%0 Journal Article %J Advanced Materials %D 2003 %T Medium effect on the electron cooling dynamics in gold nanorods and truncated tetrahedra %A Link, Stephan %A Hathcock, D. J. %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X A study on the electron relaxation dynamics and thermal cooling of colloidal gold nanoparticles (see Figure) in air and water finds that the local energy exchange with the surrounding medium occurs on the picosecond time scale, comparable with the electron-phonon relaxation, while a slow heat dissipation by water ensures that the particles remain heated for hundreds of picoseconds. %B Advanced Materials %V 15 %P 393-+ %8 Mar %@ 0935-9648 %G eng %M WOS:000181713900003 %R 10.1002/adma.200390088 %0 Journal Article %J Chemistry of Materials %D 2003 %T Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method %A Nikoobakht, Babak %A El-Sayed, Mostafa A %B Chemistry of Materials %I American Chemical Society %V 15 %P 1957 - 1962 %8 2003 %@ 0897-4756 %G eng %U http://dx.doi.org/10.1021/cm020732l %N 10 %! Chem. Mater. %0 Journal Article %J The Journal of Physical Chemistry AThe Journal of Physical Chemistry A %D 2003 %T Surface-Enhanced Raman Scattering Studies on Aggregated Gold Nanorods %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Surface-enhanced Raman scattering (SERS) of adsorbed molecules on gold nanorods (NRs) with dimensions of 10 nm ? 27 nm was studied on silica surface with low to high surface coverage of NRs. The study was carried out to investigate both the dependence of the SERS intensity on the number of NRs and the NRs spacing on the silica surface. SERS of adsorbed molecules such as 2-aminothiophenol (2-ATP) and the capping molecules (hexadecyltrimethylammonium bromide) was studied on these surfaces using a near-IR laser excitation source (1064 nm). To produce silica surfaces covered with NRs, two approaches were used. In the first approach, monodispersed NRs gradually deposited from solution to silica surface and their number was increased by increasing the deposition time. In the second one, the NRs were first aggregated in solution and then deposited on the surface. Although using the first approach it was possible to prepare surfaces with high NR surface coverage, SERS intensity was found to be stronger for adsorbed molecules on surfaces covered with aggregated NRs. The observed increase in the SERS intensity in the case of aggregation was attributed to the enhancement of the electric field between the particles in the aggregates. It is shown that aggregated NRs in comparison with aggregated nanospheres (NSs) have stronger SERS enhancement under similar experimental conditions. In this comparison, some of the enhanced vibrational bands of 2-ATP on aggregated NRs are weakly enhanced or absent on aggregated NSs. Monitoring the SERS intensity of adsorbed 2-ATP versus its exposure time to the aggregated NRs shows that the SERS intensity of the adsorbed molecules reaches saturation, whereas the peak intensities of the capping molecules remain unchanged. The intensity saturation was discussed in terms of factors such as the saturation of the SERS active sites for 2-ATP on the gold surface and the partial damping of the plasmon band due to the stronger interaction of the adsorbate molecules with the metal surface.Surface-enhanced Raman scattering (SERS) of adsorbed molecules on gold nanorods (NRs) with dimensions of 10 nm ? 27 nm was studied on silica surface with low to high surface coverage of NRs. The study was carried out to investigate both the dependence of the SERS intensity on the number of NRs and the NRs spacing on the silica surface. SERS of adsorbed molecules such as 2-aminothiophenol (2-ATP) and the capping molecules (hexadecyltrimethylammonium bromide) was studied on these surfaces using a near-IR laser excitation source (1064 nm). To produce silica surfaces covered with NRs, two approaches were used. In the first approach, monodispersed NRs gradually deposited from solution to silica surface and their number was increased by increasing the deposition time. In the second one, the NRs were first aggregated in solution and then deposited on the surface. Although using the first approach it was possible to prepare surfaces with high NR surface coverage, SERS intensity was found to be stronger for adsorbed molecules on surfaces covered with aggregated NRs. The observed increase in the SERS intensity in the case of aggregation was attributed to the enhancement of the electric field between the particles in the aggregates. It is shown that aggregated NRs in comparison with aggregated nanospheres (NSs) have stronger SERS enhancement under similar experimental conditions. In this comparison, some of the enhanced vibrational bands of 2-ATP on aggregated NRs are weakly enhanced or absent on aggregated NSs. Monitoring the SERS intensity of adsorbed 2-ATP versus its exposure time to the aggregated NRs shows that the SERS intensity of the adsorbed molecules reaches saturation, whereas the peak intensities of the capping molecules remain unchanged. The intensity saturation was discussed in terms of factors such as the saturation of the SERS active sites for 2-ATP on the gold surface and the partial damping of the plasmon band due to the stronger interaction of the adsorbate molecules with the metal surface. %B The Journal of Physical Chemistry AThe Journal of Physical Chemistry A %I American Chemical Society %V 107 %P 3372 - 3378 %8 2003 %@ 1089-5639 %G eng %U http://dx.doi.org/10.1021/jp026770+ %N 18 %! J. Phys. Chem. A %R 10.1021/jp026770+ %0 Journal Article %J Photochemistry and Photobiology %D 2002 %T The quenching of CdSe quantum dots photoluminescence by gold nanoparticles in solution %A Nikoobakht, Babak %A Burda, Clemens %A Braun, Markus %A Hun, M. %A El-Sayed, Mostafa A %X The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the {110} facets only in the NR, which have higher surface energy. %B Photochemistry and Photobiology %V 75 %P 591-597 %8 Jun %@ 0031-8655 %G eng %M WOS:000176364000007 %R 10.1562/0031-8655(2002)075<0591:tqocqd>2.0.co;2 %0 Journal Article %J Chemical Physics Letters %D 2002 %T Surface-enhanced Raman scattering of molecules adsorbed on gold nanorods: off-surface plasmon resonance condition %A Nikoobakht, Babak %A Wang, Jianping %A El-Sayed, Mostafa A %X The Raman spectra of several molecules adsorbed on gold nanospheres (NSs) (12 nm in diameter) and nanorods (NRs) (25 nm x 10 nm) are studied using an off-plasmon resonance excitation condition. The studies are carried out in colloidal solution and on solid substrates. Enhancement factors on the order of 10(4)-10(5) are observed for the adsorbed molecules on the NRs, however, no such enhancement was observed on NSs under similar condition. These factors are two orders of magnitude larger than the calculated value using the Wang and Kerker electromagnetic model. This suggests a contribution from the chemical mechanism in the observed enhancement. (C) 2002 Published by Elsevier Science B.V. %B Chemical Physics Letters %V 366 %P 17-23 %8 Nov %@ 0009-2614 %G eng %M WOS:000179253000003 %R 10.1016/s0009-2614(02)01492-6 %0 Journal Article %J Langmuir %D 2001 %T Evidence for bilayer assembly of cationic surfactants on the surface of gold nanorods %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X The surface structure of gold nanorods (NRs) capped with cationic surfactants in water was studied by FTIR, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). For gold nanorods, the FTIR results show the formation of new bands, which indicate binding of the surfactant headgroup to the surface of the NR. These bands are stable at temperatures as high as 350 degreesC. For a surfactant mixture (used as capping material), TGA shows a weak weight loss peak at 235 degreesC and a strong peak at 298 degreesC assigned to the surfactant molecules in monomer and aggregated forms, respectively. For gold nanorods, three weight loss peaks at about 230, 273, and 344 degreesC are observed. For gold nanospheres (NSs), TGA shows a strong mass loss at 225 degreesC and two weak mass loss peaks at 255 and 288 degreesC. The released material after combustion in the TGA process was analyzed by FTIR spectroscopy and found to be CO2. Our results suggest the following for both NRs and NSs: (1) There are two different binding modes for the surfactant molecules capping these nanoparticles. (2) Surfactant molecules form a bilayer structure around the gold nanoparticles in which the inner layer is bound to the gold surface via the surfactant headgroups. (3) With increase of the temperature, the outer layer desorbs at lower temperature and consequently the inner layer leaves the surface at higher temperature. (4) The higher desorption temperature of the bilayer in the NRs compared to NSs is explained in terms of the difference in packing of the surfactant molecules and their adsorption energy to the different facets present in these nanoparticles. (5) TEM results suggest that the shape transformation of NRs to NSs occurs as the inner layer is released from the surface. (6) The CH2 rocking mode at 720 cm(-1) suggests that the methylene chains have free rotation and surfactants are packed in a hexagonal structure. %B Langmuir %V 17 %P 6368-6374 %8 Oct %@ 0743-7463 %G eng %M WOS:000171305700053 %R 10.1021/la010530o %0 Journal Article %J Physical Review B %D 2000 %T Femtosecond transient-absorption dynamics of colloidal gold nanorods: Shape independence of the electron-phonon relaxation time %A Link, Stephan %A Burda, Clemens %A Mohamed, MB %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X We studied the femtosecond dynamics of colloidal gold nanorods encapsulated in micelles after excitation with 400 nm pulses of 100 fs duration. It is found that the laser heating of the electron gas of gold nanorods with an average aspect ratio of 3.8 leads to the bleaching of both the transverse and longitudinal mode of the surface plasmon oscillation at 520 and 750 nm. The bleach recovers with the same time constant for both the transverse and longitudinal oscillation, for gold nanodots prepared by photothermal reshaping of the rods as well as for nanodots synthesized chemically by citrate reduction (and known to have twin boundaries and surface defects). Since the bleach recovery on the 3 ps time scale is assigned to electron-phonon relaxation processes, these results suggest that phonon dependent relaxation processes in gold nanoparticles are independent of the shape, size, type of the surfaces, or the mode of the surface plasmon, oscillation excited. The fact that the mean free path of the electron in metallic gold is in the nanometer length scale (similar to 50 nm) raised the question of the importance of surface scattering to the electron-phonon relaxation process in gold nanoparticles. Our previous studies showed little dependence of the relaxation rate of the size of gold nanodots (from 9 to 48 nm). In the present study, the electron-phonon relaxation is measured in gold nanorods, which have different facets from those of gold nanodots. %B Physical Review B %V 61 %P 6086-6090 %8 Mar %@ 1098-0121 %G eng %M WOS:000085707100051 %R 10.1103/PhysRevB.61.6086 %0 Journal Article %J Journal of Physical Chemistry B %D 2000 %T Laser-induced shape changes of colloidal gold nanorods using femtosecond and nanosecond laser pulses %A Link, Stephan %A Burda, Clemens %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Gold nanorods have been found to change their shape after excitation with intense pulsed laser irradiation. The final irradiation products strongly depend on the energy of the laser pulse as well as on its width. We performed a series of measurements in which the excitation power was varied over the range of the output power of an amplified femtosecond laser system producing pulses of 100 fs duration and a nanosecond optical parametric oscillator (OPO) laser system having a pulse width of 7 ns. The shape transformations of the gold nanorods are followed by two techniques: (1) visible absorption spectroscopy by monitoring the changes in the plasmon absorption bands characteristic for gold nanoparticles; (2) transmission electron microscopy (TEM) in order to analyze the final shape and size distribution. While at high laser fluences (similar to 1 J cm(-2)) the gold nanoparticles fragment, a melting of the nanorods into spherical nanoparticles (nanodots) is observed when the laser energy is lowered. Upon decreasing the energy of the excitation pulse, only partial melting of the nanorods takes place. Shorter but wider nanorods are observed in the final distribution as well as a higher abundance of particles having odd shapes (bent, twisted, phi-shaped, etc.). The threshold for complete melting of the nanorods with femtosecond laser pulses is about 0.01 J cm(-2). Comparing the results obtained using the two different types of excitation sources (femtosecond vs nanosecond laser), it is found that the energy threshold for a complete melting of the nanorods into nanodots is about 2 orders of magnitude higher when using nanosecond laser pulses than with femtosecond laser pulses. This is explained in terms of the successful competitive cooling process of the nanorods when the nanosecond laser pulses are used. For nanosecond pulse excitation, the absorption of the nanorods decreases during the laser pulse because of the bleaching of the longitudinal plasmon band. In addition, the cooling of the lattice occurring on the 100 ps time scale can effectively compete with the rate of absorption in the case of the nanosecond pulse excitation but not for the femtosecond pulse excitation. When the excitation source is a femtosecond laser pulse, the involved precesses (absorption of the photons by the electrons (100 fs), heat transfer between the hot electrons and the lattice (<10 ps), melting (30 ps), and heat loss to the surrounding solvent (>100 ps) are clearly separated in time. %B Journal of Physical Chemistry B %V 104 %P 6152-6163 %8 Jul %@ 1089-5647 %G eng %M WOS:000088057100012 %R 10.1021/jp000679t %0 Journal Article %J Journal of Physical Chemistry B %D 2000 %T Self-assembly of gold nanorods %A Nikoobakht, Babak %A Wang, Z.L. %A El-Sayed, Mostafa A %X Self-assembly of gold nanorods (NRs) with aspect ratio of similar to 4.6 (12 nm in diameter and 50-60 nm in length) has been studied using transmission electron microscopy (TEM). Under appropriate conditions such as nanoparticle concentration, solvent evaporation, narrow size distribution, ionic strength, and surfactant concentration of the parent solution, gold nanorods assemble into one-, two-, and three-dimensional structures. Some of the three-dimensional assemblies extend to superlattices of NRs. The translation and orientation symmetries of the self-assembled structures are determined. The factors affecting the formation of the ordered self-assembly are discussed. %B Journal of Physical Chemistry B %V 104 %P 8635-8640 %8 Sep %@ 1089-5647 %G eng %M WOS:000089268000002 %R 10.1021/jp001287p %0 Journal Article %J Journal of Physical Chemistry B %D 2000 %T Surface reconstruction of the unstable 110 surface in gold nanorods %A Wang, Z.L. %A Gao, R. P. %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Gold nanorods prepared electrochemically and capped in micelles are examined using high-resolution transmission electron microscopy (TEM), It is found that they have an axial growth direction of [001] and have surfaces made of {100} and the unstable {110} facets. A detailed examination of the defect sites of both of these facets shows that while the defective regions of the stable {100} facets show atom-height steps with no reconstruction, the less stable higher energy {110} surfaces show missing-row reconstruction. The role of micelles in stabilizing the {110} facet in the gold nanorod is briefly discussed. %B Journal of Physical Chemistry B %V 104 %P 5417-5420 %8 Jun %@ 1089-5647 %G eng %M WOS:000087779300005 %R 10.1021/jp000800w %0 Journal Article %J Chemical Physics Letters %D 1999 %T How long does it take to melt a gold nanorod? A femtosecond pump-probe absorption spectroscopic study %A Link, Stephan %A Burda, Clemens %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Using pump-probe femtosecond transient absorption spectroscopy, we determined the rate of the bleach of absorption around 700-800 nm due to the longitudinal surface plasmon band of gold nanorods. Using TEM of the spotted, completely irradiated solutions suggest that the dominant products of the photothermal conformation of the rods are spheres of comparable volume. This lead to the conclusion that the melting of the rods is at least 30-35 ps, independent of the power used (5-20 mu J) or the nanorod aspect ratio (1.9-3.7). (C) 1999 Elsevier Science B.V. All rights reserved. %B Chemical Physics Letters %V 315 %P 12-18 %8 Dec %@ 0009-2614 %G eng %M WOS:000084321900003 %R 10.1016/s0009-2614(99)01214-2 %0 Journal Article %J Journal of Physical Chemistry A %D 1999 %T Laser photothermal melting and fragmentation of gold nanorods: Energy and laser pulse-width dependence %A Link, Stephan %A Burda, Clemens %A Mohamed, MB %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X We studied the shape transformation (by use of TEM and optical absorption spectroscopy) of gold nanorods in micellar solution by exposure to laser pulses of different pulse width (100 fs and 7 ns) and different energies (mu J to mJ) at 800 nm, where the longitudinal surface plasmon oscillation of the nanorods absorb. At moderate energies, the femtosecond irradiation melts the nanorods to near spherical particles of comparable volumes while the nanosecond pulses fragment them to smaller near-spherical particles. At high energies, fragmentation is also observed for the femtosecond irradiation. A mechanism involving the rate of energy deposition as compared to the rate of electron-phonon and phonon-phonon relaxation processes is proposed to determine the final fate of the laser-exposed nanorods, i.e., melting or fragmentation. %B Journal of Physical Chemistry A %V 103 %P 1165-1170 %8 Mar %@ 1089-5639 %G eng %M WOS:000079150000001 %R 10.1021/jp983141k