Ge quantum dot arrays grown by ultrahigh vacuum molecular-beam epitaxy on the Si(001) surface: nucleation,morphology, and CMOS compatibility

Issues of morphology, nucleation, and growth of Ge cluster arrays deposited by ultrahigh vacuum molecular beam epitaxy on the Si(001) surface are considered. Difference in nucleation of quantum dots during Ge deposition at low (≲600°C) and high (≳600°C) temperatures is studied by high resolution scanning tunneling microscopy. The atomic models of growth of both species of Ge huts--pyramids and wedges-- are proposed. The growth cycle of Ge QD arrays at low temperatures is explored. A problem of lowering of the array formation temperature is discussed with the focus on CMOS compatibility of the entire process; a special attention is paid upon approaches to reduction of treatment temperature during the Si(001) surface pre-growth cleaning, which is at once a key and the highest-temperature phase of the Ge/Si(001) quantum dot dense array formation process. The temperature of the Si clean surface preparation, the final high-temperature step of which is, as a rule, carried out directly in the MBE chamber just before the structure deposition, determines the compatibility of formation process of Ge-QD-array based devices with the CMOS manufacturing cycle. Silicon surface hydrogenation at the final stage of its wet chemical etching during the preliminary cleaning is proposed as a possible way of efficient reduction of the Si wafer pre-growth annealing temperature.     

Initial stage growth of GexSi1?x layers and Ge quantum dot formation on GexSi1?x surface by MBE

Critical thicknesses of two-dimensional to three-dimensional growth in Ge_xSi_1−x layers were measured as a function of composition for different growth temperatures. In addition to the (2 × 1) superstructure for a Ge film grown on Si(100), the Ge_xSi_1−x layers are characterized by the formation of (2 × n) reconstruction. We measured n for all layers of Ge/Ge_xSi_1−x/Ge heterosystem using our software with respect to the video recording of reflection high-energy electron diffraction (RHEED) pattern during growth. The n reaches a minimum value of about 8 for clear Ge layer, whereas for Ge_xSi_1−x films, n is increased from 8 to 14. The presence of a thin strained film of the Ge_xSi_1−x caused not only the changes in critical thicknesses of the transitions, but also affected the properties of the germanium nanocluster array for the top Ge layer. Based on the RHEED data, the hut-like island form, which has not been previously observed by us between the hut and dome islands, has been detected. Data on the growth of Ge/Ge_xSi_1−x/Ge heterostructures with the uniform array of islands in the second layer of the Ge film have been received.     

Enhanced photoluminescence of multilayer Ge quantum dots on Si(001) substrates by increased overgrowth temperature

Four-bilayer Ge quantum dots (QDs) with Si spacers were grown on Si(001) substrates by ultrahigh vacuum chemical vapor deposition. In three samples, all Ge QDs were grown at 520 °C, while Si spacers were grown at various temperatures (520 °C, 550 °C, and 580 °C). Enhancement and redshift of room temperature photoluminescence (PL) were observed from the samples in which Si spacers were grown at a higher temperature. The enhancement of PL is explained by higher effective electrons capturing in the larger size Ge QDs. Quantum confinement of the Ge QDs is responsible for the redshift of PL spectra. The Ge QDs’ size and content were investigated by atomic force microscopy and Raman scattering measurements.     

Morphological evolution of Ge/Si(001) quantum dot rings formed at the rim of wet-etched pits

We demonstrate the formation of Ge quantum dots in ring-like arrangements around predefined {111}-faceted pits in the Si(001) substrate. We report on the complex morphological evolution of the single quantum dots contributing to the rings by means of atomic force microscopy and demonstrate that by careful adjustment of the epitaxial growth parameters, such rings containing densely squeezed islands can be grown with large spatial distances of up to 5 μm without additional nucleation of randomly distributed quantum dots between the rings.     

Miniband-related 1.4–1.8 μm luminescence of Ge/Si quantum dot superlattices

The luminescence properties of highly strained, Sb-doped Ge/Si multi-layer heterostructures with incorporated Ge quantum dots (QDs) are studied. Calculations of the electronic band structure and luminescence measurements prove the existence of an electron miniband within the columns of the QDs. Miniband formation results in a conversion of the indirect to a quasi-direct excitons takes place. The optical transitions between electron states within the miniband and hole states within QDs are responsible for an intense luminescence in the 1.4–1.8 μm range, which is maintained up to room temperature. At 300 K, a light emitting diode based on such Ge/Si QD superlattices demonstrates an external quantum efficiency of 0.04% at a wavelength of 1.55 μm.     

Structural and optical properties of germanium nanostructures on Si(100) and embedded in high-k oxides

The structural and optical properties of Ge quantum dots (QDs) grown on Si(001) for mid-infrared photodetector and Ge nanocrystals embedded in oxide matrices for floating gate memory devices are presented. The infrared photoluminescence (PL) signal from Ge islands has been studied at a low temperature. The temperature- and bias-dependent photocurrent spectra of a capped Si/SiGe/Si(001) QDs infrared photodetector device are presented. The properties of Ge nanocrystals of different size and density embedded in high-k matrices grown using radio frequency magnetron sputtering have been studied. Transmission electron micrographs have revealed the formation of isolated spherical Ge nanocrystals in high-k oxide matrix of sizes ranging from 4 to 18 nm. Embedded nanocrystals in high band gap oxides have been found to act as discrete trapping sites for exchanging charge carriers with the conduction channel by direct tunneling that is desired for applications in floating gate memory devices.     

Electromodulated reflectance study of self-assembled Ge/Si quantum dots

We perform an electroreflectance spectroscopy of Ge/Si self-assembled quantum dots in the near-infrared and in the mid-infrared spectral range. Up to three optical transitions are observed. The low-energy resonance is proposed to correspond to a band-to-continuum hole transition in the Ge valence band. The other two modulation signals are attributed to the spatially direct transitions between the electrons confined in the L and Δ(4) valleys of the Ge conduction band, and the localized hole states at the Γ point.     

Beneficial defects: exploiting the intrinsic polishing-induced wafer roughness for the catalyst-free growth of Ge in-plane nanowires

We outline a metal-free fabrication route of in-plane Ge nanowires on Ge(001) substrates. By positively exploiting the polishing-induced defects of standard-quality commercial Ge(001) wafers, micrometer-length wires are grown by physical vapor deposition in ultra-high-vacuum environment. The shape of the wires can be tailored by the epitaxial strain induced by subsequent Si deposition, determining a progressive transformation of the wires in SiGe faceted quantum dots. This shape transition is described by finite element simulations of continuous elasticity and gives hints on the equilibrium shape of nanocrystals in the presence of tensile epitaxial strain.

PACS

81.07.Gf; 68.35.bg; 68.35.bj; 62.23.Eg     

In situ Control of Si/Ge Growth on Stripe-Patterned Substrates Using Reflection High-Energy Electron Diffraction and Scanning Tunneling Microscopy

Si and Ge growth on the stripe-patterned Si (001) substrates is studied using in situ reflection high-energy electron diffraction (RHEED) and scanning tunneling microscopy (STM). During Si buffer growth, the evolution of RHEED patterns reveals a rapid change of the stripe morphology from a multifaceted “U” to a single-faceted “V” geometry with {119} sidewall facets. This allows to control the pattern morphology and to stop Si buffer growth once a well-defined stripe geometry is formed. Subsequent Ge growth on “V”-shaped stripes was performed at two different temperatures of 520 and 600°C. At low temperature of 520°C, pronounced sidewall ripples are formed at a critical coverage of 4.1 monolayers as revealed by the appearance of splitted diffraction streaks in RHEED. At 600°C, the ripple onset is shifted toward higher coverages, and at 5.2 monolayers dome islands are formed at the bottom of the stripes. These observations are in excellent agreement with STM images recorded at different Ge coverages. Therefore, RHEED is an efficient tool for in situ control of the growth process on stripe-patterned substrate templates. The comparison of the results obtained at different temperature reveals the importance of kinetics on the island formation process on patterned substrates.     

Formation of Nanopits in Si Capping Layers on SiGe Quantum Dots

In-situ annealing at a high temperature of 640°C was performed for a low temperature grown Si capping layer, which was grown at 300°C on SiGe self-assembled quantum dots with a thickness of 50 nm. Square nanopits, with a depth of about 8 nm and boundaries along 〈110〉, are formed in the Si capping layer after annealing. Cross-sectional transmission electron microscopy observation shows that each nanopit is located right over one dot with one to one correspondence. The detailed migration of Si atoms for the nanopit formation is revealed by in-situ annealing at a low temperature of 540°C. The final well-defined profiles of the nanopits indicate that both strain energy and surface energy play roles during the nanopit formation, and the nanopits are stable at 640°C. A subsequent growth of Ge on the nanopit-patterned surface results in the formation of SiGe quantum dot molecules around the nanopits.     

Formation mechanisms of nano and microcones by laser radiation on surfaces of Si,Ge, and SiGe crystals

In this work we study the mechanisms of laser radiation interaction with elementary semiconductors such as Si and Ge and their solid solution SiGe. As a result of this investigation, the mechanisms of nanocones and microcones formation on a surface of semiconductor were proposed. We have shown the possibility to control the size and the shape of cones both by the laser. The main reason for the formation of nanocones is the mechanical compressive stresses due to the atoms’ redistribution caused by the gradient of temperature induced by strongly absorbed laser radiation. According to our investigation, the nanocone formation mechanism in semiconductors is characterized by two stages. The first stage is characterized by formation of a p-n junction for elementary semiconductors or of a Ge/Si heterojunction for SiGe solid solution. The generation and redistribution of intrinsic point defects in elementary semiconductors and Ge atoms concentration on the irradiated surface of SiGe solid solution in temperature gradient field take place at this stage due to the thermogradient effect which is caused by strongly absorbed laser radiation. The second stage is characterized by formation of nanocones due to mechanical plastic deformation of the compressed Ge layer on Si. Moreover, a new 1D-graded band gap structure in elementary semiconductors due to quantum confinement effect was formed. For the formation of microcones Ni/Si structure was used. The mechanism of the formation of microcones is characterized by two stages as well. The first stage is the melting of Ni film after irradiation by laser beam and formation of Ni islands due to surface tension force. The second step is the melting of Ni and subsequent manifestations of Marangoni effect with the growth of microcones.     

CMOS-compatible dense arrays of Ge quantum dots on the Si(001) surface: hut cluster nucleation, atomic structure and array life cycle during UHV MBE growth

We report a direct observation of Ge hut nucleation on Si(001) during UHV molecular beam epitaxy at 360°C. Nuclei of pyramids and wedges were observed on the wetting layer (WL) (M × N) patches starting from the coverage of 5.1 Å and found to have different structures. Atomic models of nuclei of both hut species have been built as well as models of the growing clusters. The growth of huts of each species has been demonstrated to follow generic scenarios. The formation of the second atomic layer of a wedge results in rearrangement of its first layer. Its ridge structure does not repeat the nucleus. A pyramid grows without phase transitions. A structure of its vertex copies the nucleus. Transitions between hut species turned out to be impossible. The wedges contain point defects in the upper corners of the triangular faces and have preferential growth directions along the ridges. The derived structure of the {105} facet follows the paired dimer model. Further growth of hut arrays results in domination of wedges, and the density of pyramids exponentially drops. The second generation of huts arises at coverages >10 Å; new huts occupy the whole WL at coverages ~14 Å. Nanocrystalline Ge 2D layer begins forming at coverages >14 Å.     

Photovoltaic Ge/Si quantum dot detectors operating in the mid-wave atmospheric window (3-5 micrometers)

ABSTRACT: Ge/Si quantum dots fabricated by molecular-beam epitaxy at 500C are overgrown with Si at different temperatures Tcap, and effect of boron delta-doping of Si barriers on the mid-infrared photoresponse was investigated. The photocurrent maximum shifts from 2.3 to 3.9 micrometer with increasing Tcap from 300 to 750C. Within the sample set, we examined devices with different positions of the delta-doping layer with respect to the dot plane, different distances between the delta-doping layer and the dot plane d, and different doping densities pB. All detectors show pronounced photovoltaic behavior implying the presence of an internal inversion asymmetry due to the placing dopants in the barriers. The best performance was achieved for the device with Tcap=600C, pB=12x10^{11} cm^{-2}, and d=5 nm in a photovoltaic regime. At a sample temperature of 90K and no applied bias, a responsivity of 0.83 mA/W and detectivity of 8x10^{10} cmHz^{1/2}/W at lambda=3.4 micrometer were measured under normal incidence infrared radiation.     

硅基纳米b-SiC量子点列阵的制备

报道了用两步自组装法制备硅基纳米碳化硅量子点列阵. 先将两种硅烷偶联剂均匀有序地偶联到洁净的单晶硅片上，其中一种偶联剂能打破C60上的碳碳双键而使C60通过偶联剂均匀有序地分布在硅片的表面上. 然后用夹心法或覆盖法将样品在900℃的氮气氛中退火20 min，使C60分解成活性碳，与周围的硅原子结合生成碳化硅，碳化硅分子的自组装形成了碳化硅纳米晶粒(量子点)，C60在硅表面的有序排列导致了纳米碳化硅量子点列阵形成.     

The curious case of exploding quantum dots: anomalous migration and growth behaviors of Ge under Si oxidation

We have previously demonstrated the unique migration behavior of Ge quantum dots (QDs) through Si₃N₄ layers during high-temperature oxidation. Penetration of these QDs into the underlying Si substrate however, leads to a completely different behavior: the Ge QDs ‘explode,’ regressing back almost to their origins as individual Ge nuclei as formed during the oxidation of the original nanopatterned SiGe structures used for their generation. A kinetics-based model is proposed to explain the anomalous migration behavior and morphology changes of the Ge QDs based on the Si flux generated during the oxidation of Si-containing layers.     

The Investigation of Selective Ge Nano-Dot Formation by Excimer Laser Annealing with Pre-Pattern Free

ABSTRACT: Localized Ge nano-dot formation by laser treatment was investigated and discussed in terms of strain distribution. The advantage of this technique is patterning localization of nano-dots without selective epitaxial growth (SEG), reducing costs and improving throughput. Self-assembled Ge nano-dots produced by excimer laser annealing statistically distributed dot density and size dependent on laser energy. Improvement in the crystallization quality of the dots was also studied, and a strain analysis was undertaken.     

Anisotropic Confinement,Electronic Coupling and Strain Induced Effects Detected by Valence-Band Anisotropy in Self-Assembled Quantum Dots

A method to determine the effects of the geometry and lateral ordering on the electronic properties of an array of one-dimensional self-assembled quantum dots is discussed. A model that takes into account the valence-band anisotropic effective masses and strain effects must be used to describe the behavior of the photoluminescence emission, proposed as a clean tool for the characterization of dot anisotropy and/or inter-dot coupling. Under special growth conditions, such as substrate temperature and Arsenic background, 1D chains of In_0.4Ga_0.6 As quantum dots were grown by molecular beam epitaxy. Grazing-incidence X-ray diffraction measurements directly evidence the strong strain anisotropy due to the formation of quantum dot chains, probed by polarization-resolved low-temperature photoluminescence. The results are in fair good agreement with the proposed model.     

Influence of delta-doping on the hole capture probability in Ge/Si quantum dot mid-infrared photodetectors

We study the effect of delta-doping on the hole capture probability in ten-period p-type Ge quantum dot photodetectors. The boron concentration in the delta-doping layers is varied by either passivation of a sample in a hydrogen plasma or by direct doping during the molecular beam epitaxy. The devices with a lower doping density is found to exhibit a lower capture probability and a higher photoconductive gain. The most pronounced change in the trapping characteristics upon doping is observed at a negative bias polarity when the photoexcited holes move toward the δ-doping plane. The latter result implies that the δ-doping layers are directly involved in the processes of hole capture by the quantum dots.     

Ge/Si异质键合界面纳米级氧化层对Ge/Si异质结光电特性调控机制

由于Ge/Si存在4.2%晶格失配,Si基外延Ge中的穿透位错密度(TDD)极高,导致器件暗电流偏大。低温Ge/Si异质键合可以通过抑制失配位错传播降低Ge薄膜中的TDD,在高质量大失配薄膜制备方面展现出巨大的潜力。然而,Ge/Si键合界面由于亲水反应形成的纳米级氧化层会对异质结性能产生影响。基于载流子基本方程,在键合界面构建载流子非局域量子隧穿模型,通过半经典近似解法研究Ge/Si异质键合界面氧化层厚度(dO)对异质结暗电流、总电流、光谱响应、带宽等性能的影响,并揭示异质结性能影响机制。研究表明:随着dO的增加,氧化层对载流子的阻挡效应增强,导致器件暗电流、总电流和光谱响应下降。由于氧化层的分压效应,dO的增加导致Ge层中电场下降,载流子速率降低,进而导致异质结高频特性变差。为确保键合Ge/Si异质结优异的光电特性,dO必须控制在0.50 nm以内。     

Excitation Intensity Driven PL Shifts of SiGe Islands on Patterned and Planar Si(001) Substrates: Evidence for Ge-rich Dots in Islands

For randomly nucleated SiGe/Si(001) islands, a significantly stronger blue-shift of the PL spectra as a function of the excitation intensity is observed when compared to islands grown on patterned substrates side by side within the same run in a solid source molecular beam epitaxy chamber. We ascribe this different PL behavior to the much larger inhomogeneity of the Ge distribution in islands on planar substrates when compared to islands grown on pit-patterned ones, as observed previously. 3D band-structure calculations show that Ge-rich inclusions of approximately 5 nm diameter at the apex of the islands can account for the observed differences in the PL spectra. The existence of such inclusions can be regarded as a quantum dot in an island and is in agreement with recent nano-tomography experiments.