Purification of Nano‐Porous Silicon for Biomedical Applications

Recently, various bio‐medical applications of nanoporous silicon (np‐Si) have been suggested. This work investigates the biocompatibility of np‐Si particles taking into account hazardous residua confined in the pores after preparation. The emphasis is on the potential application of such particles as oxygen photosensitizer for photodynamic therapy of cancer, which requires both negligible toxicity of np‐Si particles in darkness and a high photo‐cyto‐toxic effect due to generation of singlet oxygen under illumination. Considerable amounts of water soluble toxic impurities are found to be present in the nanoporous shell of micrometer‐sized np‐Si particles immediately after their preparation by chemical etching of bulk silicon powder. The effects of several ordinary cleaning treatments are investigated by using thermal effusion mass‐spectroscopy and FTIR spectroscopy. A particular purification procedure is developed, capable to reduce the concentration of residual impurities to levels acceptable for bio‐medical applications while preserving the required photo‐activity of the np‐Si particles.     

Phonon scattering enhancement in silicon nanolayers

Dimensional confinement in silicon nanowires (NWs) is well-known for enhancing phonon scattering, thus leading to a pronounced reduction of thermal conductivity κ with respect to bulk material. The effect of confinement on phonon scattering in nanolayers (NLs), however, has not been fully understood. In this work, thermal conductivity on polycrystalline silicon NLs with roughened surfaces and thicknesses ranging from 30 to 100 nm has been experimentally investigated. For measurement purposes, the nanostructures were fabricated with a dedicated surface nano-machining process, thus producing vertical silicon nanostructures suspended on Al/Si electrodes on a silicon substrate, using SiO₂ as a sacrificial layer. By designing such structures in a four-terminal configuration, their κ could be determined by the current-voltage method. Boron doped silicon NLs were examined, at resistivity ranging between 2 and 10 m $\Upomega$ cm. We found an increase of phonon scattering from the confinement, since κ decreased steadily with the thickness from values typical of thick films (around 30 W m^?1 K^?1) down to <15 W m^?1 K^?1. Compared to NWs, NLs had displayed figures of merit smaller by one order of magnitude. However, due to the larger filling factor, they were able of generating more than five times the electric power per area unit that could be obtained with high-density stacks of top-efficiency NWs.     

Nanoporous Si as an efficient thermoelectric material

Room-temperature thermoelectric properties of n-type crystalline Si with periodically arranged nanometer-sized pores are computed using a combination of classical molecular dynamics for lattice thermal conductivity and ab initio density functional theory for electrical conductivity, Seebeck coefficient, and electronic contribution to the thermal conductivity. The electrical conductivity is found to decrease by a factor of 2-4, depending on doping levels, compared to that of bulk due to confinement. The Seebeck coefficient S yields a 2-fold increase for carrier concentrations less than 2 x 10(19) cm(-3), above which S remains closer to the bulk value. Combining these results with our calculations of lattice thermal conductivity, we predict the figure of merit ZT to increase by 2 orders of magnitude over that of bulk. This enhancement is due to the combination of the nanometer size of pores which greatly reduces the thermal conductivity and the ordered arrangement of pores which allows for only a moderate reduction in the power factor. We find that while alignment of pores is necessary to preserve power factor values comparable to those of bulk Si, a symmetric arrangement is not required. These findings indicate that nanoporous semiconductors with aligned pores may be highly attractive materials for thermoelectric applications.     

(Mg2Si1-xSbx)0.4-（Mg2Sn）0.6固溶体合金的制备及热电输运特性

以Mg、Si、Sn、Sb块体为原料,采用熔炼结合放电等离子烧结(SPS)技术制备了n型(Mg2Si1-xSbx)0.4-(Mg2Sn)0.6(0≤x≤0.0625)系列固溶体合金.结构及热电输运特性分析结果表明:当Mg原料过量8wt%时,可以弥补熔炼过程中Mg的挥发损失,形成单相(Mg2Si1-xSbx)0.4-(Mg2Sn)0.6固溶体.烧结样品的晶胞随Sb掺杂量的增加而增大;电阻率随Sb掺杂量的增加先减小后增大,当样品中Sb掺杂量x≤0.025时,样品电阻率呈现出半导体输运特性,Sb掺杂量x>0.025时,样品电阻率呈现为金属输运特性.Seebeck系数的绝对值随Sb掺杂量的增加先减小后增大;热导率κ在Sb掺杂量x≤0.025时比未掺杂Sb样品的热导率低,在Sb掺杂量x>0.025时高于未掺杂样品的热导率,但所有样品的晶格热导率明显低于未掺杂样品的晶格热导率.实验结果表明Sb的掺杂有利于降低晶格热导率和电阻率,提高中温区Seebeck系数绝对值;其中(Mg2Si0.95Sb0.05)0.4-(Mg2Sn)0.6合金具有最大ZT值,并在723 K附近取得最大值约为1.22.     

Characterization of nanoporous silicon layer to reduce the optical losses of crystalline silicon solar cells

Reduction of optical losses in crystalline silicon solar cells by surface modification is one of the most important issues of silicon photovoltaics. Porous Si layers on the front surface of textured Si substrates have been investigated with the aim of improving the optical losses of the solar cells, because an anti-reflection coating and a surface passivation can be obtained simultaneously in one process. We have demonstrated the feasibility of a very efficient porous Si AR layer, prepared by a simple, cost effective, electrochemical etching method. Silicon p-type CZ (100) oriented wafers were textured by anisotropic etching in sodium carbonate solution. Then, the porous Si layers were formed by electrochemical etching in HF solutions. After that, the properties of porous Si in terms of morphology, structure and reflectance are summarized. The structure of porous Si layers was investigated using SEM. The formation of a nanoporous Si layer on the textured silicon wafer result in a reflectance lower than 5% in the wavelength region from 500 to 900 nm. Such a surface modification allows improving the Si solar cell characteristics. An efficiency of 13.4% is achieved on a monocrystalline silicon solar cell using the electrochemical technique.     

Thermal transport in suspended and supported few-layer graphene

We report thermal conductivity (κ) measurements from 77 to 350 K on both suspended and supported few-layer graphene using a thermal-bridge configuration. The room temperature value of κ is comparable to that of bulk graphite for the largest flake, but reduces significantly for smaller flakes. The presence of a substrate lowers the value of κ, but the effect diminishes for the thermal transport in the top layers away from the substrate. For the suspended sample, the temperature dependence of κ follows a power law with an exponent of 1.4 ± 0.1, suggesting that the flexural phonon modes contribute significantly to the thermal transport of the suspended graphene. The measured values of κ are generally lower than those from theoretical studies. We attribute this deviation to the phonon-boundary scattering at the graphene-contact interfaces, which is shown to significantly reduce the apparent measured thermal conductance of graphene.     

Influence of polymeric residue on the thermal conductivity of suspended bilayer graphene

The thermal conductivity (κ) of two bilayer graphene samples each suspended between two microresistance thermometers was measured to be 620 ± 80 and 560 ± 70 W m(-1) K(-1) at room temperature and exhibits a κ ∝ T(1.5) behavior at temperatures (T) between 50 and 125 K. The lower κ than that calculated for suspended graphene along with the temperature dependence is attributed to scattering of phonons in the bilayer graphene by a residual polymeric layer that was clearly observed by transmission electron microscopy.     

Thermal conductivity measurements of suspended graphene with and without wrinkles by micro-Raman mapping

The thermal conductivity (κ) of suspended graphene membranes made by chemical vapor deposition (CVD) was measured by micro-Raman mapping. Cracks and wrinkles present in these suspended graphene membranes were identified by micro-Raman mapping, and κ values and their statistics were obtained on membranes free of such imperfections in a single mapping. Based on this new technique, an average κ value of 1875?±?220?W?m(-1)?K(-1) at 420?K was measured on 26 suspended graphene membranes that were free of wrinkles, ～27% higher than the average value measured from 12 graphene membranes with wrinkles. These results suggest that the variation in published thermal conductivity values for suspended graphene samples could, at least in part, be due to the presence or absence of wrinkles.     

Beating Thermal Coarsening in Nanoporous Materials via High-Entropy Design

Controlling the feature sizes of 3D bicontinuous nanoporous (3DNP) materials is essential for their advanced applications in catalysis, sensing, energy systems, etc., requiring high specific surface area. However, the intrinsic coarsening of nanoporous materials naturally reduces their surface energy leading to the deterioration of physical properties over time, even at ambient temperatures. A novel 3DNP material beating the universal relationship of thermal coarsening is reported via high-entropy alloy (HEA) design. In newly developed TiVNbMoTa 3DNP HEAs, the nanoporous structure is constructed by very fine nanoscale ligaments of a solid-solution phase due to enhanced phase stability by maximizing the configuration entropy and suppressed surface diffusion. The smallest size of 3DNP HEA synthesized at 873 K is about 10 nm, which is one order of magnitude smaller than that of conventional porous materials. More importantly, the yield strength of ligament in 3DNP HEA approaches its theoretical strength of G/2π of the corresponding HEA alloy even after thermal exposure. This finding signifies the key benefit of high-entropy design in nanoporous materials—exceptional stability of size-related physical properties. This high-entropy strategy should thus open new opportunities for developing ultrastable nanomaterials against its environment.     

Highly Porous Silicon Membranes Fabricated from Silicon Nitride/Silicon Stacks

Nanopore formation in silicon films has previously been demonstrated using rapid thermal crystallization of ultrathin (15 nm) amorphous Si films sandwiched between nm‐thick SiO₂ layers. In this work, the silicon dioxide barrier layers are replaced with silicon nitride, resulting in nanoporous silicon films with unprecedented pore density and novel morphology. Four different thin film stack systems including silicon nitride/silicon/silicon nitride (NSN), silicon dioxide/silicon/silicon nitride (OSN), silicon nitride/silicon/silicon dioxide (NSO), and silicon dioxide/silicon/silicon dioxide (OSO) are tested under different annealing temperatures. Generally the pore size, pore density, and porosity positively correlate with the annealing temperature for all four systems. The NSN system yields substantially higher porosity and pore density than the OSO system, with the OSN and NSO stack characteristics fallings between these extremes. The higher porosity of the Si membrane in the NSN stack is primarily due to the pore formation enhancement in the Si film. It is hypothesized that this could result from the interfacial energy difference between the silicon/silicon nitride and silicon/silicon dioxide, which influences the Si crystallization process.     

The preparation of nanoporous gold electrodes by electrochemical alloying/dealloying process at room temperature and its properties

A novel method of preparing nanoporous gold has been developed: nanoporous gold materials have been prepared on the bulk gold substrates by galvanostatic electrochemical alloying and galvanostatic electrochemical dealloying processes at 0.05 mA in 1 M LiPF₆, EC/DMC(1:1, v/v) solution at room temperature. The result shows that the particle size ranges from 50 nm to 100 nm on the surface of the prepared nanoporous gold by Quanta 200FEG scanning electron microscope. And it is determined that the maximum anodic current for the nanoporous gold electrode is 50 times higher than that of the polished gold electrode in 0.5 M KOH by the cyclic voltammograms.     

Electrochemical deposition of Ni and Cu onto monocrystalline n-Si(100) wafers and into nanopores in Si/SiO2 template

Nickel and copper were potentiostatically deposited onto monocrystalline n-Si (100) wafers and in nanoporous SiO₂/Si template from 0.5 M NiSO₄ + 0.5 M H₃BO₃ and 0.005 M CuSO₄ + 0.5 M H₃BO₃ solutions. Nanoporous SiO₂/Si template was formed by etching in dilute HF solution of ion tracks. The latter were produced by high-energy (380 MeV) Au⁺ ions bombardment of silicon oxide thermally grown on silicon (100) substrate. The deposition of metals was studied using cyclic voltammetry (CV), chronoamperometry; the structure and morphology of products were ex-situ investigated by SEM and XRD. The level of pores filling was controlled by deposition time. Electrodeposition occurred selectively into nanopores and the deposition on SiO₂ layer was excluded. It was found out that Ni and Cu electrodeposited into nanopores of SiO₂/Si system formed the same structures as at electrodeposition on the surface of monocrystalline n-Si—granules for Ni and scale-shaped particles for Cu deposits.     

Thermal conductivity of ge and ge-si core-shell nanowires in the phonon confinement regime

Heterostructure core-shell semiconductor nanowires (NWs) have attracted tremendous interest recently due to their remarkable properties and potential applications as building blocks for nanodevices. Among their unique traits, thermal properties would play a significant role in thermal management of future heterostructure NW-based nanoelectronics, nanophotonics, and energy conversion devices, yet have been explored much less than others. Similar to their electronic counterparts, phonon spectrum and thermal transport properties could be modified by confinement effects and the acoustic mismatch at the core-shell interface in small diameter NWs (<20 nm). However, fundamental thermal measurement on thin core shell NWs has been challenging due to their small size and their expected low thermal conductivity (κ). Herein, we have developed an experimental technique with drastically improved sensitivity capable of measuring thermal conductance values down to ～10 pW/K. Thermal conductivities of Ge and Ge-Si core-shell NWs with diameters less than 20 nm have been measured. Comparing the experimental data with Boltzmann transport models reveals that thermal conductivities of the sub-20 nm diameter NWs are further suppressed by the phonon confinement effect beyond the diffusive boundary scattering limit. Interestingly, core-shell NWs exhibit different temperature dependence in κ and show a lower κ from 300 to 388 K compared to Ge NWs, indicating the important effect of the core-shell interface on phonon transport, consistent with recent molecular dynamics studies. Our results could open up applications of Ge-Si core shell NWs for nanostructured thermoelectrics, as well as a new realm of tuning thermal conductivity by "phononic engineering".     

Nanopatterned silicon emitters of a solar cell fabricated by anodic aluminum oxide masks

We investigated the nanopattern transferring process by a template of anodic aluminum oxide and the formation of a nanoporous aluminum oxide layer on a Si solar cell by the anodization process of Al thin films. The anodization process provided a template to transfer the nanopattern onto the Si surface. The small-sized nanoporous alumina template was attached to be covered on the textured surface and played the role of etching mask in the F-based dry etching process. Furthermore, we deposited an Al thin film onto the Si surface and the subsequent anodization process was performed. The alumina formulated on the deposited Al thin film did not show the array of nanoporous structure and no nanopatterns were transferred onto the surface. The large-areal alumina deposited on the Si surface showed enhanced photo-absorption in the ultraviolet spectral region of 243 nm, but increased the photo-reflectance in the visible and infrared spectral regions when compared to the Si-bare sample.     

Effect of thermal coarsening on the thermal conductivity of nanoporous gold

The thermal conductivities of nanoporous gold (NPG) microwires annealed at different temperatures have been measured in the temperature range from 100 to 320 K. Considering the electron-surface scattering, the thermal conductivity is expected to increase with the increase of ligament diameter. However, the thermal conductivity of NPG microwire is found to decrease after thermal coarsening, and has a maximum value at around 250 K for the as-dealloyed sample. We suggest that the defects accumulating at a relatively high temperature and the reduction in defect spacing may cause these temperature behaviors of thermal conductivity. Taking into account the electron scattering on ligament surfaces and defects, a modified theoretical model for the thermal conductivity of nanoporous metal is proposed to agree with our experimental results.     

Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film

Effect of the thermal expansion coefficient of electrode on the electrical properties in lead zirconate titanate (PZT) with morphotropic phase boundary (Pb(Zr_0.53,Ti_0.47)O₃: MPB) composition film was demonstrated in this paper. The lanthanum nickel oxide (LaNiO₃: LNO) and lanthanum strontium cobalt oxide ((La_0.5,Sr_0.5)CoO₃: LSCO) was deposited by chemical solution deposition (CSD) as bottom electrode on Si wafer. Highly (100)-oriented LSCO layers were successfully prepared by CSD on Si wafer using (100)-oriented LNO layers as seeding layer for the crystal orientation control. As a result, (100) and (001) oriented PZT film was also successfully prepared on LSCO/LNO/Si stacking structure. The obtained dielectric and ferroelectric properties changed according to the thermal stress which was influenced by the bottom electrode thickness.     

Phonon engineering in carbon nanotubes by controlling defect concentration

Outstanding thermal transport properties of carbon nanotubes (CNTs) qualify them as possible candidates to be used as thermal management units in electronic devices. However, significant variations in the thermal conductivity (κ) measurements of individual CNTs restrict their utilizations for this purpose. In order to address the possible sources of this large deviation and to propose a route to solve this discrepancy, we systematically investigate the effects of varying concentrations of randomly distributed multiple defects (single and double vacancies, Stone-Wales defects) on the phonon transport properties of armchair and zigzag CNTs with lengths ranging between a few hundred nanometers to several micrometers, using both nonequilibrium molecular dynamics and atomistic Green's function methods. Our results show that, for both armchair and zigzag CNTs, κ converges nearly to the same values with different types of defects, at all lengths considered in this study. On the basis of the detailed mean free path analysis, this behavior is explained with the fact that intermediate and high frequency phonons are filtered out by defect scattering, while low frequency phonons are transmitted quasi-ballistically even for several micrometer long CNTs. Furthermore, an analysis of variances in κ for different defect concentrations indicates that defect scattering at low defect concentrations could be the source of large experimental variances, and by taking advantage of the possibility to create a controlled concentration of defects by electron or ion irradiation, it is possible to standardize κ with minimizing the variance. Our results imply the possibility of phonon engineering in nanostructured graphene based materials by controlling the defect concentration.     

Ion beam doping of silicon nanowires

We demonstrate n- and p-type field-effect transistors based on Si nanowires (SiNWs) implanted with P and B at fluences as high as 10(15) cm (-2). Contrary to what would happen in bulk Si for similar fluences, in SiNWs this only induces a limited amount of amorphization and structural disorder, as shown by electrical transport and Raman measurements. We demonstrate that a fully crystalline structure can be recovered by thermal annealing at 800 degrees C. For not-annealed, as-implanted NWs, we correlate the onset of amorphization with an increase of phonon confinement in the NW core. This is ion-dependent and detectable for P-implantation only. Hysteresis is observed following both P and B implantation.     

Nanoheteroepitaxy of GaN on a nanopore array of Si(111) surface

Nanoheteroepitaxial (NHE) growth of GaN using AlN/AlGaN as a graded buffer layer by metalorganic chemical vapor deposition has been demonstrated on the nanoporous patterned Si(111) substrates. The nanopore array on Si(111) has been fabricated by using anodized aluminum oxide membrane as an induced couple plasma dry etching mask. The reduction of the threading dislocation density and relaxation of the tensile stress in NHE GaN are revealed by transmission electron microscopy (TEM), micro-Raman spectrum and photoluminescence spectrum, respectively. Cross-sectional TEM analysis shows that dislocations nucleated at the interface are forced to bend into (0001) basal plane. Red shift in the E₂ (TO) phonon peak of micro-Raman spectrum indicates the relaxation of tensile stress in the nanoheteroepitaxial lateral overgrowth of GaN. A single step ELO without mask on nanopatterned Si(111) substrates is a simple and promising way for the improvement of the quality of GaN on Si substrates.     

基于第一抗热震因子的BN纳米管/Si_3N_4复合材料抗热震性能评价

利用Kingery抗热震断裂理论构建了BN纳米管(BNNTs)强韧化陶瓷复合材料的第一抗热震因子模型,通过真空热压烧结法制备了四组BNNTs含量分别为0.5wt%、1.0wt%、1.5wt%和2.0wt%的BNNTs/Si_3N_4复合材料,并采用水浴淬冷法和三点弯曲法测试了复合材料的抗热震性能(震后弯曲强度和临界热震断裂温差)。测试结果验证了在急剧加热和急剧冷却条件下第一抗热震因子模型的正确性。结果表明:添加BNNTs使BNNTs/Si_3N_4复合材料第一抗热震因子增大,抗热震性能提升。分布在晶界上的BNNTs起到裂纹钉扎、桥联和裂纹偏转作用,增加了裂纹扩展的阻力;纳米管孔隙的存在改变了裂纹扩展路径,提高了BNNTs/Si_3N_4的断裂韧度,从而有效提高了其抗热震断裂能力。