Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

First principles modelling of nucleation and growth during atomic layer deposition onto III-V substrates

Atomic layer deposition (ALD) is now used in semiconductor fabrication lines to deposit nanometre-thin oxide films, and has thus enabled the introduction of high-permittivity dielectrics into the CMOS gate stack. With interest increasing in transistors based on high mobility substrates, such as GaAs, we are investigating the surface treatments that may improve the interface characteristics. We focus on incubation periods of ALD processes on III-V substrates. We have applied first principles Density Functional Theory (DFT) to investigate detailed chemistry of these early stages of growth, specifically substrate and ALD precursor interaction. We have modelled the ‘clean-up’ effect by which organometallic precursors: trimethylaluminium (TMA) or hafnium and titanium amides clean arsenic oxides off the GaAs surface before ALD growth of dielectric commences and similar effect on Si3N4 substrate. Our simulations show that ‘clean-up’ of an oxide film strongly depends on precursor ligand, its affinity to the oxide and the redox character of the oxide. The predominant pathway for a metalloid oxide such as arsenic oxide is reduction, producing volatile molecules or gettering oxygen from less reducible oxides. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides (e.g. SiO2) to be cleaned-up. First principles study shows also that alkylamides are more susceptible to decomposition rather than migration on the oxide surface. This improved understanding of the chemical principles underlying ‘clean-up’ allows us to rationalize and predict which precursors will perform the reaction. The comparison is made between selection of metal chlorides, methyls and alkylamides precursors.

Atomic layer deposition of interface control layers for the fabrication of III/V MOS devices

The continued advancement of metal oxide semiconductor field effect transistor (MOSFET) technology has shifted the focus from Si/SiO2 transistors towards high-κ/III-V transistors for high performance, faster devices. This has been necessary due to the limitations associated with the scaling of the SiO2 thickness below ~1 nm and the associated increased leakage current due to direct electron tunnelling through the gate oxide. The use of these materials exhibiting lower effective charge carrier mass in conjunction with the use of a high-κ gate oxide allows for the continuation of device scaling and increases in the associated MOSFET device performance. The high-κ/III-V interface is a critical challenge to the integration of high-κ dielectrics on III-V channels. The interfacial chemistry of the high-κ/III-V system is more complex than Si, due to the nature of the multitude of potential native oxide chemistries at the surface with the resultant interfacial layer showing poor electrical insulating properties when high-κ dielectrics are deposited directly on these oxides. It is necessary to ensure that a good quality interface is formed in order to reduce leakage and interface state defect density to maximise channel mobility and reduce variability and power dissipation. In this work, the ALD growth of aluminium oxide (Al2O3) and hafnium oxide (HfO2) after various surface pre-treatments was carried out, with the aim of improving the high-κ/III-V interface by reducing the Dit – the density of interface defects caused by imperfections such as dangling bonds, dimers and other unsatisfied bonds at the interfaces of materials. A brief investigation was performed into the structural and electrical properties of Al2O3 films deposited on In0.53Ga0.47As at 200 and 300oC via a novel amidinate precursor. Samples were determined to experience a severe nucleation delay when deposited directly on native oxides, leading to diminished functionality as a gate insulator due to largely reduced growth per cycle. Aluminium oxide MOS capacitors were prepared by ALD and the electrical characteristics of GaAs, In0.53Ga0.47As and InP capacitors which had been exposed to pre-pulse treatments from triethyl gallium and trimethyl indium were examined, to determine if self-cleaning reactions similar to those of trimethyl aluminium occur for other alkyl precursors. An improved C-V characteristic was observed for GaAs devices indicating an improved interface possibly indicating an improvement of the surface upon pre-pulsing with TEG, conversely degraded electrical characteristics observed for In0.53Ga0.47As and InP MOS devices after pre-treatment with triethyl gallium and trimethyl indium respectively. The electrical characteristics of Al2O3/In0.53Ga0.47As MOS capacitors after in-situ H2/Ar plasma treatment or in-situ ammonium sulphide passivation were investigated and estimates of interface Dit calculated. The use of plasma reduced the amount of interface defects as evidenced in the improved C-V characteristics. Samples treated with ammonium sulphide in the ALD chamber were found to display no significant improvement of the high-κ/III-V interface. HfO2 MOS capacitors were fabricated using two different precursors comparing the industry standard hafnium chloride process with deposition from amide precursors incorporating a ~1nm interface control layer of aluminium oxide and the structural and electrical properties investigated. Capacitors furnished from the chloride process exhibited lower hysteresis and improved C-V characteristics as compared to that of hafnium dioxide grown from an amide precursor, an indication that no etching of the film takes place using the chloride precursor in conjunction with a 1nm interlayer. Optimisation of the amide process was carried out and scaled samples electrically characterised in order to determine if reduced bilayer structures display improved electrical characteristics. Samples were determined to exhibit good electrical characteristics with a low midgap Dit indicative of an unpinned Fermi level

Organometallic Hydroxides of Transition Elements

Northern Illinois University DeKalb,Institut fu¨r Anorganische Chemie & Southern Methodist University

Protection of short-time enamel erosion by different tetrafluoride compounds

objective: This in vitro study aimed to analyse the protective effect of differently concentrated titanium (TiF4), zirconium (ZrF4) and hafnium (HfF4) tetrafluoride on enamel erosion. Methods: Polished enamel surfaces of 36 bovine crowns were covered with tape leaving 4 enamel windows each 3 mm in diameter exposed. The crowns were randomly assigned to six groups (each n = 6) and pretreated with 4% TiF4, 10% TiF4, 4% ZrF4, 10% ZrF4, 4% HfF4 or 10% HfF4 for 4 min (first window), 10 min (second window) or 15 min (third window). The fourth window of each crown was not pretreated and served as control. Erosion was performed stepwise with 1% HCl (pH 2) in five consecutive intervals of each 15 s (total 75 s). Enamel dissolution was quantified by colorimetric determination of phosphate release into the acid. For each tooth, cumulative phosphate loss of enamel pretreated with one of the tetrafluoride compounds was calculated as percentage of the respective control and statistically analysed using two-way ANOVA.Results: Enamel erosion was significantly reduced by TiF4, ZrF4 and HfF4 application. Cumulative phosphate loss (mean % of control, 75 s erosion) after 4-15 min application was significantly lower for 4% ZrF4 (7-11%), 10% ZrF4 (2-6%), 4% HfF4 (11-9%) and 10% HfF4 (12-16%) compared to 4% TiF4 (42-27%) and 10% TiF4 (54-33%). Only for 4% and 10% TiF4, phosphate loss decreased with increasing duration of application, but also increased with increasing acid intervals.Conclusion: TiF4, ZrF4 and HfF4 might protect enamel against short-time erosion, but protection was more enhanced by ZrF4 and HfF4 compared to TiF4 application overtime. (C) 2008 Elsevier Ltd. All rights reserved.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Morphology and Photoluminescence of HfO2 Obtained by Microwave-Hydrothermal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Rare earth doped HfO2 nanoparticles embedded in SiO2-HfO2 planar waveguides. Preparation, optical, structural and spectroscopic characterization

In this work we present results on the preparation of planar waveguides based on HfO2 and HfO2-SiO2. Stable sols containing europium and erbium doped HfO2 nanoparticles have been prepared and characterized. The nanosized sol was either deposited (spin-coating) on quartz substrates or embedded in (3-glycidoxipropil)trimethoxisilane (GPTS) used as a hybrid host for posterior deposition. The refractive index dispersion and luminescence characteristics were determined for the resulting HfO2 films. The optical parameters of the waveguides such as refractive index, thickness and propagation losses were measured for the hybrid composite. The planar waveguides present thickness of a few micra and support well confined propagating modes.

Erbium-activated HfO2-based waveguides for photonics

70SiO2 - 30HfO2 planar waveguides, activated by Er3+ concentration ranging from 0.3 to 1 mol%, were prepared by solgel route, using dip-coating deposition on silica glass substrates. The waveguides showed high densification degree, effective intermingling of the two components of the film, and uniform surface morphology. Propagation losses of about 1 dB/cm were measured at 632.8 nm. When pumped with 987 nm or 514.5 nm continuous-wave laser light, the waveguides showed the 4I 13/2→4I15/2 emission band with a bandwidth of 48 nm. The spectral features were found independent both on erbium content and excitation wavelength. The 4I13/2 level decay curves presented a single exponential profile, with a lifetime between 2.9-5.0 ms, depending on the erbium concentration.

Discovery and cross-section measurement of neutron-rich isotopes in the element range from neodymium to platinum with the FRS

Using the high-resolution performance of the fragment separator FRS at GSI we have discovered 60 new neutron-rich isotopes in the atomic number range of 60 <= Z <= 78. The new isotopes were unambiguously identified in reactions with a U-238 beam impinging on a Be target at 1 GeV/nucleon. The production cross-section for the new isotopes have been measured down to the pico-barn level and compared with predictions of different model calculations. For elements above hafnium fragmentation is the dominant reaction mechanism which creates the new isotopes, whereas fission plays a dominant role for the production of the new isotopes up to thulium. (C) 2012 Elsevier B.V. All rights reserved.

Microstructural characterization of as-cast hf-b alloys

An accurate knowledge of several metal-boron phase diagrams is important to evaluation of higher order systems such as metal-silicon-boron ternaries. The refinement and reassessment of phase diagram data is a continuous work, thus the reevaluation of metal-boron systems provides the possibility to confirm previous data from an investigation using higher purity materials and better analytical techniques. This work presents results of rigorous microstructural characterization of as-cast hafnium-boron alloys which are significant to assess the liquid composition associated to most of the invariant reactions of this system. Alloys were prepared by arc melting high purity hafnium (minimum 99.8%) and boron (minimum 99.5%) slices under argon atmosphere in water-cooled copper crucible with non consumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy, using back-scattered electron image mode and X-ray diffraction. In general, a good agreement was found between our data and those from the currently accepted Hafnium-Boron phase diagram. The phases identified are αHfSS and B-RhomSS, the intermediate compounds HfB and HfB2 and the liquide L. The reactions are the eutectic L ⇔ αHfSS + HfB and L ⇔ HfB2 + B-Rhom, the peritectic L + HfB2 ⇔ HfB and the congruent formation of HfB2.

Entwicklung einer online-Chromatographie für Element 106 (Seaborgium)

Das Studium chemischer Eigenschaften der schwersten Elemente, der Transactiniden, erfordert immer leistungsfähigere Apparaturen. Wegen ihrer kurzen Halbwertszeiten müssen diese Elemente schnell von der Targetkammer mittels Gasjet zur Apparatur transportiert und dort in die wässrige Phase überführt werden. Das sollte zur Vermeidung von Verlusten durch vorzeitigen Zerfall möglichst online betrieben werden, d.h. die in der Kernreaktion gebildeten Atome werden kontinuierlich aus der Targetkammer ausgespült und in der Apparatur in die wässrige Phase überführt. Dabei stellt sich das Problem, die kleinen Aerosol-Partikel (100-200 nm und etwa 1010 Teilchen pro Liter) bei einem Gasfluss von 2 bis 3 Liter Jet-Gas pro min in eine mit 1 bis 2 mL/min fließende wässrige Lösung zu überführen. Hierzu wurden zwei verschiedene Systeme am TRIGA-Reaktor Mainz entwickelt und in Experimenten an den Schwerionenbeschleunigern am PSI und der GSI erfolgreich eingesetzt. Da die diskontinuierlich arbeitende Chemieapparatur ARCA, mit der bisher chemische Eigenschaften der Elemente 101, 103, 104, 105 und 106 bestimmt wurden, wegen niedriger Produktionsraten bei Element 106 an ihre technologischen Grenzen stößt, bestand eine weitere Aufgabe der vorliegenden Arbeit darin, ein kontinuierlich arbeitendes Chromatographiesystem aufzubauen, mit dem Verteilungskoeffizienten des Elements 106 gemessen werden können. Bei der in dieser Arbeit entwickelten und in Versuchen mit kurzlebigen Hafnium-, Wolfram- und Rutherfordium-Isotopen getesten, kontinuierlich arbeitenden Mehrsäulentechnik wird der direkte Nachweis des Transactinids aufgegeben, und die Retentionszeit in dem chromatographischen System über die Menge der während der Retention zerfallenen Atome bestimmt. Neben der apparativen Entwicklung dieser Technik, die geringste Totvolumina im System erfordert, mussten bei der Auswahl des geeigneten chemischen Systems die engen Grenzen dieser Methode beachtet werden, was umfangreiche Kenntnisse zur trägerfreien Chemie der homologen Elemente erfordert. Neben Batchexperimenten mit trägerfrei produzierten Nukliden wurde für offline-Experimente auch ARCA erfolgreich eingesetzt. Der Vergleich von Kd-Werten, die in Batchexperimenten, mit ARCA und mit der prinzipiell neuen Methode der Mehrsäulentechnik bestimmt wurden, zeigten dabei gute Übereinstimmungen. Für die Anwendbarkeit der Mehrsäulentechnik sind aber auch geeignete radioaktive Zerfallsketten notwendig, die in einem langlebigen Isotop enden sollten, welches über lange Experimentierzeiten akkumuliert werden kann. Dabei ist die Diskriminierung von einzelnen Atomen langlebiger Actiniden als Endglieder der Zerfallskette der Transactiniden gegen den natürlichen und elektronischen Untergrund sehr anspruchsvoll und möglicherweise der limitierende Faktor dieser Technik. Neben Beiträgen zur Fluoridkomplexierung von Elementen der 4. Nebengruppe (inklusive Rutherfordium) und der 6. Nebengruppe, wurde die Hydrolyse von Elementen der 6. Nebengruppe untersucht. Hier zeigen sich bei Verwendung von trägerfreien Aktivitäten abweichende Resultate gegenüber der Literatur.Auf der Grundlage dieser Daten wurde ein Mehrsäulenexperiment für 7,4-s 265Sg (Element 106) vorbereitet, für dessen Einsatz sowohl ein drehendes Targetradsystem für eine erhöhte Produktionsrate getestet wurde, als auch der Einsatz von speziell funktionalisierten Ionenaustauscherharzen.

Design and optimization of components and processes for plasma sources in advanced material treatments

The research activities described in the present thesis have been oriented to the design and development of components and technological processes aimed at optimizing the performance of plasma sources in advanced in material treatments. Consumables components for high definition plasma arc cutting (PAC) torches were studied and developed. Experimental activities have in particular focussed on the modifications of the emissive insert with respect to the standard electrode configuration, which comprises a press fit hafnium insert in a copper body holder, to improve its durability. Based on a deep analysis of both the scientific and patent literature, different solutions were proposed and tested. First, the behaviour of Hf cathodes when operating at high current levels (250A) in oxidizing atmosphere has been experimentally investigated optimizing, with respect to expected service life, the initial shape of the electrode emissive surface. Moreover, the microstructural modifications of the Hf insert in PAC electrodes were experimentally investigated during first cycles, in order to understand those phenomena occurring on and under the Hf emissive surface and involved in the electrode erosion process. Thereafter, the research activity focussed on producing, characterizing and testing prototypes of composite inserts, combining powders of a high thermal conductibility (Cu, Ag) and high thermionic emissivity (Hf, Zr) materials The complexity of the thermal plasma torch environment required and integrated approach also involving physical modelling. Accordingly, a detailed line-by-line method was developed to compute the net emission coefficient of Ar plasmas at temperatures ranging from 3000 K to 25000 K and pressure ranging from 50 kPa to 200 kPa, for optically thin and partially autoabsorbed plasmas. Finally, prototypal electrodes were studied and realized for a newly developed plasma source, based on the plasma needle concept and devoted to the generation of atmospheric pressure non-thermal plasmas for biomedical applications.

Thermoelectric properties of TiNiSn and Zr 0.5 Hf 0.5 NiSn thin films and superlattices with reduced thermal conductivities

Durch steigende Energiekosten und erhöhte CO2 Emission ist die Forschung an thermoelektrischen (TE) Materialien in den Fokus gerückt. Die Eignung eines Materials für die Verwendung in einem TE Modul ist verknüpft mit der Gütezahl ZT und entspricht α2σTκ-1 (Seebeck Koeffizient α, Leitfähigkeit σ, Temperatur T und thermische Leitfähigkeit κ). Ohne den Leistungsfaktor α2σ zu verändern, soll ZT durch Senkung der thermischen Leitfähigkeit mittels Nanostrukturierung angehoben werden.rnBis heute sind die TE Eigenschaften von den makroskopischen halb-Heusler Materialen TiNiSn und Zr0.5Hf0.5NiSn ausgiebig erforscht worden. Mit Hilfe von dc Magnetron-Sputterdeposition wurden nun erstmals halbleitende TiNiSn und Zr0.5Hf0.5NiSn Schichten hergestellt. Auf MgO (100) Substraten sind stark texturierte polykristalline Schichten bei Substrattemperaturen von 450°C abgeschieden worden. Senkrecht zur Oberfläche haben sich Korngrößen von 55 nm feststellen lassen. Diese haben Halbwertsbreiten bei Rockingkurven von unter 1° aufgewiesen. Strukturanalysen sind mit Hilfe von Röntgenbeugungsexperimenten (XRD) durchgeführt worden. Durch Wachstumsraten von 1 nms 1 konnten in kürzester Zeit Filmdicken von mehr als einem µm hergestellt werden. TiNiSn zeigte den höchsten Leistungsfaktor von 0.4 mWK 2m 1 (550 K). Zusätzlich wurde bei Raumtemperatur mit Hilfe der differentiellen 3ω Methode eine thermische Leitfähigkeit von 2.8 Wm 1K 1 bestimmt. Es ist bekannt, dass die thermische Leitfähigkeit mit der Variation von Massen abnimmt. Weil zudem angenommen wird, dass sie durch Grenzflächenstreuung von Phononen ebenfalls reduziert wird, wurden Übergitter hergestellt. Dabei wurden TiNiSn und Zr0.5Hf0.5NiSn nacheinander abgeschieden. Die sehr hohe Kristallqualität der Übergitter mit ihren scharfen Grenzflächen konnte durch Satellitenpeaks und Transmissionsmikroskopie (STEM) nachgewiesen werden. Für ein Übergitter mit einer Periodizität von 21 nm (TiNiSn und Zr0.5Hf0.5NiSn jeweils 10.5 nm) ist bei einer Temperatur von 550 K ein Leistungsfaktor von 0.77 mWK 2m 1 nachgewiesen worden (α = 80 µVK 1; σ = 8.2 µΩm). Ein Übergitter mit der Periodizität von 8 nm hat senkrecht zu den Grenzflächen eine thermische Leitfähigkeit von 1 Wm 1K 1 aufgewiesen. Damit hat sich die Reduzierung der thermischen Leitfähigkeit durch die halb-Heusler Übergitter bestätigt. Durch die isoelektronischen Eigenschaften von Titan, Zirkonium und Hafnium wird angenommen, dass die elektrische Bandstruktur und damit der Leistungsfaktor senkrecht zu den Grenzflächen nur schwach beeinflusst wird.rn

Peak Last Glacial weathering intensity on the North American continent recorded by the authigenic Hf isotope composition of North Atlantic deep-sea sediments

We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.