Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

Germanium on sapphire

This paper explores the potential of germanium on sapphire (GeOS) wafers as a universal substrate for System on a Chip (SOC), mm wave integrated circuits (MMICs) and optical imagers. Ge has a lattice constant close to that of GaAs enabling epitaxial growth. Ge, GaAs and sapphire have relatively close temperature coefficients of expansion (TCE), enabling them to be combined without stress problems. Sapphire is transparent over the range 0.17 to 5.5 µm and has a very low loss tangent (a) for frequencies up to 72 GHz. Ge bonding to sapphire substrates has been investigated with regard to micro-voids and electrical quality of the Ge back interface. The advantages of a sapphire substrate for integrated inductors, coplanar waveguides and crosstalk suppression are also highlighted. MOS transistors have been fabricated on GeOS substrates, produced by the Smart-cut process, to illustrate the compatibility of the substrate with device processing. © 2008 World Scientific Publishing Company.

Electrical characterization of ALD Al2O3 and HfO2 films on germanium

Al2O3 and HfO2 films were deposited on germanium substrates by atomic layer deposition (ALD) and analyzed by MOS capacitor electrical characterization. In-situ plasma nitridation performed prior to ALD was found to improve the stability of the interface. For Al 2O3/GeON/Ge capacitors, a 450°C anneal in nitrogen ambient reduced hysteresis and oxide fixed charge to 90 mV and 1012 cm-2 respectively, with low leakage current density. On the contrary, degradation was observed for un-nitrided Al2O3/Ge capacitors after 300 and 400°C post-metal anneals. HfO2/GeON/Ge capacitors benefitted from a 400°C densification anneal but exhibited degradation after post-metal anneals at temperatures greater than 300°C. This degradation is attributed to the influence of Al electrodes on the HfO 2 gate stack. HfO2 is considered to be a suitable material for the gate stack and Al2O3 for the buried dielectric in a GeOI structure. ©The Electrochemical Society.

Design, Manufacture and Performance of Germanium Bipolar Transistors

Germanium NPN bipolar transistors have been manufactured using phosphorus and boron ion implantation processes. Implantation and subsequent activation processes have been investigated for both dopants. Full activation of phosphorus implants has been achieved with RTA schedules at 535?C without significant junction diffusion. However, boron implant activation was limited and diffusion from a polysilicon source was not practical for base contact formation. Transistors with good output characteristics were achieved with an Early voltage of 55V and common emitter current gain of 30. Both Silvaco process and device simulation tools have been successfully adapted to model the Ge BJT(bipolar junction transistor) performance.

Time dependence of the spatial coherence of the 23.6- and 23.2-nm radiation from the germanium soft-x-ray laser

The time dependence of the spatial coherence of the combined spectral lines at 23.2 and 23.6 nm from the Ge XXIII collisionally pumped soft-x-ray laser with a double-slab target is examined within a single nanosecond pulse by use of Young's interference fringes and a streak camera. High source intensity is linked with low spatial coherence and vice verse. Calculations of the source intensity, size, and position have also been made; these calculations refer to a single-slab source. Comparison between the observed and calculated intensities, and of the source sizes both calculated and derived from the Young's fringes by interpretation with a Gaussian model of source emission, show good agreement in general trends. (C) 1998 Optical Society of America [S0740-3224(98)01905-5].

A study to optimise the temporal drive pulse structure for efficient XUV lasing on the J=0-1, 19.6 nm line of Ge XXIII

Short pulses of 100 ps FWHM duration at 1.06 mu m wavelength are used as the pump source for driving the J = 0-1, 19.6 nm, Ne-like germanium X-ray laser. Different combinations of short pulses are investigated and quantitatively compared. Configurations investigated include a single pulse, double pulses at 400 ps and 800 ps separation, single pulses with prepulses and double pulses with prepulses. Data are presented in the form of integrated energy measurements, and supported by modelling. The most efficient short pulse configurations are shown to be orders of magnitude more effective than pumping with nanosecond duration pulses. (C) 1997 Elsevier Science B.V.

LASING PROPERTIES OF THE J = 0-1 AND THE J = 2-1 LINES OF A NEON-LIKE GERMANIUM SOFT-X-RAY LASER

Lasing properties of a collisional-excitation Ne-like Ge soft-x-ray laser have been studied with exploding-foil, single-slab, and double-slab targets under identical pumping conditions. Experimental results for the angular intensity distributions and the temporal variations of the lasing intensities are examined with a hydrodynamic code and ray-trace calculations. The observed angular distribution are well reproduced by these analyses, and it is found that the effective gain regions are located on the high-density side of the expected gain regions. It is shown that the observed lasing intensity of the J = 0 to J = 1 line is strongly correlated with the temporal change of the calculated electron temperature for both the slab and the exploding-foil targets.

AN INJECTOR AMPLIFIER DOUBLE TARGET CONFIGURATION FOR THE NE-LIKE GE X-RAY LASER SCHEME

The XUV lasing output from one germanium slab target has been efficiently coupled into, and further amplified in, a second plasma produced by irradiation of a similar target from the opposite direction. The operation of such a double target was shown to be strongly dependent on the distance by which the two target surfaces were displaced. The line brightness peaked for a surface displacement of approximately 200-mu-m and it was observed that the pointing direction of one output beam could be controlled by the surface separation in an asymmetric geometry. Gain length products of approximately 16 with estimated output powers close to the megawatt level were achieved on both the 23.2 and 23.6 nm J=2-1 transitions for an optimised target configuration. Maximum effective coupling efficiencies of the individual outputs from double targets, comprising 2.2 and 1.4 cm length components, approached 100% for beams propagating from the shorter to the longer target.

High temperature thermal stability of the HfO2/Ge (100) interface as a function of surface preparation studied by synchrotron radiation core level photo emission

High resolution soft x-ray photoemission spectroscopy (SXPS) have been used to study the high temperature thermal stability of ultra-thin atomic layer deposited (ALD) HfO2 layers (∼1 nm) on sulphur passivated and hydrofluoric acid (HF) treated germanium surfaces. The interfacial oxides which are detected for both surface preparations following HfO2 deposition can be effectively removed by annealing upto 700 °C without any evidence of chemical interaction at the HfO2/Ge interface. The estimated valence and conduction band offsets for the HfO2/Ge abrupt interface indicated that effective barriers exist to inhibit carrier injection.

Fermi level de-pinning of aluminium contacts to n-type germanium using thin atomic layer deposited layers

Fermi-level pinning of aluminium on n-type germanium (n-Ge) was reduced by insertion of a thin interfacial dielectric by atomic layer deposition. The barrier height for aluminium contacts on n-Ge was reduced from 0.7 eV to a value of 0.28 eV for a thin Al2O3 interfacial layer (∼2.8 nm). For diodes with an Al2O3 interfacial layer, the contact resistance started to increase for layer thicknesses above 2.8 nm. For diodes with a HfO2 interfacial layer, the barrier height was also reduced but the contact resistance increased dramatically for layer thicknesses above 1.5 nm.

Nanocrystalline Ge Flash Memories: Electrical Characterization and Trap Engineering

Conventional floating gate non-volatile memories (NVMs) present critical issues for device scalability beyond the sub-90 nm node, such as gate length and tunnel oxide thickness reduction. Nanocrystalline germanium (nc-Ge) quantum dot flash memories are fully CMOS compatible technology based on discrete isolated charge storage nodules which have the potential of pushing further the scalability of conventional NVMs. Quantum dot memories offer lower operating voltages as compared to conventional floating-gate (FG) Flash memories due to thinner tunnel dielectrics which allow higher tunneling probabilities. The isolated charge nodules suppress charge loss through lateral paths, thereby achieving a superior charge retention time. Despite the considerable amount of efforts devoted to the study of nanocrystal Flash memories, the charge storage mechanism remains obscure. Interfacial defects of the nanocrystals seem to play a role in charge storage in recent studies, although storage in the nanocrystal conduction band by quantum confinement has been reported earlier. In this work, a single transistor memory structure with threshold voltage shift, Vth, exceeding ~1.5 V corresponding to interface charge trapping in nc-Ge, operating at 0.96 MV/cm, is presented. The trapping effect is eliminated when nc-Ge is synthesized in forming gas thus excluding the possibility of quantum confinement and Coulomb blockade effects. Through discharging kinetics, the model of deep level trap charge storage is confirmed. The trap energy level is dependent on the matrix which confines the nc-Ge.

Theoretical investigation of Hf and Zr defects in c-Ge

The introduction of high-permittivity gate dielectric materials into complementary metal oxide semiconductor technology has reopened the interest in Ge as a channel material mainly due to its high hole mobility. Since HfO(2) and ZrO(2) are two of the most promising dielectric candidates, it is important to investigate if Hf and Zr may diffuse into the Ge channel. Therefore, using ab initio density functional theory calculations, we have studied substitutional and interstitial Hf and Zr impurities in c-Ge, looking for neutral defects. We find that (i) substitutional Zr and Hf defects are energetically more favorable than interstitial defects; (ii) under oxygen-rich conditions, neither Zr nor Hf migration towards the channel is likely to occur; (iii) either under Hf- or Zr-rich conditions it is very likely, particularly for Zr, that defects will be incorporated in the channel.

Sequential IRMPD of XGe(OEt)(4)(-) ions: Gas-phase synthesis of novel oxy-germanium anions

The gas-phase ion/molecule reactions of F(-) and EtO(-) with Ge(OEt)(4) yield readily and exclusively pentacoordinated complexes XGe(OEt)(4)(-) (X = F, EtO) at pressures in the 10(-8) T range as observed by FT-ICR techniques. These hypervalent species are prone to undergo sequential fragmentations induced by infrared multiphoton excitation that lead to a variety of germyl and germanate anions. In the case of FGe(OEt)(4)(-), three primary competitive channels are observed in the IRMPD process that can be identified as (EtO)(3)GeO(-), F(EtO)(2)GeO(-) and (EtO)(3)Ge(-). Ab initio calculations have been carried out to characterize the primary fragmentation paths induced by IRMPD and the most favorable structure of the resulting anions. The gas-phase acidity of a number of these germanium-containing ions have been estimated by bracketing experiments and by theoretical calculations. Germanate anions such as (EtO)(3)GeO(-) undergo some interesting reactions with H(2)S to give rise to anions such as (EtO)(3)GeS(-) and (EtO)(2)Ge(OH)S(-). (C) 2010 Elsevier B.V. All rights reserved.

Characterization of supported cylinder-planar germanium waveguide sensors with synchrotron Infrared radiation

Cylinder-planar Ge waveguides are being developed as evanescent-wave sensors for chemical microanalysis. The only non-planar surface is a cylinder section having a 300-mm radius of curvature. This confers a symmetric taper, allowing for direct coupling into and out of the waveguide's 1-mm² end faces while obtaining multiple reflections at the central <30-μm-thick sensing region. Ray-optic calculations indicate that the propagation angle at the central minimum has a strong nonlinear dependence on both angle and vertical position of the input ray. This results in rather inefficient coupling of input light into the off-axis modes that are most useful for evanescent-wave absorption spectroscopy. Mode-specific performance of the cylinder-planar waveguides has also been investigated experimentally. As compared to a blackbody source, the much greater brightness of synchrotron-generated infrared (IR) radiation allows a similar total energy throughput, but restricted to a smaller fraction of the allowed waveguide modes. However, such angle-selective excitation results in a strong oscillatory interference pattern in the transmission spectra. These spectral oscillations are the principal technical limitation on using synchrotron radiation to measure evanescent-wave absorption spectra with the thin waveguides.