Arsenic deposition as a precursor layer on silicon (211) and (311) surfaces

We investigate the properties of arsenic (As) covered Si(211) and Si(311) surfaces by analyzing data from x-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED) images. We then create a model using total surface energy calculations. It was found that both Si(211) and Si(311) had 0.68±0.08 surface As coverage. Si(211) had 0.28±0.04 Te coverage and Si(311) had 0.24±0.04 Te coverage. The Si(211) surface replaces the terrace and trench Si atoms with As for a lower surface energy, while the Si edge atoms form dimers. The Si(311) surface replaces all terrace atoms and adsorbs an As dimer every other edge site. These configurations imply an improvement in the mean migration path from the bare silicon surface by allowing the impinging atoms for the next epitaxial layer, tellurium (Te), to bind at every other pair of edge atoms, and not the step terrace sites. This would ensure a nonpolar, B-face growth.     

Anatase (101) Reconstructed Surface with Novel Functionalities: Desired Bandgap for Visible Light Absorption and High Chemical Reactivity

Unreconstructed surfaces of anatase TiO₂ are known to have two main limitations for their application as photocatalysts, namely, low efficiency for sun‐light absorption due to the wide bandgap, and low chemical reactivity. Strategies to overcoming the two limitations and to enhancing TiO₂'s photocatalytic efficiency have been highly sought. To this end, a global search of anatase reconstructed surfaces is performed based on the evolutionary method. It is found that the newly predicted anatase (101) reconstructed surface possesses a desired bandgap whose value is within the energy domain of visible light as well as notably high chemical reactivity compared to the unreconstructed anatase (101) surface. In particular, it is predicted that under Ti‐richness condition, the anatase (101) reconstructed surface is energetically very stable. The anatase (101) reconstructed surface exhibits similar topmost surface structure as the unreconstructed anatase (101) surface but different subsurface structure. Not only the fivefold coordinated Ti atoms (Ti_5c) in the topmost surface layer but also the sixfold coordinated Ti atoms in the subsurface layer contribute to the desirable gap states. The high chemical reactivity of anatase (101) reconstructed surface can be attributed to the extra electrons drawn by the surface Ti_5c atoms and subsurface Ti_6c atoms.     

Infrared Aluminum Metamaterial Perfect Absorbers for Plasmon‐Enhanced Infrared Spectroscopy

Matured surface chemistry and excellent chemical stability have enabled gold to become the material‐of‐choice for plasmonic sensing in both visible and infrared wavelength range. Here, successful surface functionalization of metamaterials made from a low‐cost abundant plasmonic material, aluminum, with phosphonic acid and subsequent detection of the C?O vibration mode via surface‐enhanced infrared absorption spectroscopy is demonstrated. The metamaterial consists of infrared perfect absorbers fabricated by colloidal lithography. Near perfect absorption is achieved at resonance wavelengths, which can be readily tuned by changing the diameters of the Al disk resonators, enabling excellent overlapping with the molecular vibration. Separately, the detection of a physically adsorbed protein layer on the Al metamaterial is also demonstrated. Surface functionalization with phosphonic acid provides various functional groups to the Al surfaces. Combined with tunable metamaterials, the work herein opens up great opportunities for Al‐based plasmonic nanostructures for biochemical sensing applications.     

X‐Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects

Chemical doping of graphene represents a powerful means of tailoring its electronic properties. Synchrotron‐based X‐ray spectroscopy offers an effective route to investigate the surface electronic and chemical states of functionalizing dopants. In this work, a suite of X‐ray techniques is used, including near edge X‐ray absorption fine structure spectroscopy, X‐ray photoemission spectroscopy, and photoemission threshold measurements, to systematically study plasma‐based chlorinated graphene on different substrates, with special focus on its dopant concentration, surface binding energy, bonding configuration, and work function shift. Detailed spectroscopic evidence of C–Cl bond formation at the surface of single layer graphene and correlation of the magnitude of p‐type doping with the surface coverage of adsorbed chlorine is demonstrated for the first time. It is shown that the chlorination process is a highly nonintrusive doping technology, which can effectively produce strongly p‐doped graphene with the 2D nature and long‐range periodicity of the electronic structure of graphene intact. The measurements also reveal that the interaction between graphene and chlorine atoms shows strong substrate effects in terms of both surface coverage and work function shift.     

Atomic Mechanisms for the Si Atom Dynamics in Graphene: Chemical Transformations at the Edge and in the Bulk

The dynamic behavior of e‐beam irradiated Si atoms in the bulk and at the edges of single‐layer graphene is examined using scanning transmission electron microscopy (STEM). A deep learning network is used to convert experimental STEM movies into coordinates of individual Si and carbon atoms. A Gaussian mixture model is further used to establish the elementary atomic configurations of the Si atoms, defining the bonding geometries and chemical species and accounting for the discrete rotational symmetry of the host lattice. The frequencies and Markov transition probabilities between these states are determined. This analysis enables insight into the defect populations and chemical transformation networks from the atomically resolved STEM data. Here, a clear tendency is observed for the formation of a 1D Si crystal along zigzag direction of graphene edges and for the Si impurity coupling to topological defects in bulk graphene.     

Surface nanocrystalline Si structure and its surface passivation for highly efficient black Si solar cells

19.5% conversion efficiency crystalline silicon (Si) solar cells having simple structure without antireflection coating have been fabricated using the surface structure chemical transfer method which produces a nanocrystalline Si layer simply by contacting catalytic platinum with Si wafers in hydrogen peroxide plus hydrofluoric acid solutions. The reflectivity becomes less than 3% after the surface structure chemical transfer method due to formation of black Si. Deposition of phosphosilicate glass and heat treatment at 925 °C performed for formation of pn‐junction effectively passivate the nanocrystalline Si surface. With this phosphosilicate glass passivation plus the hydrogen treatment at 400 °C, the internal quantum efficiency is greatly improved and reaches 81% at a wavelength of 400 nm. Analysis of ellipsometry data shows that incident light with wavelength shorter than 400 nm is almost completely absorbed by the nanocrystalline Si layer. The high internal quantum efficiency for short wavelength light is attributed to effective surface passivation and the nanocrystalline Si layer band‐gap energy which decreases with the distance from the top of the network structure of the nanocrystalline Si layer. Copyright © 2017 John Wiley & Sons, Ltd.     

First-principles calculation of atomic configurations of carbon and tin near the surface of a silicon thin film used for solar cells

To achieve higher engineering efficiency in solar cells, group-IV compound semiconductors, such as silicon (Si) or germanium (Ge), in the form of thin films containing carbon (C) and/or tin (Sn) atoms, are gaining attention as alternatives to poly-silicon crystals. Atomic configurations of C and Sn atoms near the (001) surface of a Si thin film were analyzed by first-principles calculation based on density functional theory (DFT). The results of the analysis are threefold. First, C and Sn atoms are most stable at the first atomic layer of the Si thin film, and the surface does not affect the stability of C or Sn atoms deeper than the fifth layer. Second, C and Sn atoms deeper than the fifth layer do not affect the stability of newly arrived C and Sn atoms at the surface during film growth. The effects of the (001) surface and interacting C and/or Sn atoms on the thermal-equilibrium concentrations of C and Sn in each layer of the Si thin film were evaluated in consideration of the degeneracy of the atomic configurations. Third, in the case of mono-doping, formation energy of C (Sn) at the (001) surface increases with increasing concentration of surface C (Sn). In the case of co-doping at C/Sn concentration ratio of 1:1, the formation energies of C and Sn decrease with increasing surface concentrations of C and Sn. It is concluded from these results that co-doping enhances the incorporation of C and Sn atoms in the Si thin film.     

Efficient Directed Energy Transfer through Size‐Gradient Nanocrystal Layers into Silicon Substrates

Spectroscopic evidence of directed excitonic energy transfer (ET) is presented through size‐gradient CdSe/ZnS nanocrystal quantum dot (NQD) layers into an underlying Si substrate. NQD monolayers are chemically grafted on hydrogen‐terminated Si surfaces via a self‐assembled monolayer of amine modified carboxy‐alkyl chains. Subsequent NQD monolayers are linked with short alkyldiamines. The linking approach enables accurate positioning and enhanced passivation of the layers. Two different sizes of NQDs (energy donors emitting at 545 nm, and energy acceptors emitting at 585 nm) are used in comparing different monolayer and bilayer samples grafted on SiO₂ and oxide‐free Si surfaces via time‐resolved photoluminescence measurements. The overall efficiency of ET from the top‐layer donor NQDs into Si is estimated to approach ≈90% through a combination of different energy relaxation pathways. These include sequential ET through the intermediate acceptor layer realized mainly via the non‐radiative mechanism and direct ET into the Si substrate realized by means of the radiative coupling. The experimental observations are quantitatively rationalized by the theoretical modeling without introducing any extraneous energy scavenging processes. This indicates that the linker‐assisted fabrication enables the construction of defect‐free, bandgap‐gradient multilayer NQD/Si hybrid structures suitable for thin‐film photovoltaic applications.     

Tailoring the Surface Chemical Reactivity of Transition‐Metal Dichalcogenide PtTe2 Crystals

PtTe₂ is a novel transition‐metal dichalcogenide hosting type‐II Dirac fermions that displays application capabilities in optoelectronics and hydrogen evolution reaction. Here it is shown, by combining surface science experiments and density functional theory, that the pristine surface of PtTe₂ is chemically inert toward the most common ambient gases (oxygen and water) and even in air. It is demonstrated that the creation of Te vacancies leads to the appearance of tellurium‐oxide phases upon exposing defected PtTe₂ surfaces to oxygen or ambient atmosphere, which is detrimental for the ambient stability of uncapped PtTe₂‐based devices. On the contrary, in PtTe₂ surfaces modified by the joint presence of Te vacancies and substitutional carbon atoms, the stable adsorption of hydroxyl groups is observed, an essential step for water splitting and the water–gas shift reaction. These results thus pave the way toward the exploitation of this class of Dirac materials in catalysis.     

Highly transparent modulated surface textured front electrodes for high‐efficiency multijunction thin‐film silicon solar cells

To further increase the efficiency of multijunction thin‐film silicon (TF‐Si) solar cells, it is crucial for the front electrode to have a good transparency and conduction, to provide efficient light trapping for each subcell, and to ensure a suitable morphology for the growth of high‐quality silicon layers. Here, we present the implementation of highly transparent modulated surface textured (MST) front electrodes as light‐trapping structures in multijunction TF‐Si solar cells. The MST substrates comprise a micro‐textured glass, a thin layer of hydrogenated indium oxide (IOH), and a sub‐micron nano‐textured ZnO layer grown by low‐pressure chemical vapor deposition (LPCVD ZnO). The bilayer IOH/LPCVD ZnO stack guarantees efficient light in‐coupling and light trapping for the top amorphous silicon (a‐Si:H) solar cell while minimizing the parasitic absorption losses. The crater‐shaped micro‐textured glass provides both efficient light trapping in the red and infrared wavelength range and a suitable morphology for the growth of high‐quality nanocrystalline silicon (nc‐Si:H) layers. Thanks to the efficient light trapping for the individual subcells and suitable morphology for the growth of high‐quality silicon layers, multijunction solar cells deposited on MST substrates have a higher efficiency than those on single‐textured state‐of‐the‐art LPCVD ZnO substrates. Efficiencies of 14.8% (initial) and 12.5% (stable) have been achieved for a‐Si:H/nc‐Si:H tandem solar cells with the MST front electrode, surpassing efficiencies obtained on state‐of‐the‐art LPCVD ZnO, thereby highlighting the high potential of MST front electrodes for high‐efficiency multijunction solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

p-Si基PTCDA的生长模式

对有机/无机光电探测器PTCDA/p-Si样品表面进行AFM测试,结果表明PTCDA呈岛状生长,各岛成圆丘状,岛的分布不均匀,PTCDA层中存在大量缺陷.原因是p-Si(100)衬底的表面原子悬挂键的作用,使硅原子横向移动满足键合需要形成台阶和其他缺陷.得出PTCDA在p-Si基底上的生长模式为:PTCDA首先在缺陷处聚集,形成许多三维岛状的PTCDA晶核,然后在PTCDA离域大π键的作用下,相邻的两层PTCDA分子存在一定程度的交叠,最终形成岛状结构.     

Mechanism of hemispherical-grained Si formation for dynamic random access memory cells by rapid thermal chemical vapor deposition

An uneven coating made of hemispherical-grained Si (HSG) was formed on an amorphous Si layer by a rapid thermal chemical vapor deposition (CVD) (RTCVD) process. The uneven coating increases the effective surface area of a capacitor electrode in dynamic random access memory (DRAM) cells. The formation of the HSG consists of “seeding” and subsequent isothermal annealing stages. During the seeding stage, nanometer size Si single crystals are formed on the surface of the amorphous Si layer. During rapid thermal annealing at 665°C, under high vacuum, the Si grains grow linearly with increasing temperature and reach an average size of 95 nm after 20 sec. The nucleation and growth of the HSG occurs within a narrow range of temperature and time, which is sufficient for a short diffusion path of Si atoms on the surface of the amorphous Si layer, but insufficient for crystallization of the amorphous Si layer: The HSG coating increases the capacitance of a memory cell by a factor of 2.     

Strained Interface Defects in Silicon Nanocrystals

The surface of silicon nanocrystals embedded in an oxide matrix can contain numerous interface defects. These defects strongly affect the nanocrystals’ photoluminescence efficiency and optical absorption. Dangling‐bond defects are nearly eliminated by H₂ passivation, thus decreasing absorption below the quantum‐confined bandgap and enhancing PL efficiency by an order of magnitude. However, there remain numerous other defects seen in absorption by photothermal deflection spectroscopy; these defects cause non‐radiative recombination that limits the PL efficiency to <15%. Using atomistic pseudopotential simulations, we attribute these defects to two specific types of distorted bonds: Si‐Si and bridging Si‐O‐Si bonds between two Si atoms at the nanocrystal surface.     

The Growth of Transition Metals on H‐Passivated Si(111) Substrates

The growth of Co and Ag layers on wet‐processed H‐passivated Si(111) substrates by molecular beam epitaxy (MBE) has been studied using high resolution scanning tunneling microscopy (STM) with regard to possible applications of the layers in magnetoelectronic devices. Roughness and intermixing at interfaces as functions of deposition temperature and layer thickness are key parameters for the performance of such devices. The initial growth of Co and Ag and the influence of Ag atoms on the Si(111) surface reconstructions provide insight into adatom–substrate interactions.     

Calculation of the variation in the work function caused by adsorption of metal atoms on semiconductors

A simple model is suggested for calculating the variation of the work function Δφ, which is caused by the adsorption of metal atoms on semiconductor surfaces. The model accounts for both the dipole-dipole repulsion of adatoms and metallization of the adsorbed layer for large coverages. The results of calculating Δφ for the adsorption of alkali metals on the Si(001) surface are in good agreement with the experimental data.     

Electrical and microstructural characterisation of an ultrathinsilicon interlayer used in a silicon dioxide/germanium-based MISstructure

Ultrathin (1.0 nm) Si layers have been deposited on Ge(100) surfaces using remote plasma-enhanced chemical vapour deposition (RPECVD) at 350°C followed by in situ RPECVD deposition of an SiO ₂ insulating layer. Micro-structural data from transmission electron microscopy along with elemental analysis from X-ray photoelectron spectroscopy and ion scattering spectroscopy indicate that the Si layer is present and may be pseudomorphic in nature. The formation of a Si/Ge heterojunction prior to oxide deposition minimises the formation of Ge oxides and thus controls the chemical nature of the Ge surface. Indeed, dramatic improvements in the electrical interfacial characteristics were observed in the SiO₂/Si/Ge over the SiO ₂/Ge MIS structure     

The Swiss‐Army‐Knife Self‐Assembled Monolayer: Improving Electron Injection,Stability, and Wettability of Metal Electrodes with a One‐Minute Process

A novel Self‐assembled Monolayer (SAM) forming molecule bisjulolidyldisulfide (9,9'‐disulfanediylbis(2,3,6,7‐tetrahydro‐1H,5H‐pyrido[3,2,1‐ij]quinoline)) is demonstrated which lowers the work function of metal surfaces by ≈1.2 eV and can be deposited in a 1 min process. Bisjulolidyldisulfide exists in a stable disulfide configuration prior to surface exposure and can therefore be stored, handled, and processed in ambient conditions. SAM from bisjulolidyldisulfide are deposited on metal surfaces (Au and Ag), including inkjet printed Ag on polyethylene terephthalate substrates, investigated by photoelectron and infrared spectroscopy, and used as electrodes in n‐type organic field effect transistor (OFET). Treatment of electrodes in OFET devices with with bisjulolidyldisulfide‐SAMs reduces the contact resistance by two orders of magnitude and improves shelf life with respect to pristine metal electrodes. The presented treatment also increases the surfaces wettability and thereby facilitates solution processing of a subsequent layer. These beneficial properties for device performance, processing, and stability, combined with ease of preparation and handling, render this SAM‐forming molecule an excellent candidate for the high‐throughput production of flexible electronic devices.     

Top‐Down Fabrication of High Quality III–V Nanostructures by Monolayer Controlled Sculpting and Simultaneous Passivation

In the fabrication of III–V semiconductor nanostructures for electronic and optoelectronic devices, techniques that are capable of removing material with monolayer precision are as important as material growth to achieve best device performances. A robust chemical treatment is demonstrated using sulfur (S)‐oleylamine (OA) solution, which etches layer by layer in an inverse epitaxial fashion and simultaneously passivates the surface. The application of this process to push the limits of top‐down nanofabrication is demonstrated by the realization of InP‐based high optical quality nanowire arrays, with aspect ratios more than 50, and nanostructures with new topologies. The findings are relevant for other III–V semiconductors and have potential applications in III–V device technologies.     

18.45%‐Efficient Multi‐Crystalline Silicon Solar Cells with Novel Nanoscale Pseudo‐Pyramid Texture

Silicon‐based cells could convert more solar energy to electrical energy if the cells could absorb more light. However, the nanostructured cells have demonstrated relatively low power conversion efficiency even when its reflection is very low; thus, they are still far from becoming real products of the photovoltaic industry. Here, nanoscale pseudo‐pyramid textured multi‐crystalline silicon (Pmc‐Si) solar cells, with the best efficiency of ≈18.45%, are fabricated by using a metal‐catalyzed chemical etching plus a post alkaline etching on an industrial production line. Such Pmc‐Si solar cells have showed similar light trapping ability as single crystalline silicon solar cells of micrometer pyramid texture, and the improved efficiency is mainly ascribed to its enhanced light absorption while the nanostructured surface still keeps acceptable passivation quality, that is, the short‐circuit current density has an increase of ≈300 mA cell^–1, while the open‐circuit voltage has only a slight decrease of ≈1 mV. Further elevations of the efficiency are expected by optimizing both micrometer‐ and nanotextures, and exploring more effective passivation technique. More excitingly, the technique presented here has been verified in the production line for several batches as a real technique of low cost and high efficiency.     

Amorphization of the surface region in epitaxial <Emphasis Type="Italic">n</Emphasis>-GaAs treated with atomic hydrogen

It was found that the atomic-hydrogen treatment of n-GaAs epitaxial samples having initially high-quality surfaces both with a SiO₂ protective film on the n-layer surface and without it can lead to the amorphization of these surfaces and a thin (≈7 nm) surface layer, which is accompanied by the formation of a hydride phase. The lack of a hydrogen sublattice in the near-surface layer can imply that the main driving forces in the amorphization of epitaxial n-GaAs are short-range chemical interactions between hydrogen atoms and also between hydrogen atoms and atoms of the basic matrix of the crystal.