Supra- and nanocrystallinities: a new scientific adventure

Nanomaterials exist in the interstellar medium, in biology, in art and also metallurgy. Assemblies of nanomaterials were observed in the early solar system as well as silicate particle opals. The latter exhibits unusual optical properties directly dependent on particle ordering in 3D superlattices.The optical properties of noble metal nanoparticles (Ag, Au and Cu) change with the ordering of atoms in the nanocrystals, called nanocrystallinity. The vibrational properties related to nanocrystallinity markedly differ with the vibrational modes studied. Hence, a drastic effect on nanocrystallinity is observed on the confined acoustic vibrational property of the fundamental quadrupolar modes whereas the breathing acoustic modes remain quasi-unchanged. The mechanical properties characterized by the Young's modulus of multiply twinned particle (MTP) films are markedly lower than those of single nanocrystals.Two fcc supracrystal growth mechanisms, supported by simulation, of Au nanocrystals are proposed: heterogeneous and homogeneous growth processes. The final morphology of nanocrystal assemblies, with either films by layer-by-layer growth characterized by their plastic deformation or well-defined shapes grown in solution, depends on the solvent used to disperse the nanocrystals before the evaporation process.At thermodynamic equilibrium, two simultaneous supracrystal growth processes of Au nanocrystals take place in solution and at the air-liquid interface. These growth processes are rationalized by simulation. They involve, on the one hand, van der Waals interactions and, on the other hand, the attractive interaction between nanocrystals and the interface.Ag nanocrystals (5 nm) self-order in colloidal crystals with various arrangements called supracrystallinities. As in bulk materials, phase diagrams of supracrystals with structural transitions from face-centered-cubic (fcc) to hexagonal-close-packed (hcp) and body-centered-cubic (bcc) structures are observed. They depend on the chain length of the coating agent and on the solvent used to disperse the nanocrystals before evaporation. The transition from fcc to hcp is attributed to specific stacking processes depending on evaporation kinetics whereas the formation of bcc supracrystals is attributed to van der Waals attractions.These results open up a new research area, which currently suffers from an extensive lack of knowledge.     

Gold nanoparticle superlattice crystallization probed in situ

The nucleation and growth of three-dimensional superlattices of gold nanoparticles has been followed directly in situ by means of small angle x-ray scattering. These assemblies spontaneously form in a dilute solution providing the particles are large enough to generate a van der Waals driven attraction sufficient to counterbalance the thermal energy. The superlattices nucleate very soon after the birth of the individual particles and their growth kinetics is slower than predicted by a mechanism of simple diffusion of the nanoparticles towards the superlattices. The superlattices are first limited in size (170 nm in diameter) and have a globular shape with a low polydispersity. They present a fcc inner structure with nanoparticles being separated by a capping agent bilayer yielding a low gold internal volume fraction (phi SL = 0.33). In a second stage, these superlattices coalesce with time.     

Obtaining of images of ordered and disordered nanocrystal structures by atomic force microscopy

The morphology of films, superlattices, and other structures of colloidal nanocrystals has been investigated by atomic force microscopy (AFM). The capabilities of ultrasharp and conventional probes for AFM are compared. The problems of detection of nanocrystal close packing are discussed.     

As保护下的生长中断时间对AlSb/InAs超晶格界面粗糙度的影响

用分子束外延设备(MBE)在GaAs(100)衬底上生长了InSb型界面的AlSb/InAs超晶格，界面生长过程中采用了As保护下不同的中断时间.运用掠入射X射线反射技术(GIXRR)对样品进行了测量，并对测量结果进行了模拟和分析，发现As保护下生长中断20 s能获得最平整的AlSb/InAs界面.结合分析显微镜下观察到的样品形貌，过短的界面中断时间会导致界面富In并形成In点，而过长的中断时间会导致AlAs型界面的形成，两者都使界面变得粗糙.另外，还讨论了生长中断在分子束外延生长中的应用. 关键词： 分子束外延 生长中断 超晶格 掠入射X射线反射     

Spatial characterization of the laser-induced plasma plumes generated by IR CO2 pulsed laser on carbon targets

We have used ferrocene and paraffin wax as novel precursor and solvent for the growth of iron oxide nanoparticles. The proposed method of growth has several advantages over existing methods of growth using iron pentacarbonyl a precursor. Highly crystalline and monodispersed particles are obtained which assemble in two- and three-dimensional hexagonal closed packed superlattices. Growth kinetics has been studied by varying concentration of the precursor and time of growth. A phenomenological model has been proposed to explain the growth kinetics.     

Optimization of absorption in InAs/InxGa1-xSb superlattices for long-wavelength infrared detection

The linear absorption coefficient of InAs/In_xGa_1-xSb superlattices is optimized based on an 8×8 envelope-function approximation (EFA) model. The effect of layer widths, indium content, buffer choice, substrate orientation, interface type, layer growth order, piezoelectricity, and layer width variations on the cutoff wavelength and the linear absorption coefficient is investigated. We propose specific superlattice parameters that optimize absorption for superlattices grown on GaSb at three cutoff wavelengths.     

Interface magnetic anisotropy in metallic superlattices

We have prepared Pd/M and Cu/M (M = Fe, Co, Ni) magnetic superlattices using a dc sputtering and standard UHV e-beam evaporation. Sample quality was confirmed by the intense satellite peaks in the θ−2θ X-ray diffraction patterns. For all the systems studied, torque measurements revealed positive intrinsic uniaxial anisotropy but less than 2πM²_s. Results showed that the main source of the interface anisotropy is Néel surface anisotropy.     

Interfaces as design tools for short-period InAs/GaSb type-II superlattices for mid-infrared detectors

The effect of interface anisotropy on the electronic structure of InAs/GaSb type-II superlattices is exploited in the design of thin-layer superlattices for mid-IR detection threshold. The design is based on a theoretical envelope function model that incorporates the change of anion and cation species across InAs/GaSb interfaces, in particular, across the preferred InSb interface. The model predicts that a given threshold can be reached for a range of superlattice periods with InAs and GaSb layers as thin as a few monolayers. Although the oscillator strengths are predicted to be larger for thinner period superlattices, the absorption coefficients are comparable because of the compensating effect of larger band widths. However, larger intervalence band separations for thinner-period samples should lead to longer minority electron Auger lifetimes and higher operating temperatures in p-type SLs. In addition, the hole masses for thinner-period samples are on the order the free-electron mass rather than being effectively infinite for the wider period samples. Therefore, holes should also contribute to photoresponse. A number of superlattices with periods ranging from 50.6 to 21.2 Å for the 4 μm detection threshold were grown by molecular beam epitaxy based on the model design. Low temperature photoluminescence and photoresponse spectra confirmed that the superlattice band gaps remained constant at 330 meV although the period changed by the factor of 2.5. Overall, the present study points to the importance of interfaces as a tool in the design and growth of thin superlattices for mid-IR detectors for room temperature operation.     

Mössbauer spectroscopy investigation of body centered cubic Co in Co/Fe superlattices prepared with MBE

A new spectrum component is observed in Mössbauer spectra of thin body centered cubic Co layers prepared in Fe/Co superlattices doped with⁵⁷Co. It is characterized by a large magnetic hyperfine field (31.2 T) and an isomer shift nearly equal to that of -Fe. The decrease of the isomer shift in bcc Co with respect to hcp Co is consistent with smaller s to d charge transfer in bcc Co as compared to hcp Co. The cubic structure of the CoFe superlattices is evidenced with X-ray diffraction and ion-channeling measurements. The Fe/Co interface is investigated with conversion electron Mössbauer spectroscopy. It is shown that the interface alloy thickness is about six monolayers for growth temperatures up to 450 K and that increasing alloying occurs for higher growth temperatures.     

Electronic properties of HgTe-CdTe superlattices

HgTe-CdTe superlattices are new quasi-two-dimensional systems which are of great technical and fundamental interest. We report here calculations of the band structure of these superlattices, evidencing in particular the existence of interface states. Magneto-optical investigations of HgTe-CdTe superlattices are described and interpreted from their theoretical band structures, yielding the interface valence band offset Λ. Finally, we discuss the value obtained for this parameter and also some aspects of these superlattices which might be useful for manufacturing infrared photodetectors.     

第一原理研究界面弛豫对InAs/GaSb超晶格界面结构、能带结构和光学性质的影响

通过广义梯度近似的第一原理全电子相对论计算, 研究了不同界面类型InAs/GaSb超晶格的界面结构、电子和光吸收特性. 由于四原子界面的复杂性和低对称性, 通过对InAs/GaSb超晶格进行电子总能量和应力最小化来确定弛豫界面的结构参数. 计算了InSb, GaAs型界面和非特殊界面(二者交替)超晶格的能带结构和光吸收谱, 考察了超晶格界面层原子发生弛豫的影响.为了证实能带结构的计算结果, 用局域密度近似和Hartree-Fock泛函的平面波方法进行了计算. 对不同界面类型InAs/GaSb超晶格的能带结构计算结果进行了比较, 发现界面Sb原子的化学键和离子性对InAs/GaSb超晶格的界面结构、 能带结构和光学特性起着至关重要的作用.     

Photoluminescence and the structure of heterointerfaces of (311)A-and (311)B-oriented GaAs/AlAs superlattices

GaAs/AlAs superlattices grown simultaneously on GaAs substrates with the (311)A and (311)B orientations have been studied by photoluminescence and high-resolution transmission electron microscopy with a Fourier analysis of images. A periodic interface corrugation is observed for (311)B superlattices. A comparison of the structure of (311)A and (311)B superlattices indicates that the corrugation occurs in both cases and its period along the $[01\overline 1 ]$ direction is equal to 3.2 nm. The corrugation is less pronounced in (311)B superlattices, wherein it exhibits an additional modulation (long-wavelength disorder) with the characteristic lateral size exceeding 10 nm. The vertical correlation of regions rich in GaAs and AlAs, which is well observed in (311)A superlattices, is weak in (311)B superlattices due to the occurrence of long-wavelength disorder. The optical properties of (311)B superlattices are similar to those of (100) ones and differ radically from those of (311)A superlattices. As distinct from (311)B, strong photoluminescence polarization anisotropy is observed for (311)A superlattices. It is shown that it is the interface corrugation rather than the crystallographic (311) surface orientation that determines the optical properties of (311)A corrugated superlattices with thin GaAs and AlAs layers.     

Electrostatic and magnetostatic modes in semiconductor superlattices

We present a study of interface optical phonons and magnetostatic modes in semiconductor superlattices. We first review the propagation of longitudinal waves propagating parallel to the superlattice axis in order to show the similarities and differences between these and the interface modes just mentioned. The interface modes are discussed with the aim to interpret experiments carried out with superlattices of diluted magnetic semiconductors.     

A simple way to prepare monolayer films of the magnetite nanocrystal by the Langmuir-Blodgett-like technique

A simple preparation of water-soluble magnetite nanoparticles protected by sodium oleate has been demonstrated. The magnetite particles are nanocrystal, which are confirmed with XRD. This kind of magnetite nanocrystal can be changed into amphiphilic particles and steadily exist at the interface of water/toluene. The amphiphilic nanocrystal can form monolayer film on hydrophilic substrate by the Langmuir-Blodgett-like technique. The results of SEM indicate that the magnetite nanocrystal film is a uniform compact monolayer film that is composed of nanosized magnetite particles. We also proposed a possible mechanism for the formation of the nanocrystal monolayer film.     

Exchange interactions of excitons localized at opposite interfaces in type-II GaAs/AlAs superlattices: Optically detected magnetic resonance and level anticrossing

Two types of excitons, localized at opposite interfaces and characterized by different magnitudes of the exchange interactions at the same radiation energies, are simultaneously in type-II GaAs/AlAs superlattices. It is shown that the additional long-wavelength luminescence line in superlattices grown with growth interruptions after the GaAs layers is due to the recombination of an exciton localized at an inverted interface in regions where the quantum-well width is increased by one monolayer. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 10, 701–706 (25 November 1996)     

Quasiparticle states in superconducting superlattices

The energy bands and the global density of states are computed for superconductor / normal-metal superlattices in the clean limit. Dispersion relations are derived for the general case of insulating interfaces, including the mismatch of Fermi velocities and effective band masses. We focus on the influence of finite interface transparency and compare our results with those for transparent superlattices and trilayers. Analogously to the rapid variation on the atomic scale of the energy dispersion with layer thicknesses in transparent superlattices, we find strong oscillations of the almost flat energy bands (transmission resonances) in the case of finite transparency. In small-period transparent superlattices the BCS coherence peak disappears and a similar subgap peak is formed due to the Andreev process. With decreasing interface transparency the characteristic double peak structure in the global density of states develops towards a gapless BCS-like result in the tunnel limit. This effect can be used as a reliable STM probe for interface transparency.     

界面动力学对过冷熔体中球晶生长界面形态的影响

考虑了在非平衡凝固条件下球晶生长过程中界面动力学系数随界面温度的变化,利用渐近分析方法求出了在过冷熔体中球晶生长温度场和界面的近似解析解,研究了非线性界面动力学过冷对于过冷熔体中球晶界面形态和生长速度的影响.研究表明,界面动力学系数越大,球晶的生长速度越快; 反之,表明界面动力学系数越小,球晶的生长速度越慢.与忽略界面动力学的情形比较,在球晶生长过程中依赖于界面温度变化的界面动力学显著地减缓了晶体生长的速度. 关键词： 球晶 界面形态 渐近分析     

Ab initio calculation of optical absorption and reflectivity of Si(0 0 1)/SiO2 superlattices with varying interfaces

Using first-principles calculations we investigate the influence of interface modification and layer thicknesses on the optical properties of Si/SiO₂ superlattices. Four interface models with different dangling-bond passivation are considered. The results demonstrate confinement effects not only for the fundamental band gaps but also for the optical properties. While for a large Si layer thickness of the Si/SiO₂ superlattices the interface dependence is small, the calculations show a significant structure dependence for thin Si layers. © 2007 Elsevier Science. All rights reserved.     

Mean free path of ballistic electrons in GaAs/AlGaAs superlattices

The mean free path of ballistic electrons in GaAs/AlGaAs superlattices was measured using the technique of hot electron spectroscopy in magnetic fields perpendicular to the growth direction. We utilize the fact that the total effective path of an injected hot electron is a function of the applied magnetic field. For a superlattice with 6.5 nm GaAs wells and 2.5 nm GaAlAs barriers we measure a mean free path of 80 nm. The experimental results of a ten-period SL sample are compared to a fully three-dimensional calculation of the transmission including interface roughness with island sizes of 10 nm. We demonstrate that the observed mfp is limited due to interface roughness scattering for temperatures up to 50 K.     

A one-dimensional SiGe superlattice grown by UHV epitaxy

One-dimensional SiGe superlattices with periods ranging from 100 to 800 Å have been deposited on Si substrates by periodically varying the Ge content of a mixed Si_1-x Ge _x multilayer structure fromx=0 tox=0.15. The deposition was successful, employing and UHV evaporation technique at a substrate temperature of 750°C fulfilling the four conditions: Single crystal growth, no interdiffusion, two-dimensional growth, and pseudomorphic growth. It is shown that mismatch above 8 · 10^?3 favours growth by three-dimensional nucleation. The experimentally determined spacing of misfit dislocations is compared with theoretical results obtained by van der Merwe. The pseudomorphic growth behaviour of layers thinner than a critical thickness could be confirmed.