REP。RTs 8. L Rustad, Nature 413, 578(2001). calculated as the product of 12.7% of the cumulative °sedh10 and again in 1999. Samples were analyze increase in net nitrogen 10.w CHN analyzer. Concentrations of inorganic nitrogen 11 wea ter tbe ihing siow the reting alone were meas: 18. This conclusion is based on a paired student'st test with aggregated data from the six experimental pling the headspace at s-min intervals Samples were ears of the experiment, then once monthly. Ly Indmark, B. Elfving, For. Ecol. iy n were ree d na sas ate het fuang ters were placed at a depth of 50 cm and evacuated to 15 inches of mercury for 24 hours before sampling. 20. P. Jarvis, S. Linder, Nature 405, 904(2000) 12.cHRm过40481o tatic chan measured 22. Y. Luo, S Wan, SHui, L Wallace, Nature 413,622 (2001 13. E.A. Davidson, S E. Trumbore, R. Amundson, Nature analyzed 23. J. Merriam, W. H. McDowell, w.S. Currie, Soil trace gas concentrations by gas chromatography. soc.Am.J60.1050(1996) 14. Net nitroge d the changes in concentration were used to cal- 24. Supported by the Office of Science, Biological and buried bag incubations Incubations were for 6 15. During 1996, we analyzed the lysimeter water sar of Energ collected and analyzed for extractable NH4+ an stimated as the difference between total nd analysis with standard autoanalyzer methods trogen(TDN)and dissolved inorganic nitrogen, Program(contract no. EPA-CR 823713-01-0): and th 8 -catalyzed combustion(23) between initial and incubated soils miner- 16. A H Magill et al, Ecosystems 3, 238(2000) 8 through 17. This additional carbon storage in woody tissue wi May 2002; accepted 7 November 2002 Shape-Controlled Synthesis of The primary reaction involved the reduc- tion of silver nitrate with ethylene glycol at o Gold and silver Nanoparticles the ethylene glycol served as both reductant o and solvent. We recently demonstrated that Yugang Sun and Younan xia this reaction could yield bicrystalline silver anowires in the presence of a capping re- monodisperse samples of silver nanocubes were synthesized in large quantities ent such as poly( vinyl pyrrolidone)(PVP) by reducing silver nitrate with ethylene glycol in the presence of poly(vinyl (24). Subsequent experiments suggested that pyrrolidone)(PVP). These cubes were single crystals and were characterized by the morphology of the product had a st a slightly truncated shape bounded by (100), (110), and (111]facets. The dependence on the reaction conditions. When presence of PVP and its molar ratio(in terms of repeating unit relative to silver the concentration of AgNO, was increased by nitrate both played important roles in determining the geometric shape and size a factor of 3 and the molar ratio between the of the product. The silver cubes could serve as sacrificial templates to generate repeating unit of PVP and AgNO, was kept at E single-crystalline nanoboxes of gold: hollow polyhedra bounded by six (100) and eight [111 facets. Controlling the size, shape and structure of metal nanoparticles is technologically important because of the strong correlation canning electron microscope(SEM) images t between these parameters and optical, electrical, and catalytic properties of a typical sample of silver nanocubes and o ndicate the large quantity and good unifor Metal nanoparticles play important roles in Many metals can now be processed into ity that were achieved using this approach. 3 many different areas. For example, they can monodisperse nanoparticles with controllable These silver nanocubes had a mean edge serve as a model system to experimentally composition and structure(13)and some- length of 175 nm, with a standard deviation probe the effects of quantum confinement on times can be produced in large quantities of 13 nm. Their surfaces were smooth, and electronic, magnetic, and other related proper- through solution-phase methods(14, 15). De- some of them self-assembled into ordered ties(1-3). They have also been widely exploit- spite this, the challenge of synthetically con- two-dimensional(2D) arrays on the silicon ed for use in photography (4), catalysis(5), trolling the shape of metal nanoparticles has substrate when the SEM sample was biological labeling(6), photonics (7), optoel been met with limited success. On the nano- pared. It is also clear from Fig. 1B that all tronics(&), information storage (9), surface- meter scale, metals(most of them are face- comers and edges of these nanocubes were enhanced Raman scattering (SERS)(10, ID), centered cubic, or fcc) tend to nucleate and slightly truncated Figure IC shows the trans- and formulation of magnetic ferrofluids(12). grow into twinned and multiply twinned par- mission electron microscope(TEM)image of The intrinsic properties of a metal nanoparticle ticles(MTPs) with their surfaces bounded by an array of silver nanocubes self-assembled are mainly determined by its size, shape, com- the lowest-energy(111) facets(16). Other on the surface of a TEM grid. The inset position, crystallinity, and structure(solid ver- morphologies with less stable facets have shows the electron diffraction pattern ob- sus hollow ). In principle, one could control any only been kinetically achieved by adding tained by directing the electron beam perpen one of these parameters to fine-tune the prop- chemical capping reagents to the synthetic dicular to one of the square faces of a cube erties of this nanoparticle. systems(17-22). Here we describe a solu- The square symmetry of this pattern indicates tion-phase route to the large-scale synthesis that each silver nanocube was a single ci ment of Chemistry, University of Washington, of silver nanocubes. Uniform gold nanoboxes bounded mainly by 1100) facets. On the Seattle wa 98195-1700 USA. with a truncated cubic shape were also gen- basis of these SEM and TEM studies, it * To whom correspondence should be addressed. E- erated by reacting the silver cubes with an clear that the slightly truncated nanocube mail xia@chem aqueous HAuCla solution could be described by the drawing shown in 2176 13DecemBer2002Vol298SciEncewww.sciencemagorg
8. L. Rustad, Nature 413, 578 (2001). 9. W. T. Peterjohn, J. M. Melillo, F. P. Bowles, P. A. Steudler, Oecologia 93, 18 (1993). 10. W. T. Peterjohn, J. M. Melillo, P. A. Steudler, K. M. Newkirk, Ecol. Appl. 4, 617 (1994). 11. CO2 flux measurements were made by placing chamber lids over anchored collars for 15 min and sampling the headspace at 5-min intervals. Samples were analyzed for trace gas concentrations by gas chromatography or infrared analysis, and the changes in concentration were used to calculate net flux rates. On each sampling date, fluxes were measured at early morning and afternoon intervals. 12. J. Grace, M. Rayment, Nature 404, 819 (2000). 13. E. A. Davidson, S. E. Trumbore, R. Amundson, Nature 408, 789 (2000). 14. Net nitrogen mineralization was measured for the organic horizon and upper 10 cm of mineral soil using in situ buried bag incubations. Incubations were for 6 weeks at a time, from April through November, and for 4 months during the winter. Initial samples were collected and analyzed for extractable NH4 and NO3 – content (extraction with 2N KCl for 48 hours and analysis with standard autoanalyzer methods). The same analysis was carried out on the incubated samples. The difference in total mineral N content between initial and incubated soils is the net mineralization rate. Soil nitrogen was assessed through sampling of organic and mineral soils in all plots in 1992 and again in 1999. Samples were analyzed for carbon and nitrogen content with a Perkin-Elmer CHN analyzer. Concentrations of inorganic nitrogen in water leaching below the rooting zone were measured with high-tension lysimetry. Soil water samples were collected from one porous cup lysimeter per plot on two occasions every month for the first 2 years of the experiment, then once monthly. Lysimeters were placed at a depth of 50 cm and evacuated to 15 inches of mercury for 24 hours before sampling. Samples were frozen until they were analyzed for NH4 and NO3 –. Nitrous oxide fluxes were measured along with CO2, with the same static chamber method, from 1991 through 1995. Samples were analyzed for trace gas concentrations by gas chromatography, and the changes in concentration were used to calculate net flux rates. 15. During 1996, we analyzed the lysimeter water samples for dissolved organic nitrogen (DON). We found very low levels of DON in lysimeters from all treatments with no clear treatment differences. DON was estimated as the difference between total dissolved nitrogen (TDN) and dissolved inorganic nitrogen, where TDN was measured by high-temperature platinum–catalyzed combustion (23). 16. A. H. Magill et al., Ecosystems 3, 238 (2000). 17. This additional carbon storage in woody tissue was calculated as the product of 12.7% of the cumulative increase in net nitrogen mineralization over the decade (41 g of nitrogen m2) and the measured carbon:nitrogen mass ratio of the wood (300 :1) as follows: 0.127 4 g of nitrogen m2 300. 18. This conclusion is based on a paired Student’s t test with aggregated data from the six experimental blocks. 19. J. Bergh, S. Linder, T. Lundmark, B. Elfving, For. Ecol. Manage. 119, 51 (1999). 20. P. Jarvis, S. Linder, Nature 405, 904 (2000). 21. J. Harte et al. Ecol. Appl. 5, 132 (1995). 22. Y. Luo, S. Wan, S. Hui, L. Wallace, Nature 413, 622 (2001). 23. J. Merriam, W. H. McDowell, W. S. Currie, Soil Sci. Soc. Am. J. 60, 1050 (1996). 24. Supported by the Office of Science, Biological and Environmental Research Program, U.S. Department of Energy, through the Northeast Regional Center of the National Institute for Global Environmental Change under cooperative agreement no. DE-FC03- 90ER61010; NSF’s Long-Term Ecological Research Program (contract no. NSF-DEB 0080592); the U.S. Environmental Protection Agency’s Global Change Program (contract no. EPA-CR 823713-01-0); and the ExxonMobil Corporation. 20 May 2002; accepted 7 November 2002 Shape-Controlled Synthesis of Gold and Silver Nanoparticles Yugang Sun and Younan Xia* Monodisperse samples of silver nanocubes were synthesized in large quantities by reducing silver nitrate with ethylene glycol in the presence of poly(vinyl pyrrolidone) (PVP). These cubes were single crystals and were characterized by a slightly truncated shape bounded by {100}, {110}, and {111} facets. The presence of PVP and its molar ratio (in terms of repeating unit) relative to silver nitrate both played important roles in determining the geometric shape and size of the product. The silver cubes could serve as sacrificial templates to generate single-crystalline nanoboxes of gold: hollow polyhedra bounded by six {100} and eight {111} facets. Controlling the size, shape, and structure of metal nanoparticles is technologically important because of the strong correlation between these parameters and optical, electrical, and catalytic properties. Metal nanoparticles play important roles in many different areas. For example, they can serve as a model system to experimentally probe the effects of quantum confinement on electronic, magnetic, and other related properties (1–3). They have also been widely exploited for use in photography (4), catalysis (5), biological labeling (6), photonics (7), optoelectronics (8), information storage (9), surfaceenhanced Raman scattering (SERS) (10, 11), and formulation of magnetic ferrofluids (12). The intrinsic properties of a metal nanoparticle are mainly determined by its size, shape, composition, crystallinity, and structure (solid versus hollow). In principle, one could control any one of these parameters to fine-tune the properties of this nanoparticle. Many metals can now be processed into monodisperse nanoparticles with controllable composition and structure (13) and sometimes can be produced in large quantities through solution-phase methods (14, 15). Despite this, the challenge of synthetically controlling the shape of metal nanoparticles has been met with limited success. On the nanometer scale, metals (most of them are facecentered cubic, or fcc) tend to nucleate and grow into twinned and multiply twinned particles (MTPs) with their surfaces bounded by the lowest-energy {111} facets (16). Other morphologies with less stable facets have only been kinetically achieved by adding chemical capping reagents to the synthetic systems (17–22). Here we describe a solution-phase route to the large-scale synthesis of silver nanocubes. Uniform gold nanoboxes with a truncated cubic shape were also generated by reacting the silver cubes with an aqueous HAuCl4 solution. The primary reaction involved the reduction of silver nitrate with ethylene glycol at 160°C. In this so-called polyol process (23), the ethylene glycol served as both reductant and solvent. We recently demonstrated that this reaction could yield bicrystalline silver nanowires in the presence of a capping reagent such as poly(vinyl pyrrolidone) (PVP) (24). Subsequent experiments suggested that the morphology of the product had a strong dependence on the reaction conditions. When the concentration of AgNO3 was increased by a factor of 3 and the molar ratio between the repeating unit of PVP and AgNO3 was kept at 1.5, single-crystalline nanocubes of silver were obtained (25). Figure 1, A and B, show scanning electron microscope (SEM) images of a typical sample of silver nanocubes and indicate the large quantity and good uniformity that were achieved using this approach. These silver nanocubes had a mean edge length of 175 nm, with a standard deviation of 13 nm. Their surfaces were smooth, and some of them self-assembled into ordered two-dimensional (2D) arrays on the silicon substrate when the SEM sample was prepared. It is also clear from Fig. 1B that all corners and edges of these nanocubes were slightly truncated. Figure 1C shows the transmission electron microscope (TEM) image of an array of silver nanocubes self-assembled on the surface of a TEM grid. The inset shows the electron diffraction pattern obtained by directing the electron beam perpendicular to one of the square faces of a cube. The square symmetry of this pattern indicates that each silver nanocube was a single crystal bounded mainly by {100} facets. On the basis of these SEM and TEM studies, it is clear that the slightly truncated nanocube could be described by the drawing shown in Department of Chemistry, University of Washington, Seattle, WA 98195–1700, USA. *To whom correspondence should be addressed. Email: xia@chem.washington.edu R EPORTS 2176 13 DECEMBER 2002 VOL 298 SCIENCE www.sciencemag.org on September 23, 2011 www.sciencemag.org Downloaded from
REP。RTs recorded from the same batch(XRD) pattern 0 58. For the slightly truncated nanocubes (111) facets(28). When PVP was intro- Fig. ID. The x-ray diffracti of sample(sup- illustrated in Fig. ID, the ratio R should have duced, it is believed that the selective inter ported on a silicon substrate as in Fig. 1A)is a value close to 0.7. If PVP was not present, action between PVP and various crystalle also displayed in Fig. ID, and the peaks were the silver atoms generated by reducing silver graphic planes of fcc silver could greatly assigned to diffraction from the(111),(200), nitrate with ethylene glycol nucleated and reduce the growth rate along the and(220) planes of fcc silver, respectively. grew into MTPs bounded by the most stable direction and/or enhance the growth rate The lattice constant calculated from this pat tern was 4.088A, a value in agreement with the literature report(a=4.086A, Joint Com- mittee on Powder Diffraction Standards file no. 04-0783. It is worth noting that the ratio between the intensities of the(200)and(lll) diffraction peaks was higher than the conven tional value(0.67 versus 0. 4), indicating that our nanocubes were abundant in 100) fac- ets, and thus their 100) planes tended to preferentially oriented (or textured) parallel to the surface of the supporting substrate (220) and (111) peaks was also slightly high- 5 8 22895s--1 um 100nm er than the conventional value (0.33 versus 0. 25) because of the relative abundance of (111) (110) facets on the surfaces of our silver oE anocubes product were found to strongly depend reaction conditions such as temperature, the concentration of AgNO3, and the molar ratio between the repeating unit of PVP and AgNO,. For example, when the temperature 5ooo was reduced to120° C or increased to I90°C, the product was dominated by nanoparticles with irregular shapes. The initial concentra- tion of AgNO, had to be higher than 0.1 M otherwise silver nanowires were the major Fig. 1. (A) Low-and (B)high-magnification SEM images of slightly truncated silver nar product. If the molar ratio between the repeat age: ng unit of PVP and AgNO, was increased A TEM image of the same batch of silver nanocubes. The inset shows the diffraction from 1.5 to 3, MTPs became the major prod- cube. (D)An XRn ing the electron beam perpendicular to one of the square faces of an i recorded by al uct. Silver nanocubes of various dimensions a u, arbitrary units. could be obtained by controlling the growth time(25). Figure 2, A and B, show TEM images for 17-and 14-min growth times, and A the nanocubes had a mean edge l15±9and95±7nm, respectively. Figure 2C shows a TEM image of the sample that was synthesized using a lower concentration time(30 min). The mean edge length of these silver nanocubes decreased to 80+ 7 nm 哪世血 nm, Fig. 2D)have also been obtained at a shorter growth time(25 min), although some c of these particles have not been able to evolve into complete cubes. These demonstrations suggest that it is possible to tune the size of silver nanocubes by controlling the experi- As illustrated by Wang(27), the shape of an fcc nanocrystal was mainly de the ratio(r) between the growt and direction and tetrahedra bounded by the most stable Fig. 2. TEM images of silver nanocubes synthesized under different conditions. (A and B)The same 111) planes will be formed when R=1.73, as in Fig. 1, except that the growth time was shortened from 45 min to 17 and 14 min and perfect cubes bounded by the less stable (C and D) The same as in Fig. 1, except that the AgNO, concentration was reduced 1100) planes will result if R is reduced to 0.125 M and the growth time was shortened to 30 and 25 min, respectively. Scale bar www.sciencemag.orgSciEnceVol29813DecemBer2002 2177
Fig. 1D. The x-ray diffraction (XRD) pattern recorded from the same batch of sample (supported on a silicon substrate as in Fig. 1A) is also displayed in Fig. 1D, and the peaks were assigned to diffraction from the (111), (200), and (220) planes of fcc silver, respectively. The lattice constant calculated from this pattern was 4.088 Å, a value in agreement with the literature report (a 4.086 Å, Joint Committee on Powder Diffraction Standards file no. 04-0783). It is worth noting that the ratio between the intensities of the (200) and (111) diffraction peaks was higher than the conventional value (0.67 versus 0.4), indicating that our nanocubes were abundant in {100} facets, and thus their {100} planes tended to be preferentially oriented (or textured) parallel to the surface of the supporting substrate (26). The ratio between the intensities of the (220) and (111) peaks was also slightly higher than the conventional value (0.33 versus 0.25) because of the relative abundance of {110} facets on the surfaces of our silver nanocubes. The morphology and dimensions of the product were found to strongly depend on reaction conditions such as temperature, the concentration of AgNO3, and the molar ratio between the repeating unit of PVP and AgNO3. For example, when the temperature was reduced to 120°C or increased to 190°C, the product was dominated by nanoparticles with irregular shapes. The initial concentration of AgNO3 had to be higher than 0.1 M, otherwise silver nanowires were the major product. If the molar ratio between the repeating unit of PVP and AgNO3 was increased from 1.5 to 3, MTPs became the major product. Silver nanocubes of various dimensions could be obtained by controlling the growth time (25). Figure 2, A and B, show TEM images for 17- and 14-min growth times, and the nanocubes had a mean edge length of 115 9 and 95 7 nm, respectively. Figure 2C shows a TEM image of the sample that was synthesized using a lower concentration (0.125 M) of AgNO3 and a shorter growth time (30 min). The mean edge length of these silver nanocubes decreased to 80 7 nm. Silver nanocubes with smaller sizes (50 nm, Fig. 2D) have also been obtained at a shorter growth time (25 min), although some of these particles have not been able to evolve into complete cubes. These demonstrations suggest that it is possible to tune the size of silver nanocubes by controlling the experimental conditions. As illustrated by Wang (27), the shape of an fcc nanocrystal was mainly determined by the ratio (R) between the growth rates along 100 and 111 directions. Octahedra and tetrahedra bounded by the most stable {111} planes will be formed when R 1.73, and perfect cubes bounded by the less stable {100} planes will result if R is reduced to 0.58. For the slightly truncated nanocubes illustrated in Fig. 1D, the ratio R should have a value close to 0.7. If PVP was not present, the silver atoms generated by reducing silver nitrate with ethylene glycol nucleated and grew into MTPs bounded by the most stable {111} facets (28). When PVP was introduced, it is believed that the selective interaction between PVP and various crystallographic planes of fcc silver could greatly reduce the growth rate along the 100 direction and/or enhance the growth rate Fig. 1. (A) Low- and (B) high-magnification SEM images of slightly truncated silver nanocubes synthesized with the polyol process. The image shown in (B) was taken at a tilting angle of 20°. (C) A TEM image of the same batch of silver nanocubes. The inset shows the diffraction pattern recorded by aligning the electron beam perpendicular to one of the square faces of an individual cube. (D) An XRD pattern of the same batch of sample, confirming the formation of pure fcc silver. a.u., arbitrary units. Fig. 2. TEM images of silver nanocubes synthesized under different conditions. (A and B) The same as in Fig. 1, except that the growth time was shortened from 45 min to 17 and 14 min, respectively. (C and D) The same as in Fig. 1, except that the AgNO3 concentration was reduced from 0.25 to 0.125 M and the growth time was shortened to 30 and 25 min, respectively. Scale bars, 100 nm. R EPORTS www.sciencemag.org SCIENCE VOL 298 13 DECEMBER 2002 2177 on September 23, 2011 www.sciencemag.org Downloaded from
REPORTS along the direction, and thus reduce self-assem R from 1.73 to 0.7. Both Fourier transform during uch a silv shape and Based hem.22,1203 fsc.7.1(1967) 17. A.. Kirkland et al., Proc Ser. A 440. 589(1993) 18. T. S. Ahmadi, oc.Bull. Fig. 3. SEM images ith(A) 0.3 ml and (B ml of aqueous HAuCL gold nanot HAuCl4 was ir the expense of {100) 2178 13 december 2002 vol 298 science www.sciencemag.org
along the 111 direction, and thus reduce R from 1.73 to 0.7. Both Fourier transform infrared and x-ray photoelectron spectroscopy measurements indicate that there exists a strong interaction between the surfaces of silver nanoparticles and PVP through coordination bonding with the O and N atoms of the pyrollidone ring (29, 30), although the exact bonding geometry and the nature of selectivity between different crystallographic planes are still not clear. We have also exploited the use of these silver nanocubes as sacrificial templates to generate gold nanoboxes with a well-defined shape and hollow structure (31–33) 3Ag(s) HAuCl4 (aq) 3 Au(s) 3AgCl(aq) HCl(aq) (1) Based on this stoichiometric relationship, it was possible to completely convert silver nanocubes into soluble species and thus leave behind a pure solid product in the form of gold nanoboxes (34). Figure 3A shows an SEM image of silver nanocubes after they had reacted with an insufficient amount of HAuCl4, as calculated from Eq. 1. The black spots represent pinholes in their surfaces, where no gold had been deposited through the replacement reaction. It is believed that the existence of such pinholes allowed for the transport of chemical species into and out of the gold boxes until the reaction had been completed. The locations of these black spots implied that the replacement reaction occurred on the surface of a template in the following order: {110}, {100}, and {111} facets. This sequence was consistent with the order of free energies associated with these crystallographic planes: {110} {100} {111} (27). The gold nanoboxes shown in Fig. 3B self-assembled into a close-packed 2D array during sample preparation. The size of these gold boxes increased by 20% as compared with that of the silver templates. Such an increase in size was in agreement with the shell thickness calculated from stoichiometric and geometric arguments. The gold nanoboxes were finished with smooth surfaces, and most of them (95%) were free of defects such as pinholes. Each box was bounded by two sets of facets (eight triangular facets and six square ones), and any one of these facets could lie against a solid substrate. The inset of Fig. 3B shows the SEM image of an individual box sitting on a silicon substrate against one of its triangular facets, illustrating the high symmetry of this polyhedral hollow nanoparticle. The crystallinity and structure of these gold nanoboxes were examined using electron diffraction. Figure 3, C and D, show the electron diffraction patterns obtained from two gold nanoboxes sitting on the TEM grids against one of their square and triangular faces, respectively. These diffraction spots suggest that each nanobox was a single crystal, with its square facets being indexed to {100} planes and triangular ones to {111} planes. On the basis of these observations, we believe that an epitaxial relationship might exist between the surfaces of the silver cubes and those of the gold boxes that greatly facilitated the transformation from the single-crystalline templates to the singlecrystalline products. Minor reconstruction also occurred in the replacement process; for example, the {110} planes that were observed as ridges on the surfaces of silver cubes disappeared, and the areas of {111} and {100} facets were enlarged and reduced, respectively. Silver nanocubes with controllable dimensions were synthesized by means of a modified polyol process that involved the reduction of silver nitrate with ethylene glycol in the presence of a capping reagent such as PVP. Although the fundamental basis of shape selectivity for this system has yet to be fully understood, it is believed that the selective adsorption of PVP on various crystallographic planes of silver played the major role in determining the product morphology. Uniform gold nanoboxes having a highly truncated cubic shape were also synthesized by reacting the silver nanocubes with an aqueous HAuCl4 solution. These silver and gold nanoparticles should find use in a variety of areas that include photonics, catalysis, and SERSbased sensing. This work and previous demonstrations from other groups (17–22) make it clear that chemical synthesis of metal nanoparticles with well-controlled shapes, sizes, and structures is a practical reality. The major requirement seems to be the selection of a capping reagent that is able to chemically modify various faces of a metal with an appropriate selectivity. References and Notes 1. W. P. Halperin, Rev. Mod. Phys. 58, 533 (1986). 2. A. C. Templeton, W. P. Wuelfing, R. W. Murray, Acc. Chem. Res. 33, 27 (2000). 3. M. A. El-Sayed, Acc. Chem. Res. 34, 257 (2001). 4. D. M.-K. Lam, B. W. Rossiter, Sci. Am. 265, 80 (May 1991). 5. L. N. Lewis, Chem. Rev. 93, 2693 (1993). 6. S. R. Nicewarner-Pen˜a et al., Science 294, 137 (2001). 7. S. A. Maier et al., Adv. Mater. 13, 1501 (2001). 8. P. V. Kamat, J. Phys. Chem. B 106, 7729 (2002). 9. C. B. Murray, S. Sun, H. Doyle, T. Betley, Mater. Res. Soc. Bull. 26, 985 (2001). 10. S. Nie, S. R. Emory, Science 275, 1102 (1997). 11. L. A. Dick, A. D. McFarland, C. L. Haynes, R. P. Van Duyne, J. Phys. Chem. B 106, 853 (2002). 12. M.-P. Pileni, Adv. Funct. Mater. 11, 323 (2001). 13. H. Bo¨nnemann, J. Hormes, U. Kreibig, in Handbook of Surface and Interfaces of Materials, H. S. Nalwa, Ed. (Academic Press, San Diego, CA, 2001), pp. 1– 87. 14. G. Schmid, Chem. Rev. 92, 1709 (1992). 15. D. V. Goia, E. Matijevic, New J. Chem. 22, 1203 (1998). 16. J. G. Allpress, J. V. Sanders, Surf. Sci. 7, 1 (1967). 17. A. I. Kirkland et al., Proc. R. Soc. London Ser. A 440, 589 (1993). 18. T. S. Ahmadi, Z. L. Wang, T. C. Green, A. Henglein, M. A. El-Sayed, Science 272, 1924 (1996). 19. J. S. Bradley, B. Tesche, W. Busser, M. Maase, M. T. Reetz, J. Am. Chem. Soc. 122, 4631 (2000). 20. V. F. Puntes, K. M. Krishnan, A. P. Alivisatos, Science 291, 2115 (2001). 21. N. Cordente et al., Nano Lett. 1, 565 (2001). 22. R. Jin et al., Science 294, 1901 (2001). 23. F. Fievet, J. P. Lagier, M. Figlarz, Mater. Res. Soc. Bull. 14, 29 (December 1989). 24. Y. Sun, Y. Xia, Adv. Mater. 14, 833 (2002). 25. In a typical synthesis of silver nanocubes, 5 ml of anhydrous ethylene glycol (Aldrich, 99.8%) was heated at 160°C for 1 hour. 3 ml of ethylene glycol solution of AgNO3 (0.25 M, Aldrich, 99%) and 3 ml of ethylene glycol solution of PVP (0.375 M in repeating unit, weight-average molecular weight 55,000, Aldrich) were simultaneously added to the ethylene glycol by means of a two-channel syringe pump at a rate of 0.375 ml/min. The reaction mixture was then continued with heating at 160°C for another 45 min. The product was dominated by cubic nanoparticles, with a small amount (5%) of silver nanowires. These nanowires could easily be separated from nanocubes through filtration because of their large difference in dimension. In this case, the reacFig. 3. SEM images of silver nanocubes (Fig. 1) after they had reacted with (A) 0.3 ml and (B) 1.5 ml of aqueous HAuCl4 solution (1 mM). As indicated by the black spots in (A), the {111} facets of gold nanoboxes were incompletely closed in the early stages of this replacement reaction, when HAuCl4 was in deficiency (as calculated from the stoichiometric equation). If excess HAuCl4 solution was added [as in (B)], the area of {111} facets could increase up to a maximum value at the expense of {100} and {110} facets. (C and D) Electron diffraction patterns of two gold nanoboxes with their square and triangular facets oriented perpendicular to the electron beam, respectively. Scale bars, 100 nm. R EPORTS 2178 13 DECEMBER 2002 VOL 298 SCIENCE www.sciencemag.org on September 23, 2011 www.sciencemag.org Downloaded from
REP。RTs tion mixture was diluted with water (25 times by 30. F K Tekaia-Elhsissen, K. V. Sarathy, Bull. color became stable. Vigorous magnetic stirring was plume)and filtered through membranes ater.Sc.23.165(2000 aintained throughout the synthesis. 31. S. ]. Oldenburg, R. D. Averitt, S. L Westcott, N.I. 35. Supported in part by the Office of Naval Research Halas, Chem. Phys. Lett. 288, 243(1998). 32. NSF (grant DMR-9983893), and a research fellowsh 26. B. D. Cullity, S.R. Stock, Elements of X-Ray Diffraction J.Am.chem.Soc.115.11644(1993 eacher Scholar(2002-2007)and n Alfred P. Sloan Research Fellow(200 noboxes, a 5-ml aliquot of the aqueous dispersion thank D. Qin of the Nanotech User Facility for SE 27. Z L. Wang, J. Phys. Chem. B 104, 1153(2000) Solid State Chem. 100, 272(1997 quots of 1 mM HAuCL4 (99.9%, Aldrich) aqueo fraction studies 29. Z. Zhang B. Zhao, L Hu, Solid solution were added dropwise to the refluxing solu- tion. This mixture was continuously refluxed until its 2 August 2002: accepted 6 November 2002 Observation of a Strongly In our experiments, Li atoms are loaded from a magneto-optical trap into an ultras Interacting Degenerate Fermi le cO, laser trap(15). The trap frequencies are o=2丌×(230±20Hz)fo 2T x Gas of atoms the axial(z)direction and a (6625 50 Hz) for the transverse direction. Rate equation pumping is used to produce the 8 K M. OHara, S L Hemmer, M. E Gehm, S.R. Granade, J. E. Thomas* 50-50 spin mixture: A broadband radio fre- quency (rf) field centered at 7. 4 MHz is We report on the observation of a highly degenerate, strongly interacting Fermi applied at a magnetic field of -8 G, nulling gas of atoms. Fermionic lithium-6 atoms in an optical trap are evaporatively the population difference according to cooled to degeneracy using a magnetic field to induce strong, resonant inter- An(o= An(O) exp(-2Ri), where R is the g actions. Upon abruptly releasing the cloud from the trap, the gas is observed pumping rate. In our experiments, 2R=600 0 to expand rapidly in the transverse direction while remaining nearly stationary in the axial direction. We interpret the expansion dynamics in terms of colli- s-, applying the rf field for i=0. s pro-a sionless superfluid and collisional hydrodynamics. For the data taken at the We achieve very low temperatures via rapid a longest evaporation times, we find that collisional hydrodynamics does not forced evaporation in the CO, laser trap. In o provide a satisfactory explanation, whereas superfluidity is plausible contrast to experiments that use magnetic traps E to achieve degeneracy (12-14, 16, 17), this As the fundamental constituents of matter are atomic Fermi gases is the possibility of high- approach has several natural advantages. First, interacting fermions, the experimental study temperature superfluids that are analogs of we are able to evaporate both spin states to of strongly interacting, degenerate Fermi gas- very high temperature superconductors(8- degeneracy at the desired magnetic field of 910 es will have an impact on theories in fields In). Our experiments produce the conditions G. As a result, the sample is never exposed to from particle physics to materials science. predicted for this type of superfluid transi- fields near 650 G where loss and heating are Although the interactions between fermions tion. Further, the anisotropic expansion we observed (19, 24). Second, the evaporation pro- are understood when they are weak (e. g, observe has been suggested as a signature of cess is identical for both spin states, thereby very strong interactions requires the develop- We interpret the observed anisotropic expan- Fermi surface matching. Third, at this field, the t ment of new theoretical approaches. Testing sion in terms of both collisionless superfluid collision cross section is extremely large and these new approaches requires experimental hydrodynamics (18)and a new form of col- unitarity-limited, so that runaway evaporation is dely tunable interaction lisional hydrodynamics expected(25 strengths, densities, and temperatures. Ultra- Strong, magnetically tunable interactions Forced evaporation is achieved by lower cold atomic Fermi gases have exactly these are achieved in our experiments by using a ing the power of the trapping laser while properties, and thus enable tests of calcula- Fermi gas comprising a 50-50 mixture of the maintaining the beam profile and angular tional techniques for fundamental systems two lowest hyperfine states of Li, i.e., the alignment. The trap depth U is reduced for anging from quarks in nuclear matter to F=%, M=+h) states in the low magnetic 3.5 s according to the trajectory U( electrons in high-temperature superconduc- field basis. This mixture has a predicted broad Uo(1 + t/r) UR (25), where UR is a For this reason, a number of Feshbach resonance near an applied magnetic small offset. The value of T is taken to be groups are developing methods for creating field of 860G(19, 20), where the energy of a 0.1 s, large compared to the time constant and exploring ultracold atomic Fermi gases bound Li-Li molecular state is tuned into estimated for achieving degeneracy at 910 G (12-17). We report on the study of a strongly coincidence with the total energy of the collid- With this choice, very high evaporation effi interacting, degenerate Fermi gas. In contrast ing atoms. This enables the interaction strength ciency is achieved, yielding extremely low to the isotropic expansion previously ob- to be widely varied(19-22). It has also been temperatures. served for a noninteracting degenerate Fermi suggested that interactions between fermions After evaporation, the trap is adiabatically gas(12), we observe anisotropic expansion can be modified by immersion in a Bose gas recompressed to full depth over 0.5 s and then when the gas is released from an optical trap. (23). Our experiments are performed at 910 G, held for 0.5 s to ensure thermal equilibrium. An exciting feature of strongly interacting where the zero-energy scattering length as is While maintaining the applied magnetic field estimated to be "-10ao(ao=0.53 X 10-8 of 910 G, the gas is released from the trap and Physics Department, Duke University, Durham, cm)and the gas has strongly attractive interac- imaged at various times to observe the anisot 27708,USA tions Resonance superfluidity has been predict- ropy. The CO, laser power is extinguished *To whom corres should be addressed. E. ed to occur at this magnetic field for sufficiently less than I us with a rejection ratio of 2 X mail: jet@phy duk ow temperatures (n) 10-5(15 www.sciencemag.orgSciEnceVol29813DeceMber2002 2179
tion mixture was diluted with water (25 times by volume) and filtered through Nucleopore membranes (Whatman, Clifton, NJ) that contained pores 1 m in diameter. The silver nanocubes could be recovered from ethylene glycol through centrifugation and then redispersed into water. 26. B. D. Cullity, S. R. Stock, Elements of X–Ray Diffraction (Prentice-Hall, Upper Saddle River, NJ, ed. 3, 2001), pp. 402– 404. 27. Z. L. Wang, J. Phys. Chem. B 104, 1153 (2000). 28. C. Ducamp-Sanguesa, R. Herrera-Urbina, M. Figlarz, J. Solid State Chem. 100, 272 (1992). 29. Z. Zhang, B. Zhao, L. Hu, J. Solid State Chem. 121, 105 (1996). 30. F. Bonet, K. Tekaia-Elhsissen, K. V. Sarathy, Bull. Mater. Sci. 23, 165 (2000). 31. S. J. Oldenburg, R. D. Averitt, S. L. Westcott, N. J. Halas, Chem. Phys. Lett. 288, 243 (1998). 32. W. Lin, T. H. Warren, R. G. Nuzzo, G. S. Girolami, J. Am. Chem. Soc. 115, 11644 (1993). 33. Y. Sun, B. T. Mayers, Y. Xia, Nano Lett. 2, 481 (2002). 34. In a typical procedure for the preparation of gold nanoboxes, a 5-ml aliquot of the aqueous dispersion containing silver nanocubes was refluxed for 10 min. Aliquots of 1 mM HAuCl4 (99.9%, Aldrich) aqueous solution were added dropwise to the refluxing solution. This mixture was continuously refluxed until its color became stable. Vigorous magnetic stirring was maintained throughout the synthesis. 35. Supported in part by the Office of Naval Research (grant N-00014-01-1-0976), a Career Award from NSF(grant DMR-9983893), and a research fellowship from the David and Lucile Packard Foundation. Y.X. is a Camille Dreyfus Teacher Scholar (2002–2007) and an Alfred P. Sloan Research Fellow (2000 –2002). We thank D. Qin of the Nanotech User Facility for SEM analysis and X. Jiang, Y. Yin, Y. Lu, B. Mayers, and T. Herricks for their help with electron and x-ray diffraction studies. 12 August 2002; accepted 6 November 2002 Observation of a Strongly Interacting Degenerate Fermi Gas of Atoms K. M. O’Hara, S. L. Hemmer, M. E. Gehm, S. R. Granade, J. E. Thomas* We report on the observation of a highly degenerate, strongly interacting Fermi gas of atoms. Fermionic lithium-6 atoms in an optical trap are evaporatively cooled to degeneracy using a magnetic field to induce strong, resonant interactions. Upon abruptly releasing the cloud from the trap, the gas is observed to expand rapidly in the transverse direction while remaining nearly stationary in the axial direction. We interpret the expansion dynamics in terms of collisionless superfluid and collisional hydrodynamics. For the data taken at the longest evaporation times, we find that collisional hydrodynamics does not provide a satisfactory explanation, whereas superfluidity is plausible. As the fundamental constituents of matter are interacting fermions, the experimental study of strongly interacting, degenerate Fermi gases will have an impact on theories in fields from particle physics to materials science. Although the interactions between fermions are understood when they are weak (e.g., quantum electrodynamics), the treatment of very strong interactions requires the development of new theoretical approaches. Testing these new approaches requires experimental systems with widely tunable interaction strengths, densities, and temperatures. Ultracold atomic Fermi gases have exactly these properties, and thus enable tests of calculational techniques for fundamental systems ranging from quarks in nuclear matter to electrons in high-temperature superconductors (1–11). For this reason, a number of groups are developing methods for creating and exploring ultracold atomic Fermi gases (12–17). We report on the study of a strongly interacting, degenerate Fermi gas. In contrast to the isotropic expansion previously observed for a noninteracting degenerate Fermi gas (12), we observe anisotropic expansion when the gas is released from an optical trap. An exciting feature of strongly interacting atomic Fermi gases is the possibility of hightemperature superfluids that are analogs of very high temperature superconductors (8– 11). Our experiments produce the conditions predicted for this type of superfluid transition. Further, the anisotropic expansion we observe has been suggested as a signature of the onset of superfluidity in a Fermi gas (18). We interpret the observed anisotropic expansion in terms of both collisionless superfluid hydrodynamics (18) and a new form of collisional hydrodynamics. Strong, magnetically tunable interactions are achieved in our experiments by using a Fermi gas comprising a 50-50 mixture of the two lowest hyperfine states of 6 Li, i.e., the F 1⁄2, M 1⁄2 states in the low magnetic field basis. This mixture has a predicted broad Feshbach resonance near an applied magnetic field of 860 G (19, 20), where the energy of a bound 6 Li-6 Li molecular state is tuned into coincidence with the total energy of the colliding atoms. This enables the interaction strength to be widely varied (19–22). It has also been suggested that interactions between fermions can be modified by immersion in a Bose gas (23). Our experiments are performed at 910 G, where the zero-energy scattering length aS is estimated to be –104 a0 (a0 0.53 108 cm) and the gas has strongly attractive interactions. Resonance superfluidity has been predicted to occur at this magnetic field for sufficiently low temperatures (11). In our experiments, 6 Li atoms are loaded from a magneto-optical trap into an ultrastable CO2 laser trap (15). The trap oscillation frequencies are z 2 (230 20 Hz) for the axial (z) direction and 2 (6625 50 Hz) for the transverse direction. Rate equation pumping is used to produce the 50-50 spin mixture: A broadband radio frequency (rf ) field centered at 7.4 MHz is applied at a magnetic field of 8 G, nulling the population difference according to n(t) n(0) exp(–2Rt), where R is the pumping rate. In our experiments, 2R 600 s1 ; applying the rf field for t 0.1 s produces precise population balance. We achieve very low temperatures via rapid forced evaporation in the CO2 laser trap. In contrast to experiments that use magnetic traps to achieve degeneracy (12–14, 16, 17), this approach has several natural advantages. First, we are able to evaporate both spin states to degeneracy at the desired magnetic field of 910 G. As a result, the sample is never exposed to fields near 650 G where loss and heating are observed (19, 24). Second, the evaporation process is identical for both spin states, thereby maintaining the initial spin balance as well as Fermi surface matching. Third, at this field, the collision cross section is extremely large and unitarity-limited, so that runaway evaporation is expected (25). Forced evaporation is achieved by lowering the power of the trapping laser while maintaining the beam profile and angular alignment. The trap depth U is reduced for 3.5 s according to the trajectory U(t) U0(1 t /) 1.45 UB (25), where UB is a small offset. The value of is taken to be 0.1 s, large compared to the time constant estimated for achieving degeneracy at 910 G. With this choice, very high evaporation efficiency is achieved, yielding extremely low temperatures. After evaporation, the trap is adiabatically recompressed to full depth over 0.5 s and then held for 0.5 s to ensure thermal equilibrium. While maintaining the applied magnetic field of 910 G, the gas is released from the trap and imaged at various times to observe the anisotropy. The CO2 laser power is extinguished in less than 1 s with a rejection ratio of 2 105 (15). Physics Department, Duke University, Durham, NC 27708, USA. *To whom correspondence should be addressed. Email: jet@phy.duke.edu R EPORTS www.sciencemag.org SCIENCE VOL 298 13 DECEMBER 2002 2179 on September 23, 2011 www.sciencemag.org Downloaded from
