Growth of GaInAs/AlInAs heterostructure nanowires for long-wavelength photon emission

We investigated the growth of GaInAs/AlInAs heterostructure nanowires on InP(111)B and Si(111) substrates in a metalorganic vapor phase epitaxy reactor. Au colloids were used to deposit Au catalysts 20 and 40 nm in diameter on the substrate surfaces. We obtained vertical GaInAs and AlInAs nanowires on InP(111)B surfaces. The GaInAs nanowires capped with GaAs/AlInAs layers show room-temperature photoluminescence. The peak exhibits a blue-shift when the Ga content in the core GaInAs nanowire is increased. For the GaInAs/AlInAs heterostructure growth, it is possible to change the Ga content sharply but Al also exists in the GaInAs layer regions. We also found that the ratios of Ga and Al contents to In content tend to increase and the axial growth rate to decrease along the nanowire toward the top. We were also able to make vertical GaInAs nanowires on Si(111) surfaces after a short growth of GaP and InP.     

Morphology- and orientation-controlled gallium arsenide nanowires on silicon substrates

GaAs nanowires were epitaxially grown on Si(001) and Si(111) substrates by using Au-catalyzed vapor-liquid-solid (VLS) growth in a solid source molecular beam epitaxy system. Scanning electron microscopy analysis revealed that almost all the GaAs nanowires were grown along <111> directions on both Si substrates for growth conditions investigated. The GaAs nanowires had a very uniform diameter along the growth direction. X-ray diffraction data and transmission electron microscopy analysis revealed that the GaAs<111> nanowires had a mixed crystal structure of the hexagonal wurtzite and the cubic zinc-blende. Current-voltage characteristics of junctions formed by the epitaxially grown GaAs nanowires and the Si substrate were investigated by using a current-sensing atomic force microscopy.     

Strain accommodation in Ga-assisted GaAs nanowires grown on silicon (111)

We study the mechanism of lattice parameter accommodation and the structure of GaAs nanowires (NWs) grown on Si(111) substrates using the Ga-assisted growth mode in molecular beam epitaxy. These nanowires grow preferentially in the zincblende structure, but contain inclusions of wurtzite at the base. By means of grazing incidence x-ray diffraction and high-resolution transmission electron microscopy of the NW-substrate interface, we show that the lattice mismatch between the NW and the substrate is released immediately after the beginning of NW growth through the inclusion of misfit dislocations, and no pseudomorphic growth is obtained for NW diameters down to 10 nm. NWs with a diameter above 100 nm exhibit a rough interface towards the substrate, preventing complete plastic relaxation. Consequently, these NWs exhibit a residual compressive strain at their bottom. In contrast, NWs with a diameter of 50 nm and below are completely relaxed because the interface is smooth.     

In(x)Ga(₁-x)As nanowires on silicon: one-dimensional heterogeneous epitaxy, bandgap engineering, and photovoltaics

We report on the one-dimensional (1D) heteroepitaxial growth of In(x)Ga(1-x)As (x = 0.2-1) nanowires (NWs) on silicon (Si) substrates over almost the entire composition range using metalorganic chemical vapor deposition (MOCVD) without catalysts or masks. The epitaxial growth takes place spontaneously producing uniform, nontapered, high aspect ratio NW arrays with a density exceeding 1 × 10(8)/cm(2). NW diameter (～30-250 nm) is inversely proportional to the lattice mismatch between In(x)Ga(1-x)As and Si (～4-11%), and can be further tuned by MOCVD growth condition. Remarkably, no dislocations have been found in all composition In(x)Ga(1-x)As NWs, even though massive stacking faults and twin planes are present. Indium rich NWs show more zinc-blende and Ga-rich NWs exhibit dominantly wurtzite polytype, as confirmed by scanning transmission electron microscopy (STEM) and photoluminescence spectra. Solar cells fabricated using an n-type In(0.3)Ga(0.7)As NW array on a p-type Si(111) substrate with a ～ 2.2% area coverage, operates at an open circuit voltage, V(oc), and a short circuit current density, J(sc), of 0.37 V and 12.9 mA/cm(2), respectively. This work represents the first systematic report on direct 1D heteroepitaxy of ternary In(x)Ga(1-x)As NWs on silicon substrate in a wide composition/bandgap range that can be used for wafer-scale monolithic heterogeneous integration for high performance photovoltaics.     

Crystal structure transfer in core/shell nanowires

Structure engineering is an emerging tool to control opto-electronic properties of semiconductors. Recently, control of crystal structure and the formation of a twinning superlattice have been shown for III-V nanowires. This level of control has not been obtained for Si nanowires, the most relevant material for the semiconductor industry. Here, we present an approach, in which a designed twinning superlattice with the zinc blende crystal structure or the wurtzite crystal structure is transferred from a gallium phosphide core wire to an epitaxially grown silicon shell. These materials have a difference in lattice constants of only 0.4%, which allows for structure transfer without introducing extra defects. The twinning superlattices, periodicity, and shell thickness can be tuned with great precision. Arrays of free-standing Si nanotubes are obtained by a selective wet-chemical etch of the core wire.     

Catalyst-free synthesis of well-aligned ZnO nanowires on In0.2Ga0.8N, GaN, and Al0.25Ga0.75N substrates

Well-aligned ZnO nanowires have been synthesized vertically on In0.2Ga0.8N, GaN, and Al0.25Ga0.75N substrates, using a catalyst-free carbon thermal-reduction vapor phase deposition method for the first time. The as-synthesized nanowires are single crystalline wurtzite structure, and have a growth direction of [0001]. Each nanowire has a smooth surface, and uniform diameter along the growth direction. The average diameter and length of these nanowires are 120-150 nm, and 3-10 )m, respectively. We suggest that the growth mechanism follow a self-catalyzing growth model. Excitonic emission peaked around 385 nm dominates the room-temperature photoluminescence spectra of these nanowires. The room-temperature photoluminescence and Raman scattering spectra show that these nanowires have good optical quality with very less structural defects.     

Surfactant effect of Au on Ga adsorption on GaAs(0001) surface

Basing on the density-functional theory, we have investigated the atomistic and electronic structures of Ga adsorption on GaAs(0001) surface with pre-absorbed Au monolayer for the understanding of the surfactant effect of Au on the growth of GaAs nanowires. The results show that the deposited Au layer enhances significantly the stability of the Ga adatom on substrate compared to the direct adsorption of Ga on GaAs(0001) surface. The reason is that more electrons of the Ga 6p levels are transferred toward surface bands of substrate because of mediation of the Au layer. It is revealed that Au plays a catalyst role to assist the adsorption of Ga on GaAs(0001) surface. These results offer valuable information in the epitaxial growth of semiconductor nanowires.     

Photoluminescence study of GaAs thin films and nanowires grown on Si(111)

Mg-doped GaAs nanowires have been grown by molecular beam epitaxy on a partially Au-coated Si(111) substrate by the vapor–liquid–solid mechanism. Outside the coated areas, a thin film of GaAs was grown epitaxially at the same time. The optical properties in both parts of the sample were investigated by photoluminescence spectroscopy, as a function of temperature. A structured emission in the range ～1.25–1.55 eV was observed at 10 K and the resemblances in both cases were identified. The radiative transitions are discussed with relevance to known defect centers in the GaAs thin films and to their possible relation with the zinc-blende and wurtzite phases in the nanowires. The presence of both crystalline phases in the nanowires was confirmed by μ-Raman spectroscopy.     

New mode of vapor-liquid-solid nanowire growth

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.     

High yield of self-catalyzed GaAs nanowire arrays grown on silicon via gallium droplet positioning

We report and detail a method to achieve growth of vertical self-catalyzed GaAs nanowires directly on Si(111) with a near-perfect vertical yield, using electron-beam-defined arrays of holes in a dielectric layer and molecular beam epitaxy. In our conditions, GaAs nanowires are grown along a vapor-liquid-solid mechanism, using in?situ self-forming Ga droplets. The focus of this paper is to understand the role of the substrate preparation and of the pre-growth conditioning. Without changing temperature or the V/III ratio, the yield of vertical nanowires is increased incrementally up to 95%. The possibility to achieve very dense arrays, with center-to-center inter-wire distances less than 100?nm, is demonstrated.     

Physical consequences of the equivalence of conditions for the steady-state growth of nanowires and the nucleation on triple phase line

A new theoretical model describing the steady-state growth and crystalline structure of semiconductor nanowires (NWs) is proposed and its physical consequences are considered. It is demonstrated that the Nebol’sin-Shchetinin condition (nonwetting of the NW side surface by the liquid drop) necessary for the steady-state growth of NWs according to the vapor-liquid-solid (VLS) mechanism is equivalent to the Glas condition of nucleation on the triple phase line for the monocentric NW growth. An energy criterion for the steady-state growth of NWs is formulated in the general case of faceted NW side surface. Effective surface energies are found that determine the activation barrier for nucleation at the NW top. Based on the proposed model, the issue of determining the III–V semiconductor NW crystal structure (cubic zinc blende type versus hexagonal wurtzite type) is considered. In particular, it is shown that a decrease in the surface energy of a catalyst must lead to the predominant formation of a cubic phase, which is confirmed by experimental data on the growth of GaAs nanowires according to the VLS mechanism with Au and Ga catalysts.     

GaAs:Mn nanowires grown by molecular beam epitaxy of (Ga,Mn)as at MnAs segregation conditions

GaAs:Mn nanowires were obtained on GaAs(001) and GaAs(111)B substrates by molecular beam epitaxial growth of (Ga,Mn)As at conditions leading to MnAs phase separation. Their density is proportional to the density of catalyzing MnAs nanoislands, which can be controlled by the Mn flux and/or the substrate temperature. After deposition corresponding to a 200 nm thick (Ga,Mn)As layer the nanowires are around 700 nm long. Their shapes are tapered, with typical diameters around 30 nm at the base and 7 nm at the tip. The wires grow along the 111 direction, i.e., along the surface normal on GaAs(111)B and inclined on GaAs(001). In the latter case they tend to form branches. Being rooted in the ferromagnetic semiconductor (Ga,Mn)As, the nanowires combine one-dimensional properties with the magnetic properties of (Ga,Mn)As and provide natural, self-assembled structures for nanospintronics.     

Growth of GaAs Nanowires on Si Substrates Using a Molecular Beam Epitaxy

Au-catalyzed GaAs nanowires were grown on Si substrates by vapor-liquid-solid growth method using a molecular beam epitaxy (MBE). The MBE growth could produce controlled crystalline orientation and uniform diameter along the wire axis of the GaAs nanowires by adjusting growth conditions including growth temperature and V/III flux ratio. Growths of GaAslang001rang as well as GaAslang111rang nanowires were observed by transmission electron microscopy and scanning electron microscopy. Epitaxially grown GaAslang111rang nanowires on a Si(111) substrate were verified through x-ray diffraction out-of-plane 2thetas/omega-scans. A strong room-temperature photoluminescence (PL) was observed from the epitaxially grown GaAslang111rang nanowires on a Si(100) substrate. Results of low-temperature (10 K) PL measurements and current-sensing atomic force microscopy indicated that the GaAs nanowires on a Si substrate were unintentionally doped with Si     

The near-infrared photoluminescence of GaAs epilayers grown on Si

In heteroepitaxial GaAs grown on Si (GaAs/Si) there exist deep levels caused by various charged states of defects because of large lattice misfit and thermal expansion mismatch between GaAs and Si. The temperature- and excitation intensity-dependent near-infrared photoluminescence spectra related to the deep levels present in GaAs/Si grown by metal–organic chemical vapour deposition with different ratios of [As]/[Ga] were studied. In terms of configuration coordinate model, the Franck–Condon shifts of near-infrared emission in GaAs/Si were obtained by measuring the variation in full width at half-maximum with temperature. The band-gap shifts with temperature and with mismatch strain in GaAs/Si were considered. Taking Franck–Condon and band-gap shifts into account, the energy relations for the transitions from donor to acceptor, from conduction band to acceptor and from donor to valence band were revised. According to these transition-energy relations and the emission characteristics of GaAs/Si epilayers, three emissions were interpreted as the recombination luminescence of donor–acceptor pairs and two emissions were caused by As interstitial–Ga vacancy complex centres. This revised version was published online in November 2006 with corrections to the Cover Date.     

硅基正六边形氮化镓纳米颗粒薄膜的制备,结构和形貌特性

本文通过在ZnO/Si(111)衬底上,利用JCK-500A型射频磁控溅射系统溅射氧化镓靶得到氧化镓薄膜.然后将硅基Ga2O3置于管武石英炉中,在850℃的氨化温度下氨化15min后,成功制备出GaN薄膜,该薄膜由正六边形的晶粒组成.X射线衍射(XRD)表明GaN具有六方纤锌矿结构,晶格常数为a=0.318nm和c=0.518nm.X射线光电子能谱(XPS)的测试确定了样品中Ga-N键的形成,并且Ga和N的化学计量比为1:1.用扫描电镜(SEM)和原子力显微镜(AFM)观察发现,样品表面非常光滑和平整.透射电镜(TEM)表明薄膜由正六边形晶粒组成.选区电子衍射(SAED)进一步验证了GaN薄膜的六方纤锌矿结构.最后,简单地讨论了其生长机制.     

Direct observation of a noncatalytic growth regime for GaAs nanowires

We identify a new noncatalytic growth regime for molecular beam epitaxially grown GaAs nanowires (NWs) that may provide a route toward axial heterostructures with discrete material boundaries and atomically sharp doping profiles. Upon increase of the As/Ga flux ratio, the growth mode of self-induced GaAs NWs on SiO(2)-masked Si(111) is found to exhibit a surprising discontinuous transition in morphology and aspect ratio. For effective As/Ga ratios <1, in situ reflection high-energy electron diffraction measurements reveal clear NW growth delay due to formation of liquid Ga droplets since the growth proceeds via the vapor-liquid-solid mechanism. In contrast, for effective As/Ga ratios >1 an immediate onset of NW growth is observed indicating a transition to droplet-free, facet-driven selective area growth with low vertical growth rates. Distinctly different microstructures, facet formation and either the presence or absence of Ga droplets at the apex of NWs, are further elucidated by transmission electron microscopy. The results show that the growth mode transition is caused by an abrupt change from As- to Ga-limited conditions at the (111)-oriented NW growth front, allowing precise tuning of the dominant growth mode.     

In(Ga)As quantum dot formation on group-III assisted catalyst-free InGaAs nanowires

Growth of GaAs and In(x)Ga(1-x)As nanowires by the group-III assisted molecular beam epitaxy growth method on (001)GaAs/SiO(2) substrates is studied in dependence on growth temperature, with the objective of maximizing the indium incorporation. Nanowire growth was achieved for growth temperatures as low as 550?°C. The incorporation of indium was studied by low temperature micro-photoluminescence spectroscopy, Raman spectroscopy and electron energy loss spectroscopy. The results show that the incorporation of indium achieved by lowering the growth temperature does not have the effect of increasing the indium concentration in the bulk of the nanowire, which is limited to 3-5%. For growth temperatures below 575?°C, indium rich regions form at the surface of the nanowires as a consequence of the radial growth. This results in the formation of quantum dots, which exhibit spectrally narrow luminescence.     

Wurtzite to zinc blende phase transition in GaAs nanowires induced by epitaxial burying

We bury vertical free-standing core-shell GaAs/AlGaAs nanowires by a planar GaAs overgrowth. As the nanowires get buried, their crystalline structure progressively transforms: whereas the upper emerging part retains its initial wurtzite structure, the buried part adopts the zinc blende structure of the burying layer. The burying process also suppresses all the stacking faults that existed in the wurtzite nanowires. We consider two possible mechanisms for the structural transition upon burying, examine how they can be discriminated from each other, and explain why the transition is favorable.     

Diameter-dependent or independent: toward a mechanistic understanding of the vapor-liquid-solid si nanowire growth rate

Si nanowires have received continued increased attention because they keep the promise of monolithic integration of high-performance semiconductors with new functionality into existing silicon technology. Most Si nanowires are grown by vapor-liquid-solid mechanism, and despite many years of study, this growth mechanism remains under lively debate. For instance, contradictory results have been reported on the effect of diameter size on nanowire growth rate. Here, we developed a universal kinetic model of Si nanowire growth based on surface diffusion which takes into account adatom diffusion from the sidewall and substrate surface into the liquid droplet as well as the Gibbs-Thomson effect. Our analysis shows that the diameter independence for Si nanowires is affected by the interplay between the Gibbs-Thomson effect and the surface diffusion, whereas the diameter dependence is mainly influenced by the Gibbs-Thomson effect. The results based on the proposed model are in good agreement with experimental data.     

Manganese-induced growth of GaAs nanowires

GaAs nanowires have been grown on SiO2 and GaAs by molecular beam epitaxy using manganese as growth catalyst. Transmission electron microscopy shows that the wires have a wurtzite-type lattice and that alpha-Mn particles are found at the free end of the wires. X-ray absorption fine structure measurements reveal the presence of a significant fraction of Mn-As bonds, suggesting Mn diffusion and incorporation during wire growth. Transport measurements indicate that the wires are p-type, as expected from doping of GaAs with Mn.