ARTICLES

Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals
Y. LALATONNE, J. RICHARDI AND M. P. PILENI*
Université Pierre et Marie Curie,Laboratoire des Matériaux Mesoscopiques et Nanométriques,U.M.R.7070,BP 52,4 place Jussieu,75005 Paris,France *e-mail: pileni@sri.jussieu.fr

Published online: XX xxxx 2003; doi:10.1038/nmat1054

The structure, thermodynamics and dynamics in many physical and chemical systems are determined by interplay of short-range isotropic and long-range anisotropic forces. Magnetic nanoparticles dispersed in solution are ideal model systems to study this interplay, as they are subjected to both isotropic van der Waals and anisotropic dipolar forces. Here we show from experiment an abrupt transition of maghemite nanocrystal organization from chain-like to random structures when nanoparticle solutions are evaporated under a magnetic field. This is explained by brownian dynamics simulations in terms of a variation of the strength of van der Waals interactions with the particle contact distance, which is tuned by the length of the molecules coating the particles. The weak dipole–dipole interactions between the maghemite particles are usually not sufficient to result in the chain formation observed here. However, due to the van der Waals interactions, when the nanocrystal contact distance is short enough, clusters of nanocrystals are formed during the evaporation process. These clusters exhibit large dipole moments compared with a single particle, which explains the formation of chain-like structures. Conversely, when the nanocrystal contact distance is too long, no nanocrystal aggregation occurs, and a random distribution of maghemite nanocrystals is obtained.[Author: Some rewording for clarity OK?]
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anocrystals dispersed in solution are subjected to two major types of attractive forces: van der Waals and dipolar interactions.In the absence of the dipolar interactions, large isotropic van der Waals interactions induce formation of spherical aggregates.For weak van der Waals interactions, the strength of the dipolar moments controls the formation of chain-like structures. This has been well established by simulations for magnetic nanoparticles1-4. Chain-like structures have been directly observed experimentally5. In fact, with no applied magnetic field, it has been shown5 that an abrupt transition from separate particles to randomly oriented chain-like aggregates occurs on increasing the particle size. Similarly, the self-organization of semiconductor CdTe nanocrystals in pearl-necklace aggregates is explained by strong electrical dipole interactions6. The influence of the van der Waals, dipolar and also nanocrystal–substrate7 interactions on the nanocrystal organization at a mesoscopic scale is a key issue,not only for practical applications but also for fundamental understanding. A variation of the length of the coating molecules[Author: OK?] is used here to tune the interaction between nanocrystals. Maghemite (γ-Fe2O3) nanocrystals are made by a slight change of the synthesis described previously8,9 (see Methods). The extracted nanocrystals are coated either with octanoic (C7H15COOH) or with dodecanoic acid (C11H23COOH), which are denoted by C8 and C12, respectively. The nanocrystals are then dispersed in cyclohexane.No particle aggregation is observed under small-angle X-ray scattering for diluted dispersions whatever the nanocrystal coating. This confirms the stability of the solutions without any phase separation. The γ-Fe2O3 nanocrystals, differing by their coatings, are characterized by the same average size (10 nm) and polydispersity (20%). The magnetic properties of these nanocrystals were determined at 3 K by SQUID (superconducting quantum interference device) using a solution with very low volume fraction (0.1%). The same reduced remanence, saturation magnetization and coercive field of 0.30, 77 e.m.u. g–1 and 360 Oe, respectively, were measured. This indicates that the nanocrystals, differing only by the chain length of their coating, are characterized by the same magnetic dipolar moments. A transmission electronic microscope (TEM) grid is deposited in the bottom of the beaker containing the solution of nanocrystals dispersed in cyclohexane (1.6 × 10–8 mol l–1). The system is subjected to a 0.59 T magnetic field, applied parallel to the substrate,during the evaporation.Figure 1 shows drastic changes in the TEM patterns with the various coatings: (i) With no applied magnetic field and a C8 coating, spherical aggregates of various sizes appear (Fig. 1a).[Author: OK? Is this what you meant?] In contrast, the C12-coated nanocrystals are randomly deposited on the
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0 nm.as shown above.In contrast.Conversely. a simulation study shows that chains of larger dipolar particles do not induce the aggregation of smaller particles in polydisperse systems10. However. even the largest particles of about 15 nm (2% of all particles) have a λ value of about 2. the TEM patterns do not show any nanocrystal organization (Fig. The evaporation speed used in the simulations is much faster than the experimental one.the influence of the size of the coating molecule on the simulation results can be studied.[Author: OK?] TEM grid (Fig. which is defined as a sum of the steric repulsion due to the coating molecules. high dipolar parameter λ.1b. a. 1 cannot be directly attributed to the magnetic properties of the γ-Fe2O3 nanocrystals. are needed for chain-formation of the particles.the dipole–dipole potential and the van der Waals attraction. At the top of the box. appears as a parameter in the equation for the steric repulsion.13.[Author: OK?] The interface is made of the solvent and the coating of the particles crossing the interface.By changing d. we calculate the dipolar parameter λ to be 0. The evaporation process is modelled as follows: a wall at the bottom of the simulation box represents the substrate. (ii) In a 0. c. 1e. striped structures in the direction of the applied field (Fig. with C12. We use the interaction model proposed in ref. the interfacial area and. The forces and torques between the particles are calculated from the interparticle interaction. Note the presence of isolated nanocrystals between the stripes for the same deposition as in b [Author: OK?]at a higher resolution. Simulations were carried out varying d from 1. denoted by d in the following.Even in the presence of the magnetic field. nature materials | ADVANCE ONLINE PUBLICATION | www. which make it possible to consider the influence 2 of the solvent on the solute by a combination of random forces and frictional terms. therefore. the chain formation cannot be directly explained by the presence of larger particles.com/naturematerials . b. 1d). which is 3 for chain formation1–4.where the explicit equations of all interaction terms are given. there is a liquid–gas interface. To explain the formation of the chain-like structures in spite of the weak dipolar interaction. The Langevin equations are integrated using an algorithm proposed by Allen12.f. Therefore. which is smaller than the threshold λ. nanocrystals coated with C8 form thick. Assuming that the edge–edge core spacing between the particles is about 1 nm due to their coating.c).The average length of the chain-like structures is several tens of micrometres.no organization appears for C12-coated nanocrystals. whereas the average diameter is around 300 nm.ARTICLES a b c 300 nm 10 µm 300 nm d e f 300 nm 10 µm 300 nm Figure 1 TEM images of g-Fe203 nanocrystals deposited with and without a magnetic field. e.The same nanocrystals deposited with a magnetic field organize in chain-like structures. Usually. Because the nanocrystals coated with C8 and C12 are characterized by the same magnetic dipolar moments. brownian dynamics simulations at a particle level investigate the evaporation of magnetic nanoparticle solutions. defined as the ratio of the magnetic dipolar to thermal energies.0 to 3.59 T magnetic field.[Author: OK?] Moreover.This energy increase confines the particles in the solution layer.69 for the average diameter of 10 nm.nanocrystals coated with C12 are randomly deposited on the TEM grid in the absence of magnetic field.f).The wall–particle interaction is defined by a steric repulsion due to the coating molecules and a van der Waals interaction between a sphere and a half-space14. A very small number of nanocrystal aggregates seem to be organized along the direction of the applied field.nature.the changes in the organization with the coating shown in Fig.The interaction parameters were adapted to the system experimentally used (see interaction and simulation parameters in Methods).5.Nanocrystals coated with C8 and deposited without a magnetic field form isotropic clusters during the evaporation process. A systematic variation of the evaporation speed in the simulations has shown that the speed used here is sufficiently large to predict qualitatively the morphology of structures. The double thickness of the layer of coating molecules. Owing to the low size dispersion of the particles. which slowly moves down during evaporation.When the particle crosses the interface. The translation and rotation of the magnetic particles are described by Langevin equations11. d. Note the presence of some nanocrystals between the stripes. which is determined by the boiling point of the solvent. the size of the organizations increases at slower evaporation. its energy increases (see explicit formula in Methods).

the most stable head–tail configuration is chosen. spherical clusters of particles are nature materials | ADVANCE ONLINE PUBLICATION | www. 2b) or not (Fig. 2d). The major changes are observed during the evaporation process: (i) For d = 1. in a field. This structure is in qualitative agreement with the particle aggregation found by 3 . e. 2f) or not (Fig.The stronger attraction leads to a condensation of the particles. but the nanoparticles are well organized in a 3D network. Furthermore. In a field.The minima of the potentials in Fig.that they are 0. c. 3 shows that the energy of the most stable head-tail configuration decreases from –3.d.6 to 1.2 nm and 1.b shows the configuration after an equilibration of ten million time steps for a coating layer of 1. 2d).e.2 nm (Fig. For the contact distance of 1.1 1.6 nm.f.11 or 11.2 nm) 1.4 1.large clusters are observed from the TEM pattern (Fig. 2e) to an applied magnetic field (0. [Author: Some rewording of caption for clarity. without applied field (c). This large variation is mainly due to the marked sensitivity of the van der Waals potential to the interparticle distance. an elongation and coalescence of droplets made of dipolar particles appear.6 nm).59 T).6 nm) VdW + steric (d = 1.3 1.2 nm before evaporation without (a) or with (b) an applied field. (ii) For d = 1. no aggregation of the particles is observed even during the evaporation when particles are subjected (Fig.2 nm.i.2 nm) Total potential (d = 1.6 nm) Total potential (d = 1.0 to –4. 1a).6 nm.6 to 1.59 T) during the evaporation process. The polydispersity of the γ-Fe2O3 nanocrystals is not low enough to observe this internal organization experimentally.com/naturematerials observed (Fig.6 nm. 3 indicate that the distance of closest contact increases from 1.5 kT on reducing d from 1.spherical clusters of particles are observed.6 nm. However this was observed for a larger dipole parameter (λ = 2. With no applied magnetic field.2 to 1. The total energy and the sum of the van der Waals attraction and the steric repulsion are shown for two values of the coating layer thickness d.0 etc? Best to label them at the actual value?] Figure 2 Snapshots of the configurations by brownian dynamics simulations.8) as in our case.do you mean that the distances should be multiplied or divided by 10. preventing any enhancement of the dipolar forces for such an assembly of particles.0 nm.2 nm.Fig.5 c d –5 –6 Particle–particle distance (/ 10 nm) e f Figure 3 Dependence of the interaction energy on the interparticle distance.For the calculation of the dipolar interaction. whereas with an applied field (d) elongated clusters of particles appear.2 1.2 nm due to the sensitivity of the van der Waals potential to the interparticle distance.b.For the coating layer thickness d = 1. similar configurations were obtained. the particles are aggregated after 14 million steps.5 kT on reducing d from 1.where no aggregation of particles occurs. To explain the formation of striped structures with γ-Fe2O3 nanocrystals in a magnetic field in spite of a low dipole interaction with respect to the thermal energy (Fig. 1) and those obtained from simulations (Fig.The aggregation observed for d = 1.In fact.2 nm.no particle aggregation is observed even during the evaporation when particles are subjected (f) or not (e) to an applied magnetic field.After evaporation.Figure 2a. It is interesting to note that similar behaviour was observed for a Stockmayer fluid on using Monte-Carlo simulations15. 2) can be observed:(i) With γ-Fe2O3 nanocrystals coated with C8. the van der Waals interactions are not strong enough to induce formation of particle clusters. 2c) whereas. Rather good agreement between the structures obtained from experiments (Fig.nature.OK?] which may explain the differences in the size of aggregates observed by simulations and experiments. a.ARTICLES a b 1 0 –1 Energy (kT) –2 –3 –4 VdW + steric (d = 1.[Author: Please can you clarify the scale on the x axis. The cluster formation considerably enhances the long-range dipolar forces compared with isolated particles with creation of a ‘macro dipolar moment’leading to an anisotropic organization of the nanoparticles. 2c) is explained by a larger interparticle attraction. All simulations are started from a configuration obtained for d = 3.no significant aggregation of particles is observed. alignments of particles are found (Fig. both van der Waals attraction and magnetic dipoles have to be taken into account:when the coating molecule is small enough ‘clusters’are formed due to the van der Waals forces.The minimum of the total energy decreases from –3. For a thicker coating (d = 1. No significant aggregation of particles is observed when they are (Fig. 2a) subjected to a magnetic field (0.0 to –4. the use of a very low evaporation speed in simulations leads to qualitatively the same mesostructures. For d = 1.

Because of the high particle concentration.f) or by simulation (Fig.ARTICLES a d 2 µm 2 µm b e 10 µm 10 µm c f 2 µm 2 µm Figure 4 SEM images of γ-Fe203 nanocrystals. a–c.OK?] observed in this system. Figure 4a shows a very rough thick film of highly compact spherical aggregates with an average diameter of 1.4 nm necessary for the disappearance of organization in simulations. The final concentrations after mixing of the reactants are 1. the cylinders tend to superimpose with a diameter ten times larger than that observed in dilute solution. the mesoscopic structure markedly changes with formation of long bands with a very regular structure (Fig.superimposed tubes are observed.2 nm (Fig. The solution is subjected to sonication for two hours at 90 °C and the precipitate that appears is washed with a large excess of ethanol and the powder is dried in air.6 × 10–8 mol l–1. whatever the coating is. this precipitate is washed with a large excess of ethanol and a solution of carboxylic acid solubilized in ethanol ([CnH2n+1COOH]= 1.form spherical aggregates.but by tilting the sample (f) only slight undulations on the surface of the thick film are observed.c) whereas aligned particles are seen by simulations (Fig. Because in dilute solution the nanocrystals are randomly dispersed (Fig. no changes in the nanocrystals dispersion are observed.random distributions of particles are observed from the TEM pattern (Fig. 1e. the film behaviour markedly differs from that of the C8 derivative. The solution is stirred vigorously for 2 h at 28. superimposed tubes with an average diameter of 3 µm are observed (Fig. X-ray diffraction lines of deposited nanocrystals indicate an inverted spinel phase with a lattice constant of 8. In an applied magnetic field.59-T magnetic field applied during the evaporation process.3 × 10–2 mol l–1 and 8. when octanthiol (C8H17SH) is replaced by dodecanthiol (C12H25SH) as the coating agent.[Author:OK?] These data are consistent with those obtained in dilute solution and explained by ‘cluster formation’. By tilting the sample. On the one hand. 2d). a magnetic field is applied parallel to the substrate plane. 2e). A TEM grid with an amorphous nature materials | ADVANCE ONLINE PUBLICATION | www. 2f). When the system is subjected to a magnetic field during the deposition process. the first step is to add dimethylamine ((CH3)2NH2OH) to an aqueous micellar solution of ferrous dodecyl sulphate (Fe(DS)2)17. deposited without a magnetic field. respectively. An idea of the interparticle spacing that can be expected for these coatings.5 °C and the resulting precipitate of uncoated nanocrystals is isolated from the supernatant by centrifugation.a very dense film is observed (d). With C12 nanocrystals.3 nm in spacing experimentally expected between C8 and C12 is similar to the small variation of 0. All the solutions are kept on a magnet for 12 hours in order to discard unstable nanoparticles and the supernatant is then collected. In a magnetic field (0. such as hydrophobic attraction or the electrostatic repulsion between charged nanoparticles. At high nanocrystal concentration.some elongated structures appear. 1b.6 nm (Fig. 4e) compared with that obtained with no applied magnetic field (Fig. During this process. [Author: Some rewording of caption for clarity.59 T).4 to 1. and c.[Author: The scale bar is missing from part d.nature.the structural and dynamical study can give fundamental insights into dipolar fluids in general. This is in good agreement with results obtained in dilute solution either experimentally or by simulation. On the other hand.36 Å. b.For nanocrystals coated with C12 and deposited without applied field. The same experimental procedure as described above has been used. 4a. (ii) With γ-Fe2O3 nanocrystals coated with C12. 4d).7 nm is 4 SYNTHESIS OF SOLUTIONS OF MAGHEMITE NANOCRYSTALS To prepare non-coated γ-Fe2O3 particles. on the nanoparticle organizations. 4d). when a magnetic field is applied during the evaporation process.with an applied field.com/naturematerials . the increase of 0. the TEM images show a striped structure when the nanocrystals are subjected to a magnetic field during the deposition process (Fig. either experimentally (Fig.by tilting the sample. On a macroscopic scale the film does not change (Fig.4 × 10–1 mol l–1) is added. these experimentally observed spacings are in reasonable agreement with the values used here in the simulations. Similarly. d–f. PREPARATION AND CHARACTERIZATION OF THE γ-FE2O3 NANOCRYSTALS DEPOSITIONS The nanocrystals are deposited on a TEM grid by evaporation of a ferrofluid solution (8 hours). 4b). METHODS simulations for d = 1.[Author: OK?] In a 0. 4f). at high nanocrystal concentration a thick. compact film with a very flat surface and is observed (Fig. is obtained from Ag2S nanocrystals coated with alkanethiols and self-assembled in hexagonal networks16. From the data described above.2 to 1. The change in the nanostructure with the coating shown above should be also found at higher particle concentration. elongated structures are formed.6 nm.should it be the same as on part a?] e.the aggregation disappears when the edge–edge core spacing between the particles is varied from 1. In simulations. 1d) as obtained by simulation for d = 1. the number of clusters increases with formation of large spherical aggregates as observed in Fig. the clusters formed induce large dipolar forces allowing the particles to form cylinders. The mesoscopic structures are now observed by scanning electron microscopy (SEM). The nanocrystals coated with octanoic acid (C8) or dodecanoic acid (C12) are dispersed in cyclohexane. it is concluded that elongated assemblies are obtained even for weakly dipolar particles by a careful choice of the coating agent.5 × 10-1 mol l–1 for Fe(DS)2 and dimethylamine.1 × 10–6 mol l–1 instead of 1. (All the chemicals were bought from Aldrich or Fluka). 2c). which is characteristic for γ-Fe2O3. as expected from above.The γFe2O3 nanocrystals provide model systems to explore the influence of other interaction terms. As the origin of these structures is quite different from that in highly dipolar fluids.Nanocrystals coated with C8: a. A similar disappearance of organization is experimentally observed when C12 instead of C8 is used as the coating. The TEM grid is replaced by HOPG (high-oriented pyrolitic graphite) and the nanocrystal concentration is 6. The TEM images of deposited nanocrystals indicate that the average diameter (10 nm) and the polydispersity (20%) of the nanocrystals remain the same. slight undulations on the surface of the thick film are observed (Fig. In the second step. An increase in the core spacing from 1. 1d). 4c).5 µm for C8 nanocrystals.

M. which is characteristic of organic solvents17. A Jeol model JSM-840A SEM was used to visualize the assemblies of ferrite nanocrystals. M. Science 297. Rosensweig. Phase coexistence of a Stockmayer fluid in an applied field. Hysteresis loops at 3 K were measured with a commercial SQUID magnetometer with fields up to 5 T. The numbers of particles used for the simulations are 125 and 512 (shown here) and the initial box lengths are fixed at 160 and 320 nm. Brownian dynamics simulation of chemical reaction in solution. Appl.. 10. J. The Hamaker constant A of the ferrite particles. Phys. where ap = (dp + d)/2 > dgp. 18.. N.[Author: Please give make and model of SQUID. A. M. G. A. & Tildesley. Correspondence and requests for materials should be addressed to M. Influence on the 2D and 3D self organization of the length of the alkyl chains used to passivate silver sulfide nanoparticles. 149. T. Press. 5976–5984 (1995). Phys. Tlusty. Butter. Chem. L. E 59. Phys. J.nature. Foundations of Colloid Science (Oxford Univ. 4104–4109 (1998). Petit for helping Y. we used the same value of σ = 18 × 10–3 J m–2. 13. T. E. J. 9. Computer Simulations of Liquids (Oxford Science. & Pileni. Magn. Ferrohydrodynamics (Cambridge Univ. M. dgp is the distance between the centre of the particle and the gas–solution interface and dp is the particle diameter. nature materials | ADVANCE ONLINE PUBLICATION | www. 16. H. Lalatonne in the synthesis and preparation of the 3D superstructures. Mod. T. S. and C. Allen. P. 50 kV. Science 290. is taken from the literature4. Ngo for providing the know-how to make the nanocrystals. M.2 mm2. N. 17. 30 mA). Press. B 13. P. For higher particle concentration.. M. Vincent for giving them the opportunity to use the SQUID equipment of CEA Saclay[Author: Please spell out CEA. J. & Pileni. Direct observation of dipolar chains in iron ferrofluids by cryogenic electron microscopy. Self-assemblies of silver sulfide nanocrystals on various substrates. 10–19 J. 11. Int. D. 1328–1331 (2000). 237–240 (2002). M. J. & Pileni. W. L. 041401 (2003). Strongly dipolar fluids at low densities compared to living polymers. An HOPG substrate is dipped into 200 µl of a solution with a nanocrystal concentration of 6.. C. M.. Z.P. Phys. published XX xxxxx 2003. S. 88–91 (2003). E 68. 3803–3812 (2000). 2. P. The time step for the simulations is 20 ps. Motte for supervising Y. Nature Mater. Tavares. 4). T. Insignificant differences between 125 and 512 particle simulations are found. respectively.. A. Cluster Structures and cluster-cluster aggregations in a two dimensional colloidal system. & Giersig. A. 12. Popplewell. PARAMETERS OF THE INTERACTION MODEL AND OF THE SIMULATIONS The magnetic moment is calculated from the γ-Fe203 bulk magnetization (3.2 × 0. M. Chem B 105. References 1. 14. Spontaneous organization of single CdTe nanoparticles into luminescent nanowires. Motte. Morimoto. M. Mater. J. 3. P. 2. A. Defect-induced phase separation in dipolar fluids. Phys. accepted 1 December 2003. J. Magn. Special thanks are due to L. Maillard. T. P.P. P. Vroege. & Pileni.] were carried out with a rotating anode generator (copper anode. Allen. & Telo da Gama. K. R. J. Controlled preparation of nanosize cobalt ferrite magnetic particles. & Safran. J. Agglomerate formation in a magnetic fluid. Ngo. Phys. 6. 8.. Adv. P. M. A small Hamaker constant of 10–20 J is chosen for the particle–wall interaction to avoid a too large attraction between particle and substrate. J. W. Ngo. 276–279 (2000). P. E. Oxford 2001) 15. The friction coefficients are calculated from Stoke’s law using a viscosity of 10–3 Kg m–1 s–1 (ref. Cambridge 1985). & Maekawa. R. A. & Maekawa. & Charles.. Assemblies of ferrite nanocrystals: Partial orientation of the easy magnetic axes. Received 19 August 2003. Dynamic analysis of a ferromagnetic colloidal system. 7. P. Rev. J. Langmuir 16. 53. 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We assume that the energy increase for a particle i crossing the gas-solution interface can be calculated from the equation: 2 2 ∆ui = 2πσap(ap – dgp) + πσ(ap – dgp ). Rev. R. Phys. We have verified that the same amount of nanoparticles (0. 5. M. Z. & Pileni. Hunter. J. 53–58 (2001). 67–71 (1995). B 102. J.73 × 105 Am–1) and the average size of the particle (10 nm). J. The first term corresponds to the energy due to the interface between the particle coating and the gas phase. Lalatonne with the SAXS experiments. Kotov. Bradbury. A 33. H. 2742–2744 (1982). 4388–4395 (1999).] 4. Motte. M. H. Mater.. Frederik. Acknowledgements The authors thank E. X-ray diffraction measurements[Author: Please give make and model of equipment used. E 51. Competing financial interests The authors declare that they have no competing financial interests. Phys. T. 40. whereas the second term is caused by the decrease in the solvent–gas interface due to the penetration of the interface by the particle. Chantrell. 2085–2092 (1999). focus size: 0.

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