Polyaniline (PAn)-coated silica spheres have been synthesized by attaching various amounts of N-[3- (trimethoxysilyl)propyl]aniline (TMSPA) and polymerizing with ammonium persulfate. The ratios of tetraethoxy orthosilicate and TMSPA were 10:1 (PAn-A), 5:1 (PAn-B), and 3:1 (PAn-C). After polymerization of the aniline moieties the –OH absorption peak drastically reduced and the new sharp peaks appeared at 1398 cm-1 and 617 cm-1 representing C-N and C-S stretching vibrations, respectively. The polymerized spheres were soaked into the acetone for three months. New absorption peak at 1712 cm-1 representing C=O stretching vibration of an ester appears after three months storage in acetone and becomes stronger with the smaller amount of PAn. Although the sphere film color is gray when it is dried, the color turned to dark when it was wetted with methanol. Complicated solvatochromic behavior was observed for whole UV-visible range depending on the solvent. The solution color changed from clear to dark brown, brown, and yellow for the PAnA, PAnB and PAnC, respectively. The absorption peaks of the dried solution for PAn-A and PAn-B at 3230, 2972, 2926, 1712, 1434/1377, and 1051 cm-1 represent C-OH, R-CH3, R2-CH2, -C=O, C-H, and Si- O-Si absorption, respectively. Photoluminescence peak of the solution shifted toward longer wavelength with the decrease the amount of PAn. The sequence of the amount of new material formation is PAn-A > PAn-B > PAn-C.
Various sizes of CdSe quantum dots have been fabricated on the surface of the monodisperse silica spheres and five diffe rent photoluminescence (PL) peaks are observed from the CdSe quantum dots. The monodisperse silica spheres were syn thesized with Stöber synthetic method. The surface of the spheres was modified with 100:1 ratio of phenylpropyltrimeth oxysilane (PTMS) and mercaptopropyltrimethoxysilane (MPTMS). The MPTMS works as a covalent bond formation wi th CdSe quantum dots, and the PTMS acts as a separating quantum dots to prevent PL quenching by neighboring quantu m dots. The Fourier transform infrared (FTIR) spectrum of the surface modified spheres (SMSiO2) shows strong absorpti on peak at 2852 and 2953 cm-1 representing the characteristic absorption of –CH or -CH2. The FTIR absorption peak at 1 741 cm-1 represents the characteristic absorption of CdSe quantum dots. The field emission scanning electron microscope image shows the average diameter of the spheres ranging approximately 418 nm. The ultraviolet-visible transmittance s pectrum shows stop band at 880 nm. The PL spectrum shows five different emission bands at 434, 451, 468, 492 and 545 nm, which indicates the formation of several different sizes of CdSe quantum dots.
A reversible color change and large absorption band shift have been observed for the disperse red-13 (DR-13) attached
on the surface of the monodisperse silica spheres. Two step synthetic processes including urethane bond formation and
hydrolysis-condensation reactions were used to attach the DR-13 on the surface of the silica spheres. After the reaction,
the characteristic absorption peak at 2270 cm-1 representing the –N=C=O asymmetric stretching vibration disappeared,
and the a new absorption peak at 1700 cm-1 corresponding the C=O stretching vibration appeared. A visual and
reversible color change was observed before and after wetting in alcohol. Although the absorption peak of DR-13 in
alcohol is at 510 nm, the absorption peak shifts to 788 nm when it is dried. The absorption peak shifts to 718 nm when it
is wetted in alcohol. This result can be explained by the formation of intramolecular charge transfer band.
The optical properties of sulforhodamine B (SRH) impregnated in photonic crystal by two step synthetic processes including a urethane bond formation between a 3-isocyanatopropyl triethoxysilane (ICPTES, -N=C=O) and a SRH with elevated temperature in pyridine and hydrolysis-condensation reactions between synthesized ICPTES/SRH (ICPSRH) and tetraethoxyorthosilicate (TEOS) in NH4OH. The monodisperse silica spheres impregnated the ICPSRH (ICPSRHS) are fabricated. The reduction of the absorption peak at 2270 cm-1 representing asymmetric stretching vibration of –N=C=O indicates the progress of the reaction and new absorption peak at 1712 cm-1 characterizing –C=O stretching vibration indicates the formation of urethane bond. The UV-visible absorption spectra show the broadened spectral line width by intermolecular interaction. The photoluminescence (PL) peak of the SRH in methanol shows a hypsochromic shift with the increase the excitation wavelength. However, the PL peak for the ICPSRH exhibits a bathochromic shift as the excitation wavelength increases. The PL peak for the ICPSRH shows no hypsochromic or bathochromic shift. The PL peaks for SRH in methanol, ICPSRH and ICPSRHS are at 568, 598 and 572 nm, respectively. The main cause of the PL peak shift is due to the intermolecular interaction.
Optical properties of disperse red-13 (DR-13) covalently attached in the silica spheres have been investigated with the two step synthetic processes including a urethane bond formation between a 3-isocyanatopropyl triethoxysilane (ICPTES, -N=C=O) and DR-13 (-OH) with different ratios (3:14, 13:14 and 23:14) of the ICPTES and the DR-13 in pyridine and hydrolysis-condensation reactions between synthesized ICPTES/DR-13 (ICPDR) and tetraethoxyorthosilicate (TEOS) in NH4OH. The absorption peak at 1704 cm-1 representing the -C=O stretching vibration of the spheres attached ICPDR (ICPDRSS) indicates the formation of the urethane bond. Several other absorption peaks originated from ICPDR appeared in the FTIR spectra. The UV-visible absorption peak of the ICPDRSS shifted toward blue with respect to that of DR-13 in methanol, which indicated the antiparallel structure of the DR-13. The photoluminescence peak shifted toward red with the increase of the ratio of DR-13 with respect to ICPTES. This result implies the increase of the intermolecular interaction between DR-13 molecules with the increase of the DR-13 concentration.
Surface modification of silica spheres with 3-(Trimethoxysilyl)propylmethacrylate (TMSPM) has been performed at
ambient condition. However, the FTIR spectra and field emission scanning electron microscope (FESEM) images show
no evidence of the surface modification. The reaction temperatures were varied from 60 to 80 °C with various reaction
periods. Small absorption shoulder of the C=O stretching vibration was at 1700 cm-1, and slightly increased with the
increase of the reaction time at 60 °C. The clear absorption peak appeared at 1698 cm-1 for the spheres reacted for 80
min at 70 °C and shifted toward 1720 cm-1 with the increase the reaction time. Strong absorption peak showed at 1698
cm-1 and shifted toward 1725 cm-1 with the increase of the reaction time at 80 °C. The spheres were dispersed to
methanol and added photoinitiator (Irgacure-184). The solution was poured to a patterned glass substrate and exposed to
the 254 nm UV-light during a self-assembly process. A large area and crack-free silica sphere film was formed. To
increase the mechanical stability, a cellulose acetate solution was spin-coated to the film. The film was lift-off from the
glass substrate to analyze the surface nanostructures. The surface nanostructures were maintained, and the film is stable
enough to use as a mold to duplicate the nanopattern and flexible.
Managing waste solvent is the most cost effective and environmentally friendly method. To reduce waste solvent, this investigation focused on the effect of the solvent ratio on the diameter of the spheres and on the structure of the photonic crystal by using recycled solvent. The sphere diameter reduced with the reduction of the NH4OH ratio. To investigate the effect of the recycled solvent on the structure of the silica spheres, the recycled solvent was repeatedly used five times. The diameter and shape of the silica spheres were similar when the solvent was used twice. However, the shape and structure of the spheres became more irregular with the increase of the recycling time. The FTIR spectra of all spheres are identical. To identify the cause of the irregular structure of the spheres, the solvent recycled five times was evaporated, and the residual compound was analyzed. As a result, the residual compound was composed of Si-O-Si and Si-OH. This residual silica compound may cause the connected and irregular structure of the spheres.
The mixture of phenyltrimethoxysilane (PTMS) and mercaptopropyltrimethoxysilane
(MPTMS) has been covalently bonded to the surface of the monodisperse silica spheres to attach
the PbS nanoclusters. The Fourier transform infrared (FTIR) spectra of the modified silica
spheres (MSSPh) with PTMS and MPTMS clearly indicates the phenyl ring and carbohydrate
absorption band. The FTIR spectra of MSSPh after attaching the Pb2+ and converting Pb2+ to PbS
show the characteristic absorption peaks. The stopband of unmodified silica spheres located at
830 nm. However, the stopband disappears after surface modification and PbS formation due to
the hydrophobic nature of the silica spheres. The field emission scanning electron microscope
images of the MSSPh and MSSPh-PbS show similar surface texture. The compositions of the
MSSPh-PbS obtained by energy dispersive spectroscopy include silicon, oxygen, carbon, sulfur
and lead with the atomic ratio (weight ratio) of 33.34 (46.31), 32.60 (25.80), 32.90 (19.55), 0.40
(0.64) and 0.75 % (7.70 %), respectively. The photoluminescence (PL) spectrum shows several
luminescence peaks between 600 to 840 nm. The PL results indicate that the PbS nanoclusters
(NCs) may have molecular characteristics with this growth process. A precisely controlled
growth can be achieved by extensive washing and centrifuge processes.
Optical properties of a azo-dye attached on the surface of the monodisperse silica
photonic crystal have been investigated. The azo-chromophore was covalently attached to a
3-isocyanatopropyl triethoxysilane (ICPTES) having isocynate functional group by a
urethane bond formation reaction. The resulting disperse red/ICPTES (DRICP) was attached
on the surface of the silica photonic crystal by hydrolysis and condensation reactions. The
FTIR spectrum of the resulting product DRICP/silica sphere (DRICPSS) shows no
characteristic isocynate absorption peak at 2270 cm-1 and shows a new absorption peat at
1700 cm-1 corresponding the C=O stretching vibration. This result indicates the complete
reaction between –N=C=O and –OH. The DRICPSS has weak brownish color when it is
dried. The color of the DRICPSS changed to intense red when it is wetted in methanol,
ethanol and 2-propanol. The near infrared absorption maximum at 788 nm shifted to 718 nm
for the ICPDRSS after wetting in methanol. This system can be applicable to a sensitive
alcohol sensor.
Large area photonic crystal has been fabricated with monodisperse silica spheres
modified the surface with 3-(trimethoxysilyl) propylmethacrylate (TMSPM). The surface of
the spheres has been modified by hydrolysis and condensation reaction of TMSPM with base
catalyst and acid catalyst. The Fourier transform infrared (FTIR) spectra, field emission
scanning electron microscope (FESEM) images no evidence that the TMSPM is corporate on
the surface of the silica spheres for the base catalyst process. However, FTIR spectra and
FESEM images clearly presents the existence of hydrolyzed TMSPM on the surface of silica
spheres for the acid catalyst process. The FTIR absorption peak at 1714 cm-1 representing
C=O stretching vibration indicates that the hydrolyzed TMSPM is corporate on the surface of
the silica spheres. Although generally the colloidal photonic crystal has large number of
cracks, surface modification and photocross-linking process during the packing process can
be avoided the crack process of the photonic crystal.
Surface morphologies of the ZnO thin films with various thicknesses have been investigated. ZnO sol was prepared with
zinc acetate dihydrate, 2-methoxyethanol, and monoethanolamine. Thicknesses of the ZnO films were controlled by a
multiple coating process. The ZnO thin films were annealed at 750 °C. The film thickness increased as the coating time
increased. From the XRD study, it is observed that the ZnO films exhibit wurtzite structure (002) and the diffraction
intensity increased as the thickness increased. Effect of thickness on Schottky behavior was evaluated by measuring
current-voltage characteristics. The pristine ZnO thin films with thickness of 132 nm exhibited Schottky diode
characteristics with high rectification ratio.
Relative phase transformation rates are compared with TiO2 sol-gel thin film and TiO2 nanorods. TiO2 thin film was
prepared with sol-gel process using titaanium isoproxide (TIP) as a precusor, ethanol as a solvent and HCl as a catalyst.
The TiO2 nanorods were synthesized with low temperature proccess (100 °C) using TIP, oleic acid, and aqueous
trimethylamine. The prepared thin film and nanorods were annealed at 850 °C for 3 h. X-ray diffraction patterns reveal
that the TiO2 thin film and TiO2 nanorods have amorphase phase and anatase phase, respectively before annealing
process. Approximately 60 and 3 % of TiO2 thin film and TiO2 nanorods transformed from anatase phase to rutile phase
after annealing at 850 °C for 3 h. Relatively small amount of TiO2 nanorods transformed to rutile phase compared with
TiO2 thin film. This small amount of phase transformation may be due to the small diameter of the TiO2 nanorods, which
have thermodynamecally favorable anatase phase.
Single-phase hexangonal wurtzite GaN nanoparticles and GaN thin film were prepared by the sol-gel techniqiue.using
Ga(NO3)3. For GaN thin films, Ga(NO3)3 was hydrolyzed with ethanol and acetic acid and aged for one day. GaO(OH)
thin layer was fabricated with spin-coating and heating at 200 °C. For GaN nanoparticles, the Ga(NO3)3 was dissolved in
concentrated nitric acid and adjusted pH to 8.5 using NH4(OH). Citric acid was added to the Ga(NO3)3 solution and
heated 80 °C for 2 h. The solution was heated at 400 °C for 4 h to obtain the Ga2O3 nanoparticles. The GaO(OH) and
Ga2O3 were annealed in a tube furnace at 900 °C for 1 h with NH3 gas flow. The thickness of GaN thin film was
approximately 46 nm. The grain size of the GaN thin film after converting from GaO(OH) to GaN, which was obtained
by atomic force microscope image, was approximately 25-35 nm. The diameter of the GaN nanoparticles is
approximately 15 nm with lattice fringes of 2.7 Α. The crystall has hexagonal wurzite structure, which is conformed by
X-ray diffraction (XRD) pattern.
The surface of directly coated TiO2 nanoparticles on the Al-electrode has many nanoscale holes and cracks. The defects
of the TiO2 layers can be removed via coating PEDOT:PSS on top of the TiO2 layer. Schottky diodes having various
thicknesses of the TiO2 layers and PEDOT:PSS layers were fabricated. The normalized forward current densities were
almost the same for the Schottky diodes fabricated with various thicknesses of the TiO2 layers. The current densities of
the Schottky diodes with double coatings have large deviation. The log(J) vs. log(V) and shows nonlinear J-V
characteristics representing the multiple electron emission mechanisms such as space-charge limited conduction, Poole-
Frenkel emission, or thermoionic emission. The plots of log(J) vs. E1/2 and log(J/E) vs. E1/2 show nonlinear behavior and
with two distinctive slopes. Based on these results, the electron emission mechanism may have two distinctive
mechanisms including Schottky emission mechanism and Poole-Frenkel emission mechanism.
Various conbinations of TiO2 sol-gel were prepared to fabricate Schottky diodes. Pure TiO2 sol-gel was spin-coated to
the various substrates such as glass, silicon wafer, and cellulose. The sol-gel driven TiO2 films were generated cracks all
over the surface during the annealing process. To prevent cracks, polyethylene glycol (PEG) was added to TiO2 sol-gel
solution. TiO2-PEG sol-gel was spin-coated to the substrate and heat treated at 100, 200, and 300°C for 1 h. The film
thicknesses were 230, 190, and 129 nm for the sample heated at 100, 200, and 300°C, respectively, and no cracks were
observed. The FTIR pesk at 3380 cm-1 corresponds to -OH stretching mode and disappeared as the heating temperature
increased. The characteristic peaks of PEG at 2875 and 1120 cm-1 also disappeared as the heating temperature increased.
The Schottky diodes comprised of Al/PEG-TiO2/Au with various heat treatment were fabricated. The forward current
was drastically increased as the annealing temperature increased. The plots of parabolic conduction curves based on
Schottky conduction model, Poole-Frenkel conduction model, and space charge limitted conduction model show
nonlinear relationship. These nonlinear relationship indicates that the conduction mechanism is not purely single
conduction mechanism.
A cellulose solution was prepared using N,N-dimethylacetamide (DMAc), LiCl, and natural pulp. Transparent
and smooth surface of the cellulose films were obtained after spin-coating and drying process. The cellulose films can be
utilized as a biodegradable and flexible microelectromechanical system (MEMS) due to its electro-active and actuation
properties. However, it is difficult to apply conventional lithography process to fabricate MEMS device because of its
hydrophilic and flexible nature. Therefore, we applied unconventional lithography process to overcome those problems.
Since polydimethylsiloxane (PDMS) has a modulus less than 10MPa, it is not suitable to fabricate high aspect ratio mold.
Polyurethaneacrylate (PUA) having a modulus in the range of several hundred was utilized as a mold for micro-contact
printing (MCP) process. Although high modulus PUA mold having more than 300MPa had edge defects during the
mold-releasing process from the photoresist, the PUA mold having a modulus between 100MPa and 300MPa did not
have the edge defect problem. Therefore, PUA mold with a modulus of 200MPa was used in this investigation. Gold was
deposited onto the PUA mold, and mercaptopropyltrimethoxysilane (MPTMS) self-assembly monolayer (SAM) was
fabricated to the gold surface. The gold was transferred to the cellulose film. The characteristics of the transferred gold
electrode on cellulose film were investigated using field emission scanning electron microscope (FESEM).
Cellulose is a beneficial material that has low cost, light weight, high compatibility, and biodegradability.
Recently electro-active paper (EAPap) composed with cellulose was discovered as a smart material for application to
variety industrial fields such as smart wall-paper, actuator, and magic carpet. It also exhibited actuator property through
ion migration and piezoelectric effect. Since cellulose acetate (CA) film has optically transparent property, we focused
on optical field application, such as electronic paper, prismsheet, and polarized film. Since CA can be easily dissolved in
variety of organic solvent, various weight % (from 1 to 25 wt. %) of CA solution in acetone was prepared.
Polydimethylsilane (PDMS) master pattern was fabricated on the silicone wafer. CA solution was poured to the master
mold and dried using spin-coating or tape casting method. Various shape and height patterns, such as circle, honeycomb,
and rectangular patterns were fabricated using 12 wt. % CA solution. The resulting pattern showed uniform size in the
large area without defect. These patterns can be utilized as a substrate and cell pattern for the electronic paper. To
investigate saponification (SA) effect to convert CA to regenerated cellulose, CA film was immersed into the sodium
methoxide solution in methanol for various times. The fabricated CA films were stretched and immersed into the sodium
methoxide solution in methanol to desubstitute the acetate group. These regenerated cellulose films have larger
mechanical strength than CA films. Although the UV-visible transmittance was decreased as increasing SA time, the
transmittance of the further SA process and stretched film backed up near untreated CA film. Although the cross-sectional
image of the saponified and unstretched CA film did not have specific directional structure, the cross-sectional
FESEM image of the saponified and stretched CA film had one directional fiber structure. The fiber was aligned to the
stretched direction. Most of the compositions were one directional ordered nanofibers having diameter of approximately
30nm.
Significant amount of pentacene can be dissolved in N-methylpyrrolidone (NMP) solvent. The solution color
changed from deep purple to intense yellow. As the dissolution time increased, UV-visible absorption increased and
several new absorption peaks were appeared. The solution was mixed with poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT:PSS). PEDOT:PSS or PEDOT:PSS doped with pentacene was
spin-coated to the Al coated substrate. Au-electrode was fabricated on top of the semiconductor. Three-layered Schottkys
diode comprised of Al, PEDOT:PSS or PEDOT:PSS-pentacene, and Au with thickness of 150nm, 420nm, and 1200nm,
respectively were fabricated. The current densities of 4.8μA/cm2 at 2.5MV/m and 440μA/cm2 at 1.9MV/m were obtained
for the Au/PEDOT:PSS/Al and Au/PEDOT:PSS-pentacene (3.2 mg)/Al Schottky diodes, respectively. The current
density of Schottky diode enhanced about two order of magnitude by doping pentacene to PEDOT:PSS.
The electro-active paper (EAPap) has been investigated as a light-weight and low power consuming actuator. The
EAPap cannot be utilized conventional lithography technique for fabrication of metal pattern due to its hydrophilic and
flexible properties. A metal pattern fabrication on the EAPap is a beginning step for the integration of the paper actuators
and micro-electronics. To overcome the drawback of the EAPap, a micro-contact printing (μ-CP) technique was utilized
to fabricate Au-patterns on EAPap. Large number of cracks or nanograins was observed on the transferred Au-pattern.
These defects were closely related with the solvent polarity during the fabrication of adhesion self-assembly monolayer
(SAM). To investigate the cause of defects, three different solvents having different polarity were utilized during the
SAM layer fabrication process. The ethanol having high polarity was utilized to investigate the effect of the 3-
mercaptopropyltrimethoxysilane (MPTMS) concentration on micro or nano-defect formation.
Polymer materials offer numerous advantages including flexible, low cost large area displays, lightweight, easy
processing, good compatibility with a variety of substrates, and easy for structural modifications. Recently electro-active
polymers (EAP) have been attractive due to their potential advantages including ease of processing and control,
mechanical flexibility, and economical advantage. Recently electro-active paper (EAPap) was discovered as a smart
material and as an actuating material with ionic and piezoelectric effects. Before cellulose acetate (CA) micro-pattern
fabrication, solvent effect of micro or nano-pore formation was investigated. Since the micropore scatter the visible light,
micropores give negative effect to apply optical device. The solvent mixture of acetone/dimethylacetamide (DMAc)
created large amount of micro or nanopores. The resulting films were not transparent. However, volatile single solvent
(acetone) did not form pores and gave transparent film. The various shapes of photoresist, such as circle and honeycomb
patterns, were fabricated onto the silicon wafer to use as the mold. Cellulose acetate (CA) was poured to the mold and
peeled off from the mold. The resulting pattern exhibited uniform size of the circle or honeycomb shape without defect.
The cellulose solution dissolved in dimethylacetamide (DMAc) and LiCl was spin-coated to the silicon wafer and removed DMAc solvent using 2-propanol and deionized water. The various metal electrodes were fabricated on the DMAc-cellulose using the following several different soft lithography processes. For the first process, gold electrodes were deposited onto the polydimethylsilane (PDMS). Self-assembly monolayer (SAM) of 3-(mercaptopropyl)trimethoxysilane (MPTMS) were fabricated on the cellulose surface using vacuum deposition method before stamping the gold electrode. Since the cellulose/SAM layer method created nano-defects on the metal electrode, tetrahydrofurane (THF)/MPTMS, toluene/MPTMS, and 2-propanol/MPTMS solution method were utilized for MPTMS SAM layer fabrication. 2-Propanol/MPTMS combination exhibited minimum defects on the metal electrodes. This result may be due to the minimum diffusion of the solvent into the stamp. For the next process, gold electrodes were deposited onto the PDMS stamp, and SAM layer of MPTMS was fabricated on the gold electrodes instead of cellulose paper. This result shows that there was no defect on the metal electrode even on the nano-scale field emission scanning electron microscope (FESEM) images. Liftoff lithography with over-developing process provided high quality metal electrodes surface and edge without nano-scale defects. This modified lithography process opened the new fabrication method of various metal electrodes to the electro-active paper (EAPap).
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