the ability of such windows to improve optical transmission within 8-14μm spectral range, as compared to non-structured window. In terms of water repellency, the structured windows enable an increase of the contact angle up to 160° with a very low hysteresis. To evaluate the advantage of the multifunctional windows for imaging devices, the windows are integrated in front of a thermal infrared camera and images analysis shows that the camera sensitivity is increased for the nanoimprint window thanks to the multifunctional window and high water repellency in presence of water.
Semiconductor quantum dots (QDs) have a wide absorption spectrum spreading from UV to the visible region and high photoluminescence (PL) quantum yield (QY) what determine possible use of their films for re-emitting coatings enhancing the photodetector spectral range. Unlike fluorescent organic dyes, the QDs absorption doesn’t saturate at high excitation intensities and can absorb more than one photon per particle due to the biexciton generation. However, due to the high rate of the Auger nonradiative relaxation, the QDs biexciton PL QY is much lower than the single-exciton one, what reduces the overall PL QY and the photodetector photosensitivity at the high excitation intensities. An employment of the Purcell effect in the plasmon nanocavities should increase the biexciton PL QY thus overcoming this limitation. To use this effect, we designed a thin-film plasmon–exciton material containing QDs and silver nanoplates (SNPs) in which the QDs’ PL band and the SNPs’ absorption band are overlapped. To demonstrate the advantage of the designed (QD-SNP)-film, we have compared effects of QD-film and (QD-SNP)-film on the photoresponse of the Si-based photodetector. The response of a photodetector to pulse excitation at 266 nm was negligible and increased after the deposition of the QD-film on its surface. However, at the high excitation intensities, the photosignal was reduced due to the biexcitons formation. The addition of SNPs increased the photoresponse at high excitation intensities. We attribute this improvement to a strong enhancement of QD biexciton PL in the QD-SNP material, which became predominate at high excitation intensities.
The presence of peculiarities in terahertz spectra of many organic compounds allows the use of THz imaging and spectroscopy for the detection of various hazardous and explosive substances. This work is devoted to the study of the detection of trace amounts of 1,3,5-Trinitro-1,3,5-triazinane (RDX) in the form of particles localized in millimeter and submillimeter sizes using THz imaging with spectral resolution. As a result of the work, images of trace amounts of RDX in reflected THz radiation were obtained. The contrast in these images made it possible to detect single particles of the powdery substance. The difference in contrast for RDX and polyethylene (PE) in the obtained terahertz images makes it possible to use THz imaging with spectral resolution not only for detection, but also for the identification of chemical compounds.
Currently, one of the most important application of flow cytometry is the real-time analysis of aerosols, in particular, to ensure biosafety. In most cases, such analysis is aimed at detecting fluorescent signals from aerosol particles corresponding to the light emission of tryptophan and nicotinamide adenine dinucleotide (NADH). Further development of the method is largely related to the improvement of the light detecting systems for recording and processing of fluorescence and scattered light signals. In this work, a comparative analysis of flow cytometers for bioaerosols detection based on photo-multiplier tubes (PMT) and avalanche photodiodes (APD) operating in analog and photon-counting modes was carried out. The limit of detection (LOD) of bioaerosols, response time and ability to detect particles with low scattering and fluorescence cross section were calculated and examined. The calculations were carried out for the well-known optical scheme of fluorescence detection based on discrete photodetectors and dichroic mirrors combined with an air flow chamber equipped with elliptical and spherical mirrors. An ultraviolet light emission diode (LED) was used as a model source of exciting radiation. To estimate the optical properties of aerosol particles, experimental results obtained for a model bovine serum albumin bioaerosol and published data on various other bioaerosols were used. The calculation of the total number of fluorescent photons, emitted by particles of various sizes while passing the flow chamber was carried out. The obtained data were compared with parameters of photodetectors operating in analog and photon-counting modes. The critical particle size was determined for the effective registration in a photon-counting mode. Considering the size distribution of aerosol particles, it was concluded that application of the photon-counting mode will reduce the LOD of bioaerosols by more than an order of magnitude.
It is known that luminescent optical sensors are perspective for detection towards nitroaromatic compounds that are a basis of a many kind of explosives. Operation of these sensors is based on quenching luminescence, which is caused by photo-induced electron transfer from a luminophore (donor) to a nitroaromatic molecule (acceptor). The conjugated polymers, small molecule dyes and metal-organic frameworks are used as a sensitive luminophores currently. One of the methods to improve these sensors is embedding the luminophore into porous matrix with properties of photonic crystal, which may be a porous silicon (pSi) Bragg mirror or a microcavity (MC). The PPV derivatives polymers are usually used as the sensitive luminophores for embedding into pSi matrix. However, there is a task to find an optimal set of luminophores to develop a highly sensitive and selective sensor. In this work we investigate embedding of 5- triphenylamino-4-(triphenylaminothiophen-2-yl)-pyrimidine (HEM-461) into pSi MC and examine the sensitivity of obtained structures. The pSi MC were fabricated using a standard electrochemical etching process. The eigenmode of the pSi MC had a width of 4-6 nm. The samples were oxidized to stabilize the surface chemical properties and to prevent quenching of luminescence of the embedded luminophores after fabrication. The embedding of the dye into the pSi MC was performed at excess pressure. Well known conjugated polymer MDMO-PPV was used as a reference. In this work, we compared the photophysical properties of MDMO-PPV and HEM-461 in solution and into pSi MC. The luminescence parameters and resistance to heat have been studied. Comparative studies of sensitivity of MDMO-PPV and HEM-461 to trinitrotoluene in liquid and gaseous phases have been carried out. It was concluded that pSi MC with embedded HEM-461 is a promising structure for developing sensors of nitroaromatic compounds.
It is known that development of optical sensors for explosives detection is currently of great interest. Among others sensors based on the luminescence quenching of conjugated polymers caused by photoinduced electron transfer have attracted considerable attention. Embedding such polymers into porous silicon (pSi) microcavity (MC) allows modify its luminescence spectrum and increase specific surface area and sensitivity of sensor. At the same time optimization of pSi MC structure and its mode of operation are important aspects of sensors design. This study presents the results of the structure and temperature optimization of pSi MC with embedded PPV derivatives polymers. The pSi MCs were fabricated using a standard electrochemical etching process. The luminescence spectra of polymers were drastically narrowed after embedding in pSi MC. It was experimentally found that optimal thickness of the front mirror is from 4 to 5 pairs of low and high porosity layers. The optimal thickness of the rear mirror is about 15 pairs of low and high porosity layers. We also discovered that temperature of pSi MC strongly influences on the rate of the polymer luminescence quenching under exposure to TNT vapors. In particular, it was shown that a decrease of MC temperature to 5° C leads to more than three times drop of quenching time. The obtained results can be applied for the design of optical sensors of explosives based on pSi MC.
We demonstrate a new way for detection ultralow concentration of explosives in this study. It combines an ion mobility spectrometry (IMS) and a promising method of laser desorption/ionization on silicon (DIOS). The DIOS is widely used in mass spectrometry due to the possibility of small molecule detection and high sensitivity. It is known that IMS based on laser ion source is a power method for the fast detection of ultralow concentration of organic molecules. However requirement of using high energy pulse ultraviolet laser increases weight and size of the device. The use of DIOS in an ion source of IMS could decrease energy pulse requirements and allows one to construct both compact and high sensitive device for analyzing gas and liquid probes. On the other hand mechanisms of DIOS in gas media is poorly studied, especially in case of nitroaromatic compounds. The investigation of the desorption/ionization on porous silicon (pSi) surface of nitroaromatic compounds has been carried out for 2,4,6-trinitrotoluene (TNT) using IMS and mass spectrometry (MS). It has been demonstrated that TNT ion formation in a gas medium is a complicated process and includes both an electron emission from the pSi surface with subsequent ion-molecular reactions in a gas phase and a proton transfer between pSi surface and TNT molecule.
Photonic crystals doped with fluorescent nanoparticles offer a plenty of interesting applications in photonics, laser
physics, and biosensing. Understanding of the mechanisms and effects of modulation of the photoluminescent properties
of photonic crystals by varying the depth of nanoparticle penetration should promote targeted development of
nanocrystal-doped photonic crystals with desired optical and morphological properties. Here, we have investigated the
penetration of semiconductor quantum dots (QDs) into porous silicon photonic crystals and performed experimental
analysis and theoretical modeling of the effects of the depth of nanoparticle penetration on the photoluminescent
properties of this photonic system. For this purpose, we fabricated porous silicon microcavities with an eigenmode width
not exceeding 10 nm at a wavelength of 620 nm. CdSe/CdS/ZnS QDs fluorescing at 617 nm with a quantum yield of
about 70% and a width at half-height of about 40 nm were used in the study. Confocal microscopy and scanning electron
microscopy were used to estimate the depth of penetration of QDs into the porous silicon structure; the
photoluminescence spectra, kinetics, and angular fluorescence distribution were also analyzed. Enhancement of QD
photoluminescence at the microcavity eigenmode wavelength was observed. Theoretical modeling of porous silicon
photonic crystals doped with QDs was performed using the finite-difference time-domain (FDTD) approach. Theoretical
modeling has predicted, and the experiments have confirmed, that even a very limited depth of nanoparticle penetration
into photonic crystals, not exceeding the first Bragg mirror of the microcavity, leads to significant changes in the QD
luminescence spectrum determined by the modulation of the local density of photonic states in the microcavity. At the
same time, complete and uniform filling of a photonic crystal with nanoparticles does not enhance this effect, which is as
strong as in the case of a very limited depth of nanoparticle penetration. Our results will help to choose the best
technology for fabrication of efficient sensor systems based on porous silicon photonic crystals doped with fluorescent
nanoparticles.
The organic ligands passivating the surface of semiconductor quantum dots (QDs) and the solvents used strongly determine the photostability of QD solutions. Highly purified QD solutions in chloroform have been shown to photodegrade upon pulsed ultraviolet (UV) irradiation, irrespectively of the type of surface ligand. However, the photostability of QDs dissolved in n-octane, a more photochemically inert solvent, strongly depends on the ligands passivating their surface. In n-octane, hexadecylamine-coated QDs are completely stable and display no photochemical response to pulsed UV laser irradiation. In solutions of octanethiol-capped QDs, the photoluminescence intensity slightly decreases under irradiation. QDs coated with trioctylphosphine oxide exhibit a more complex pattern of photobleaching, which depends on the initial value of fluorescence quantum yield of QDs. This complex pattern may be accounted for by two competing processes: (1) ligand photodesorption accompanied by photobleaching due to specific alignment of the band levels of QDs and highest occupied molecular orbital of the ligand and (2) photoinduced decrease in the population of trapping states. Furthermore, practically no thermodynamic degradation of QD solutions has been observed for the micromolar QD concentration used in the study, in contrast to lower concentrations, thus confirming the photoinduced origin of the changes caused by UV irradiation. Obtained results show that the photostability of QDs may be strongly increased by careful selection of the ligands passivating their surface and the solvents used in the experiments.
Quantum dots (QDs) have numerous applications in optoelectronics due to their unique optical properties. Novel hybrid
organic light-emitting diodes (OLEDs) containing QDs as an active emissive layer are being extensively developed. The
performance of QD–OLED depends on the charge transport properties of the active layer and the degree of localization
of electrons and holes in QDs. Therefore, the type and the density of the ligands on the QD surface are very important.
We have fabricated OLEDs with a CdSe/ZnS QD active layer. These OLEDs contain hole and electron injection layers
consisting of poly(9-vinyl carbazole) and ZnO nanoparticles, respectively. The energy levels of these materials ensure
efficient injection of charge carriers into the QD emissive layer.
In order to enhance the charge transfer to the active QD layer and thereby increase the OLED efficiency, the QD surface
ligands (tri-n-octyl phosphine oxide, TOPO) were replaced with a series of aromatic amines and thiols. The substituents
were expected to enhance the charge carrier mobility in the QD layer. Surprisingly, the devices based on the original
TOPO-coated QDs were found to have the best performance, with a maximum brightness of 2400 Cd/m2 at 10 V. We
assume that this was due to a decrease in the charge localization within QDs when aromatic ligands are used. We
conclude that the surface ligands considerably affect the performance of QD–OLEDs, efficient charge localization in QD
cores being more important for good performance than a high charge transfer rate.
It is known that manufacturing and applications of photonic crystals is currently an area of much interest. One of the
focuses of special attention in this area is various microcavity (MC) devices. Porous silicon is one of the most promising
materials for manufacturing such devices because it is simple to prepare, its optical parameters are precisely controllable,
and it has an enormous surface area. This allows to inject different kinds of luminophores into porous silicon MC
devices. Apparently, semiconductor quantum dots (QDs) are among the most interesting of them. QDs are characterized
by a wide absorbance spectrum, large absorption cross-section, high quantum yield, and excellent photostability. To date,
there have been few studies on QD injection into porous silicon photonic structures. In addition, many structures used
lack the desired characteristics; the depth of QD penetration also remains a question. This is the first study to analyze the
photoluminescence spectrum and kinetics of QDs in a high-quality porous silicon MC. A drastic narrowing of the
luminescence spectrum has been observed after QD injection. We have found that the MC morphology considerably
affects the penetration of QDs. The kinetics of photoluminescence has also been investigated. Measurements have shown
a decrease in the QD characteristic photoluminescence decay time after QD injection into a porous silicon MC compared
with the QD photoluminescence decay time in a toluene solution. However, we have not observed a significant
difference between the photoluminescence decay times of QDs in an MC and in single-layer porous silicon.
Solar energy converters based on organic semiconductors are inexpensive, can be layered onto flexible surfaces, and
show great promise for photovoltaics. In bulk heterojunction polymer solar cells, charges are separated at the interface of
two materials, an electron donor and an electron acceptor. Typically, only the donor effectively absorbs light. Therefore,
the use of an acceptor with a wide absorption spectrum and high extinction coefficient and charge mobility should
increase the efficiency of bulk heterojunction polymer solar cells. Semiconductor nanocrystals (quantum dots and rods)
are good candidate acceptors for these solar cells. Recently, most progress in the development of bulk heterojunction
polymer solar cells was achieved using PCBM, a traditional fullerene acceptor, and two low band gap polymers, poly[N-
9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) and poly
(PTB7). Therefore, the possibility of combining these polymers with semiconductor nanocrystals
deserves consideration.
Here, we present the first comparison of solar cells based on PCDTBT and PTB7 where CdSe quantum dots serve as
acceptors. We have found that PTB7-based cells are more efficient than PCDTBT-based ones. The efficiency also
strongly depends on the nanocrystal size. An increase in the QD diameter from 5 to 10 nm causes a more than fourfold
increase in the cell efficiency. This is determined by the relationship between the nanoparticle size and energy spectrum,
its pattern clearly demonstrating how the mutual positions of the donor and acceptor levels affect the solar cell
efficiency. These results will help to develop novel, improved nanohybrid components of solar cells based on organic
semiconductors and semiconductor nanocrystals.
Optical properties of the films with high concentration of semiconductor core-shell CdSe/ZnS nanocrystals under
action of visible laser radiation in a wide range of power densities have been investigated. It's shown that in the films
with ultimate concentration ofthe nanocrystals a quantum-size effect is observed. High concentration of the nanocrystals
in the films and the presence of dipoles caused by nanoparticles asymmetry lead to strong shift of quantum-size peaks in
absorption and luminescence spectra compared to the solution and the films with low concentration of the nanoparticles.
The altitude of the shift depends on the thickness of the films and varies from 35 nm to 50 nm. The luminescence spectra
of the films don't change until the power density of exciting laser radiation exceeds 1x106 W/cm2. The regimes of laser
action on the films of the nanoparticles with power densities beyond the threshold of films destruction (from 5x106 W/cm2
to 1x109 W/cm2) have been investigated.
CdSe/ZnS quantum dots in solution ad in condensed phase have been investigated by methods of laser induced
luminescence. Anti-stokes photoluminescence (APL) of CdSe/ZnS nanoparticles in the solutions and in the films has
been studied under action of laser radiation of various wavelengths. The dependencies of APL of CdSe/ZnS
nanoparticles ensembles on exciting radiation intensity, temperature and quantum dots concentration have been studied.
It is shown that the mechanism of APL formation in CdSe/ZnS nanoparticles is thermal.
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