Size- and shape-dependent energetics of nanocrystal interfaces: experiment and simulation

We study the interface energetics of Ag nanocrystals on a H-passivated Si(111) surface by a transmission electron microscopy experiment and molecular dynamics simulations. The annealed nanocrystals are oriented with Ag(111)||Si(111). Azimuthally, epitaxy is preferred for nanocrystals with an interface larger than a coincident-site-lattice (CSL) cell. The equilibrium orientation, or interface energy minimum, depends on the interface size and shape. For interfaces approaching a CSL cell in size ( approximately 2 nm nanocrystals), fluctuations of a single atom at an interface can lead to large variations in nanocrystal orientations.     

Theory of interface structure, energetics, and electronic properties of embedded Si/a-SiO2 nanocrystals

We examine the interrelation of the structural and bonding alterations, when Si nanocrystals are embedded in amorphous silicon dioxide, with the electronic properties of the resulting nanocomposite system. Monte Carlo simulations using a valence force-field model obtain the equilibrium structure of the interface, and investigate its energetics, stability and disorder as a function of the nanocrystal size. It is found that when the size is smaller than 2 nm, the embedded nanocrystals get heavily distorted. First-principles calculations of such small nanocrystals reveal a drastic reduction of the energy gap compared to the free-standing case. The origin of this pinning is attributed to the structural deformations, while oxygen states at the interface seem to play a minor role.     

Size dependent charge storage characteristics of MBE grown Ge nanocrystals on surface oxidized Si

We have demonstrated the growth of size controlled Ge nanocrystals by molecular beam epitaxy on oxidized Si for the fabrication of floating gate memory structure. The size and density of the nanocrystals have been controlled by varying the growth temperature. The role of interface states and nanocrystals on the memory characteristics has been studied using frequency dependent conductance-voltage measurements. Superior retention characteristics and an enhanced memory window width have been achieved by replacing SiO₂ with high-k Al₂O₃ as a blocking oxide with a higher barrier height.     

Size dependence of phase transition temperatures of ferromagnetic, ferroelectric and superconductive nanocrystals

With the miniaturization of devices, size and interface effects become increasingly important for the properties and performances of nanomaterials. Here, we present a thermodynamic approach to the mechanism behind size-induced unusual behavior in the phase stabilities of ferromagnetic (FM), antiferromagnetic (AFM), ferroelectric (FE), and superconductive (SC) nanocrystals, which are different dramatically from their bulk counterparts. This method is based on the Lindemann criterion for melting, Mott’s expression for the vibrational melting entropy, and the Shi model for the size-dependent melting temperature. Simple and unified functions, without any adjustable parameter, are established for the size and interface dependences of thermal and phase stabilities of FM, AFM, FE and SC nanocrystals. According to these analytic functions, as the size of nanocrystals is reduced, the thermal and phase stabilities may strengthen or weaken, depending on the confluence of the surface/volume ratio of nanocrystals and the FM(AFM, FE or SC)/substrate interface situations. The validity of this model is confirmed by a large number of experimental results. This theory will be significant for the choice of materials and the design of devices for practical application.     

Size dependence of phase transition temperatures of ferromagnetic ,ferroelectric and superconductive nanocrystals

With the miniaturization of devices, size and interface effects become increasingly important for the properties and performances of nanomaterials. Here, we present a thermodynamic approach to the mechanism behind size-induced unusual behavior in the phase stabilities of ferromagnetic (FM), antiferromagnetic (AFM), ferroelectric (FE), and superconductive (SC) nanocrystals, which are different dramatically from their bulk counterparts. This method is based on the Lindemann criterion for melting, Mott’s expression for the vibrational melting entropy, and the Shi model for the size-dependent melting temperature. Simple and unified functions, without any adjustable parameter, are established for the size and interface dependences of thermal and phase stabilities of FM, AFM, FE and SC nanocrystals. According to these analytic functions, as the size of nanocrystals is reduced, the thermal and phase stabilities may strengthen or weaken, depending on the confluence of the surface/volume ratio of nanocrystals and the FM(AFM, FE or SC)/substrate interface situations. The validity of this model is confirmed by a large number of experimental results. This theory will be significant for the choice of materials and the design of devices for practical application.      

Absorption cross-sections and lifetimes as a function of size in Si nanocrystals embedded in SiO2

The photoluminescence (PL) emission yield of Si nanocrystals embedded in SiO₂ depends on their size and on Si–SiO₂ interface passivation. In this work we aim at clarifying the relative importance of both contributions by studying lifetimes and absorption cross-sections as a function of size, for samples with and without passivation in forming gas. We find that while the PL lifetime increases steadily (quasi-linear dependence), the radiative lifetime increases exponentially with the nanocrystal size. Thus, as expected, radiative oscillator strengths are much smaller for large nanocrystals, but this reduction is partially compensated by a less effective quenching at interfacial non-radiative states. The absorption cross-section per nanocrystal rises as the nanocrystal size decreases, for all excitation wavelengths, implying that the variation of oscillator strength dominates over the reduction of the density of states. Passivation processes do not affect the emission mechanism and increase the emission yield while reducing the density of non-radiative recombination centers at the Si–SiO₂ interface (P_b centers).     

硅基硒纳米颗粒的发光特性研究

由于尺寸缩小引起的量子效应, 硒(Se) 材料的低维纳米结构具有更高的光响应和低的阈值激射等特性, 因此成为纳米电子与纳米光电子器件领域一个重要的研究方向. 本文通过对非晶硒薄膜的快速热退火来制备硒纳米颗粒, 退火温度在100–180℃之间时, 结晶后的硒纳米颗粒均为三角晶体结构, 其颗粒尺寸随退火温度的增加而线性增大. 光致发光谱测试发现三个发光峰, 分别位于1.4eV, 1.7eV和1.83eV. 研究发现位于1.4eV处的发光峰来源于非晶硒缺陷发光, 位于1.83eV处的发光峰来源于晶体硒的带带跃迁发光; 而位于1.7eV处的发光峰强度随激发功率增强而指数增大, 且向短波长移动, 该发光峰应该来源于非晶硒与硒纳米颗粒界面处的施主-受主对复合发光. 关键词： 硅基 硒纳米颗粒 光致发光 施主-受主对     

Polar oxide interface stabilization by formation of metallic nanocrystals

In situ x-ray photoelectron spectroscopy and ex situ transmission electron microscopy and diffraction studies of a model Fe3O4(111)/MgO(111) polar oxide interface exclude stabilization by interface faceting, reconstruction, or by formation of a continuous interfacial layer with altered stoichiometry, and uncover stabilization by dominant formation of metallic Fe(110) nanocrystals. The iron nanocrystals nucleate both at the interface and within the magnetite film and grow in a Nishiyama-Wasserman orientation relationship with a bimodal size distribution related to twinning. Minority magnetite nanocrystals were also observed, growing in the less polar (100) orientation than the magnetite (111) film. Electron transfer and bond hybridization mechanisms are likely at the metal/oxide and oxide/oxide interfaces and remain to be explored.     

Atom probe tomography of size‐controlled phosphorus doped silicon nanocrystals

Doping of silicon nanocrystals is essential to control their electronic and optical properties. The incorporation of an impurity into a silicon nanovolume is a nontrivial task due to the self‐purification effect. Here, a systematic atom probe tomography study of the phosphorus distribution and incorporation in size‐controlled silicon nanocrystals embedded in silicon dioxide is presented. Qualitatively, it turns out that the phosphorus distribution in the system follows a universal, nanocrystal‐size independent trend: phosphorus‐enrichment at the interface with a substantial phosphorus‐incorporation in the silicon nanocrystal as small as 2 nm in diameter. This clearly contradicts strict self‐purification. These observations are explained by the bulk‐solubility and ‐segregation behaviour, kinetic effects related to the diffusion lengths, and nanoscale interface strain. The quantitative determination of the amount of phosphorus atoms per quantum dot enables a systematic understanding of phosphorus‐induced effects on optical and electronic properties of silicon nanovolumes.     

Voltage-controlled electroluminescence from SiO2 films containing Ge nanocrystals and its mechanism

Luminescent SiO₂ films containing Ge nanocrystals are fabricated by using Ge ion implantation, and metal–oxide–semiconductor structures employing these films as the active layers show yellow electroluminescence (EL) under both forward and reverse biases. The EL spectra are strongly dependent on the applied voltage, but slightly on the mean size of Ge nanocrystals. When the forward bias increases towards 30 V, the EL spectral peak shifts from 590 nm to 485 nm. It is assumed that the EL originates from the recombination of injected electrons and holes in Ge nanocrystals near the Si/SiO₂ interface, or through luminescent centers in the SiO₂ matrix near the SiO₂/metal interface. The mismatch of the injection amounts between holes and electrons results in the low EL efficiency. Received: 28 February 2000 / Accepted: 28 March 2000 / Published online: 5 July 2000     

Self-purification in semiconductor nanocrystals

Doping of nanocrystals is an important and very difficult task. "Self-purification" mechanisms are often claimed to make this task even more difficult, as the distance a defect or impurity must move to reach the surface of a nanocrystal is very small. We show that self-purification can be explained through energetic arguments and is an intrinsic property of defects in semiconductor nanocrystals. We find the formation energies of defects increases as the size of the nanocrystal decreases. We analyze the case of Mn-doped CdSe nanocrystals and compare our results to experimental findings.     

Bimodal growth of Au on SrTiO3(001)

We have investigated the vapor phase growth of Au on SrTiO3(001)-(2 x 1) substrates by UHV scanning tunneling microscopy. Submonolayer (ML) coverages below 300 degrees C wet the surface as disordered metastable 2D islands. Beyond 0.75 ML fcc nanocrystals with a (111) interface are nucleated and ripen by dewetting the surrounding layer. Some multiply twinned fivefold symmetric clusters are also created. Above 400 degrees C dewetting occurs for all coverages and the surface is only populated by nanocrystals and fivefold clusters. A planar ground state configuration for small Au clusters and a higher interface energy for crystals than for wetted 2D ML films explains these results.     

Soft chemical routes to semiconductor nanostructures

Soft chemistry has emerged as an important means of generating nanocrystals, nanowires and other nanostructures of semiconducting materials. We describe the synthesis of CdS and other metal chalcogenide nanocrystals by a solvothermal route. We also describe the synthesis of nanocrystals of AlN, GaN and InN by the reaction of hexamethyldisilazane with the corresponding metal chloride or metal cupferronate under solvothermal conditions. Nanowires of Se and Te have been obtained by a self-seeding solution-based method. A single source precursor based on urea complexes of metal chlorides gives rise to metal nitride nanocrystals, nanowires and nanotubes. The liquidliquid interface provides an excellent medium for preparing single-crystalline films of metal chalcogenides.     

Quantum confinement and interface structure of Si nanocrystals of sizes 3–5 nm embedded in a-SiO2

Spectroscopic ellipsometry and Monte Carlo simulations are employed to answer the fundamental question whether the energy gaps of Si nanocrystals with sizes in the range of 3–5 nm, which are embedded in amorphous silica, follow or deviate from the quantum confinement model, and to examine their interfacial structure. It is shown that the optical properties of these nanocrystals are well described by the Forouhi–Bloomer interband model. Analysis of the optical measurements over a photon-energy range of 1.5–5 eV shows that the gap of embedded nanocrystals with a mean size of 3.9 nm follows closely quantum confinement theory. A large band gap expansion (0.65 eV) compared to bulk Si is observed. The Monte Carlo simulations reveal a non-abrupt interface and a large fraction of interface oxygen bonds. This, in conjunction with the experimental observations, indicates that oxygen states and the chemical disorder at the interface have a negligible influence on the optical properties of the material in this size regime.     

Embedded silicon nanocrystal interface structure and strain

The structure of nanocrystal-matrix interface and strain in embedded nanocrystals are studied using large-scale atomistic simulations, with the examples of Si nanocrystal embedded in amorphous matrix of SiO₂. Photoluminescence from silicon nanocrystals embedded in a dielectric matrix like SiO₂ and Si₃N₄ are promising for Si-based optical devices. The nanocrystal-matrix interface plays a crucial role in understanding its optical and electrical properties. Nanocrystals with diameters varying from 2.17 to 4.56 nm are studied. A detailed quantitative analysis of the variation of Si/SiO₂ interface structure and strain distribution with nanocrystal diameter is reported. A linear variation of the interface width with nanocrystal diameter is observed with thinner interfaces for larger nanocrystals. Local deformation analysis reveals that the smaller nanocrystals are highly strained, whereas the strain in the larger ones shifts to the interface. This is in accordance with observed increase in total percentage of defect states in the interface from 39 to 70% for diameter increasing from 2.17 to 4.56 nm. Moreover, based on the atomic arrangements at the interface, optically active defects like Pb centres, E centres and non-bridging oxygen centres are identified and a dominance of Pb centres is observed for all the nanocrystals. The detailed structural characterization-related investigations using the proposed simulation approach will find useful application in designing system-level response of embedded nanocrystals and also to correlate various experimental observations.     

用巯基乙酸作稳定剂制备CdSe纳米晶的光学性质

以巯基乙酸为稳定剂制备了CdSe纳米晶，通过尺寸选择沉淀得到2nm到3nm之间不同尺寸的纳米晶，利用室温光吸收，光致发光（PL）和光致发光激发（PLE）谱来研究了CdSe纳米团簇的光学性质。紫外－可见吸收谱给了具有清晰激光特征的尖锐吸收边，这表明样品的尺寸分布很窄。光致发光研究表明，样品有两个发射带，一个具有较高能量位于吸收边，来自电子－空穴对从最低激发态能级弛豫后的辐射复合，另一个低能发射带归属于基质与纳米晶界面存在的俘获中心。PLE谱中有2个吸收带，分别是S－S和P－P跃迁。最后还给出了不同激发能量下的发光特性。     

Two-photon spectroscopy and microscopy of II–VI semiconductor nanocrystals

We review our recent nonlinear spectroscopies of nanocrystals and synthetic efforts to improve their luminescence properties. A two-photon spectroscopic study of CdSe nanocrystals as a function of size is presented and compared with predictions from the effective mass model with spherical confinement. We also detail our efforts at improving the luminescence properties of nanocrystals which have culminated in a 50% fluorescence quantum yield for inorganic capping of some sizes of CdSe nanocrystals. Finally, we present the application of two-photon microscopy to resolve fluorescence from single nanocrystals at room temperature and cryogenic temperatures.     

Tailored nanoheterojunctions for optimized light emission

We present coupled classical and quantum simulations of 1 to 2 nm Si nanocrystals (NCs) embedded in amorphous SiO(2) and we show that by tuning the density of the oxide matrix one may change the relative alignment of Si NC and SiO(2) electronic states at the interface. We find that interfacial strain plays a key role in determining the variation of the nanaoparticle gap as a function of size, as well as of conduction band offsets with the oxide. In particular, our results show that it is the variation of the valence band offset with size that is responsible for the gap change. Our findings suggest that the elastic properties of the embedding matrix may be tuned to tailor the energy levels of small Si NCs so as to optimize their performance in optoelectronic devices and solar cells.     

Effect of nonuniform permittivity of a solid-state matrix on the spectral width of erbium ion luminescence

The Stark splitting of the energy levels of Er³⁺ ions implanted in a structure made up of alternating layers of silicon dioxide and quasi-ordered silicon nanocrystals is calculated. The level splitting is caused by the electric field of the image charges induced at the interfaces between layers with different permittivities. The splitting was established to increase as the contrast in permittivity between the silicon dioxide and silicon nanocrystal layers increases, as well as when the erbium ions approach the layer interface. The results obtained offer an adequate explanation of the experimentally observed additional broadening of the erbium photoluminescence band (0.8 eV) with increasing characteristic size of the silicon nanocrystals.     

Optical property investigation of SiGe nanocrystals formed by electrochemical anodization

We report on the optical property investigation of SiGe nanocrystals (NCs) prepared by electrochemical anodization (ECA) of SiGe layer grown by ultrahigh vacuum chemical vapor deposition (UHVCVD). At room temperature, SiGe NCs with higher Ge content demonstrate a redshift of the photoluminescence (PL) peak compared to Si NCs. It was found that the surface chemical composition, density, and the size of the SiGe NCs were very sensitive to the annealing conditions. Various spectroscopy measurements such as PL, FTIR, and XPS have been carried out to reveal the mechanism of the PL peak transition. The results indicated that the PL peak position was determined by two major factors, namely, interface state density and the size of SiGe NCs. It was shown that the higher the interface state density, the more significant the redshift of the peak position. While the smaller the size of the SiGe NCs, the more significant the quantum size effects become, resulting in the blueshift of the PL peak position.