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Strain-driven phase boundaries in BiFeO3 thin films studied by atomic force microscopy and x-ray diffraction
(2012-01-17)
Liu, Heng-Jui
;
Liang, Chen-Wei
;
Liang, Wen-I
;
Chen, Hsiang-Jung
;
Yang, Jan-Chi
We report a detailed study on the strain-driven phase transition between the tetragonal-like and rhombohedral-like phases in epitaxial BiFeO3 (BFO) thin films which focuses on their structural nature, thermodynamic stability, and ferroelectric/piezoelectric properties. We first show that the tetragonal-like phase, which has a large c/a ratio (similar to 1.2), in the compressively strained BFO is thermodynamically more favorable at high temperature and high strain state (small thickness). We also report a phase transition between two monoclinic phases at 150 degrees C. The two monoclinic phases are differentiated by their c-axis parameters and tilting angles: The low-temperature phase (M-C) has a c-axis parameter of 4.64 angstrom and a tilting angle (beta = 88.5 degrees) along the a axis, while the high-temperature phase (M-A) has a c-axis parameter of 4.66 angstrom and a tilting angle (beta = 86.8 degrees) along both of the a and b axes. We further show that samples undergoing the M-C-M-A phase transition exhibit ferroelectric polarization rotation and piezoelectric enhancement. Our findings directly unveil the close links between structural changes, polarization rotation, and large piezoelectricity at morphotropic phase boundaries in BiFeO3.
Enhanced visible photoluminescence from ultrathin ZnO films grown on Si-nanowires by atomic layer deposition
(2010-09-24)
Chang, Yuan-Ming
;
Jian, Sheng-Rui
;
Lee, Hsin-Yi
;
Lin, Chih-Ming
;
Juang, Jenh-Yih
Bright room temperature visible emission is obtained in heterostructures consisting of similar to 3.5 nm thick ZnO ultrathin films grown on Si-nanowires produced by means of self-masking dry etching in hydrogen-containing plasma. The ZnO films were deposited on Si-nanowires by using atomic layer deposition (ALD) under an ambient temperature of 25 degrees C. The orders of magnitude enhancement in the intensity of the room temperature photoluminescence peaked around 560 nm in the present ZnO/Si-nanowire heterostructures is presumably due to the high aspect (surface/volume) ratio inherent to the Si-nanowires, which has, in turn, allowed considerably more ZnO material to be grown on the template and led to markedly more efficient visible emission. Moreover, the ordered nanowire structure also features an extremely low reflectance (similar to 0.15%) at 325 nm, which may further enhance the efficiency of emission by effectively trapping the excitation light.
Annealing effect on the optical response and interdiffusion of n-ZnO/p-Si, (111) heterojunction grown by atomic layer deposition
(2010-11-01)
Ku, Ching-Shun
;
Huang, Jheng-Ming
;
Cheng, Ching-Yuan
;
Lin, Chih-Ming
;
Lee, Hsin-Yi
Optical and structural properties of n-ZnO films grown on a p-Si (111) substrate by atomic layer deposition were observed using in situ synchrotron x-ray diffraction during annealing. The photoluminescence showed a complicated photon response with increasing annealing temperature. In situ x-ray diffraction indicated the growth of grains for an annealing temperature from 500 to 800 degrees C with the orientation altering from polycrystalline to preferential (200). Measurements with a time-of-flight secondary-ion mass spectrometer indicated that the outgassing of hydrogen atoms and ZnO/Si interdiffusion behavior were correlated with the intensity and position of emissions in photoluminescence spectra. (c) 2010 American Institute of Physics. [doi:10.1063/1.3511284]
Fabrication of epitaxial ZnO films by atomic-layer deposition with interrupted flow
(2009-12-31)
Ku, Ching-Shun
;
Huang, Jheng-Ming
;
Lin, Chih-Ming
;
Lee, Hsin-Yi
;
材料科學與工程學系
We formed epitaxial ZnO thin films on a (0001) c-plane sapphire substrate through deposition of atomic layers (ALD) at 25-160 degrees C using diethylzinc (DEZn) and deionized water as precursors in combination with interrupted flow. High-resolution X-ray diffraction measurements were employed to characterize the microstructure of these films. With interrupted flow, we obtained ZnO thin films with an optimal growth window in a range of 40-160 degrees C, effectively decreasing the growth temperature by about 120 degrees C relative to a conventional method involving continuous flow. X-ray reflectivity measurements showed that the rate of growth increased also between 20 degrees C and 120 degrees C. The XRD results indicate that the stock time might extend the reaction of DEZn and water through an increased duration. All results show that a low temperature for growth improves the crystalline quality and is consistent with thermodynamically blocked self-compensation. (C) 2009 Elsevier B.V. All rights reserved.
Ligands affect the crystal structure and photovoltaic performance of thin films of PbSe quantum dots
(2011)
Kuo, Chih-Yin
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Su, Ming-Shin
;
Ku, Ching-Shun
;
Wang, Shu-Min
;
Lee, Hsin-Yi
We have prepared thin films of PbSe quantum dots (QDs) featuring three different ligands, oleic acid (OA), butylamine (BA), and 1,2-ethanedithiol (EDT), which have pronounced affects on the arrangement and photovoltaic performance of the PbSe QDs in the thin films. Transmission electron microscopy revealed that ligands that altered the inter-QD spacing induced significant changes in the packing of the PbSe QDs in localized regions of small areas (300 x 300 nm) of the thin films: from a superlattice of OA-capped PbSe QDs to a chaotic pattern of EDT-capped PbSe QDs. Using a synchrotron X-ray reflectivity probe and data fitting, we determined that the roughness decreased and the average densities increased for large-area (1.5 x 1.5 cm) PbSe QD thin films capped with BA and EDT, relative to those of the OA-capped PbSe QD film. In particular, the PbSe QDs' vertical packing density, which is critical for charge transport, increased substantially for the system incorporating EDT ligands. As a result, devices containing the EDT-treated PbSe QD film as the active layer displayed much improved power conversion efficiencies (PCEs) relative to those of corresponding devices featuring either the OA-or BA-capped PbSe QD films as active layers. Adopting a layer-by-layer technique, we fabricated a EDT-capped PbSe QD device that exhibited a PCE of 2.45%.
Ultrathin Oriented BiFeO3 Films from Deposition of Atomic Layers with Greatly Improved Leakage and Ferroelectric Properties
(2014-01-08)
Liu, Yen-Ting
;
Ku, Ching-Shun
;
Chiu, Shang-Jui
;
Lee, Hsin-Yi
;
Chen, San-Yuan
Highly (001)-oriented BiFeO3 ultrathin films of total thickness of less than 10 nm were deposited on Si(001) substrates via deposition of atomic layers (ALD) with a LaNiO3 buffer. A radio-frequency (RF)-sputtered sample of the same thickness was prepared for comparison. The ALD combined with interrupted flow and an exchange reaction between Bi and Fe precursors provides a superior method to grow ternary compounds. According to X-ray diffraction, upon deposition at a temperature of less than 550 degrees C, the only phase in the film was BiFeO3. Anomalous fine structure from synchrotron X-ray diffraction certified the valence bonding through the BiFeO3 (001) diffraction signal. The stoichiometric ratio of BiFeO3 obtained from X-ray photoelectron spectroscopy indicated that ALD has a proportion much improved over the RF preparation, and this is also in agreement with the results for diffraction anomalous fine structure. The use of high-resolution transmission electron and atomic force microscopes showed that the layer structure and morphology from ALD presented a satisfactory coverage, more conformal than that with the RF method. The BiFeO3 thin film deposited with ALD shows excellent leakage, improved at least 1000 times with respect to the RF preparation, making this method suitable for the fabrication of ferroelectric random-access memory devices. From the hysteresis loop, the largest remanent polarization was observed as 2P(r) = 2.0 mu C cm(-2).
Growth of high-quality epitaxial ZnO films on (10-10) sapphire by atomic layer deposition with flow-rate interruption method
(2013-09-01)
Huang, Jheng-Ming
;
Ku, Ching-Shun
;
Lee, Hsin-Yi
;
Lin, Chih-Ming
;
Chen, San-Yuan
A novel process in an atomic layer deposition system with "flow-rate interruption" (FRI) was developed to obtain epitaxial ZnO films of high quality. The m-plane ZnO thin films were grown on m-plane sapphire substrates by atomic layer deposition with FRI or a conventional continuous-flow method at the temperature in the range of 25-260 degrees C; 200 degrees C appeared optimal. Measurements of X-ray reflectivity indicated that the thickness of ZnO films with FRI is almost twice than that grown with the continuous-flow method. The structural, optical and electrical properties were investigated with X-ray diffraction (XRD), photoluminescence and Hall measurements. The diffraction results indicated that the interrupted flow might extend the reaction of diethylzinc and water through an increased duration to improve the crystallographic quality of the films. According to the results from XRD at high resolution, to substantiate the epitaxial relation between the thin film and the substrate, an off-normal azimuthal scan along ZnO (201) demonstrated two-fold symmetry that indicated the ZnO films to be in epitaxial growth on sapphire. The photoluminescence results showed a strongly enhanced near-band-edge emission of an FRI sample, and the donor-bond exciton appearing in films also indicated superior crystalline qualities. The Hall mobility of the FRI method was up to 64.7 cm(2) V-1 s(-1). The FRI method evidently improved the structural, optical and electrical properties of the ZnO films with small consumption of precursors. (C) 2012 Elsevier B.V. All rights reserved.
Annealing treatment improves the morphology and performance of photovoltaic devices prepared from thieno[3,4-c]pyrrole-4,6-dione-based donor/acceptor conjugated polymers and CdSe nanostructures
(2011-06-01)
Kuo, Chih-Yin
;
Su, Ming-Shi
;
Chen, Guan-Yu
;
Ku, Ching-Shun
;
Lee, Hsin-Yi
We have prepared photovoltaic devices based on blend films of CdSe tetrapods and the donor/acceptor conjugated polymer PDTTTPD, which comprises 2,5-di(thiophen-2-yl) thieno[3,2-b]thiophene and thieno[3,4-c]pyrrole-4,6-dione units. The AM1.5 power conversion efficiency (PCE) of a photovoltaic device containing a PDTTTPD/CdSe tetrapod blend (1:9, w/w) that had experienced thermal annealing (130 degrees C, 20 min) was three times greater than that of the corresponding device incorporating the as-prepared PDTTTPD/CdSe tetrapod blend (2.9% vs. 1.0%). Synchrotron X-ray reflectivity revealed that annealing (i.e., removal of pyridine ligands from the surfaces of the CdSe tetrapods) caused the thickness of the PDTTTPD/CdSe tetrapod blend film to decrease (and its average density to increase) relative to that of the as-prepared blend film. Transmission electron microscopy and atomic force microscopy revealed that thermal annealing enhanced the degree of aggregation of the CdSe tetrapods and induced denser morphologies, leading to substantially increased charge transport, which enhanced the PCE of the device.
Diagonals and numerical ranges of direct sums of matrices
(2013-11-01)
Lee, Hsin-Yi
;
應用數學系
;
Department of Applied Mathematics
For any n-by-n matrix A, we consider the maximum number k = k(A) for which there is a k-by-k compression of A with all its diagonal entries in the boundary partial derivative W(A) of the numerical range W (A) of A. If A is a normal or a quadratic matrix, then the exact value of k(A) can be computed. For a matrix A of the form B circle plus C, we show that k(A) = 2 if and only if the numerical range of one summand, say, B is contained in the interior of the numerical range of the other summand C and k(C) = 2. For an irreducible matrix A, we can determine exactly when the value of k(A) equals the size of A. These are then applied to determine k(A) for a reducible matrix A of size 4 in terms of the shape of W (A). (C) 2013 Elsevier Inc. All rights reserved.
Enhanced field emission characteristics in metal-coated Si-nanocones
(2013)
Chang, Yuan-Ming
;
Kao, Pin-Hsu
;
Tai, Hung-Ming
;
Wang, Hau-Wei
;
Lin, Chih-Ming
Metallic gold (Au) and platinum (Pt) thin films were deposited on silicon nanocones (Si-NCs) by sputtering to elucidate the effects of work function and conductivities on the field electron emission characteristics of surface-modified Si-NCs. The results showed that for Pt/Si-NCs and Au/Si-NCs, although the turn-on field defined at a corresponding current density of 10 mu A cm(-2) only improved from 4.20 V mu m(-1) for bare Si-NCs to 3.65 and 2.90 V mu m(-1), respectively, the emission current density measured at 5.00 V mu m(-1) was enhanced by orders of magnitude, reaching 1.82 mA cm(-2) for Au/Si-NCs. Compared to those obtained from various surface-modified Si-nanostructures, such as ZnO/Si-nanopillars and ferroelectrics/Si-nanotips, the current results represent an interesting alternative route for producing surface-modified Si-NCs that might be useful for optical and electronic applications.

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