Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

RF plasma MOCVD of Y2O3 thin films: Effect of RF self-bias on the substrates during deposition

Yttrium oxide (Y203) thin films have been deposited by radio frequency plasma assisted metal organic chemical vapor deposition (MOCVD) process using (2,2,6,6-tetramethy1-3,5-heptanedionate) yttrium (commonly known as Y(thd)3) precursor in a plasma of argon and oxygen gases at a substrate temperature of 350 C. The films have been deposited under influence of varying RF self-bias (-50 V to 175 V) on silicon, quartz, stainless steel and tantalum substrates. The deposited coatings are characterized by glancing angle X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry and scanning electron microscopy (SEM). GIXRD and FTIR results indicate deposition of Y2 03 (BCC structure) in all cases. However, XPS results indicate nonstoichiometric cubic phase deposition on the surface of deposited films. The degree of nonstoichiometry varies with bias during deposition. Ellipsometry results indicate that the refractive index for the deposited films is varying from 1.70 to 1.83 that is typical for Y203. All films are transparent in the investigated wavelength range 300-1200 nm. SEM results indicate that the microstructure of the films is changing with applied bias. Results indicate that it is possible to deposit single phase cubic Y203 thin films at low substrate temperature by RF plasma MOCVD process. RF self-bias that decides about the energy of impinging ions on the substrates plays an important role in controlling the texture of deposited Y203 films on the substrates. Results indicate that to control the structure of films and its texture, it is important to control the bias on the substrate during deposition. The films deposited at high bias level show degradation in the crystallinity and reduction of thickness. (C) 2013 Elsevier B.V. All rights reserved.

La2O3对Yb：Y2O3透明陶瓷光谱性能的影响

研究了La2O3对Yb：Y2O3透明陶瓷光谱性能的影响，添加适量La2O3以后，Yb：Y2O3透明陶瓷的吸收峰和发射峰的位置不变，但由于La^3＋的离子半径大于Y^3＋的离子半径，在Y2O3中引入La^3＋离子后，导致Y2O3晶格常数变大，晶场强度变弱，同时降低了Y2O3晶体的有序度，致使发射峰强度有所下降，发射截面变小．过量的№La2O3（x=0．16）造成yb^3＋激活离子发射强度明显下降；其荧光寿命在添加La2O3后总体增大45％-60％.

Phase transformation in the surface region of zirconia and doped zirconia detected by UV Raman spectroscopy

The phase evolution of yttrium oxide and lanthanum oxide doped zirconia (Y2O3-ZrO2 and La2O3-ZrO2, respectively) from their tetragonal to monoclinic phase has been studied using UV Raman spectroscopy, visible Raman spectroscopy and XRD. UV Raman spectroscopy is found to be more sensitive at the surface region while visible Raman spectroscopy and XRD mainly give the bulk information. For Y2O3-ZrO2 and La2O3-ZrO2, the transformation of the bulk phase from the tetragonal to the monoclinic is significantly retarded by the presence of yttrium oxide and lanthanum oxide. However, the tetragonal phase in the surface region is difficult to stabilize, particularly when the stabilizer's content is low. The phase in the surface region can be more effectively stabilized by lanthanum oxide than yttrium oxide even though zirconia seemed to provide more enrichment in the surface region of the La2O3-ZrO2 sample than the Y2O3-ZrO2 sample, based on XPS analysis. The surface structural tension and the enrichment of the ZrO2, component in the surface region of ZrO2-Y2O3 and ZrO2-La2O3 might be the reasons for the striking difference between the phase change in the surface region and the bulk. Accordingly, the stabilized tetragonal surface region can significantly prevent the phase transition from developing into the bulk when the stabilizer's content is high.

Energy transfer and upconversion luminescence properties of Y2O3 : Sm and Gd2O3 : Sm phosphors

Y2O3:Sm and Gd2O3:Sm powder phosphors were prepared by carbonate coprecipitation method. The purified crystalline phases of Y2O3:Sm and Gd2O3:SM were obtained at 600degreesC, and the crystallinity increases with increase in annealing temperature. Both samples contain aggregated phosphor particles. An energy transfer (ET) from Y2O3 and Gd2O3 hosts to sm(3+) has been observed, and the ET efficiency in the latter is higher than that in the former because an energy migration process like Gd3+-(Gd3+)(n)-Sm3+ has occurred in the latter. Furthermore, an upconversion luminescence from the (4)G(5/2) level of Sm3+ has been observed in both Y2O3 and Gd2O3 under the excitation of 936 nm infrared, whose mechanisms are proposed. Both the up and downconversion emission intensities of Sm3+ in Gd2O3 are stronger than those in Y2O3.

Monte Carlo Analysis and Physics Characterization of a Novel Nanoparticle Detector for Medical and Micro-dosimetry Applications

The outcomes for both (i) radiation therapy and (ii) preclinical small animal radio- biology studies are dependent on the delivery of a known quantity of radiation to a specific and intentional location. Adverse effects can result from these procedures if the dose to the target is too high or low, and can also result from an incorrect spatial distribution in which nearby normal healthy tissue can be undesirably damaged by poor radiation delivery techniques. Thus, in mice and humans alike, the spatial dose distributions from radiation sources should be well characterized in terms of the absolute dose quantity, and with pin-point accuracy. When dealing with the steep spatial dose gradients consequential to either (i) high dose rate (HDR) brachytherapy or (ii) within the small organs and tissue inhomogeneities of mice, obtaining accurate and highly precise dose results can be very challenging, considering commercially available radiation detection tools, such as ion chambers, are often too large for in-vivo use.

In this dissertation two tools are developed and applied for both clinical and preclinical radiation measurement. The first tool is a novel radiation detector for acquiring physical measurements, fabricated from an inorganic nano-crystalline scintillator that has been fixed on an optical fiber terminus. This dosimeter allows for the measurement of point doses to sub-millimeter resolution, and has the ability to be placed in-vivo in humans and small animals. Real-time data is displayed to the user to provide instant quality assurance and dose-rate information. The second tool utilizes an open source Monte Carlo particle transport code, and was applied for small animal dosimetry studies to calculate organ doses and recommend new techniques of dose prescription in mice, as well as to characterize dose to the murine bone marrow compartment with micron-scale resolution.

Hardware design changes were implemented to reduce the overall fiber diameter to <0.9 mm for the nano-crystalline scintillator based fiber optic detector (NanoFOD) system. Lower limits of device sensitivity were found to be approximately 0.05 cGy/s. Herein, this detector was demonstrated to perform quality assurance of clinical 192Ir HDR brachytherapy procedures, providing comparable dose measurements as thermo-luminescent dosimeters and accuracy within 20% of the treatment planning software (TPS) for 27 treatments conducted, with an inter-quartile range ratio to the TPS dose value of (1.02-0.94=0.08). After removing contaminant signals (Cerenkov and diode background), calibration of the detector enabled accurate dose measurements for vaginal applicator brachytherapy procedures. For 192Ir use, energy response changed by a factor of 2.25 over the SDD values of 3 to 9 cm; however a cap made of 0.2 mm thickness silver reduced energy dependence to a factor of 1.25 over the same SDD range, but had the consequence of reducing overall sensitivity by 33%.

For preclinical measurements, dose accuracy of the NanoFOD was within 1.3% of MOSFET measured dose values in a cylindrical mouse phantom at 225 kV for x-ray irradiation at angles of 0, 90, 180, and 270˝. The NanoFOD exhibited small changes in angular sensitivity, with a coefficient of variation (COV) of 3.6% at 120 kV and 1% at 225 kV. When the NanoFOD was placed alongside a MOSFET in the liver of a sacrificed mouse and treatment was delivered at 225 kV with 0.3 mm Cu filter, the dose difference was only 1.09% with use of the 4x4 cm collimator, and -0.03% with no collimation. Additionally, the NanoFOD utilized a scintillator of 11 µm thickness to measure small x-ray fields for microbeam radiation therapy (MRT) applications, and achieved 2.7% dose accuracy of the microbeam peak in comparison to radiochromic film. Modest differences between the full-width at half maximum measured lateral dimension of the MRT system were observed between the NanoFOD (420 µm) and radiochromic film (320 µm), but these differences have been explained mostly as an artifact due to the geometry used and volumetric effects in the scintillator material. Characterization of the energy dependence for the yttrium-oxide based scintillator material was performed in the range of 40-320 kV (2 mm Al filtration), and the maximum device sensitivity was achieved at 100 kV. Tissue maximum ratio data measurements were carried out on a small animal x-ray irradiator system at 320 kV and demonstrated an average difference of 0.9% as compared to a MOSFET dosimeter in the range of 2.5 to 33 cm depth in tissue equivalent plastic blocks. Irradiation of the NanoFOD fiber and scintillator material on a 137Cs gamma irradiator to 1600 Gy did not produce any measurable change in light output, suggesting that the NanoFOD system may be re-used without the need for replacement or recalibration over its lifetime.

For small animal irradiator systems, researchers can deliver a given dose to a target organ by controlling exposure time. Currently, researchers calculate this exposure time by dividing the total dose that they wish to deliver by a single provided dose rate value. This method is independent of the target organ. Studies conducted here used Monte Carlo particle transport codes to justify a new method of dose prescription in mice, that considers organ specific doses. Monte Carlo simulations were performed in the Geant4 Application for Tomographic Emission (GATE) toolkit using a MOBY mouse whole-body phantom. The non-homogeneous phantom was comprised of 256x256x800 voxels of size 0.145x0.145x0.145 mm3. Differences of up to 20-30% in dose to soft-tissue target organs was demonstrated, and methods for alleviating these errors were suggested during whole body radiation of mice by utilizing organ specific and x-ray tube filter specific dose rates for all irradiations.

Monte Carlo analysis was used on 1 µm resolution CT images of a mouse femur and a mouse vertebra to calculate the dose gradients within the bone marrow (BM) compartment of mice based on different radiation beam qualities relevant to x-ray and isotope type irradiators. Results and findings indicated that soft x-ray beams (160 kV at 0.62 mm Cu HVL and 320 kV at 1 mm Cu HVL) lead to substantially higher dose to BM within close proximity to mineral bone (within about 60 µm) as compared to hard x-ray beams (320 kV at 4 mm Cu HVL) and isotope based gamma irradiators (137Cs). The average dose increases to the BM in the vertebra for these four aforementioned radiation beam qualities were found to be 31%, 17%, 8%, and 1%, respectively. Both in-vitro and in-vivo experimental studies confirmed these simulation results, demonstrating that the 320 kV, 1 mm Cu HVL beam caused statistically significant increased killing to the BM cells at 6 Gy dose levels in comparison to both the 320 kV, 4 mm Cu HVL and the 662 keV, 137Cs beams.

Film based on Y2O3: Eu3+ (5 mol% of Eu3+) for flat panel display

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)