Vertically Well-Aligned ZnO Nanoscintillator Arrays with Improved Photoluminescence and Scintillation Properties.

ZnO nanoarrays were grown via a low-temperature hydrothermal method. Solutions, each with different additive combinations, were prepared and evaluated. The effects of the additives involved in the growth procedure, i.e., ammonium hydroxide and sodium citrate, were studied in terms of the morphological, optical and scintillation properties of the ZnO nanostructures. Measurement of the nanorod (NR) length, corresponding photoluminescence (PL) and scintillation spectra and their dependence on the additives present in the solution are discussed. ZnO NRs grown on a silica substrate, whose UV transmission was found to be better than glass, showed high-quality structural and optical properties. It was found that the addition of sodium citrate significantly reduced defects and correspondingly increased the intrinsic near-band-edge (NBE) UV emission intensity at ~380 nm. To obtain high-quality nanostructures, samples were annealed in a 10% H2 + 90% N2 atmosphere. The anneal in the forming gas atmosphere enhanced the emission of the UV peak by reducing defects in the nanostructure. NRs are highly tapered towards the end of the structure. The tapering process was monitored using time growth studies, and its effect on PL and reflectance spectra are discussed. A good alpha particle response was obtained for the grown ZnO NRs, confirming its potential to be used as an alpha particle scintillator. After optimizing the reaction parameters, it was concluded that when ammonium hydroxide and sodium citrate were used, vertically well-aligned and long ZnO nanoarrays with highly improved optical and scintillation properties were obtained.

Formamidinium Lead Halide Perovskite Nanocomposite Scintillators.

While there is great demand for effective, affordable radiation detectors in various applications, many commonly used scintillators have major drawbacks. Conventional inorganic scintillators have a fixed emission wavelength and require expensive, high-temperature synthesis; plastic scintillators, while fast, inexpensive, and robust, have low atomic numbers, limiting their X-ray stopping power. Formamidinium lead halide perovskite nanocrystals show promise as scintillators due to their high X-ray attenuation coefficient and bright luminescence. Here, we used a room-temperature, solution-growth method to produce mixed-halide FAPbX3 (X = Cl, Br) nanocrystals with emission wavelengths that can be varied between 403 and 531 nm via adjustments to the halide ratio. The substitution of bromine for increasing amounts of chlorine resulted in violet emission with faster lifetimes, while larger proportions of bromine resulted in green emission with increased luminescence intensity. By loading FAPbBr3 nanocrystals into a PVT-based plastic scintillator matrix, we produced 1 mm-thick nanocomposite scintillators, which have brighter luminescence than the PVT-based plastic scintillator alone. While nanocomposites such as these are often opaque due to optical scattering from aggregates of the nanoparticles, we used a surface modification technique to improve transmission through the composites. A composite of FAPbBr3 nanocrystals encapsulated in inert PMMA produced even stronger luminescence, with intensity 3.8× greater than a comparative FAPbBr3/plastic scintillator composite. However, the luminescence decay time of the FAPbBr3/PMMA composite was more than 3× slower than that of the FAPbBr3/plastic scintillator composite. We also demonstrate the potential of these lead halide perovskite nanocomposite scintillators for low-cost X-ray imaging applications.

Flexible Polymer X-ray Detectors with Non-fullerene Acceptors for Enhanced Stability: Toward Printable Tissue Equivalent Devices for Medical Applications.

There is growing interest in the development of novel materials and devices capable of ionizing radiation detection for medical applications. Organic semiconductors are promising candidates to meet the demands of modern detectors, such as low manufacturing costs, mechanical flexibility, and a response to radiation equivalent to human tissue. However, organic semiconductors have typically been employed in applications that convert low energy photons into high current densities, for example, solar cells and LEDs, and thus existing design rules must be re-explored for ionizing radiation detection where high energy photons are converted into typically much lower current densities. In this work, we report the optoelectronic and X-ray dosimetric response of a tissue equivalent organic photodetector fabricated with solution-based inks prepared from polymer donor poly(3-hexylthiophene) (P3HT) blended with either a non-fullerene acceptor (5Z,5'Z)-5,5'-((7,7'-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene))bis(3-ethyl-2-thioxothiazolidin-4-one) (o-IDTBR) or a fullerene acceptor, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Indirect detection of X-rays was achieved via coupling of organic photodiodes with a plastic scintillator. Both detectors displayed an excellent response linearity with dose, with sensitivities to 6 MV photons of 263.4 ± 0.6 and 114.2 ± 0.7 pC/cGy recorded for P3HT:PCBM and P3HT:o-IDTBR detectors, respectively. Both detectors also exhibited a fast temporal response, able to resolve individual 3.6 µs pulses from the linear accelerator. Energy dependence measurements highlighted that the photodetectors were highly tissue equivalent, though an under-response in devices compared to water by up to a factor of 2.3 was found for photon energies of 30-200 keV due to the response of the plastic scintillator. The P3HT:o-IDTBR device exhibited a higher stability to radiation, showing just an 18.4% reduction in performance when exposed to radiation doses of up to 10 kGy. The reported devices provide a successful demonstration of stable, printable, flexible, and tissue-equivalent radiation detectors with energy dependence similar to other scintillator-based detectors used in radiotherapy.

Towards high spatial resolution tissue-equivalent dosimetry for microbeam radiation therapy using organic semiconductors.

Spatially fractionated ultra-high-dose-rate beams used during microbeam radiation therapy (MRT) have been shown to increase the differential response between normal and tumour tissue. Quality assurance of MRT requires a dosimeter that possesses tissue equivalence, high radiation tolerance and spatial resolution. This is currently an unsolved challenge. This work explored the use of a 500 nm thick organic semiconductor for MRT dosimetry on the Imaging and Medical Beamline at the Australian Synchrotron. Three beam filters were used to irradiate the device with peak energies of 48, 76 and 88 keV with respective dose rates of 3668, 500 and 209 Gy s-1. The response of the device stabilized to 30% efficiency after an irradiation dose of 30 kGy, with a 0.5% variation at doses of 35 kGy and higher. The calibration factor after pre-irradiation was determined to be 1.02 ±â€…0.005 µGy per count across all three X-ray energy spectra, demonstrating the unique advantage of using tissue-equivalent materials for dosimetry. The percentage depth dose curve was within ±5% of the PTW microDiamond detector. The broad beam was fractionated into 50 microbeams (50 µm FHWM and 400 µm centre-to-centre distance). For each beam filter, the FWHMs of all 50 microbeams were measured to be 51 ±â€…1.4, 53 ±â€…1.4 and 69 ±â€…1.9 µm, for the highest to lowest dose rate, respectively. The variation in response suggested the photodetector possessed dose-rate dependence. However, its ability to reconstruct the microbeam profile was affected by the presence of additional dose peaks adjacent to the one generated by the X-ray microbeam. Geant4 simulations proved that the additional peaks were due to optical photons generated in the barrier film coupled to the sensitive volume. The simulations also confirmed that the amplitude of the additional peak in comparison with the microbeam decreased for spectra with lower peak energies, as observed in the experimental data. The material packaging can be optimized during fabrication by solution processing onto a flexible substrate with a non-fluorescent barrier film. With these improvements, organic photodetectors show promising prospects as a cost-effective high spatial resolution tissue-equivalent flexible dosimeter for synchrotron radiation fields.

Assessing the suitability of three proxy sources for the development of detectors of special nuclear materials.

Numerous techniques and equipment have been developed to provide a capability for the detection of special nuclear materials (SNM), but due to the necessary security measures surrounding these materials alternate, or proxy, neutron sources are often utilised in their stead. In this paper we report the neutron and gamma pulse shape discrimination response of plastic scintillator to mixed neutron/gamma beams produced from two radionuclide neutron sources, and also from an SNM source of weapons-grade plutonium. We discuss the suitability of using radionuclide sources, with appropriate shielding configurations as proxy sources for SNM. A 3σnth-γ discrimination level has been achieved for an SNM source at a low-level energy threshold of ∼220 keVee when a shielding configuration of 5 cm of lead was implemented. Varying amounts of lead and high-density polyethylene (HDPE) shielding were also investigated with the 3σ limit being reached by ∼240 keVee. This work shows that an AmBe neutron source serves as an appropriate SNM proxy achieving a comparable value for figure of merit above ∼1 MeVee. For energies below 1 MeVee down to ∼100 keVee a closer approximation of the expected FoM for SNM can be attained when using 252Cf as a proxy source or by utilising an 'enhanced' AmBe source with the addition of a further low energy γ ray source.

Boron-Loaded Polymeric Sensor for the Direct Detection of Thermal Neutrons.

We report the first demonstration of a solid-state, direct-conversion sensor for thermal neutrons based on a polymer/inorganic nanocomposite. Sensors were fabricated from ultrathick films of poly(triarylamine) (PTAA) semiconducting polymer, with thicknesses up to 100 µm. Boron nanoparticles (NPs) were dispersed throughout the PTAA film to provide the neutron stopping power arising from the high thermal neutron cross section of the isotope 10B. To maximize the quantum efficiency (QE) of the sensor to thermal neutrons, a high volume fraction of homogeneously dispersed boron nanoparticles was achieved in the thick PTAA film using an optimized processing method. Thick active layers were realized using a high molecular weight of the PTAA so that molecular entanglements provide a high cohesive strength. A nonionic surfactant was used to stabilize the boron dispersion in solvent and hence suppress the formation of agglomerates and associated electrical pathways. Boron nanoparticle loadings of up to ten volume percent were achieved, with thermal neutron quantum efficiency estimates up to 6% resulting. The sensors' neutron responses were characterized under a high flux thermal neutron exposure, showing a linear correlation between the response current and the thermal neutron flux up to ∼107 cm-2 s-1. Polymer-based boron nanocomposite sensors offer a new neutron detection technology that uses low-cost, scalable solution processing and provides an alternative to traditional neutron sensors that use rare isotopes, such as 3He.

Characterization of an organic semiconductor diode for dosimetry in radiotherapy.

PURPOSE: The development of novel detectors for dosimetry in advanced radiotherapy modalities requires materials that have a water equivalent response to ionizing radiation such that characterization of radiation beams can be performed without the need for complex calibration procedures and correction factors. Organic semiconductors are potentially an ideal technology in fabricating devices for dosimetry due to tissue equivalence, mechanical flexibility, and relatively cheap manufacturing cost. The response of a commercial organic photodetector (OPD), coupled to a plastic scintillator, to ionizing radiation from a linear accelerator and orthovoltage x-ray tube has been characterized to assess its potential as a dosimeter for radiotherapy. The radiation hardness of the OPD has also been investigated to demonstrate its longevity for such applications. METHODS: Radiation hardness measurements were achieved by observing the response of the OPD to the visible spectrum and 70 keV x rays after pre-exposure to 40 kGy of ionizing radiation. The response of a preirradiated OPD to 6-MV photons from a linear accelerator in reference conditions was compared to a nonirradiated OPD with respect to direct and indirect (RP400 plastic scintillator) detection mechanisms. Dose rate dependence of the OPD was measured by varying the surface-to-source distance between 90 and 300 cm. Energy dependence was characterized from 29.5 to 129 keV with an x-ray tube. The percentage depth dose (PDD) curves were measured from 0.5 to 20 cm and compared to an ionization chamber. RESULTS: The OPD sensitivity to visible light showed substantial degradation of the broad 450 to 600 nm peak from the donor after irradiation to 40 kGy. After irradiation, the spectral shape has a dominant absorbance peak at 370 nm, as the acceptor better withstood radiation damage. Its response to x rays stabilized to 30% after 35 kGy, with a 0.5% difference between 770 Gy increments. The OPD exhibited reproducible detection of ionizing radiation when coupled with a scintillator. Indirect detection showed a linear response from 25 to 500 cGy and constant response to dose rates from 0.31 Gy/pulse to 3.4 × 10-4  Gy/pulse. However, without the scintillator, response increased by 100% at low dose rates. Energy independence between 100 keV and 1.2 MeV advocates their use as a dosimeter without beam correction factors. A dependence on the scintillator thickness used during a comparison of the PDD to the ionizing chamber was identified. A 1-mm-thick scintillator coupled with the OPD demonstrated the best agreement of ± 3%. CONCLUSIONS: The response of OPDs to ionizing radiation has been characterized, showing promising use as a dosimeter when coupled with a plastic scintillator. The mechanisms of charge transport and trapping within organic materials varies for visible and ionizing radiation, due to differing properties for direct and indirect detection mechanisms and observing a substantial decrease in sensitivity to the visible spectrum after 40 kGy. This study proved that OPDs produce a stable response to 6-MV photons, and with a deeper understanding of the charge transport mechanisms due to exposure to ionizing radiation, they are promising candidates as the first flexible, water equivalent, real-time dosimeter.

Enhanced X-ray Sensitivity of MAPbBr3 Detector by Tailoring the Interface-States Density.

An important factor for the high performance of light-harvesting devices is the presence of surface trappings. Therefore, understanding and controlling the carrier recombination of the organic-inorganic hybrid perovskite surface is critical for the device design and optimization. Here, we report the use of aluminum zinc oxide (AZO) as the anode to construct a p-n junction structure MAPbBr3 nuclear radiation detector. The AZO/MAPbBr3/Au detector can tolerate an electrical field of 500 V·cm-1 and exhibit a very low leakage current of ∼9 nA, which is 1 order of magnitude lower than that of the standard ohmic contact device. The interface state density of AZO/MAPbBr3 contact was reduced from 2.17 × 1010 to 8.7 × 108 cm-2 by annealing at 100 °C under an Ar atmosphere. Consequently, a photocurrent to dark current ratio of 190 was realized when exposed to a green light-emitting diode with a wavelength of 520 nm (∼200 mW·cm-2). Simultaneously, a high X-ray sensitivity of ∼529 µC·Gyair-1 cm-2 was achieved under 80 kVp X-ray at an electric field of 50 V·cm-1. These results demonstrate the use of surface engineering to further optimize the performance of MAPbBr3 detectors, which have many potential applications in medical and security detection with low radiation dose brought to the human body.

High Energy Resolution Hyperspectral X-Ray Imaging for Low-Dose Contrast-Enhanced Digital Mammography.

Contrast-enhanced digital mammography (CEDM) is an alternative to conventional X-ray mammography for imaging dense breasts. However, conventional approaches to CEDM require a double exposure of the patient, implying higher dose, and risk of incorrect image registration due to motion artifacts. A novel approach is presented, based on hyperspectral imaging, where a detector combining positional and high-resolution spectral information (in this case based on Cadmium Telluride) is used. This allows simultaneous acquisition of the two images required for CEDM. The approach was tested on a custom breast-equivalent phantom containing iodinated contrast agent (Niopam 150®). Two algorithms were used to obtain images of the contrast agent distribution: K-edge subtraction (KES), providing images of the distribution of the contrast agent with the background structures removed, and a dual-energy (DE) algorithm, providing an iodine-equivalent image and a water-equivalent image. The high energy resolution of the detector allowed the selection of two close-by energies, maximising the signal in KES images, and enhancing the visibility of details with the low surface concentration of contrast agent. DE performed consistently better than KES in terms of contrast-to-noise ratio of the details; moreover, it allowed a correct reconstruction of the surface concentration of the contrast agent in the iodine image. Comparison with CEDM with a conventional detector proved the superior performance of hyperspectral CEDM in terms of the image quality/dose tradeoff.

Toward Low-Voltage and Bendable X-Ray Direct Detectors Based on Organic Semiconducting Single Crystals.

Organic materials have been mainly proposed as ionizing radiation detectors in the indirect conversion approach. The first thin and bendable X-ray direct detectors are realized (directly converting X-photons into an electric signal) based on organic semiconducting single crystals that possess enhanced sensitivity, low operating voltage (≈5 V), and a minimum detectable dose rate of 50 µGy s(-1) .

Direct detection of 6 MV x-rays from a medical linear accelerator using a semiconducting polymer diode.

Recently, a new family of low-cost x-radiation detectors have been developed, based on semiconducting polymer diodes, which are easy to process, mechanically flexible, relatively inexpensive, and able to cover large areas. To test their potential for radiotherapy applications such as beam monitors or dosimeters, as an alternative to the use of solid-state inorganic detectors, we present the direct detection of 6 MV x-rays from a medical linear accelerator using a thick film, semiconducting polymer detector. The diode was subjected to 4 ms pulses of 6 MV x-rays at a rate of 60 Hz, and produces a linear increase in photocurrent with increasing dose rate (from 16.7 to 66.7 mGy s(-1)). The sensitivity of the diode was found to range from 13 to 20 nC mGy(-1) cm(-3), for operating voltages from -50 to -150 V, respectively. The diode response was found to be stable after exposure to doses up to 15 Gy. Testing beyond this dose range was not carried out. Theoretical calculations show that the addition of heavy metallic nanoparticles to polymer films, even at low volume fractions, increases the x-ray sensitivity of the polymer film/nanoparticle composite so that it exceeds that for silicon over a wide range of x-ray energies. The possibility of detecting x-rays with energies relevant to medical oncology applications opens up the potential for these polymer detectors to be used in detection and imaging applications using medical x-ray beams.

Locking carbon nanotubes in confined lattice geometries--a route to low percolation in conducting composites.

A significant reduction in the electrical percolation threshold is achieved by locking carbon nanotubes (CNTs) in a predominantly hexagonally close-packed (HCP) colloidal crystal lattice of partially plasticized latex particles. Contrary to other widely used latex processing where CNTs are randomly distributed within the latex matrix, for the first time, we show that excluding CNTs from occupying the interior volume of the latex particles promotes the formation of a nonrandom segregated network. The electrical percolation threshold is four times lower in an ordered segregated network made with colloidal particles near their glass transition temperature (T(g)) in comparison to in a random network made with particles at a temperature well above the T(g). This method allows for a highly reproducible way to fabricate robust, stretchable, and electrically conducting thin films with significantly improved transparency and lattice percolation at a very low CNT inclusion which may find applications in flexible and stretchable electronics as well as other stretchable technologies. For instance, our technology is particularly apt for touch screen applications, where one needs homogeneous distribution of the conductive filler throughout the matrix.

Achieving a stable time response in polymeric radiation sensors under charge injection by X-rays.

Existing inorganic materials for radiation sensors suffer from several drawbacks, including their inability to cover large curved areas, lack of tissue-equivalence, toxicity, and mechanical inflexibility. As an alternative to inorganics, poly(triarylamine) (PTAA) diodes have been evaluated for their suitability for detecting radiation via the direct creation of X-ray induced photocurrents. A single layer of PTAA is deposited on indium tin oxide (ITO) substrates, with top electrodes selected from Al, Au, Ni, and Pd. The choice of metal electrode has a pronounced effect on the performance of the device; there is a direct correlation between the diode rectification factor and the metal-PTAA barrier height. A diode with an Al contact shows the highest quality of rectifying junction, and it produces a high X-ray photocurrent (several nA) that is stable during continuous exposure to 50 kV Mo Kalpha X-radiation over long time scales, combined with a high signal-to-noise ratio with fast response times of less than 0.25 s. Diodes with a low band gap, 'Ohmic' contact, such as ITO/PTAA/Au, show a slow transient response. This result can be explained by the build-up of space charge at the metal-PTAA interface, caused by a high level of charge injection due to X-ray-induced carriers. These data provide new insights into the optimum selection of metals for Schottky contacts on organic materials, with wider applications in light sensors and photovoltaic devices.

Improvement of Electron Field Emission in Patterned Carbon Nanotubes by High Temperature Hydrogen Plasma Treatment.

In this paper, we report a significant improvement of electron field emission property in patterned carbon nanotubes films by using a high temperature (650 °C) hydrogen plasma treatment. This treatment was found to greatly increase the emission current, emission uniformity and stability. The mechanism study showed that these enhanced properties are attributed to the lowering of the potential barrier and the creation of geometrical features through the removal of amorphous carbon, catalyst particles and the saturation of dangling bonds after such a hydrogen plasma treatment.