text:
|Publication number
|Publication type
|Application number
|Publication date
|16 Jun 2009
|Filing date
|30 May 2006
|Priority date
|4 Apr 2003
|Fee status
|Also published as
|Publication number
|Craig Metzner, Shreyas Kher, Yeong Kwan Kim, M. Noel Rocklein, Steven M. George
|Original Assignee
|Applied Materials, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (102), Non-Patent Citations (55), Referenced by (9), Classifications (45), Legal Events (3)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a divisional application of co-pending U.S. patent application Ser. No. 10/407,930, filed Apr. 4, 2003, which is incorporated by reference herein.
Embodiments of the present invention generally relate to methods to deposit materials on substrates, and more specifically, to methods for depositing metal oxides, metal nitrides, metal oxynitrides, metal silicates and metal silicon oxynitrides using atomic layer deposition processes.
In the field of semiconductor processing, flat-panel display processing or other electronic device processing, chemical vapor deposition has played an important role in forming films on substrates. As the geometries of electronic devices continue to shrink and the density of devices continues to increase, the size and aspect ratio of the features are becoming more aggressive, e.g., feature sizes of 0.07 microns and aspect ratios of 10 or greater are being considered. Accordingly, conformal deposition of materials to form these devices is becoming increasingly important.
While conventional chemical vapor deposition has proved successful for device geometries and aspect ratios down to 0.15 microns, the more aggressive device geometries require new, innovative deposition techniques. One technique that is receiving considerable attention is atomic layer deposition (ALD). In the scheme, reactants are sequentially introduced into a processing chamber where each reactant chemisorbs onto the surface of the substrate and a surface reaction occurs. A purge step is typically carried out between the delivery of each reactant gas. The purge step may be a continuous purge with the carrier gas or a pulse purge between the delivery of the reactant gases.
U.S. Pat. No. 6,287,965 describes a method of ALD to form a metal nitride layer having the structure of A-B-N, where A is a metal, B is an element to prevent crystallization and N is nitrogen. The preferred embodiment teaches a method to make TiAIN. No incorporation of oxygen into these films is disclosed; in fact, the invention teaches away from oxygen incorporation by sequentially stacking oxygen diffusion barrier layers between the metal nitride layers for oxygen protection.
U.S. Pat. No. 6,200,893, entitled "Radical-assisted Sequential CVD", describes a method for CVD deposition on a substrate wherein radical species such as hydrogen and oxygen or hydrogen and nitrogen are used in an alternative step with a molecular precursor to form one cycle. A composite integrated film is produced by repetitive cycles of the method. In a preferred embodiment, the deposited material from the molecular precursor are metals and the radicals, in the alternate steps, are used to remove ligands left from the metal precursor reactions. The radicals oxidize or nitridize the metal surface in subsequent layers in order to respectively yield metal oxide or nitride. In various embodiments of the reference, metallic hafnium and hafnium oxide are made from a halogen-containing precursor. However, the reference does not address complex hafnium compounds (tertiary, quaternary or pentanary) produced from metal organic compounds. Furthermore, the reference requires the use of radicals to incorporate oxygen and/or nitrogen into the film.
Therefore, there is a need for a process for depositing hafnium compounds such as nitrides, silicates, oxynitrides, silicon nitrides, silicon oxynitrides, aluminum oxynitrides and aluminum silicon oxynitrides from organometallic compounds.
In one embodiment, the present invention is a method for forming a layer comprising hafnium on a substrate surface, sequentially comprising: a) exposing the substrate surface to a hafnium precursor to form a hafnium containing layer on the substrate surface; b) purging the chamber with a purge gas; c) reacting a second precursor with the hafnium containing layer; d) purging the chamber with the purge gas; e) reacting a third precursor with the hafnium containing layer; f) purging the chamber with the purge gas; g) reacting a fourth precursor with the hafnium containing layer; and h) purging the chamber with the purge gas.
In another embodiment, the present invention is a method for growing a layer comprising hafnium, comprising exposing a substrate sequentially to at least four precursors during an ALD cycle to deposit a compound film comprising hafnium and at least three elements selected from the group consisting of silicon, aluminum, oxygen and nitrogen.
In another embodiment, the present invention is a method for depositing a hafnium compound on a substrate in a chamber during an atomic layer deposition process, comprising conducting a first half reaction comprising a hafnium precursor, conducting a second half reaction comprising an oxygen precursor, conducting a third half reaction comprising a nitrogen precursor and conducting a fourth half reaction comprising a silicon precursor.
In another embodiment, the present invention is a composition of a semiconductor material, comprising HfSixOyNz, wherein x is at least about 0.2 and less than about 4, y is at least about 0.5 and less than about 4 and z is at least about 0.05 and less than about 2.
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of the invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
The present invention provides methods for preparing hafnium compounds used in a variety applications including high k dielectric materials. The methods use atomic layer deposition (ALD) to have elemental control of the composition of hafnium compounds. The elemental control is generally separated by half reactions.
Half reactions are abstractly demonstrated via the reaction:
wherein AB is the product compound and CD is the secondary compound or secondary product.
For example, a half reaction is demonstrated by each of the following steps:
*NH2+(Et2N)4Hf→*N═Hf(NEt2)2+2HNEt2 (1)
*N═Hf(NEt2)2+NH3→*N═Hf═NH+2HNEt2, (2)
wherein the half reaction of step 1 is initiated by the functional group NH2 and * is an atom or molecule that is part of the substrate, film or surface group. The hafnium precursor reacts with the NH2 group and forms a Hf—N bond. Ligands are protonated from the hafnium precursor to form a secondary product. During the half reaction in step 2, ammonia reacts with the hafnium complex bound to the surface. The remaining ligands are protonated and removed while another Hf—N bond and another functional group (NH) are formed as the product compound. In each half reaction of steps 1 and 2, diethyl amine (HNEt2) can be made as a secondary compound. Other secondary compounds are amines and hydrazines and include radicals, ions and variations to ligands, such as Et2N, (Et2N)2, EtNH and (EtNH)2. Generally, these secondary compounds are readily removable, such as by vacuum and/or purge. The reaction schemes are not necessarily stoichiometric, but have a wide range of atomic ratios. Throughout the disclosure, reaction examples lack specific stoichiometry, bonding order and bonding connectivity of the product compounds and secondary compounds.
Another example of a half reaction is demonstrated by each of the following steps:
*OH+(Et2N)4Hf→*O—Hf(NEt2)x+HNEt2 (3)
*O—Hf(NEt2)x+H2O→*O—Hf—(OH)+HNEt2, (4)
wherein the half reaction of step 3 is initiated by the functional OH group and forms a Hf—O bond. Step 4 proceeds to form another Hf—O bond as well as the terminus and functional OH group.
Therefore, in general, a first half reaction initiates with the reaction of a first functional group, establishes at least one product compound bond and establishes a second functional group. The second half reaction initiates with a reaction of the second functional group, establishes at least one product compound bond and establishes a third functional group. The third functional group, in many examples, is the same or similar to the first functional group. However, the second half reaction is still complete even when the third functional group is different. Examples with tertiary, quaternary and higher product compounds require half reactions with more than two precursors. Therefore, half reactions are not limited to only binary product compounds and may contain any number of half reactions. Most half reactions are sequentially separated by gas and/or vacuum purges.
Embodiments of the processes described herein deposit hafnium-containing materials on many substrates and surfaces. Substrates on which embodiments of the invention may be useful include, but are not limited to semiconductor wafers, such as crystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers silicon nitride and patterned or non-patterned wafers. Surfaces include bare silicon wafers, films, layers and materials with dielectric, conductive and barrier properties and include aluminum oxide and polysilicon. Pretreatment of surfaces includes polishing, etching, reduction, oxidation, hydroxylation, annealing and baking.
A substrate can be pretreated to be terminated with a variety of functional groups such as hydroxyls (OH), alkoxy (OR, where R=Me, Et, Pr or Bu), haloxyls (OX, where X=F, Cl, Br or I ), halides (F, Cl, Br or I ), oxygen radicals, aminos (NH or NH2) and amidos (NR or NR2, where R=Me, Et, Pr or Bu). A pretreatment can be accomplished by administering a reagent, such as NH3, B2H6, SiH4, SiH6, H2O , HF, HCl, O2, O3, H2O2, H2, atomic-H, atomic-N, atomic-O, alcohols or amines.
Once the surface of the substrate is pretreated, an ALD cycle is started. For many of the hafnium compounds, the hafnium precursor adsorption is self-limiting under certain process conditions, and generally must be at low temperatures (<500� C.) to exhibit this behavior. Some examples of half reactions that are self-limiting for the hafnium precursor include:
wherein, hafnium is added to produce either *O—Hf(NEt2)x or *N—Hf(NEt2)x. An atom, such as a nitrogen or oxygen, can anchor the hafnium atom to the substrate or surface. *Hf(NEt2)x is self-limiting because the hafnium precursor will not react further; therefore, this is the first half reaction. To proceed with other half reactions, either an oxygen source (e.g., water) or a nitrogen source (e.g., ammonia) is added.
The first half reaction with a hafnium precursor initiates a series of many half reactions to make binary, tertiary, quaternary and more complex compounds. The first half reaction does not have to include a hafnium precursor, but can include any precursor to which a particular element is incorporated into the film. The following examples will portray hafnium precursors as the first half reaction in order to more clearly explain aspects of the invention.
One embodiment of the invention is directed to a process which proceeds with the half reaction of NH3 to *Hf(NEt2)x to produce *Hf—NH. Hafnium nitride is synthesized by sequentially proceeding with a half reaction of the hafnium precursor and a half reaction of a nitrogen source.
In one embodiment, a method for forming a semiconductor material by atomic layer deposition includes pulsing a hafnium precursor and a nitrogen precursor sequentially and cyclically. The hafnium nitride is deposited to the substrate surface wherein the hafnium nitride has a formula HfNx and x is at least about 1.1 and less than about 1.3. In one aspect, the hafnium precursor is TDEAH and the nitrogen precursor is NH3. In another aspect, the hafnium precursor is HfCl4 and the nitrogen precursor is a radical nitrogen, such as atomic nitrogen.
Another embodiment of the invention is directed to a process which proceeds with the half reaction of H2O to *Hf(NEt2)x and produce *Hf—OH. Hafnium oxide is synthesized by sequentially proceeding with a half reaction of the hafnium precursor and a half reaction of an oxygen source.
The processes to grow the hafnium nitride or hafnium oxide films, as described above, can be modified to achieve other materials, namely tertiary compounds. Hafnium nitride is porous and reacts with water to form hafnium oxynitride, Hf—O—N. Therefore, to the hafnium nitride cycle, a half reaction of an oxygen source (e.g., water) is added to synthesize hafnium oxynitride. The ratio of Hf:O:N is controlled and varied to the desired characteristics of the product compound. In one embodiment, an oxygen precursor half reaction is included into the half reaction cycle. Such a cycle comprises a hafnium precursor half reaction, a nitrogen precursor half reaction, another hafnium precursor half reaction and an oxygen precursor half reaction. The oxygen precursor half reaction can be added into the cycle at any ratio relative to the hafnium and nitrogen precursor half reactions. As an example, an oxygen precursor half reaction is added at every ten complete cycles of hafnium and nitrogen precursor half reactions. Furthermore, the ratio can be varied in order to control the oxygen stoichiometry by film depth. Hence, a graded film is formed. In one embodiment, the process conditions are as follows, pressure is about 1 Torr, temperature is about 225� C., argon carrier flow is about 200 sccm, H2O and NH3 are dosed into the argon carrier flow in the range from about 1 second to about 4 seconds and TDEAH is dosed at about 20 seconds.
Graded films can be used to transition between various materials. One embodiment uses the method to transition between hafnium nitride and hafnium oxide. Within the hafnium nitride film, the elemental ratios N:Hf:O start out at 10:10:0, progress to 10:10:1, progress to 5:10:5, progress to 1:10:10 and finally 0:10:10, such that the film at the exposed surface following deposition is hafnium oxide. Graded films have advantageous characteristics, such as allowing control of electrical properties throughout the depth of the film, as well as higher levels of film adhesion.
Additional embodiments include methods to synthesize hafnium oxynitride. Due to the porosity of hafnium nitride, multiple layers are susceptible to oxygen enrichment. Instead of incorporating oxygen into each surface layer via half reactions, an excess oxygen precursor (e.g., water) is used to penetrate multiple layers of hafnium nitride and form a hafnium oxynitride graded film such as:
HfN—HfN—HfN—HfN—HfN+xs H2O →HfN—HfN—HfON—HfON—HfON.
Therefore, hafnium nitride can be formed by ALD, CVD, PVD or other techniques and thereafter oxygenated with an oxygen precursor.
Other embodiments of the invention include methods to synthesize tertiary hafnium nitride compounds incorporating silicon. Preferred silicon precursor compounds include (Me2N)4Si and (Me2N)3SiH. In one embodiment, a silicon precursor half reaction is included into the half reaction cycle for hafnium nitride formation. The cycle includes a hafnium precursor half reaction, a nitrogen precursor half reaction, a silicon precursor half reaction and another nitrogen precursor half reaction. The silicon precursor half reaction is added into the cycle at any ratio relative to the hafnium and nitrogen precursor half reactions. As an example, a silicon precursor half reaction is added about at every two complete cycles of hafnium and nitrogen precursor half reactions. Furthermore, the ratio can be varied in order to control the ratio of the silicon incorporated by depth of the film. Similarly to hafnium oxynitride, the method enables control of the Hf:Si:N stoichiometry.
Other embodiments of the invention are methods to synthesize tertiary hafnium oxide compounds incorporating nitrogen. Similarly as discussed above, the method reverses to use of oxygen and nitrogen to synthesize hafnium oxynitride. In one embodiment, a nitrogen precursor half reaction is included into the half reaction cycle of hafnium oxide. The cycle comprises a hafnium precursor half reaction, an oxygen precursor half reaction, another hafnium precursor half reaction and a nitrogen precursor half reaction. The nitrogen precursor half reaction is added into the cycle at any ratio relative to the hafnium and oxygen precursor half reactions. As an example, a nitrogen precursor half reaction is added at every two complete cycles of hafnium and oxygen precursor half reactions. Furthermore, the ratio can be varied in order to control the ratio of the nitrogen incorporated by depth of the growing film.
Other embodiments of the invention include methods to synthesize tertiary hafnium oxide compounds incorporating silicon, namely hafnium silicate (Hf—Si—O), as depicted in
Embodiments of the invention include multiple methods to synthesize quaternary compounds, especially hafnium silicon oxynitride (HfSiON), as depicted in
In one embodiment, a nitrogen source half reaction is included into the half reaction cycle of hafnium silicate. Such a cycle comprises a silicon precursor half reaction, an oxygen precursor half reaction, a hafnium precursor half reaction and a nitrogen precursor half reaction. The nitrogen precursor half reaction can be added into the cycle at any ratio relative to the hafnium, silicon and oxygen precursor half reactions. As an example, a nitrogen precursor half reaction can be added at about every two complete cycles of hafnium, silicon and oxygen precursor half reactions. Furthermore, the cycle ratio can be varied in order to control the nitrogen ratio incorporated within film depth. Some embodiments grow hafnium silicon oxynitride graded films with higher concentrations of nitrogen near the top of the film.
In one aspect, the surface is terminated with a *SiOH group. The half reaction cycles are conducted with a hafnium precursor, a nitrogen precursor, a silicon precursor and an oxygen precursor, each separated with a purge. The respective precursors can be TDEAH, ammonia, Tris-DMAS and water. In another aspect, the respective precursors are HfCl4, radical nitrogen, Si2Cl6 and O3. The composition is controlled to form a semiconductor material, comprising HfSixOyNz, wherein x is at least about 0.2 and less than about 4, y is at least about 0.5 and less than about 4 and z is at least about 0.05 and less than about 2.
Embodiments of the invention include multiple methods to synthesize pentanary compounds, especially hafnium aluminum silicon oxynitride (HfAlSiON). Half reactions of hafnium, aluminum, nitrogen, oxygen and silicon precursors are added at particular cycles, providing complete control to the Al:N:O:Si ratios relative to hafnium. In one aspect of the process, one cycle of half reaction pulses will include, in the respective order, water, TDEAH, ammonia, Tris-DMAS, water and TMA. In another aspect of the process, one cycle of half reaction pulses will include, in the respective order, water, HfCl4, ammonia, Tris-DMAS, water and TMA.
Therefore, any stoichiometry of the following compounds is made by methods of the process: HfO, HfN, HfON, HfSiO, HfSiN, HfSiON, HfAlO, HfAlN, HfAlON, HfSiAlO, HfSiAlN, HfSiAlON. Therefore, ALD provides stoichiometric control during the deposition of product compounds. The stoichiometry may be altered by various procedures following the deposition process, such as when Hf3N4 is thermally annealed to form HfN. Stoichiometry is also controlled by altering the precursor ratios during deposition.
Many industrial applications exist for the product compounds synthesized by the various embodiments of the invention. Within the microelectronics industry, the product compounds are used as high-k transistor gate dielectric materials, transistor gate interface engineering, high-k capacitor dielectric materials (DRAMs), seed layers, diffusion barrier layers, adhesion layers, insulator layers, conducting layers and functionalized surface groups for patterned surfaces (e.g., selective deposition). In the realm of microelectromechanical systems (MEMS), the materials formed by the claimed invention are used as insulating, conducting or structural films. The materials can also serve as functionalized surface groups to reduce stiction. Additional functionality of surface groups is used in gas or liquid chromatography, chemical sensors and active sites for chemical attachment, patterned surfaces (e.g., combinatorial chemistry). Silicon nitride is also used as a hardening coating on tools and within optical devices.
Many precursors are within the scope of the invention. One important precursor characteristic is to have a favorable vapor pressure. Precursors may be a plasma, gas, liquid or solid at ambient temperature and pressure. However, within the ALD chamber, precursors are volatilized. Organometallic compounds or complexes include any chemical containing a metal and at least one organic group, such as alkyls, alkoxyls, alkylamidos and anilides. Precursors comprise of organometallic and halide compounds.
Exemplary hafnium precursors include hafnium compounds containing ligands such as alkylamidos, cyclopentadienyls, halides, alkyls, alkoxides and combinations thereof. Alkylamido hafnium compounds used as hafnium precursors include (RR′N)4Hf, where R or R′ are independently hydrogen, methyl, ethyl, propyl or butyl. Specific hafnium precursors include: (Et2N)4Hf, (Me2N)4Hf, (EtMeN)4Hf, (tBuC5H4)2HfCl2, (C5H5)2HfCl2, (EtC5H4)2HfCl2, (Me5C5)2HfCl2, (Me5C5)HfCl3, (iPrC5H4)2HfCl2, (iPrC5H4)HfCl3, (tBuC5H4)2HfMe2, (acac)4Hf, (hfac)4Hf, (tfac)4Hf, (thd)4Hf, Br4Hf, Cl4Hf, I4Hf, (NO3)4Hf, (tBuO)4Hf, (iPrO)4Hf, (EtO)4Hf and (MeO)4Hf.
Exemplary silicon precursors include: alkylamidosilanes (e.g, (Me2N)4Si, (Me2N)3SiH, (Me2N)2SiH2, (Me2N)SiH3, (Et2N)4Si, (Et2N)3SiH), Si(NCO)4, MeSi(NCO)3, SiH4, Si2H6, SiCl4, Si2Cl6, MeSiCl3, HSiCl3, Me2SiCl2, H2SiCl2, silanols (e.g., MeSi(OH)3, Me2Si(OH)2), (EtO)4Si and various alkoxy silanes (e.g., (RO)4-nSiLn, where R=methyl, ethyl, propyl and butyl and L=H, OH, F, Cl, Br or I and mixtures thereof). Also, higher silanes are used as silicon precursors by processes of the invention. Higher silanes are disclosed in U.S. provisional patent applications, 60/419,426, 60/419,376 and 60/419,504, each filed on Oct. 18, 2002, assigned to Applied Material, Inc., and each entitled, "Low temperature deposition with silicon compounds" and are incorporated herein by reference in entirety for the purpose of describing silicon precursors.
Exemplary nitrogen precursors include: NH3, N2, hydrazines (e.g., N2H4 or MeN2H3), amines (e.g., Me3N, Me2NH or MeNH2), anilines (e.g., C6H5NH2), organic azides (e.g., MeN3 or Me3SiN3), inorganic azides (e.g., NaN3 or CP2CoN3) and radical nitrogen compounds (e.g., N3, N2, N, NH or NH2). Radical nitrogen compounds can be produced by heat, hot-wires and/or plasma.
Exemplary oxygen precursors include: H2O, H2O2, O3, O2, NO, N2O, NO2, N2O5, alcohols (e.g., ROH, where R=Me, Et, Pr and Bu), peroxides (organic and inorganic) carboxylic acids and radical oxygen compounds (e.g., O, O2, O3 and OH radicals). Radical oxygen compounds can be produced by heat, hot-wires and/or plasma.
Exemplary aluminum precursors include: aluminum alkyls such as: Me3Al, Et3Al, Pr3Al, Bu3Al, Me2AlH, Et2AlH, Me2AlCl, Et2AlCl, aluminum alkoxyls such as: (MeO)3Al, (EtO)3Al, (PrO)3Al and (BuO)3Al, aluminum dimmers, aluminum halides and aluminum hydrides.
The processes of the invention can be carried out in equipment known in the art of ALD. The apparatus brings the sources into contact with a heated substrate on which the films are grown. Hardware that can be used to deposit films is an ALD apparatus as disclosed in U.S. patent application Ser. No. 10/251,715, filed Sep. 20, 2002, assigned to Applied Material, Inc., Santa Clara, Calif. and entitled "An Apparatus for the Deposition of High Dielectric Constant Films", and is incorporated herein by reference in entirety for the purpose of describing the apparatus. Carrier gases or purge gases include N2, Ar, He, H2, forming gas and mixtures thereof.
In one embodiment, hydrogen gas is applied as a carrier gas, purge and/or a reactant gas to reduce halogen contamination from the film. Precursors that contain halogen atoms (e.g., HfCl4, SiCl4 and Si2Cl6) readily contaminate the film. Hydrogen is a reductant and will produce hydrogen chloride as a volatile and removable by-product. Therefore, hydrogen is used as a carrier gas or reactant gas when combined with a precursor compound (i.e., hafnium, silicon, aluminum, oxygen or nitrogen precursors) and can include another carrier gas (e.g., Ar or N2). In one aspect, a water/hydrogen mixture, at a temperature in the range from about 250� C. to about 650� C., is used to reduce the halogen concentration and increase the oxygen concentration of the film.
The present invention provides methods for preparing the following compounds. The subscripts (w, x, y, z) imply that stoichiometry is intentionally varied (i.e., compositionally controlled) via ALD dosing sequences to form the following product compounds:
hafnium aluminate: HfAlxOy hafnium oxide: HfO2 and HfOx hafnium nitride: Hf3N4, HfN and HfNx hafnium oxynitride: HfOxNy hafnium aluminum oxynitride: HfAlxOyNz hafnium silicate: HfSiO4, Hf4SiO10, Hf3SiO8, Hf2SiO6, HfSiO2, HfxSiyO2(x+y) and HfxSiyO aluminum silicate: Al6Si2O13 and AlxSiyO hafnium aluminum silicate: Hf2Al6Si4O21 and HfxAlySizO hafnium silicon nitride: HfxSiyN hafnium silicon oxynitride: Hf2Si2N2O5 and HfSixOyNz aluminum silicon oxynitride: AlSixOyNz hafnium aluminum silicon oxynitride: HfAlwSixOyNz
The list of product compounds is only partial and other materials are prepared with the methods of the invention. Other elements, such as carbon, titanium, tungsten, ruthenium, tantalum, zirconium, molybdenum, iridium, nickel, copper, tin, boron or phosphorus may be incorporated into the films as product compounds. Therefore, a product compound may comprise hafnium silicon oxynitride and carbon. Examples of half reactions are listed below. Note, that *=surface species.
Reactivity of Precursors with Surface Hydroxyl Groups (—OH)
Al—OH*+TDMAS(g)→Al—O—Si(N(CH3)2)*+xs HN(CH3)2(g)
Al—OH*+TrisDMAS(g)→Al—O—SiH(N(CH3)2)*+xs HN(CH3)2(g)
Al—OH*+TrisDMAS(g)→Al—O—Si(N(CH3)2)*+xs HN(CH3)2(g)+H2(g)
Al—OH*+TDEAH(g)→Al—O—Hf(N(CH2CH3)2)*+xs HN(CH2CH3)2(g)
Al—OH*+TMA(g)→Al—O—AlCH3*+xs CH4(g)
Hf—OH*+TDMAS(g)→Hf—O—Si(N(CH3)2)*+xs HN(CH3)2(g)
Hf—OH*+TrisDMAS(g)→Hf—O—SiH(N(CH3)2)*+xs HN(CH3)2(g)
Hf—OH*+TrisDMAS(g)→Hf—O—Si(N(CH3)2)*+xs HN(CH3)2(g)+H2(g)
Hf—OH*+TDEAH(g)→Hf—O—Hf(N(CH2CH3)2)*+xs HN(CH2CH3)2(g)
Hf—OH*+TMA(g)→OH—AlCH3*+xs CH4(g)
Si—OH*+TDMAS(g)→Si—O—Si(N(CH3)2)*+xs HN(CH3)2(g)
Si—OH*+TrisDMAS(g)→Si—O—SiH(N(CH3)2)*+xs HN(CH3)2(g)
Si—OH*+TrisDMAS(g)→Si—O—Si(N(CH3)2)*+xs HN(CH3)2(g)+H2(g)
Si—OH*+TDEAH(g)→Si—O—Hf(N(CH2CH3)2)*+xs HN(CH2CH3)2(g)
Si—OH*+TMA(g)→Si—O—AlCH3*+xs CH4(g)
Reactivity of Surface Products with H2O(g) to Regenerate Surface Hydroxyl (—OH) Groups.
Al—O—Si(N(CH3)2)*+H2O→Al—O—Si(OH)*+xs HN(CH3)2(g)
Al—O—SiH(N(CH3)2)*+H2O→Al—O—SiH(OH)*+xs HN(CH3)2(g)
Al—O—SiH(N(CH3)2)*+H2O→Al—O—Si(OH)*+xs HN(CH3)2(g)+H2(g)
Al—O—Si(N(CH3)2)*+H2O→Al—O—Si(OH)*+xs HN(CH3)2(g)
Al—O—Hf(N(CH2CH3)2)*+H2O→Al—O—Hf(OH)*+xs HN(CH2CH3)2(g)
Al—O—AlCH3*+H2O→Al—O—Al(OH)*+xs CH4(g)
Hf—O—Si(N(CH3)2)*+H2O→Hf—O—Si(OH)*+xs HN(CH3)2(g)
Hf—O—SiH(N(CH3)2)*+H2O→Hf—O—SiH(OH)*+xs HN(CH3)2(g)
Hf—O—SiH(N(CH3)2)*+H2O→Hf—O—Si(OH)*+xs HN(CH3)2(g)+H2(g)
Hf—O—Si(N(CH3)2)*+H2O→Hf—O—Si(OH)*+xs HN(CH3)2(g)
Hf—O—Hf(N(CH2CH3)2)*+H2O→Hf—O—Hf(OH)*+xs HN(CH2CH3)2(g)
Hf—O—AlCH3*+H2O→Hf—O—Al(OH)*+xs CH4(g)
Si—O—Si(N(CH3)2)*+H2O→Si—O—Si(OH)*+xs HN(CH3)2(g)
Si—O—SiH(N(CH3)2)*+H2O→Si—O—SiH(OH)*+xs HN(CH3)2(g)
Si—O—SiH(N(CH3)2)*+H2O→Si—O—Si(OH)*+xs HN(CH3)2(g)+H2(g)
Si—O—Si(N(CH3)2)*+H2O→Si—O—Si(OH)*+xs HN(CH3)2(g)
Si—O—Hf(N(CH2CH3)2)*+H2O→Si—O—Hf(OH)*+xs HN(CH2CH3)2(g)
Si—O—AlCH3*+H2O→Si—O—Al(OH)*+xs CH4(g)
Reactivity of Surface Products with NH3(g) to Generate Surface Amine (—NH2, —NH) Groups.
Al—O—Si(N(CH3)2)*+NH3→Al—O—Si(NH2)*+xs HN(CH3)2(g)
Al—O—SiH(N(CH3)2)*+NH3→Al—O—SiH(NH2)*+xs HN(CH3)2(g)
Al—O—SiH(N(CH3)2)*+NH3→Al—O—Si(NH)*+xs HN(CH3)2(g)+H2(g)
Al—O—Si(N(CH3)2)*+NH3→Al—O—Si(NH2)*+xs HN(CH3)2(g)
Al—O—Hf(N(CH2CH3)2)*+NH3→Al—O—Hf(NH2)*+xs HN(CH2CH3)2(g)
Al—O—AlCH3*+NH2(p)→Al—O—Al(NH2)*+xs CH4(g)
Hf—O—Si(N(CH3)2)*+NH3→Hf—O—Si(OH)*+xs HN(CH3)2(g)
Hf—O—SiH(N(CH3)2)*+NH3→Hf—O—SiH(NH)*+xs HN(CH3)2(g)
Hf—O—SiH(N(CH3)2)*+NH3→Hf—O—Si(NH)*+xs HN(CH3)2(g)+H2(g)
Hf—O—Si(N(CH3)2)*+NH3→Hf—O—Si(NH)*+xs HN(CH3)2(g)
Hf—O—Hf(N(CH2CH3)2)*+NH3→Hf—O—Hf(NH)*+xs HN(CH2CH3)2(g)
Hf—O—AlCH3*+NH2(p)→Hf—O—Al(NH)*+xs CH4(g)
Si—O—Si(N(CH3)2)*+NH3→Si—O—Si(NH)*+xs HN(CH3)2(g)
Si—O—SiH(N(CH3)2)*+NH3→Si—O—SiH(NH)*+xs HN(CH3)2(g)+H2(g)
Si—O—SiH(N(CH3)2)*+NH3→Si—O—Si(NH)*+xs HN(CH3)2(g)+H2(g)
Si—O—Si(N(CH3)2)*+NH3→Si—O—Si(NH)*+xs HN(CH3)2(g)
Si—O—Hf(N(CH2CH3)2)*+NH3→Si—O—Hf(NH)*+xs HN(CH2CH3)2(g)
Si—O—AlCH3*+NH2(p)→Si—O—Al(NH)*+xs CH4(g)
Reactivity of Precursors with Surface Amine Groups (—NH or —NH2)
Hf—NH*+TrisDMAS(g)→Hf—N—SiH(N(CH3)2)*+xs HN(CH3)2(g)
Hf—NH*+TrisDMAS(g)→Hf—N—Si(N(CH3)2)*+xs HN(CH3)2(g)+H2(g)
Hf—NH*+TDEAH(g)→Hf—N—Hf(N(CH2CH3)2)*+xs HN(CH2CH3)2(g)
Hf—NH*+TMA(g)→Hf—N—AlCH3*+xs CH4(g)
Si—NH*+TrisDMAS(g)→Si—N—SiH(N(CH3)2)*+xs HN(CH3)2(g)
Si—NH*+TrisDMAS(g)→Si—N—Si(N(CH3)2)*+xs HN(CH3)2(g)+H2(g)
Si—NH*+TDEAH(g)→Si—N—Hf(N(CH2CH3)2)*+xs HN(CH2CH3)2(g)
Si—NH*+TMA(g)→Si—N—Al(CH3)*+xs HN(CH2CH3)2(g)
Reactivity of Surface products with NH3 to Regenerate Surface Amine Groups.
Hf—N—SiH(N(CH3)2)*+NH3(g)→Hf—N—Si(NH)*+xs HN(CH3)2(g)+H2(g)
Hf—N—SiH(N(CH3)2)*+NH3(g)→Hf—N—SiH(NH2)*+xs HN(CH3)2(g)
Hf—N—Si(N(CH3)2)*+NH3(g)→Hf—N—Si(NH2)*+xs HN(CH3)2(g)
Hf—N—Hf(N(CH2CH3)2)*+NH3(g)→Hf—N—Hf(NH2)*+xs HN(CH2CH3)2(g)
Hf—N—AlCH3*+NH2(p)→Hf—N—Al(NH2)*+xs HN(CH2CH3)2(g)
Hf—N—SiH(N(CH3)2)*+NH3(g)→Si—N—Si(NH)*+xs HN(CH3)2(g)+H2(g)
Hf—N—SiH(N(CH3)2)*+NH3(g)→Si—N—SiH(NH2)*+xs HN(CH3)2(g)
Si—N—Si(N(CH3)2)*+NH3(g)→Si—N—Si(NH2)*+xs HN(CH3)2(g)
Si—N—Hf(N(CH2CH3)2)*+NH3(g)→Si—N—Hf(NH2)*+xs HN(CH2CH3)2(g)
Si—N—Al(CH3)*+NH2(p)→Si—N—Al(NH2)*+xs HN(CH2CH3)2(g)
Reactivity of Surface Products with H2O(g) to Generate Surface Hydroxyl Groups
Hf—N—SiH(N(CH3)2)*+H2O→Hf—N—Si(OH)*+xs HN(CH3)2(g)+H2(g)
Hf—N—SiH(N(CH3)2)*+H2O→Hf—N—SiH(OH)*+xs HN(CH3)2(g)
Hf—N—Si(N(CH3)2)*+H2O→Hf—N—Si(OH)*+xs HN(CH3)2(g)
Hf—N—Hf(N(CH2CH3)2)*H2O→Hf—N—Hf(OH)*+xs HN(CH2CH3)2(g)
Hf—N—AlCH3*+H2O→Hf—N—Al(OH)*+xs CH4(g)
Si—N—SiH(N(CH3)2)*+H2O→Si—N—Si(OH)*+xs HN(CH3)2(g)+H2(g)
Si—N—SiH(N(CH3)2)*+H2O→Si—N—SiH(OH)*+xs HN(CH3)2(g)
Si—N—Si(N(CH3)2)*+H2O→Si—N—Si(OH)*+xs HN(CH3)2(g)
Si—N—Hf(N(CH2CH3)2)*+H2O→Si—N—Hf(OH)*+xs HN(CH2CH3)2(g)
Si—N—Al(CH3)*+H2O→Si—N—Al(OH)*+xs HN(CH2CH3)2(g)
The ALD processes are maintained in a temperature range from about 20� C. to about 650� C., preferably from about 150� C. to about 300� C., more preferably at about 225� C. Materials grown may be similar throughout a wider temperature range assuming that saturating ALD behavior is maintained. The ALD processes are conducted with a pressure in the range from about 0.1 Torr to about 100 Torr, preferably in the range from about 1 Torr to about 10 Torr. Materials grown may be similar from high vacuum to high pressures assuming saturating ALD behavior is maintained. The flow is maintained viscous to encourage reactant separation. Carrier gas (e.g., N2) is maintained in the range from about 50 sccm to about 1,000 sccm, preferably at about 300 sccm with a speed of about 1 m/s. Higher speeds may create particle transport issues while lower speeds could allow particle formation due to inefficient purging, affecting electrical behavior of thin films. Films are deposited with thickness in the range from about 2 Å to about 1,000 Å, preferably, from about 5 Å to about 100 Å, and more preferably in the range from about 10 Å to about 50 Å.
In one example, a hafnium oxide film is grown by ALD in the presence of hydrogen gas. Hydrogen is used to reduce levels of halogen contaminates (e.g., F or Cl) within hafnium-containing films. Flow A, containing hafnium tetrachloride and at least one carrier gas (e.g., Ar, N2 and H2), is pulsed sequentially with Flow B, containing water, hydrogen and an optional carrier gas. Flows A and B are each pulsed for about 1 second and purge flows of argon are pulsed for about 1 second between each pulse of Flows A and B. The temperature is maintained in the range from about 250� C. to about 650� C.
In another example, a hafnium silicate film is grown by ALD in the presence of hydrogen gas. Flow A, containing hafnium tetrachloride and at least one carrier gas (e.g., Ar, N2 and H2), is pulsed sequentially with Flow B, containing water, hydrogen and an optional carrier gas and Flow C, containing Tris-DMAS and at least one carrier gas. Flows A, B and C are each pulsed for about 1 second and purge flows of argon are pulsed for about 1 second between each pulse of Flows A, B and C. The temperature is maintained in the range from about 450� C. to about 650� C.
In another example, a hafnium silicon oxynitride film is grown by ALD in the presence of hydrogen gas. Flow A, containing hafnium tetrachloride and at least one carrier gas (e.g., Ar, N2 and H2), is pulsed sequentially with Flow B, containing water, hydrogen and an optional carrier gas and Flow C, containing Tris-DMAS and at least one carrier gas and Flow D, containing a nitrogen plasma and an optional carrier gas. Flows A, B, C and D are each pulsed for about 1 second and purge flows of argon are pulsed for about 1 second between each pulse of Flows A, B, C and D. The temperature is maintained in the range from about 450� C. to about 650� C.
Materials are deposited by dosing chemicals separately in an alternating fashion to achieve the desired film composition or characteristics with selected half reactions. The above half reactions, however, do not dictate the exact bonding connectivity or the stoichiometry of the resulting film. Stoichiometry is largely controlled by thermodynamics; however, kinetically controlled films may be achieved. Thus, the dosing sequence may be modified to effect the overall composition and qualities of the film. The types of thin-film materials that can be grown with ALD half reactions generally are:
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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|Notification of First Office Action dated May 23, 2008 for Chinese Patent Application No. 200480008427.0.
|Ohshita, et al. "HfO2 Growth by Low-pressure Chemical Vapor Deposition Using the Hf(N(C2H5)2)4/O2 Gas System," Journal of Crystal Growth 233 (2001) 292-297.
|Ohshita, et al., "Hf1-xSixO2 deposition by metal organic chemical vapor deposition using the Hf)NEt2)4/SiH(NEt2)3/O2 gas system", Preparation and Characterization, Elsevier Sequioa, NL, vol. 416, No. 1-2, Sep. 2, 2002, pp. 208-211.
|Paranjpe, et al. "Atomic Layer Deposition of AlO3 for Thin Film Head Gap Applications," J. Elec. Soc., vol. 148, No. 9 Sep. 2001 pp. G465-471.
|Renaud Fix et al, "Chemical Vapor Deposition of Titanium, Zirconium, and Hafnium Nitride Thin Films." 6135 Chemistry of Materials, 3 Nov./Dec. 1991, No. 6, BNS pp. 1-11.
|Ritala, et al. "Atomic Layer Deposition of Oxide Thin Films with Metal Alkoxides as Oxygen Sources," Science vol. 288 Apr. 14, 2000.
|Ritala, et al. "Perfectly Conformal TiN and Al2O3 Films Deposited by Atomic Layer Deposition," Chem. Vap. Deposition 1999, 5, No. 1.
|Ritala, et al. Ann. Acad. Sci. Fenn. Ser. A II. Chemica 257 (1994) 1-48.
|Ritala, et al., "Development of Crystallinity and Morphology in Hafnium Dioxide Thin Films Grown by Atomic Layer Epitaxy," Thin Solid Films, vol. 250, No. 1-2, (Oct. 1, 1994), p. 72-80.
|Sekine, et al. "Nitrogen profile control by plasma nitridation technique for poly-Si gate HfSiON CMOSFET with excellent interface property and ultra-low leakage current," International Electron Devices Meeting 2003. IEDM. Technical Digest. Washington, DC, Dec. 8-10, 2003, New York, NY, IEEE, US, Dec. 8, 2003, pp. 103-106.
|Shanware et al. Reliability of HfSiON gate dielectric film with 12.8 A SiO2 equivalent thickness. Electron Devices Meeting, 2001. IEDM Technical Digest, International. Aug. 7, 2002. p. 6.6.1-6.6.4.
|Visokay et al. Application of HfSiON as a gate dielectric material. Applied Physics Letters, vol. 80, No. 17. Apr. 29, 2002. p. 3183-3185.
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|Citing Patent
|Filing date
|Publication date
|16 Apr 2010
|11 Jan 2011
|Canon Anelva Corporation
|Method of manufacturing dielectric film that has hafnium-containing and aluminum-containing oxynitride
|14 Apr 2010
|4 Oct 2011
|Canon Anelva Corporation
|Dielectric film and semiconductor device using dielectric film including hafnium, aluminum or silicon, nitrogen, and oxygen
|10 Sep 2010
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|Canon Anelva Corporation
|Dielectric film and semiconductor device using dielectric film including hafnium, aluminum or silicon, nitrogen, and oxygen
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|U.S. Classification
|257/411, 438/763, 438/590, 438/493, 438/785, 438/786, 257/410
|International Classification
|Cooperative Classification
|European Classification
|30 May 2006
Owner name: APPLIED MATERIALS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ROCKLEIN, M. NOEL;GEORGE, STEVEN M.;METZNER, CRAIG;AND OTHERS;REEL/FRAME:017692/0644;SIGNING DATES FROM 20030512 TO 20030515
|18 Aug 2009
|Certificate of correction
|4 Oct 2012
|Fee payment
Year of fee payment: 4


text:
The South Coast League boys water polo race delivered another upset Tuesday.
Goalie Brett Argersinger made 15 saves and Ryan Villanueva added four goals as Aliso Niguel stunned visiting San Clemente, 9-8.
On Monday, San Clemente knocked off No. 3 El Toro, 11-10, to move into contention to claim at least a share of the league title. But Aliso Niguel sank those aspirations.
"I wasn't shocked — I'd say other people were shocked," Aliso Niguel coach Erick Lynch said of the victory. "We have the talent."Aliso Niguel finished the Division 1 league at 2-6. With the Wolverines' victory and Dana Hills' 20-8 triumph against Capistrano Valley, the Dolphins (20-7, 6-1) clinched at least a share of the league title.
On Thursday, Dana Hills plays at San Clemente (4-3 in league) while El Toro (5-2) plays at Capistrano Valley (1-6).
In nonleague matches:
No. 1 Mater Dei 14, Long Beach Wilson 9: Jon Walters scored nine goals and McQuin Baron made 21 saves at Belmont Plaza to lead the visiting Monarchs (25-0), who played without attacker James Walters (ill).
No. 3 El Toro 11, No. 6 Laguna Beach 9: The host Chargers (19-8) scored four goals in the fourth to rally past the Breakers (18-9), who played without Riley Thomas (facial cut).
In the Pacific Coast League:
University 13, No. 10 Northwood 9: Jake Sanders and Griffin Chappell each scored five goals as the host Trojans (20-8, 7-3) force a second-place with the Timberwolves (20-9, 7-3).
Northwood won the coin flip for the No. 2 seed.

subset: commoncrawl


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Climb El Misti
Climbing El Misti is a thrilling adventure if you like to trek, hike, or climb mountains. It is not a technical climb, but with that said, it isn't an easy climb no matter what anyone tells you, even if you are in shape. The altitude is nothing to mess with and the infamous "saroche" or altitude sickness can affect anyone without warning whether you are an experienced climber or not. There is a great website sponsored by the International Society for Mountain Medicine that explains all about altitude sickness and signs and symptoms and treatments to prevent it and what to do if you actually get it. Here is a link to their website Altitude Sickness.
El Misti is actually a volcano that is still active but hasn't erupted since 1784. To put things in perspective on how tall this mountain is, Mount Kilamanjaro in Africa is 5895m (19340 ft) at its summit and Mount Everest in Nepal is 8850m (29,035 ft). Misti is 5822m (19,101 ft). Per my husband, it is a glorious experience to reach the top of Misti despite the 2 grueling days of hiking that make you question "Why the heck am I doing this on my vacation?" To explain how difficult it is to reach the top, my husband was only 2 of the 4 of our group that was actually able to reach the top, and of the other person who reached the top, my husband basically helped push him up the mountain. At the summit you will find a crater (remember Misti is a volcano) and a beautiful metal cross and the most stunning views of the nearby mountain ranges (Chachani) that make you question whether you are standing in heaven. My husband said they went so high up that they walked higher than some clouds. With all that said, the most important thing you can do is make sure you go with an experienced guide and company. We went with Incaventura and our guide was Herman. Here is a link to their website Incaventura.
Equipment: -good backpack (you will be carrying this yourself for an entire day so make sure it fits)
-sleeping bag (one that is able to tolerate temps as low as 20 degrees F in April)
-good waterproof hiking boots (there is snow at summit)
-4 liters of water per person
-2 pairs of wool socks (cotton kills hiking)
-thermal underwear (thank god I had mine)
-good hiking khakis with plenty of pockets
-underarmor bra and panties or underwear for guys (keeps the sweat off of you)
-long sleeve shirt
-fleece sweater (Denali from North Face worked perfect)
-short sleeve tee
-chapstick or lip balm
-hat to cover your head from the blazing sun
-good warm gloves (our fingers were freezing mostly)
-camera (for the brilliant shots you will see and to prove you reached the top)
-ipod (helps with the ascent to get your mind off things)
-good head lamp (the second day you start hiking at 2 am)
-tylenol or motrin for headache/aches and pains
-diamox if you are taking it to prevent altitude sickness
-most tour companies will provide a tent (and crampons if needed) but if you can carry the weight, bring your own
-meals, fuel, stove and dishware should be provided by your tour company
-winter cap (make sure it covers your ears)
-winter coat (a ski coat works perfectly)
-moleskin for blisters (make sure you also have scissors to cut it)
-plenty of determination
- Camping
- Hiking and Walking
- Mountain Climbing
El Misti Part Deux
Just so you know what you are getting into before you plan your next excursion to El Misti, know that the trip takes 2 days. The first day you will spend hiking up the base of the mountain, which is challenging at times but mostly a very nice leisurely trek. You leave at about 8 am and reach base camp at about 5pm. At base camp, in April anyway, you will find that once the sun goes down, the temperature significantly drops to the point that it is just bone chilling cold. At our base camp the temperature was around 30 degrees F. At base camp you will help your guide pitch your tent and you will eat dinner. The night in the tent is awful. You basically get no sleep because of the altitude and you will most likely than not be sleeping on a slope with many rocks and your tent will get very damp (why I recommend you bring your own good equipment).
The second day you will start your hike in very cold temps at 2 am. This is where the trek becomes quite strenuous. Not only are you exhausted from the previous day's hike, and extremely tired from the lack of sleep, you have to deal with the cold and very steep climbs. You will climb a bit and then you will reach an area where your guide will ask your group whether or not you think you can continue on. If you think you can't then stop! Your guide will return you to the base camp to wait out the rest of the group. I kept going and I reached about 17,000 ft where there I found I was completely spent and could hike no longer. So instead of waiting in a nice tent at base camp, I had to spend 4 hours on the side of a mountain, hutched under a makeshift shelter by my guide while I waited for the others in our group to reach the summit. Thank God for my Ipod.
Once you reach the summit, you then hike back down the entire mountain. This is much quicker as a significant portion of it you hike down the opposite side of the mountain from which you came which is volcanic ash. The final part is a hike over rocky terrain to reach your jeep that takes you home.
- Mountain Climbing
- Hiking and Walking
- Eco-Tourism
I suggest 3 hikes of 1 day around Arequipa, with different landscapes and difficulty levels.
Tiabaya-El Huayco. Hike through the green fields along the Rio Chili. Low difficulty.
Chiguata-Yumina. Follow the gorge of the Rio Andamayo in the river bed up to the cultivated terraces of Yumina. Moderate difficulty.
Pocsi-Yarabamba. Hike down the gorge of Rio Polobaya through the picturesque villages of Sogay and Polobaya. Moderate to high difficulty
Clasical "tour campiña"
By car, you wander through the surroundings of Arequipa, making stops at the main spots of interest such as the square and church of Cayma, mirador of Yanahuara and Sachaca, Sabandía watermill, Mansión del Fundador, inca terraces of Yumina and village of Characato (3-4 hours) .
Climb a volcano!
With volcanoes surrounding Arequipa, why not give climbing one a go? There is the majestic El Misti at 5825 meters. There are guided climbs or you can hike a 4 WD to bring you up to 3300m for about $50. Cachani at over 6000 meters requires ice ax and crampons and unless very experienced, a good guide! We didn't have the time or money and opted for a "climb" down into the Colca Canyon, another great option close to Aqreuipa.
Enjoy the feeling of biking freely through the fields, a few hours or the whole day. You can rent a bike
Ride a horse for 2 or 3 hours through the agricultural terraces of Yumina, built under the reign of the Inca Mayta Capac and still in use today
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You'll go WILD for 99 Flavored Schnapps bold new flavor - 99 Black Cherries! This delicious new taste treat is perfect for shooters, mixers, or even chilled and served up straight. So do yourself a flavor and try 99 Black Cherries in your next cocktail or shot.
Made from distilled cherries. Used in Fondue dishes or as a digestive aid. Always clear because it is not aged in would like vodka. Servered ice cold.
Since 1818, this cherry cordial has been produced in Denmark without any artifical ingredients, colors, or flavors from a tip secret Herring family recipe. The sweet, full-bodied liqueur became famous in 1915 with the creation of the Singapore Sling. HEERING® Cherry Liqueur is a classic liqueur that is matured for three...
Clear Creek Cherry Brandy 375ml
Fresh Oregon and Washington sweet cherries are crushed, fermented, and distilled into clear, powerful Kirschwasser (cherry Schnapps) in the traditional German fashion. The flavor and great vanilla/almond nose come only from the cherries, as does the alcohol. As in all other Clear Creek products no colors, flavors, or sugars are added....
Cruzan Black Cherry Rum is a sweet and smoothly flavored Cruzan with distinct character of cherry. It can be enjoyed over ice or mixed with fresh fruit juices to create a refreshing summer cocktail.
DeKuyper Cheri-Beri Pucker 1.0L
DeKuyper Pucker Cherry is a vibrant blend of sweet and sour flavor. Simply add a splash of any Pucker flavor to your ordinary drink to create an exciting bumped up cocktail. DeKuyper Pucker, the Brand Bartenders Trust.
Made from distilled cherries. Used in Fondue dishes or as a digestive aid. Always clear because it is not aged in would like vodka. Servered ice cold.
Dr. McGillicuddy's Cherry Schnapps
Deep ruby color. Bright maraschino cherry and almond paste aromas. A silky entry leads to a lightly sweet medium body of crushed maraschino cherries flavors. Finishes with a sweet, very slightly tangy fade. A pleasant and clean cherry cordial.
Evan Williams Cherry Reserve Kentucky Liqueur
PROOF 70 Proof COLOR Pale amber NOSE Cherry and berry fruits, cinnamon spice TASTE Plum and cherry sweetness, then caramel FINISH Cherry pipe tobacco and marzipan
Hiram Walker® Cherry Brandy is smooth and delicious. It has a brilliant, sparkling color, delicate bouquet and true, tart cherry flavor.
Hiram Walker Kirshwasser Cherry
Made from the heart or pit of the Kirsch cherry, Hiram Walker® Kirschwasser is a crisp, tart and full flavored liqueur
The Leroux family of distillers dates back over 100 years. Its products originated in Belgium but are today produced in the U.S. They are made with the finest natural ingredients, and the entire line is certified Kosher, a unique point of differentiation. The Leroux flavored brandies are top sellers in the...
Luxardo Maraschino is a specialty known and appreciated around the world. Luxardo Maraschino Originale is a classic, and the Luxardo family still produces this wonderful liqueur according to the original formula used by Girolamo Luxardo in 1821. The patented, hand-woven, straw-plaited round bottle has become an iconic symbol of the brand....
PAMA captures the complex, sweet yet tart taste and seductive ruby color of all-natural pomegranates. PAMA is made with all-natural pomegranate juice, premium vodka and a touch of imported tequila. Bottled at 34 proof, PAMA is highly mixable in a range of cocktails such as PAMA and Champagne, PAMA Cosmo and...
Pinnacle is the ideal French vodka - clean, smooth and extremely mixable. Every sip of Pinnacle is inspired by a time honored recipe handed down from generation to generation. Made with a tradition and ancestral recipe, Pinnacle is produced with modern equipment in the Distillerie de la Tour, ensuring the highest...


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November 29, 2015
LEXINGTON, Ky. (WKYT) - The fine for parking in a handicap spot without proper tags in Lexington went up this week.
City Council voted to increase the fine from $15 to $250. They say the increase was prompted because Lexington had one of the lowest fines in the state.
"These are situations that people alert us to," said Lexington Police Spokesperson Sherelle Roberts. "We're not driving around looking for people in violation of handicap parking spaces for the most part."
WKYT spent a couple of afternoons looking for violators. Mostly, we found people sitting in a handicap spot waiting for someone without handicap tags, or people that have handicap tags but forgot to display them where people can see. Both, police say, are finable actions.
As a reminder, if you have handicap tags, they need to be visible from the front and back of the car. Tags either need to be hanging on the rear-view mirror, on the dashboard, or on the license plate.
Click Here to access the online Public Inspection File
Viewers with disabilities can get assistance accessing this station's FCC Public Inspection File by contacting the station with the information listed below. Questions or concerns relating to the accessibility of the FCC's online public file system should be directed to the FCC at 888-225-5322, 888-835-5322 (TTY), or firstname.lastname@example.com.


text:
November 28, 2015
GADSDEN, Ala. (AP) - The woman who staged her son's kidnapping
last week to cover up his death was charged with capital murder
Monday, the day the boy was buried.
25-year-old Shalinda Glass has been held without bond in the Etowah County jail since she was charged with hindering prosecution last Tuesday, when the body of five-year-old Geontae Glass was found in the trunk of her boyfriend's car.
District Attorney Jimmie Harp said the decision to charge Glass with capital murder was based partly on forensic evidence and prosecutors' and investigators' conclusion that this charge is "only appropriate," The Huntsville Times reported on its Web site.
Glass' boyfriend, 31-year-old Kevin Andre Towles, is also being held without bond on capital murder charges.
(Copyright 2006 by The Associated Press. All Rights Reserved.)
Click Here to access the online Public Inspection File
Viewers with disabilities can get assistance accessing this station's FCC Public Inspection File by contacting the station with the information listed below. Questions or concerns relating to the accessibility of the FCC's online public file system should be directed to the FCC at 888-225-5322, 888-835-5322 (TTY), or firstname.lastname@example.com.


text:
Mary Teresa (Karpinski) Mudry, 91, of Asheville, N.C., died Oct. 19, 2003. At the age of 11, she came to Ellis Island, N.Y., with her parents and two sisters and a brother, who are all deceased. In 1931, she married Joseph Mudry of Staten Island, N.Y., deceased.
Services: Were held in Asheville, N.C., on Oct. 22.
Survivors: Sons, Edward Mudry, St. Augustine, and Joseph Mudry, Euless, Texas; daughter, Carol (Mudry) Dolab of Asheville, N.C.; seven grandchildren and six great-grandchildren.
In charge: West Funeral Home, Weaverville, N.C.
© 2015. All Rights Reserved. Terms of Service | Privacy Policy / About Our Ads


text:
Search Results for: in-store
February 12, 2013
Clarks Americas Teams Up With Invodo Video Solutions for Best In-Store Experience
Clarks Americas, a global designer and footwear retailer, has teamed up with Invodo to focus on creating the best in-store experience through video, according to a release from Invodo.
The retailer has revamped its site by offering product videos that …
December 14, 2012
The True Story of a Seamless In Store Return at Old Navy
On Nov. 26, or a day better known to the ecommerce world as Cyber Monday, I was given the assignment to use my iPhone 4S to shop online using any personal email promotion I received for that day in my inbox. …More...
December 12, 2012
Office Depot Announces In-Store Pick Up Within Hour for Online Orders
Office Depot has announced that customers can now pick up most of its online inventory at a traditional brick and mortar store within an hour of ordering from the web.
In a press release, the office supply retail chain said …
December 3, 2012
5 Tips to Turn Showrooming Consumers into In-store Customers
Is that a competitor lurking in aisle 7?! Retailers nowadays are increasingly contending with questions like this one. No, they're not being infiltrated by a new and insidious breed of corporate spies. Rather, consumers – via their mobile devices – are inviting …More...
September 25, 2012
Buy Online and Pickup in Store for iPhone 5
Rumors have been flying all over the internet for the past several days, but it turns out that Apple will in fact offer a buy online and pick up in store option for the much sought after iPhone 5.
Follow US! @…
July 11, 2012
In-Store Pickup: The New Retail Requirement
Source: ShopatronMore...
In Infographics
March 6, 2012
Continuing the Customer Conversation In-Store and Online
I'm growing tired of this question: How do I drive an in-store customer online and vice versa? It's not a bad question, but I do feel that it is being asked in the wrong way. The question should …More...
December 8, 2011
Amazon Encouraging Mobile Shopping In-Store
The warning signs about confident consumers shopping on Amazon while browsing your store's merchandise have been evident, and now the ecommerce giant is encouraging smartphone owners to do so. As an added incentive, Amazon is giving customers using Price Check …More...
December 1, 2015
Vista Equity Simultaneously Buys MarketLive and Shopatron
AUSTIN, Texas–(BUSINESS WIRE)–MarketLive Inc. and Shopatron, leading providers of software solutions for the global retail industry, today jointly announced that the companies will be acquired simultaneously by Vista Equity Partners ("Vista"), a leading private equity firm that focuses …More...
In News, PR Newswire
December 1, 2015
All Sorts of Sales Records Set on Cyber Monday 2015
Related Cyber Weekend News
Stores that Closed Doors on Thanksgiving and Black Friday Outperformed Competitors Online
Editor's Notebook: My Big Fat Omnichannel Thanksgiving Shopping Day
No Surprise: Thanksgiving Ecommerce Sales on the Rise
Editor's Notebook: Black Friday and …More...
In News, PR Newswire


text:
From Wikipedia, the free encyclopedia
|Look up NH or nH in Wiktionary, the free dictionary.
NH may refer to
- All Nippon Airways, Japan's largest airline, formerly Nippon Helicopter
- National Highway, a road designation in many countries
- National Hose Thread, a threaded connection standard used on hose couplings
- NetHack, a computer game
- New Hampshire, one of the states of the United States
- New Haven, Connecticut, a city in the United States
- New York, New Haven and Hartford Railroad
- NH Hoteles, a Spanish-based hotel chain
- Nishan-e-Haider, a Pakistani military award
- No-hitter, a baseball term
- Nordsjælland Håndbold, a Danish handball team
- North Holland, a province in the Netherlands
In science, medicine and technology[edit]
- Interstellar nitrogen monohydride, the NH molecule detected in outer space
- Nh (digraph), an orthographic concept
- Nickel hydride, a type of rechargeable battery
See also[edit]
|This disambiguation page lists articles associated with the title NH.
If an internal link led you here, you may wish to change the link to point directly to the intended article.


text:
Win Free Tickets to Social Media Success Summit 2012
***UPDATE*** Congrats to Joy Dekkers and Taylor Howe, the winners of this free ticket contest. See Joy's winning comment here.
Want to win a free ticket to the largest online social media marketing event of the year?
Social Media Examiner has worked hard to bring you our fourth-annual Social Media Success Summit. This is our best event ever! And we've come up with a fun way to get you involved.
First, what is this event?
Social Media Success Summit 2012 is a large online conference dedicated to helping marketers and business owners master social media marketing.
More than 1400 businesses have already signed up, including Wells Fargo, Motorola, Kraft Foods, Fox Broadcasting, Autodesk, Salesforce.com, Hubbell, American Heart Association, NASA, Marriott, Vanguard, HP, Verizon Wireless, McGraw-Hill, and hundreds of smaller businesses.
Twenty-seven of the world's most respected social media experts will share their strategies with you.
9 Social Media Marketing Tips From the Pros
Are you looking for some new ideas to simplify your social media marketing?
Do you wonder how others use social media to attract customers?
We asked the pros for their hottest social media tips. Here's their advice to help you power up your social media marketing.
#1: Draw Attention to Your Custom Tabs in the New Facebook Timelines
If you have a special offer on your website, why not use Facebook to showcase your freebie?
With the new Facebook Timelines fan pages, you can no longer have a custom tab as a default landing tab, so now you will have to draw attention to your freebie with the custom tab photo and the custom tab name.
HubSpot has done a great job of that with their custom tab photo advertising their free ebook and the Customer Case Studies title on one of their other apps.
Businesses to Fully Embrace Social Media In 2012
The vast majority of Americans are actively using social media. Has your business acted on this fact?
Are you looking for a way to keep pace with the quickly evolving field of social media marketing?
If so, Social Media Examiner has some exciting news…
But first, consider this story.
Imagine your business competing for your state's "Best Brand" title against huge names such as Target, Dairy Queen and Wheaties.
Now imagine simply leveraging the power of social media and taking the grand prize! Wouldn't that just blow your mind?
Win Free Tickets to Social Media Success Summit 2011
**UPDATE** We have announced our two winners. The winner of the comment/blog portion of the contest, receiving two tickets to the Social Media Success Summit is Kaarina Dillabough, read her comment here . The winner of the Twitter contest is Billings Info Tech, an information technology service in Billings, MT. Thanks to everyone who participated in the event. We look forward to seeing you all in a couple of weeks!
Want to win a free ticket to the largest online social media event of the year?
Social Media Examiner has worked hard to bring you our third-annual Social Media Success Summit. This is our best event ever! And we've come up with a fun way to get you involved.
First, what is this event?
Social Media Success Summit 2011 is a large online conference dedicated to help businesses master social media marketing.
More than 1400 businesses have already signed up, including Microsoft, General Mills, Honda, Tyco, IEEE, SAP, Wells Fargo, Warner Music Group, Timex, Junior Achievement, SAP, LexisNexis, Stonyfield Farm, Cisco, Mayo Clinic, Coca-Cola and hundreds of smaller businesses.
Social Media Has Changed: Are You Ready?
When Michael Stelzner started Social Media Examiner in October 2009, he never dreamed it would become so successful so quickly.
As of March 2011, Social Media Examiner has 59,000 email subscribers, 33,000 Facebook fans, over 60 writers and half a million page views per month.
In addition, the site has generated almost $2 million in sales; ranks among the top 12 websites on two Technorati lists – business and small business; and ranks among the top 1,500 websites in the entire United States, according to Alexa.
"We didn't do anything unique," Stelzner said. "We simply employed great content with smart social media marketing and our community did the rest. And any business can achieve great results."
12 Social Media Secrets From World's Top Superstars
It's no secret that social media marketing is the most powerful business-building tool on the planet. Now any business can directly reach customers, anytime and anyplace.
To take your social media marketing to the max, here are hot social media tips direct from 12 of the top industry masters. You're going to want to model their priceless advice:
#1: Engage Your Facebook Fans With Questions
The Social Media Examiner Story: Proof Social Media Works
Back in October of 2009 we launched SocialMediaExaminer.com. The response was immediate and it was big (I'll share some of the back story in the video below).
We relied 100% on social media tactics to drive traffic to this site.
In less than 5 months, Social Media Examiner was declared the #1 small business blog in the world by Technorati, added more than 13,000 email subscribers, brought nearly 100,000 people a month to the site and is ranked as one of the top 4200 websites in all of America by Alexa.
We didn't advertise, didn't rely on the press and almost none of our traffic is coming from search engines. Nearly overnight, this site has become a top destination for businesses.


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Poll: What is your favorite type of Twilight fanfiction to read? Vote Now!
Author has written 14 stories for Twilight, and Skip Beat!.
My name is Ria.
Rawr. Officially 17 years old. Fear it.
And, before you say anything, I loved Breaking Dawn. Personally, I am offended by all of these "Breaking Dawn Ruined Twilight For Me!" people. Ha. Some Twilighters you all turned out to be. I didn't like New Moon, and Eclipse rubbed me the wrong way, but I stuck with Stephenie Meyer because I had faith that she knew what she was doing and would find a way to make everyone happy in the end. Guess what: I was right! Breaking Dawn was amazing and stole the place of my second favorite book, after Twilight naturally. Yes, I loved Breaking Dawn; so bite me!
I've taken to roleplaying again, also. It's like fanfiction, but you get to interact with other people more, so I think it's a bit more fun. If you are ever in the urge to roleplay, look me up on Neopets, or send me a PM with a forum. 9 out of 10 times, I'll jump at the chance.
And read soveryunpretty's wonderful stories if you haven't already! If you like me, I can guarantee you will LOVE her. Clicky-click: http://www.fanfiction.net/u/1286676/soveryunpretty
Ria's stats-
Completed Stories: 11/13
Status: I'm baaack!
Neopets accounts: little_miss_ria
Myspace: URL
iChat AIM : littlexMissxRia


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(The following press release from Heidelberger Druck AG was received by e-mail. It was not confirmed by the sender.) Heidelberg Further Expands its Consumables Business 10/30/2012 - Takeover of the OFS Group in Switzerland - Customers benefit from a comprehensive range of consumables from a single source Heidelberger Druckmaschinen AG (Heidelberg) is further expanding its consumables business in Switzerland by taking over the Pfaffnau-based OFS Group (OFS). With a workforce of around 25, OFS is one of the leading suppliers of prepress systems and consumables in Switzerland, and has been active in the market for over 40 years. The main focus of the company has been on the sale of platesetters in conjunction with the corresponding printing plates from Kodak for the sheetfed offset and newspaper market. As a result of this takeover, Heidelberg Schweiz AG is now the largest dealer in consumables in the graphics industry. "The OFS Group and Heidelberg have a comprehensive sales and service network in Switzerland. By combining the activities of the two companies in the area of consumables, customers now have access to a wide range of products from a single source. At the same time, they will benefit from the renowned high quality and service standards of Heidelberg," says Peter Tix, Head of Consumables and CtP at Heidelberg. Heidelberg plans to pool all of its Swiss consumables activities at the OFS's former headquarters in Pfaffnau. In the future, customers will not only be able to purchase the OFS Group's existing range of CtP systems and printing plates for the offset and newspaper market from Kodak, they will also have access to the full Heidelberg range of SAPHIRA consumables including inks, varnishes, washup cloths, blankets, chemicals, rollers, and the SAPHIRA Eco Line of environmentally friendly consumables – all from a single source. Heidelberg will also be underlining its high standard of service with a new color mixing station – a fully-automated, high-precision system that is among the most state-of-the-art in Switzerland. Customers in Switzerland can order most products online at www.shop.heidelberg.com. "For Kodak, the Heidelberg takeover of the OFS Group means a long-term, successful presence in Switzerland. Concentrating the consumables business in Pfaffnau ensures that our customers will receive the high standard of service they have come to expect in the consumables business. What's more, this will also give us the opportunity to establish a stronger position for Kodak products on the Swiss market. The successful newspaper business will continue as usual," states Olivier Claude, Regional Business Manager for Print, Vice President Commercial Business EAMER at Kodak. After the takeover of OFS, the share of total sales by the Heidelberg sales company in Switzerland accounted for by consumables has risen to over 25 percent. The Swiss Heidelberg sales company currently employs a staff of around 135. The portfolio focuses on the value-added chain in offset printing, ranging from prepress and press to postpress and including software, services, and consumables. Figure: Heidelberg is further expanding its consumables business in Switzerland by taking over the Pfaffnau-based OFS Group: (left to right) Roland Wymann, Managing Director Finances and Carsten Heitkamp, Chairman of the Management Board, both Heidelberg Switzerland, as well as Beatrice Müller and Kurt Steidle, both members of the OFS Holding AG Administrative Board, subsequent to the contract signing of both companies in Olten, Switzerland. Images and further company information are available in the press portal of Heidelberger Druckmaschinen AG at www.heidelberg.com. For further information, please contact: Heidelberg Schweiz AG: www.ch.heidelberg.com OFS Group: www.ofsgroup.ch Further information for journalists: Heidelberger Druckmaschinen AG Corporate Public Relations Matthias Hartung Phone: +49 (0)6221 92-5077 Fax: +49 (0)6221 92-995077 E-mail: email@example.com Important note: This press release contains forward-looking statements based on assumptions and estimations by the Management Board of Heidelberger Druckmaschinen Aktiengesellschaft. Even though the Management Board is of the opinion that those assumptions and estimations are realistic, the actual future development and results may deviate substantially from these forward-looking statements due to various factors, such as changes in the macro-economic situation, in the exchange rates, in the interest rates and in the print media industry. Heidelberger Druckmaschinen Aktiengesellschaft gives no warranty and does not assume liability for any damages in case the future development and the projected results do not correspond with the forward-looking statements contained in this press release. Link to recent news: http://www.heidelberg.com/www/html/en/content/articles/press_lounge/company/gene ral/2012/121030_takeover_ofs Heidelberger Druckmaschinen AG Chairman of the Supervisory Board: Robert J. Koehler Management Board: Dr. Gerold Linzbach, Chairman - Dirk Kaliebe – Marcel Kießling - Stephan Plenz Principal place of business: Heidelberg - Amtsgericht Mannheim (competent registry court) - Commercial Register HRB 330004 - VAT Number DE 143455661 Here you can update your details or unsubscribe the Newsletter.: http://www.heidelberg.com/corp/www/en/newsletter/subscribe?id=su1qt1juxZeXoty1mw i0zMe (C) Copyright Heidelberger Druckmaschinen AG
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The TapouT crew travels to Hawaii to sign up B. J. Penn's Brazilian Jiu-jitsu trainer, Renato "Charuto" Verissimo. After a tour of the island, the boys return to California to attend to some business watch video >>
Fighting Hurts Episode 1UK's verstion of TUF. TUF meets American Idol. watch video >>
Fighting Hurts Episode 2 watch video >>
Fighting Hurts Episode 3 watch video >>
Fighting Hurts Episode 6 Finale watch video >>
Eriq is a wannabe rapper with a bad attitude and he makes life miserable for his ex-girlfriend, Linda. Mayhem Miller offers $10k to settle things in the cage with MMA fighter, John Murphy watch video >>
We take a look at UFC 134 and the UFC's return to Rio, we catch up with Dominick Cruz and we sit down with the Scrap Pack for a discussion on all things UFC and we also sit down with some B/R contrib watch video >>
UFC lightweight Joe Lauzon continues his ascent to the top of the division as he prepares for his UFC Fight Night: Shogun vs Sonnen opponent, Michael Johnson. Episode 5 takes us through the brutal st watch video >>
Ronda Rousey's Mom, and former World Judo champion, Ann Maria DeMars stops by, fighters struggle to eat clean, and David Grant and Louis Fisette prepare for their bout on episode 5 of The Ultimate Fi watch video >>
On episode #5 of the 7-part fight week series, UFC Embedded, the UFC's biggest stars press their luck. At Zuffa HQ, Dana White takes a call from Nick Diaz, deals with Jon Jones' manager, and gets his watch video >>


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I love magazines like Parents and Parenting, but I they seem more and more irrelevant to our crunchier lifestyle. I'm thinking about Kiwi, but wonder if there are any others.
crunchy mom type magazines?
Jen (38) married to my college sweetheart for 16 years.
Crunchy mom to A (15), J (12), O (7) and V(3).
It's not exclusive to moms but I like to get this one sometimes: http://www.naturalhomemagazine.com/
Also, have you tried Mothering? http://www.mothering.com/
Mom to Autumn (DSD) 11/07/01, Dillon 10/04/08, & 2 angels in Heaven (m/c 06/06 & 03/07)
~Elaine, Semi-crunchy mama to "Sky" 3/21/06, "Ry" 7/14/09, and "Trev" 1/13/12
I like Mothering half the time. The other half the time they piss me off by encouraging New Age woo-woo. I don't know why they assume that people who want to breastfeed and babywear are anti-science :-(
"I choose to laugh but that's to hide my pain and incredulity." - Ms. Miyagi
It is your burden to determine how much of the above should be taken seriously.
I really dislike doing all my reading online...but I guess it is greener...
Oh really..no more print mag for Mothering?! Bummer...my sister in law just paid to renew my subscription for 2 more years as an x-mas present. I get the "greener" thing but there is something about a physical magazine that you simply cannot acheive online :( I also like bathroom material !
Really disapointed to hear this...
that's disappointing about Mothering. I have a subscription and really don't like reading it on the computer.
Erica married to Matt since 7/1/07
AP, BF, BLW, BS, BW, CD, NUCB, Christian SAHM to Juliet Elizabeth 10/12/10
( . ) ( . ) Gold and going for Diamond!
Mothering's last digital issue is the March/April issue. They are no longer a magazine effective immediately.


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Obama's LEGAL immigration reform 2015.What does it mean? Listen to video discussions by Attorney Rajiv S. Khanna on Immigration.com YouTube Channel. Subscribe to Our YouTube channel to be notified when new updates are posted.
F1, marrying citizen in May. H1 from October. Can file tax as married?
Discussion in 'General F Visa and Related Issues' started by Imogen, Mar 20, 2012.


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The 38th Somerset County Tournament wasn't short on milestones.
Bound Brook went 8-1 in the championship round, winning its third straight title and sixth overall with 258 points. Watchung Hills was second with 159½ and Bridgewater-Raritan third with 128.
The Crusaders set an event record with eight champs though they were 16 points shy of the SCT points record they set in 1998. Bound Brook had 12 finalists in 1998, going 6-6. ...


text: Sorry for all these new posts but it seems its almost impossible to find anything!! Im trying to take my front bumper off my 1979 corona and just want to know how to do it. I took off the 4 support bolts but it still wont budge, feels there is something else holding this up... any help?