text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 21, 1987
|Filing date
|May 5, 1986
|Priority date
|May 5, 1986
|Fee status
|Publication number
|Robert D. Engelken, Hal E. McCloud
|Original Assignee
|Engelken Robert D, Mccloud Hal E
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|Patent Citations (4), Non-Patent Citations (10), Referenced by (50), Classifications (18), Legal Events (9)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates to deposition of thin films of one, two, and/or three semiconducting tin sulfide phases (SnS, Sn2 S3, and/or SnS2) by below-solution electroless plating and/or above-solution self-induced chemical vapor deposition onto both nonconductive and conductive substrates from a chemical bath of an organic acid, Sn(II), elemental yellow sulfur, and water.
Methods for electroplating metallic tin coatings onto electrically conductive coatings have been well known in the art for many years. Immersion plating of metallic tin onto metallic substrates by ion displacement of tin ions for the parent metal atoms is also a common industrial process. The book by F. A. Lowenheim (Modern Electroplating, The Electrochemical Society, Inc., Pennington, N.J.) provides an in-depth survey of both techniques and an extensive list of pertinent references and patents.
Although the mechanisms for true electroless plating of tin onto nonconductive substrates have been reported (e.g. (1) U.S. Pat. No. 3,063,850 to Mikulski; (2) M. E. Warwick and B. J. Shirley, Trans. Inst. Met. Finish, 58,9 (1980), (3) A. Molenaar and J. J. C. Coumans, Surf. Tech., 16,265 (1982), (4), A. Molenaar, Extended Abstracts, Vol. 84-2, The Electrochemical Society, Pennington, N.J., 634 (1984), and (5) H. M. Van Noort et al., J. Electrochem. Soc. 133,263 (1986)), the quality and reproducibility of the films are often poor and appear to arise from the self-catalyzed reaction
2 Sn(II).sub.(aq) =Sn(IV).sub.(aq) +Sn(0).sub.s
since other reducing agents are not required (but may participate to some extent; e.g. V(II), Cr(II)). The use of Sn(II), notably SnCl2, as a sensitizing/catalyzing agent in electroless deposition of other electropositive metals such as palladium is also standard practice (e.g. U.S. Pat. No. 4,554,182 to Bupp et al., and prior art cited therein), but is not directly related to Sn(0) thin film formation.
Electroless deposition of nonmetallic semiconducting or insulating compounds, especially metal sulfides and selenides, has been reported in the literature (e.g. (1) P. Pramanik and S. Biswas, J. Electrochem. Soc., 133,350 (1986), (2) S. Biswas, et al., J. Electrochem. Soc., 133,48 (1986), (3) R. A. Boudreau and R. D. Rauh, J. Electrochem. Soc., 130, 513 (1983), (4) R. N. Bhattacharya and P. Pramanik, J. Electrochem. Soc., 129,332 (1982), and (5) K. L. Chopra et al., Physics of Thin Films-Vol. 12, Academic Press (1982), and references contained therein.) In all cases, the nonmetal (S, Se)=X reagent is a S or Se-containing compound in which S,Se exists in the anionic state and which slowly decomposes/disproportionates into S.sup.═ or Se.sup.═ without involvment of reducing agents or catalysts. The metal chalcogenide film is formed by precipitation of these generated chalcogenide anions and metal cations released by the slow disproportionation of metal complexes (chelates). This precipitation is energetically favored on solid surfaces that provide a bounty of nucleation sites. The continuous and very slow precipitation of these ions, when the Mx Xy solubility product is exceeded, leads to growth of macroscopic films with thickness of order of 0.1-1 μm.). The technique (e.g. Reference 5 above) appears applicable to nearly all metal chalcogenides in which the metal has a chelate that can slowly release free metal cations.
Major disadvantages of prior art electroless compound plating include (1) The use of relatively expensive and normally toxic sulfur/selenium compounds where X.sup.═ already exists as a branch of the molecule, (2) Slow deposition rates and small terminal film thicknesses due to the slow formation of X.sup.═ ions, (3) Tendency toward amorphous film formation due to the low growth rates, and (4) The requirement of careful control of pH and metal ion complexing agents.
Weakly adsorbed films of collodial particles of metal compounds can be produced by the method described in S. M. Kulifay, Am. Chem. Soc., 23,4916 (1961) in which metal cations (e.g. Te+4, HSeO3 -, AsO3 -, SbO+) of the "nonmetals" tellurium, selenium, arsenic, or antimony, and strong reducing agents such as hydrazine (N2 H4), methanol, etc. are dissolved in aqueous solutions and heated. The separate reducing agent reduces both the metal and nonmetal ions to solid particles which subsequently react to form Mx Xy particles which can stick/adsorb (not nucleate onto) to solid surfaces.
Small numbers of nonmetal anions (e.g. Te.sup.═) may be directly generated by the strongly favored electron transfer from the reducing agent to the electropositive nonmetal ion (e.g. HTeO2 +). In this case, the precipitation/nucleation reaction can again occur directly on the solid surfaces
(e.g. Cd.sup.++.sub.(aq) +Te.sup.═.sub.(aq) =CdTe(s)).
Experiment has shown that most of the reactants form powder suspended in solution.
This method is not satisfactory for producing adherent, strong deposits. Major disadvantages include (1) Requirement of a separate, strong, and usually toxic/flammable/explosive chemical reducing agent (e.g. N2 H4, CH3 OH), and (2) Film formation only by adhesion/occlusion of colloidal particles formed in the solution and not by true ion/ion condensation and nucleation and, thus, very weak and nonuniform films.
Chemical vapor deposition, another standard, common-knowledge technique of producing compound/alloy films, involves the reaction of multiple gases or vapors containing the film elements on the surface of a heated substrate. These compressed, ultrapure gases are fed into an evacuated or inert reaction chamber via expensive, corrosion-resistant, and fail-safe plumbing connected, through appropriate controls, to purchased cylinders. Normally, these gases are extremely toxic and expensive. For example, arsine (AsH3) and trimethylgallium ((CH3)Ga) can be simultaneously fed into a chamber where they react on a hot (700� C.) substrate according to
AsH.sub.3 +(CH.sub.3).sub.3 Ga=GaAs+3CH.sub.4.
The books by Chopra and Das (Thin Film Solar Cells, Plenum Press, New York, 240-256 (1983)) and Vossen and Derr (Thin Film Processes, Academic Press, New York (1978)), and references therein, include surveys of the state of the art in chemical vapor deposition as well as other thin film deposition techniques. Major disadvantages in the prior art of chemical vapor deposition include (1) The very high (several hundred �C.) temperatures normally required to activate the chemical reactions, (2) The use of externally stored and fed toxic/corrosive gases, and associated safety problems, (3) The required extreme purity of the gases, (4) Need for evacuation or inert gas flooding of the reaction chamber, and (5) The great expense of the process due to (1) through (4).
By spraying a fine mist of solutions of strong reducing agents and metal/nonmetal salts onto hot (T 300�-700� C.) substrates, the solvent is nearly instantaneously vaporized and the chemical reduction of the salts to the elements and their subsequent reaction to form the compound are strongly enhanced due to the temperature. The resultant films are much more adherent, uniform, and crystalline than in the wet bath procedure of Kulifay. However, in addition to the disadvantages listed under Kulifay, this apparatus includes a pressurized solution vessel, chemical tubing, inert gas propellant, heater etc., all relatively expensive. The book by Chopra et al., (Physics of Thin Films-Vol. 12, Academic Press (1982)) reviews this "spray pyrolysis" procedure. Hill and Chamberelin (U.S. Pat. No. 3,148,084) were pioneers in this area.
Schneble (U.S. Pat. No. 4,027,055) discloses a method for depositing smooth and easily solderable tin metal coatings onto metallized surfaces from aqueous baths containing a soluble stannous salt, a sulfur component which comprises a mixture of alkali metal polysulfides and at least one other sulfur-containing compound, a mineral acid, and a wetting agent. The technique is basically an ion displacement/cementation (immersion) process where the metal substrate provides the electrons required for Sn++ reduction. It does not work on nonconductive substrates. Schneble found that polysulfide ions (Sx.sup.═) generated via disproportionation of the added sulfur compounds (e.g. thiourea) were necessary to produce high quality tin films. Quite likely, Sx.sup.═ x=simply complexed Sn++ and, hence, slowed down the ion displacement rate, served as a surface blocking agent (brightener), and produced bright, smooth deposits, as is commonly found with complexing/brightening agents during electro- or electroless deposition of metals.
Schneble did observe pale green and coffee colors upon heating his solutions, probably due to formation of SnS2.sup.═.sub.(aq) and SnS.sub.(s), respectively, within the solution. He speculates that the coffee color is believed to be due to the formation of a precipitate, stannous sulfide. "The precipitate will do-deposit on any parts being plated during the transitional period, causing grey-black deposits and occasionally a rust-colored dusty deposit. These deposits can easily be removed by a light brushing of the part with water." Evidently these so-called "deposits" are simply adhesions/occlusions of the precipitate easily predicted to be formed within the bath and not a true adherent deposit. Furthermore, Schneble makes it more than clear that this SnS formation is not desirable to his process and discusses ways to avoid or circumvent it. He does not mention Snx S formation and does not discuss the controlled formation of other Snx S phases and associated multiple layer devices. Furthermore, he, in all cases, utilized sulfur compounds in aqueous solutions and nowhere mentions elemental sulfur molecularly dissolved in predominantly organic acid solutions.
Howes (U.S. Pat. No. 2,757,104) discusses a process to form electrical resistors from alloy films of predetermined and predictable electrical characteristics. The process involves deposition of a "primary" metallic film onto a substrate by any suitable method (electroless deposition, spraying, evaporation or sputtering). The precision alloy is formed by submerging the primary film in a bath containing more electropositive ions of another metal. These ions exchange for atoms of the primary film by ion displacement and electron exchange. This exchange will shift the open circuit voltage of the films positively until the Nernst potentials of the primary film and ion elements become equal and the process ceases. This should correspond to a well defined composition and, hence, resistivity. Subsequent annealing can stabilize and oxidize the films, producing higher resistivity metal oxide resistors.
Howes' process is an ion exchange process dependent upon the pre-existence of a primary metal film. The alloy can not be deposited on a nonconductive substrate in a single step due to this requirement. The ion exchange reaction requires ions more electropositive than the primary film. Howes specifies silver as the primary film and this restricts the ions to those of nobler but often expensive elements such as palladium. Howes makes no mention of tin metal or tin sulfide formation. Since sulfur has no simple ionic cations capable of undergoing this ion exchange, metal sulfides can not be formed.
Byatt (U.S. Pat. No. 4,375,125) discusses the formation of a semi-insulating, passivating metal oxide, metal chalcogenide, or silicon layer on pre-existent p-n junctions (notably silicon) by "generic" chemical conversion treatments (nonspecific). This patent teaches one of a multitude of applications of metal chalcogenides and one of a multitude of ways to improve p-n junction electrical characteristics, but does not deal specifically with improvement in the art of metal chalcogenide, notably Snx S, film deposition or the creation of p-n junction themselves from metal chalcogenides such as Snx S.
The present invention relates to a novel wet bath, chemical technique to inexpensively and rapidly deposit, in very adherent, relatively uniform, and thick form, both within and above the solution, and onto both conductive and nonconductive substrates, Snx S films (0.5≦�≦1) at temperatures less than 150� C. from low pH and relatively nontoxic organic acid solutions containing only low cost, elemental sulfur, dissolved with large solubilities in molecular form, optional trace amounts of H2 O, simple tin salts such as SnCl2, and optional Sn++ complexing agents such as tartaric acid, potassium gluconate, etc. without the need for separate reducing agents, bottled gases, or complex, expensive apparatus. The H2 O and complexing agent concentrations determine how fast and which of the three chemically related but electronically and optically different Snx S semiconducting compounds: (1) gray-black p-SnS, (2) brown-amber Sn2 S3, and (3) golden n-SnS2, are deposited. The existence of both p and n compounds in the same chemical system (Sn-S) and the controlled deposition of either or both of these both within the solution by electroless deposition and above the solution by self-induced chemical vapor deposition, by control of the H2 O and complexing ion concentrations and temperature cycle, allow many possible (but not limited to) optical, electronic, decorative, and protective applications of single Snx S layers/regions and fabrication of p-SnS/n-SnS2-x p-n junctions or other multiple layer/region devices onto both conductive and nonconductive substrates from the same or sequential baths via simple thermal activation of the bath.
It is an object of the present invention to provide an electroless (chemical bath) process for the deposition of uniform, adherent, and thick (up to ten's of microns) films of the three tin sulfide phases, grey-black SnS, brown Sn2 S3, and amber-yellow SnS2-x, at temperatures below 150� C. from baths of an organic acid, Sn(II) salts, elemental yellow sulphur, and optional complexing agents and/or water onto either conductive or nonconductive substrates.
It is a further object of the present invention to provide a new process for the electroless (chemical bath) deposition of thin tin sulfide films using a nontoxic chemical bath.
It is a further object of the present invention to provide an acidic solution in which elemental yellow sulfur is soluble in large concentrates (>0.1M) in nonionized, molecular form.
It is a further object of the present invention to provide a new process for an electroless deposition of tin sulfide which requires no separate reducing agent, and wherein the tin (II) ions serve both as the metal source and the reducing agent.
It is a further object of the present invention to provide a new process of electroless (chemical bath) deposition having the capacity to deposit three different tin sulfide semiconductor compounds of similiar chemical composition but substantially different electrical and optical characteristics from the same basic chemical bath type by slight variations in water or complexing agent additions.
It is a further object of the present invention to provide a new process for electroless (chemical bath) deposition which is temperature activated and controlled.
It is a further object of the present invention to provide a method for improving the smoothness and uniformity of the said Snx S deposits by prolonged immersion in the bath and slow dissolution and renucleation of defects of large surface area.
It is a further object of the present invention to provide a new process for the deposition of multiple layer structures onto the same substrate from identical or similiar chemical baths by use of successive water or complexing agent additions, such as the formation of p-SnS/n-SnS2 or p-SnS/n-Sn2 S3 heterojunctions and metal/Snx S Schottky Barriers.
It is a further object of the present invention to provide a method for depositing multiple layer thin film structures or mosaic-like thin film structures by a combination of a chemical bath (below-solution) deposition and vapor (above-solution) deposition.
It is a further object of the present invention to provide a new process for the low temperature chemical vapor deposition of tin sulfide phase (SnS, Sn2 S3 and SnS2) thin films on conducting or nonconducting substrates.
It is a further object of the present invention to provide a new process for the chemical vapor (above-solution) deposition of grey-black SnS, brown Sn2 S3, and golden SnS2 thin films on any solid surface above a chemical bath solution due to reaction/disproportionation of volatile tin and sulfur species generated in-situ in the chemical bath solution.
It is a further object of the present invention to provide a new process for direct fabrication of electronic/photovoltaic p-n junctions and metal-semiconductor junctions (Schottky Barriers) based upon thin films of p-SnS, Sn2 S3, and/or n-SnS2 deposited by low temperature chemical bath (electroless) or chemical vapor deposition from baths of Sn(II), sulfur, organic acid, and the following optional ingredients: complexing agents, and water.
It is a further object of the present invention to provide a new process for producing multiple layers of various semiconductor tin sulfide compounds such as, for example, Sn/p-SnS, p-SnS/n-SnS2 and p-SnS/n-Sn2 S3.
According to a preferred embodiment of the present invention, a chemical bath is prepared by mixing Sn(II) salts such SnCl2 and elemental sulfur powder with organic acids such as acetic, propionic and butyric. As explained hereinafter, complexing agents such as potassium gluconate and tartaric acid, and water may be added. Stirring of the mixture aids in the dissolution of the chemicals. The temperature of the bath is raised above 90� C. at which point abrupt changes occur in the solution color from clear to black, brown or amber, depending upon the concentration of Sn(II) ions, sulfur, water, and complexing agent, and one or more of the tin sulfide phases, SnS (gray-black), Sn2 S3 (brown) or SnS2 -x (amber) deposit below the solution-air interface in adherent thin film form on a substrate and other objects in the solution.
The principles believed to be involved in the deposition process are that free Sn(II) ions either (1) reduce molecularly dissolved sulfur according to the general reaction
Sn(II)+S.sub.x (O)=Sn(IV)+S.sub.x (-II),
after which Sx (-II) combines both with Sn(II) and Sn(IV) ions preferentially on solid surfaces (due to large number of nucleation sites) to form SnS, Sn2 S3 and/or SnS2 because the solubility products of Sn(II, IV) and S(-II) are exceeded due to the relatively large number of free Sn(II) in solution; or, less likely, (2) disproportionate simultaneously into Sn(IV) and tin metal which nucleates on the solid surfaces and subsequently reacts with dissolved sulfur to form the compound(s).
The following example exemplifies the gist of the process and is set forth for illustration purposes only.
1. To 50 ml propionic acid-H2 O solution (19:1) are added glass slides, and SnCl2 and yellow sulfur in weights equivalent to 0.3M and 0.6M, respectively. The slides sit near vertically against the beaker walls. The solution is stirred rapidly and heated on a stirring hot plate with Teflon-coated stir bar. Near 50� C., residual undissolved SnCl2 looks dark. A very faint brownish above-solution vapor deposit was noted near 45� C. (3 minutes after initial heating).
2. After 4 more minutes, the heater was turned up; T=47.5� C. The solution is just slightly "murkey". The brown above-solution vapor deposit is spreading.
3. After 2 more minutes, T=67� C. and is increasing rapidly.
4 After 1 more minute, T=89� C. and much sulfur is dissolved. The brown above-solution deposit is spreading and thickening, and a black vapor deposit appears 1/8 inch above the solution.
5. After 3 more minutes, the solution rapidly turns opaque brown/black and is beginning to boil; T=100� C. The vapor deposit is still spreading.
6. After 2 more minutes, the beaker walls below the solution are brown and solution appears black. Much of the vapor deposit is turning yellow. The heat is turned off.
7. After 3 more minutes, T=90� C. and is falling. A lot of black vapor deposit appears on one slide.
8. After 3 more minutes, T=83� C. and is rapidly falling. The solution is dark brown and thick.
Upon removing and rinsing the slides, the below-solution, electroless deposits are smooth, uniform, thick, adherent, and black. The thick above-solution deposit has black, brown, and yellow regions but is not completely uniform. The below-solution deposits exhibited pronounced Sn1 S X-ray diffraction structure and had a Sn:S ratio near 1:1. The above-solution deposit is a mixture of Sn1+x S (black), Sn2 S3 (brown), and SnS2-x (yellow). The below-solution deposit exhibite ˜1 μm.
Experimental observations show that the chemical bath solution abruptly changes color between 80� C. and 110� C., usually near 90� C. which is considered to be the high temperature required to turn on the bath. The color change is due to formation of Snx S and SnS2,3(lip.).sup.═ species within the solution, because of S.sup.═ formation and subsequent precipitation with Sn(II, IV) due to the reducing nature of Sn(II). A low pH of the bath is an inherent result of the organic acids used, it appearing that pH below 7 would work well due to free Sn++ present, but generally pH is in the 0-2 range. It is recognized that the inclusion of relatively inert, nonacidic organic solvents (e.g. propyleneglycol) to the bath would raise the pH without a substantial sacrifice in sulfur solubility. Absolute and relative concentrations of the SnCl2 and sulfur are not critical as long they are reasonably large (>0.01M) and of the same order of magnitude. Generally, 0.1-0.5M concentrations are used for both. Lower concentration values produce deposition, but at much slower rates, and thinner, less uniform deposits. To effectively "tie up" the free Sn++ and slow the process, the complexing agent must be present with a molarity comparable to that of the Sn++.
Once "activiated", the deposition has little dependence upon subsequent heating or cooling. Thus, the heat is generally turned off after the pronounced bath color change near 90� C. However, the cooling of the solution is not necessary and film formation occurs, with no notable difference, even when the elevated temperature is maintained.
The water content of the solution is believed to control the dissociation of the acid, tin salt and tin complexing agent. An absence of water allows little ionization of the organic acid molecules and the Sn++ stays linked to propionate, acetate, or other ions so the rate of Sx.sup.═, HS-, or H2 S formation from the Sn(II)+S(O)=Sn(IV)+S(-II) is slowed and, thus, the rate of precipitation of both Sn(II) and Sn(IV) ions with S(-II), which causes nucleation and deposition, is also slowed.
Rapid stirring of the solution isn't mandatory, but is desirable to enhance the homogeneity of the reaction and the uniformity of the deposits.
Experimental observations disclose that substrates positioned vertically within the solution are more uniformly coated than are substrates which are positioned horizontally.
The ingredients of the chemical bath solution may be present in the following ranges of concentration based upon the total bath composition:
______________________________________Ingredient Concentrations______________________________________Sn(II) salt 0.01 M-to saturationElemental sulfur 0.01 M-to saturationTin Complexing Agent ˜Sn(II) concentration (optional)Organic Acid 50%-100%Water 50%-0% (usually < 10%) - (optional)______________________________________
The Sn(II) ions serve as a metal source and reduce molecularly dissolved (S(O) to S(-II). The elemental sulfur serves as the sulfur source and a safe, inexpensive free reagent for S(-II) formation, and the tin complex (chelating) agents tie up Sn++ ions and slow the rate at which they reduce sulfur to S(-II) and subsequent precipitation with Sn(II) and Sn(IV) ions, leading to slower deposition rates and thinner deposits. The organic acid provides a very large elemental sulfur solubility and sufficient free H+ to keep Sn++ relatively free (except when deliverately tied up). The water (when present) enhances the acid ionization and lowers the pH; experimentally, the presence of water is found to be the key stoichiometry-controlling factor; it may assist H2 S formation which aids in thin film deposition. The Sn(II) salts, sulfur, and organic acid components are essential. The water and complexing agents may be essential in some cases to control the stoichiometry and, hence, the electrical and optical properties of the thin film deposits. Any easily ionized Sn(II) salt will suffice. Heavy salts of Sn(II) are considered chelated and, again, lead to slow and thin depositions. There are a large number of possible complexing agents, for example, sodium, potassium, H+, or NH4 + : citrate, tartrate, gluconate, glycolate, EDTA, and lactate. Most would suffice, but the different ionization constants would slightly vary the rate of deposition and, thus, possibly the stoichiometry and thickness of the deposit. Of the light weight organic acids, for example, acetic, propionic and butyric, will suffice. It is also likely that appropriate mixtures of mineral acids and nonacidic organic solvents, for example, HCl in propylene glycol, could be made to perform the same function.
Although the tin salt and sulfur are usually added to the solvent simultaneously prior to heating, this is not the only feasible procedure. For example, films are produced when either or both components are added to an already hot solution. This tends to minimize premature formation of above-solution deposits with T<90� C. No film, either above or below solution, is formed unless both Sn(II) and elemental sulfur are present; hence, a late addition of one to a hot solution containing the other can also be used as a "trigger" to the process. For example, a propionic acid solution containing only sulfur can be heated to T>90� C. T>110� C. melts sulfur and greatly increases its rate of dissolution. A separate propionic acid solution of SnCl2 at the same temperature can then be added. An immediate and robust reaction will occur and produce brown deposits above and below the solution. If either solution contains water, the below-solution films will be black. If the SnCl2 solution contains complexing agents, the reaction will not be as brisk and the below-solution films will be yellower. Alternately, one of the solutions could be colder than the other and when the temperature of the mixture reached 90� C., again the reactions would be triggered.
The reducing characteristics of Sn(II) also should produce reduction and incorporation of trace amounts of other elements into the deposit. Although having negligible effect upon the gross composition of the deposit, these elements could have dramatic effects upon the electrical, optical, and structural characteristics of the deposit as is a standard phenomenom in doping of semiconductors (e.g. B in Si) and inclusion of trace metals in alloys (e.g. Mn, V in steel). For example, in the case of copper, one or both of the following mechanisms might apply
Sn.sup.++ +Cu.sup.++ =Sn(IV)+Cu
.sub.x Cu+S=Cu.sub.x S, or
Sn+++S.sub.x =Sn(IV)+S.sub.x.sup.═
S.sub.x.sup.═ +Cu.sup.++ =CuS+S.sub.x-1.
In both cases, Cux S would be incorporated in trace amounts in the deposit, even though most of the Cux S would occur within the solution.
For example, we have found that trace (˜10 mg/100 ml) of CuCl2 or CuNa2 EDTA added to the Sn(II), S, acid bath (with or without H2 O) produces a deposit slightly smoother/adherent and yellower than without Cu, presumably due to small amount of Cux S in the deposit. The following example exemplifies this process and is for illustration purposes only.
1. A pure propionic acid solution 0.3M in SnCl2 is stirred rapidly and heated. When T=106� C., sulfur, with a weight equivalent to 0.3M, is added.
2. The SnCl2 browns quickly and a few mg of CuCl2 is added.
3. After another minute, T=110� C. and solution is very brown. The above solution vapor deposition is forming.
4. After another 5 minutes, T=117� C. and a below-solution deposit is visible on an immersed glass slide. The color of the solution is extremely dark brown.
Upon removal of slide and water rinsing, a uniform, smooth, and transparent yellowish-brown film is noted below the solution. The beaker walls above solution are brown. The shade of yellow is obviously different than that of pure SnS2-x grown without Cu.
The below-solution electroless deposits begin to form simultaneously with the bath color change between 90� and 100� C., are existent within 5 minutes, and reach close to their maximum thickness usually within 15-30 minutes of the color change. It has been observed, however, that a small additional thickness may be added if the films are left in the cooling to room temperature solution for several hours to days, presumably due to surface nucleation of the residual Sn(II), S in the solution and/or the Sn(II), S.sup.═ produced by the minor amount of dissolution of the Snx S in-solution precipitate. Prolonged immersion also increases the smoothness and uniformity of the films. Evidently, defects, irregularities, and outcroppings on the film surface preferentially dissolve due to the large surface area in contact with the solution and when the solubility product (very small but nonzero) of Snx S is exceeded, Sn(II) and S.sup.═ renucleate on the film surface in a much smoother form. The net effect is transport of Snx S from areas of high surface area to areas of lower surface area. In principle, Snx S powder (e.g. our precipitate) could be added to a mixed organic acid/H2 O solution and with sufficient time (and possibly mild heating and stirring) would be transported via very slow dissolution, diffusion, and renucleation onto the substrates and beaker walls. Because of this smoothing effect, the standard experimental procedure is to raise the substrates within 30 minutes of the color change to verify the existence of below-solution deposit, but leave the substrates immersed for up to 4 days before final removal.
The electroless (chemical bath) method of depositing tin sulfide semiconducting films on either conductive or nonconductive substrates improves on the prior art techniques. The method of the present invention requires no separate reducing agents such as hydrazine (N2 H4) because the tin (II) ions serve both as the metal source and the reducing agent. The present invention uses only a nontoxic and inexpensive elemental yellow sulfur that dissolves in the organic acid in molecular rather than ionic form, thus avoiding the need for an anionic sulfur species such as thiourea. The organic acid provides a large elemental sulfur solubility not found in aqueous solutions and which simultaneously provides a sufficiently low pH that the Sn(II) ions are relatively free in the absence of any deliberately added complexing agents, leading to rapid deposition times as low as 5 minutes and deposition thickness of 10's of microns. The chemical bath of the present invention is nontoxic and is temperature activated at relatively low temperatures. The apparatus required to practice the present invention is relatively simple and readily available, including beaker, stirring bar, thermometer, and stirring hot plate, rather than the sophisticated and elaborate equipment required for the prior art processes which involved high temperatures, high vacuums, toxic and expensive nonmetal compounds, and in which pH control was critical.
In practicing the invention, the chemical bath without water yields a thin brown Sn2 S3 deposit. Very small amounts of water (approximately 1-10 ml=in≈100 ml acid, ≦10%) yields a thick black-gray SnS deposit. Large amounts of water tend to yield thick brown Sn2 S3 films. The presence of Sn++ complexing agents, for example, potassium gluconate, slow the rate of S(-II) formation and subsequent combination with Sn(II) and Sn(IV) and causes a slower deposition of a thin (≦1μm) amber (yellow-brown) SnS2-x film. By use of a 2-stage water addition technique to the same bath, or by dipping the substrate in two different baths, one can form multiple layer structures, for example, p-SnS/n-SnS2, which could serve as electronic p-n heterojunctions, solar cells, or other electrical devices. The present invention has the capability to deposit three different semiconductor compounds of similar chemical composition but substantially different electrical and optical characteristics from the same basic chemical bath type by small variations in water content or complexing agent additions.
In addition to the deposition of three tin sulfide semiconducting films on either conductive or nonconductive substrates within the chemical bath solution, the present invention has the capability of a low temperature chemical vapor deposition of SnS, Sn2 S3 and SnS2 thin films on either conducting or nonconducting substrates above the chemical bath solution. As practiced in this embodiment, the present invention produces through chemical vapor deposition gray-black SnS, brown Sn2 S3 and golden SnS2 thin films on any solid surface above the chemical bath solution described above due to reaction/disproportionation of volatile tin and sulfur species generated in-situ in the solution.
The principles involved in the application of the invention in this embodiment are basically the same as described above for the in-solution deposition with the addition that generated gaseous H2 S and SnCl4 vapor, as well as possible tin-sulfur organic compounds, leave the solution and condense above the solution on the cooler substrate surfaces where they react to form Snx S films.
Example A, previously stated, also serves as an only illustrative example for the chemical vapor deposition.
The above-solution vapor deposition begins at temperatures as low as 45� C. and is quite feasible at 60� C. Thus, it is possible to perform vapor deposition without significant below-solution electroless deposition. It is difficult to perform below-solution deposition without above-solution deposition but above-solution deposition could be minimized by use of complexing agents, surface foams, or beaker evacuation/gas purging. Although water is required to produce the gray-black electroless SnS deposits, it is not required to produce the brown Sn2 S3 or amber SnS2-x below-solution deposits. Pure organic acid solutions of Sn(II) and S without complexing agents or water yield thick, uniform, adherent chocolate-brown Sn2 S3 deposits both above and below the solution-air interface. Pure acid solutions of Sn(II), S and complexing agents such as gluconate, tartrate, or EDTA, but not water, produce still uniform and adherent but thinner and yellower SnS2-x films below the solution and thinner chocolate-brown Sn2 S3 films above the solution. Trace amounts of water yield gray-black SnS below-solution deposits and predominately brown Sn2 S3 above-solution deposits. Larger amounts of water tend to yield a mixed brown-black below-solution deposit and a mosiac mixture of brown, black, and golden (SnS2) above-solution deposits. The complexing agents are more effective in the presence of water; i.e. have a more dramatic effect in slowing the rate of deposition and yielding thinner, yellower films, presumably because of the larger number of free Sn++ ions, released from SnCl2 in the water environment, which are immediately tied up by the complexing agents and hinder SnCl4 vapor and subsequent free Sn++ ion formation.
The present invention when used as a low temperature chemical vapor deposition technique possesses key advantages over prior art chemical deposition techniques which require bottled gases, reaction chambers, high temperatures, and inert gas atmospheres. Advantages of the present method are low temperature deposition of the three tin sulfide compounds directly above the solution and in-situ generation of the volatile gas species from reaction of solid and liquid chemicals rather than by use of expensive and hazardous bottled gas. The present invention is operable in air and normal atmospheric pressure, and is extremely simple, inexpensive and safe. The present invention has the capability of growing all three stable Snx S phases; while the brown Sn2 S3 is the predominant phase, the black SnS and golden SnS2 also may be produced by use of water.
The current application of the present invention generates the volatile tin and sulfur species (probably H2 S and SnCl4 vapors) in-situ in solution from the tin chloride-sulfur-organic acid-water bath described above. Thus, safety precautions are much less stringent and reagent costs are much less. Application of the invention may involve (but doesn't require) a normal fume hood or exhaust fan because the great majority of H2 S formed is substantially simultaneously transformed to Snx S on the substrates and solid surfaces in-solution and above-solution and therefore doesn't escape. The SnCl4 vapor is only mildly toxic, although it is corrosive. The invention in the chemical vapor deposition mode is operable at temperatures under 100� C., at atmospheric pressures and in a normal air atmosphere. The low substrate temperatures preclude SnO or SnO2 formation. The thin film formation is produced by the reaction of volatile and sulfur species on the substrate and container walls above the solution, and, to a lesser extent, by the transport and subsequent reaction of the SnCl2 and sulfur above the solution due to water and acid vapor. This reaction evidently requires a low temperature (45�-100� C.) to activate. The simplicity of the apparatus and chemicals involved in the low temperature vapor deposition technique leads to a very inexpensive system. The tolerance of the system to broad chemical concentration changes leads to easy deposition.
In accordance with the present invention, a simple, nontoxic and inexpensive method of producing multiple layers of various semiconducting tin sulfide compounds on themselves, or on other prior semiconducting layers, or metals specifically includes the growth of electronic junctions such as Sn/p-SnS, p-SnS/Sn2 S3, and/or p-SnS/n-SnS2-x layers deposited by a low temperature chemical bath (electroless) or chemical vapor deposition from baths of Sn(II), sulfur, organic acid and water.
Prior techniques for the production of multiple layers of semiconducting films require very expensive equipment capable of handling high temperatures, high vacuums, and hazardous chemicals. Many of the techniques require very toxic and expensive gases and most require the use of extremely controlled impurities (homojunction) or the use of two different compound families (heterojunctions) which may tend to alloy and form poorly defined interfaces. In distinction, the present invention is operable at temperatures below 100� C., at atmospheric pressure and in normal atmospheric conditions. The apparatus required is extremely simple and inexpensive. The reactant gases are generated in-situ from reaction of inexpensive and relatively non-toxic liquid and solid chemicals. The present invention allows the above-solution and below-solution deposition of the three tin sulfide compounds (SnS, Sn2 S3, and SnS2) and, thus, layered structures from the same or sequential baths by variation in experimental conditions such as concentration of ingredients, pH control, and heating cycle.
Additionally, the three semiconducting tin sulfide compounds have different electrical and optical properties. For example, SnS is gray-black with a bandgap near 1.3 eV and is p-type; Sn2 S3 is brown with a bandgap near 1.6 eV and is weakly n-type; and SnS2 is golden-yellow to amber with a bandgap near 2.1 eV and is n-type. All three bandgaps are in or very near the visible range and are conducive to photovoltaic applications. The existence of opposite conductivity types leads to easy fabrication of p-n heterojunctions (p-SnS/n-SnS2 or p-SnS/n-Sn2 S3), from the same or sequential baths through appropriate variations in the process conditions. Further, the fabrication of Snx S/metal Schottky Barriers is also easy to perform. All of these devices have potential for solar cells and other electronic applications. Other possible multiple layer structures include optical filters, decorative coatings, and strained-layer superlattices.
It is possible that a combination of below and above solution deposition methods can be used to create the junctions. For example, the best SnS films are produced below solution and the best SnS2 films are produced above the solution. A relatively crystalline and thick black SnS film could be deposited below-solution on a high work function metal (for example, Au, Ag, or Mo) to form an ohmic contact. With the addition of more SnCl2, sulfur and water to the bath, more SnCl4 and H2 S vapor would be generated, leave the solution, and react above the solution on the raised SnS film to form a golden SnS2 or brown Sn2 S3 film and, hence, a p-SnS/n-Sn2 S3 heterojunction.
The practice of the present invention for the formation of multiple layers of tin sulfide semiconducting films involves (1) either two separate additions of the Sn(II) salt, sulfur and water, or the raising/lowering of the substrate just prior to the second addition, but only when both the in-solution and above-solution deposition techniques are used; or (2) moving of the substrate from a first chemical bath container where the first film was formed (either above or below solution), to a second bath container where a second film (either above or below solution) would be formed.
It is possible to form the multiple layer structure from the same bath with no new chemical additions. For example, brown Sn2 S3 normally forms above the solution near 60� C. from a bath with no or little water. This film could be formed on a metal substrate via very slow heating and then immersed into the solution. Near 90� C., a black SnS film could be grown below the solution yielding a n-Sn2 S3 /p-SnS heterojunction.
The application of the present invention to produce multiple layers of semiconducting tin sulfide compounds has many potential applications.
The Snx S system has three stable semiconductor compounds (p-SnS (Eg=1.3 eV), n-Sn2 S3 (Eg≈1.6 eV), n-SnS2 (Eg=2.1 ev)) with different optical and electrical properties. Thus, electronic applications could be developed analogously to those of Cu2 S, CdS, and ZnS (photosensitivity/luminescence). The SnS films are moderately photoconductive. One potential use is the fabrication and development of a n-SnS2 /p-SnS hetero-p-n junction as an alternate to the n-CdS/p-Cu2 S junction currently used in solar cells. The fact that both compounds contain the same elements would minimize impurity problems associated with atom diffusion across the junctions and permit the direct fabrication of the junctions from the same bath in two consecutive steps.
The amber SnS2-x to golden SnS2 films are attractive, durable, and uniform and can serve as good decorative coatings on metal, glass or plastic (e.g. inside of a light bulb). The fact that these films are deposited by a chemical, rather than an electrochemical, process allows deposition on any substrate not seriously attacked by the solution. The brown Sn2 S3 and gray-black SnS could also be used for decorative coatings.
The gray-black SnS has an anomalously large infrared absorbance not exhibited by SnS films grown at higher temperatures. Furthermore, it has a low reflectance. These properties would allow it to serve as a heat absorber in solar-thermal applications.
These materials could serve as attractive protective coatings on metals when of low porosity and resistant to atmosphere chemical changes.
Snx S films deposited in inert substrates such as glass, Teflon, graphite, or titanium could serve as anodes or cathodes in batteries, similarly to how FeS2 and CuS are now being used in new battery investigations.
Due to the great sensitivity of the optical and electrical properties of the Snx S film to minor deviations in x between 1 and 1/2, these films could be used as transducers in sulfur or tin compound (H2 S, SnCo4, etc.) detectors.
The following three (3) examples serve to illustrate preferred embodiments of the inventive method and are not intended to limit the teachings as set forth herein.
Three precleaned and dried glass slides were immersed in ≈100 ml of propionic acid (reagent grade-Alfa Chemical, Danvers, Mass.) 0.3M in both SnCl2 and yellow, elemental sulfur (both initially undissolved) and containing approximately 1:100 parts deionized water. Upon rapid heating and stirring the following observations were made:
1. After 2 minutes, T=70� C. and the solutes were beginning to dissolve. The bottom region of the beaker began to turn black.
2. After 4 minutes, T=90� C. and the bottom half of the solution was getting blacker. Dark brown above-solution chemical vapor deposits formed 1/2 inch above the solution-air interface and spread upward.
3. After 6 minutes, T=103� C. and the solution was near boiling. Considerable black precipitate appeared within the solution and the entire solution became a brownish-black color. The stirring bar was turned off and the heat slightly reduced. A larger brown (Sn2 S3) area of vapor deposit existed 1/2 inch above the solution around the entire perimeter of the beaker wall and on the slides.
4. After 8 minutes, T=100� C. and the solution was black/brown and opaque. The vapor deposition spread upward on the beaker wall and slides.
5. After 30 minutes, T=80� C. The electroless, below-solution deposits on the beaker walls and slides were becoming black and thick. The vapor deposits were dark brown and nearly opaque. The heater was turned off.
Upon removing the slides and rinsing/soaking them in deionized water, the below-solution deposits were observed to be smooth, uniform, gray, and totally opaque and the above-solution deposits dark brown but still transparent. The beaker walls were also opaque black below the interface and brown above it. The below-solutions films were found, via X-ray microanalysis, to have a Sn:S ratio near 1:1 and the above-solution films near 2:3. The gray below-solution films exhibited a strong SnS X-ray diffraction peak structure while the brown above-solution deposits exhibited mixed Sn2 S3 /SnS2 structures.
1. L-tartaric acid, SnCl2, and yellow sulfur were added to pure propionic acid in weights equivalent to 0.1M, 0.3M, and 0.3M, respectively. The solution was then rapidly heated and stirred after immersion of glass sides.
2. After 4 minutes, T=99� C. and the solution was beginning to boil. The bottom of the solution darkened and the sulfur began to melt on the beaker floor.
3. After 7 minutes, T=115� C., and the stirring was ceased. The solution exhibited a light-yellow (straw-like) color.
4. After 9 minutes, the heater was turned down.
5. After 25 minutes, T=110� C. and the solution was a cloudy yellow-brown color.
6. After 30 minutes, the solution was cloudier and still yellowish-brown. There was no vapor deposit above the solution. Residual, undissolved solutes appeared black.
7. After 40 minutes, T=110� C., and the solution was a nearly opaque yellow-brown color.
8. After 45 minutes, T=110� C. and the solution was totally brown. A very thin brown vapor deposit appeared 1 inch above the solution-air interface.
9. After 65 minutes, T=110� C. and the heat was turned off. More above-solution deposit formed.
Upon removing and rinsing the slides, the below-solution deposits were yellow-brown (straw colored) (1/2<Sn:S<2/3) and relatively thin with a few black crystals (SnS) appearing on the surface. Interference effects imparted a greenish cast to the below-solution deposits. The above-solution deposits were brown (Sn2 S3). Evidently, the tartaric acid (as does potassium gluconate) complexed the Sn++ ions and greatly reduced the rate at which they could reduce S to and precipitate with H2 S, HS-, or Sx.sup.═, and hence nucleate a film out on the immersed substrates.
1. A pure (glacial) acetic acid (regent grade-Alfa Chemicals, Danvers, Mass.) solution with added SnCl2 and yellow sulfur weights (initially undissolved) equivalent to 0.3M (both) was rapidly heated and stirred after immersion of glass slides.
2. After 2 minutes, T=52� C., and sulfur grains were blackening.
3. After 4 minutes, T=71� C., and brown specks formed on the beaker walls.
4. After 5 minutes, T=75� C., and the stirring was ceased. Above-solution chemical vapor deposition appeared.
5. After 10 minutes, T=88� C., and the undissolved solutes and bottom of the solution were turning black.
6. After 14 minutes, T=93� C., and the solution rapidly turned dark brown. The submerged beaker walls were being coated with a uniform brown deposit.
7. After 16 minutes, T=95� C., and the solution was a nearly opaque, dark brown/black color.
8. After 19 minutes, T=96� C., and deposition seemed to have ceased.
Upon removing and rinsing the slides, the below-solution deposits were uniform, thick, and dark brown (Sn2 S3) with a few black patches. The above-solution deposit was thinner and brownish-black.
While this invention has been described in connection with certain embodiments thereof, it is to be understood that this is by way of illustration and not by way of limitations; and the scope of the appended claims should be construed as broadly as the prior art will permit.
|Cited Patent
|Filing date
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|Feb 12, 1952
|Vulcan Detinning Company
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|Molenaar, A., Autocatalytic Deposition of Gold and Tin , Extended Abstracts of the Electrochemical Society, abstract No. 442, Fall Meeting, Oct. 1984.
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|International Classification
|Cooperative Classification
|European Classification
|Feb 19, 1991
|Maintenance fee reminder mailed
|Jun 14, 1991
|Fee payment
Year of fee payment: 4
|Jun 14, 1991
|Surcharge for late payment
|Feb 28, 1995
|Maintenance fee reminder mailed
|Jul 11, 1995
|Fee payment
Year of fee payment: 8
|Jul 11, 1995
|Surcharge for late payment
|Feb 9, 1999
|Maintenance fee reminder mailed
|Jul 18, 1999
|Lapse for failure to pay maintenance fees
|Sep 28, 1999
|Expired due to failure to pay maintenance fee
Effective date: 19990721


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Nutrition & Mesothelioma
Proper nutritional regimens are now being included in comprehensive cancer treatment plans and are a staple of integrative oncology. While pleural mesothelioma is far from the only cancer that demands proper nutrition in patients, it is particularly important because of its aggressive nature. Learn more about mesothelioma and how proper nutrition can help those coping with mesothelioma chemotherapy.
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|19 Sep 2012
660ti GPU utilisation is just 42-58 % while heavy games like BF3 GTX 4
GPU utilisation is just 42-58 % while heavy games like GTX 4 episode from Liberty ,
also in crysis 2 many times it is just 70-80% at 1600*900 resulution
and quality is maxout
in COD MW3 and black opps it fails to maintain 60 FPS constant
in Battlefield 3 Armod kill utilization is just 43-73 % while FPS are below 30-45
and why effective memory is 3000 Mhz instead of 6000 mhz
while few days back my gpu utilization was 90-110 % in bf3 but in 2-3 days it is making me sad
why gpu utilisation sucks in most of games while it was working fine during 1st 5 days when i buy
is my gpu is half-Dead and go for replacement ??
my specifications are i5-650 , 16 gb 1333 MHZ ram , and PCIe 2.0 slot
and 3000 mhz memory is a problem of PCIe 2.0 ??
and many times it underclock gpu , utilisation 30 % and fps 20 , hollyshit
help me I think i made big mistake buying gtx 660ti instead of HD7950
|My System Specs
|19 Sep 2012
If i'm correct, isn't your cpu bottle necking it?
As i own a 660ti and i can max out any game and play at 60fps + perfectly.
|My System Specs
|21 Sep 2012
Windows 7 Professional x64 w/SP1
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Jeanne Leccese new NRGC Executive Director
The Niagara River Greenway Commission announced in September 2016 that Jeanne Leccese has joined as Executive Director. Most recently, Jeanne served as Senior Research Associate at the University at Buffalo Food Systems Planning and Healthy Communities Lab. She coordinated Growing Food Connections, a federally-funded national multi-year project that integrates research, education, and policy engagement activities with teams across seven states and multiple public, private and civic organizations. She earned her Master's in Urban Planning from the University at Buffalo. Jeanne's undergraduate degree is from Le Moyne College in Syracuse, NY where she studied Sociology.
Jeanne brings with her significant experience in food systems planning, planning for public health, housing, and community development. Previously, Jeanne served as the Project Coordinator for Creating Healthy Places to Live, Work and Play, an initiative of the Human Service Coalition of Tompkins County in Ithaca, New York. In this position, Jeanne was responsible for coordinating the work of multiple public and private sector partners to execute strategies promoting healthy eating and active living in Ithaca and its surrounding county. Prior to this, Jeanne served as a Senior Planner for Tompkins County, NY, where she was steeped in the practice of local government planning which focused on three primary areas of planning on a county-wide level: (1) implementation of the County's affordable housing strategies, (2) managing the economic development efforts offered through the Tompkins County Planning Department and (3) overseeing land management practices for County-owned land.


text:
Specialism:Year 11 Textiles
What will my child be studying?
Students will be working for the AQA GCSE Textiles syllabus, learning the theory of textile fibres and fabrics, methods of decorating textiles as well as a range of construction methods. This will be completed through a range of activities, practical and theory, to ensure thorough knowledge and understanding of all aspects of the syllabus. They will complete their work on the Controlled Assessment task started during Year 10. Time will be spent ensuring that students are prepared for the terminal exam at the end of the course.
How is the course assessed?
The course consists of coursework worth 60% of the whole and 40% as a terminal exam based on all the theory studied. Assessments based on GCSE descriptors for each grade and are made throughout the course to ensure that students know the level at which they are working as well as how to improve.
Are there Controlled Assessments?
There is one Controlled Assessment which is completed under a level of medium control. This consists of a design folder and a final piece or set of pieces based on one of many design contexts set by the exam board. This work should take approximately 45 hours. The coursework will have been started in Year 10 and be completed by February in Year 11.
How long are the examinations?
There is a mock examination taken around Christmas. This does not count towards the final GCSE grade, but helps the students to understand what is needed in the exam which will be taken in May or June. It is 2 hours long and includes a design section as well as more formal theory questions.
What equipment should my child have?
Students should always have drawing equipment as well as pens and will have small textiles equipment that they purchased at the beginning of Year 10.
What texts would you recommend?
GCSE Design and Technology for AQA: Student Book: Textiles Technology (GCSE Design and Technology for AQA: Textiles Technology) by Rose Sinclair (Author), Mr Geoff Hancock (Editor)
Textiles Technology: Revision Guide (Collins GCSE Essentials) Paperback by Various authors
What websites would you recommend?
How can I support my child's learning?
Please ensure that your child prepares for lessons, completes homework tasks and brings in necessary resources to enable him/her to complete classwork to the highest possible standard.
It may also be necessary or desirable for your child to attend Coursework Catchup sessions, in which case arrangements will need to be made for transport home from school.
For further information, please contact:
Mrs K Baker at: email@example.com


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Living Still Trailer (2015)
"That Has Made All The Difference" 29 September 2015 Drama 48 mins
Living Still follows protagonist Kyle on his trip through lucid dreaming and love on the onset of his beginning college years. Abstract, symbolic and a visceral experience, Living Still is a haunting, profound portrayal of the journey(s) we take in our lives. What pathway will you follow?
Watch the official Living Still 2015 trailer in HD below or find more Living Still videos on Vidimovie.


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"Amounts appropriated under this section, and outlays flowing from such appropriations, shall not be taken into account for purposes of any budget enforcement procedures including allocations under section 302(a) and (b) of the Balanced Budget and Emergency Deficit Control Act and budget resolutions for fiscal years during which appropriations are made from the Fund"
Yes, that says what you think it does: They will spend the money, but it doesn't get counted in the cost of the bill. So when the Congressional Budget Office reports the cost of the bill, that part of it is excluded.
According to Jamie Dupree, similar wording also appears in Section 164, and it is possible that it might appear elsewhere.
So how much does this bill REALLY cost? Who knows? But like burglary victims, we won't know how much our politicians have stolen until it's gone.


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14-15 September 2011, Royal Flemish Academy of Belgium for Science and the Arts, Brussels
The one-day conference will present key findings of the FP7 CLAMER project. Leading experts on climate change science (including a representative of the Intergovernmental Panel on Climate Change) will give presentations in the morning of 15 September, while three parallel discussion groups (on European marine policies; on science and public awareness; and on research agenda for the future) will be held in the afternoon.
The findings include:
The conference will be anticipated on the evening of 14 September with the premiere of the CLAMER documentary "Living with a warming ocean", filmed in seven European countries and focusing on the attitudes towards science communication regarding climate change and its impacts on marine waters.
Participation is free of charge, but registration for the pre-event and/or the conference and discussion groups is required.
Further information
15 September 2011, Brussels
The annual Transport NCPs Meeting will provide detailed information on the open calls (Work Programme 2012) and recent developments in European transport policies. National Contact Points are invited to attend.
Further information
13 September 2011, Brussels
Some representatives from EU Member States and the main European research stakeholder organisations meet in Brussels to mark the launch of the public consultation on the ERA Framework. This public consultation will run from 13 September - 30 November and will gather stakeholder views on the main obstacles and untapped potential affecting the European research sector, and possible measures to address these issues.
The conference can be followed online - see below.
1 September 2011, Brussels
The WORKCARE SYNERGIES project will present research findings trying to answer to questions such as: what happens to people as they move between different employment statuses, do part-time and temporary workers remain in these jobs, do they move on to something better, or do they fall out of employment, and what factors and policies are associated with these transitions.
Further information
18-19 July 2011, Brussels (Charlemagne)
The next round of calls proposals for transport research under the Seventh Framework Programme (FP7) will be published end of July 2011. In order to support the preparation of project proposals, the European Commission's Directorate General for Research and Innovation will organise two 'Information Days'.
Further information


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First Pin Up Girl of the Year...
...YES! This is my first pin up girl painting for 2014. I really enjoyed painting the classic pin up girls last year for the calendar, so I though why stop. This one is called Cave Girl:
I have a long list of pin up girls I'll be painting over the coming year, all will be in the classic 40s-50s style that I have come to love working in. This one was inspired by a few odd things, the main drive was that I want to to a crack at painting a lion. The rest fell into place from there.
MORE Coming soon.
Artwork ©Simon Breeze 2014


text: Can connect to WiFi on android note pad by pressing designated button upon opening breeze app. This will not work on iPhone after software upgrade.resetting iPhone still unable to connect via breeze app. Opened 'settings', then 'WiFi' on iPhone. Found breeze under 'networks', selected it and entered the breeze password there. Then upon opening Breeze app, it immediately connected to drone. Since it works on android an not on iPhone after upgrade, concluded it is in the breeze software, since the app will not access WIFI connection.


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- Home
- Nissan
- Nissan RB20 & RB25 & RB26
- Exhaust
- TOMEI EXPREME Turbine Outlet Pipe - Nissan RB26DETT
Tomei began operations in 1968 as a race car tuner in Japan. Over the last 40 years Japan has emerged as one of the leaders in automotive research, racing, and culture. Tomei products have been utilized in nearly every motor sport imaginable. Tomei's racing heritage means their research and design team have first hand knowledge of the extreme demands racing puts on an engine. Using only the highest quality materials means that Tomei's products can handle the intense strain and heat a purpose built engine will experience whether it be on the street or the track. Tomei's attention to detail is second to none. All of their products are thoroughly researched and engineered to achieve optimal efficiency. Because of even miniscule differences in measurements can cause catastrophic engine failure, all Tomei products fall within strict tolerances. Tomei machines all of their engine components to enhance airflow and ensure proper fitment and seal.
The stock turbine outlet pipes internal diameters are small and restrictive which raises the secondary exhaust pressure. When the secondary exhaust pressure rises it will cause power loss and lack of response with unstable boost pressure. The TOMEI outlet pipes have been specifically designed with the larger internal diameter to improve exhaust gas flow efficiency with the reduction in the secondary exhaust gas pressure. This design has been proven effective on the engine bench dyno R&D as well as in the real world environment as proven on the race tracks with our ARMS turbines.
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About the Coaching
Why Choose Natural Running Coaching (NRC)?
We teach the skills of running so that you can:
- Improve your running health and safety by avoiding injuries
- Run faster and farther while saving energy with enhanced running economy
- Achieve all your running goals and outcomes no matter what type of running you enjoy
We provide:
- High-quality, detailed, personalized analysis of your current running form
- Specific and targeted recommendations for improving your form
- Organized, straightforward, step-by-step materials to teach you everything you need to know about Natural Running and how to achieve it
How does Coaching work?
We offer four coaching options:
1) Online Coaching
Simply take a short video of yourself running, following our helpful hints, and upload it directly to our site with our quick and easy submission form. Online Coaching includes an Introduction to Natural Running or a Natural Running Form Follow-up. We provide a half-hour phone/skype call option to give you the opportunity to talk directly to us and ask any questions you may have.
2) In-person Coaching
Currently offered in parts of Alberta, Canada by Tina Dubois and Washington, U.S.A. by Angie Bee Hotz. In-person Coaching includes One-on-One Coaching as well as Small Group and Large Group Clinics, which can be tailored to suit your needs.
3) Teaching Tools for Schools
We now offer unlimited access to our coaching materials for physical education teachers to teach their school's students the most efficient and least injurious form of running.
4) Running Form For Sport
For individual or team sports involving running, we now offer a package of educational material to teach coaches and athletes how to run with increased endurance and decreased risk of injury.
For more information or to book any of these coaching options, check out our Services.
About the Coaches
Tina Dubois started running in 2000 in an effort to get fit and live a healthier lifestyle during her university years. What developed was a passion for finding the most efficient and pain-free form of running, which lead to the creation of Natural Running Coaching.
After suffering numerous running-related injuries for years and always being disappointed with the 'injury–recovery–run again' cycle, Tina discovered that the answer to her injury problems laid in changing her running form and did so through the use of minimalist shoes. This discovery led Tina down the path to learning proper running biomechanics and inspired her to learn how to teach it to others.
Angie Bee Hotz started running because of a strong desire to move her body for stress relief, alone-time, and maintaining an overall healthy lifestyle. She finds that running is an activity that takes care of various needs and makes her a better person overall as it has such a positive effect on all aspects of her life.
Angie began running barefoot in 2009 in an effort to improve her running form and heal from constant shin splints and chronic low back pain that developed as a result of her running endeavors. Running barefoot accomplished those goals and became her favorite way to run. It also blossomed a desire to learn and share the benefits of running with good form, no matter what you wear for footwear.
Latest Blog Posts
Natural Running Coaching For Sale
Are you passionate about running and want to share that passion with others? Do you want to help others discover running with an efficient and safe form right off the starting line? Do you wish you could help injured runners rekindle their running passion with a coaching method that maximizes efficiency and minimizes risk of injury? Then you could be the next owner of Natural Running Coaching. Read More
Introducing Running Form for Sport
Natural Running Coaching is very excited to introduce a new coaching service: Running Form for Sport! This new service is intended for coaches of sports clubs or associations to teach their athletes about natural running form including human biomechanics, anatomy, potential injuries associated with other forms of running, and how to safely transition.
A Successful 2015 PHE Canada Conference
This past weekend's 2015 PHE Canada and HPEC Conference was a wonderful experience!
NRC Attending the 2015 PHE Canada National Conference
Physical & Health Education (PHE) Canada and Health & Physical Education Council (HPEC) Alberta are hosting their 2015 National Conference in Banff, Alberta, and NRC will be attending as an Exhibitor!


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What to expect on your first visit
Visiting any church for the very first time can be a tough experience. Well, we want to put you at ease. Your first visit to Mid State Baptist will be refreshing, friendly, and enjoyable for your whole family.
We want you to experience inspiring music, helpful teaching and preaching, friendly people, and a place where you feel welcome and "at home"! Here are a few answers to your questions and what you might expect on your first visit.
We are sharing Life Community Church building at 3770 Ruth Way, Paso Robles, California. There is parking all around our building with special spaces for guests, seniors, and those who are disabled. As you approach our main entrance, one of our hospitality greeters will meet you and direct you to the right classes and services. They can also answer other questions you may have.
During the 1:30 PM hour, there are children's Sunday School and adult Bible classes. These classes are smaller group settings where you are invited to meet people, enjoy perhaps some coffee and donuts, and hear a teaching lesson more directly applicable to your life-stage. The best way to get to know people at Mid State Baptist Church is to visit one of these adult Bible classes.
Next, you'll enjoy our 2:30 PM worship service where you'll enjoy the uplifting and inspiring congregational singing. The music is always followed by a clear, helpful, and challenging Bible message from Pastor Fore. This service is a little over one hour in length.
Where Do I Take My Children?
Starting with excellent nurseries, there is something special for every age child. At every service there are safe, clean, and highly staffed nurseries for children three years old and under. For children four years old through sixth grade there are fun, friendly, and Bible-centered classes.
These classes are staffed with trained, friendly, and well-qualified teachers and helpers who will make church exciting and memorable for your child. Our greeters and ushers are located in the lobby and will gladly help direct and even escort you to the right place.
What About My Teens?
Our student ministries are designed to encourage young people to develop a heart for God. Most of the teens attend the 1:30 PM class for one hour and then the worship service another hour with their parents.
Am I Expected to Participate in the Offering?
No. We don't invite you to Mid State Baptist Church for your offering. We want our service to be a gift to you. We hope you will find in this place a warm family spirit, truth from God's Word, and a place where you can grow in God's grace. Please don't feel any obligation to participate in the offering as a guest.
Other Questions?
If there's something we missed on this list, just give us a call, or ask someone when you arrive. Whether you're new to the area and looking for a church home, or if it's been a long time since you've attended church at all, we hope your first visit at Mid State Baptist will be awesome! We exist to serve you and your family, and we are looking forward to meeting you personally. We hope you'll feel right at home from the very first moment you step onto campus! Let us know how we can serve you better, and we hope to meet you this Sunday!


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GLOW NUTRITION - Health Coaching - Nutritional Counseling
Jessica Idleman, CHHC, AADP
Health Counseling is an integrative and cutting-edge trend in the health and nutrition field. As your Health Counselor, my personal approach is recognizing food selection, preparation, and eating as a healing art.
Transition is not black and white. Restrictions of "good" or "bad" foods, counting calories, and deprivation are not effective long term. There are many reasons why diets do not work. I work with my clients to create positive, long-term changes in a way that is flexible, free of denial, and rewarding.
Together we will discover the approach that works best for you at this point in your life. I will help you make gradual changes enabling you to reach your current and future health goals. I will guide you to find the food and lifestyle choices that best supportyou and your daily challenges
Optimal Health and Acupuncture
Laced Photography and Design


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I am sorry of the passing of your husband Nick Edwards. I am interested in his pyramid energy technology. How can I obtain his products?
Nick Edwards Power Pyramids
Nick Edwards, the maker of the Nick Edwards pyramids passed away from a brain aneurism on April 18th. Mr. Edwards is survived by his wife Janet and a daughter.


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There are lots of factors to consider while choosing the right place to start you technology business. Doing a thorough study before starting up can help you take the right decision. Here are some tips and tricks to know exactly which place would be your best bet.
Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.
[email protected] www.valuecoders.com


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April 17, 2008
NC Coastal Boating Maps
If you are interested in NC boating, get your free Coastal Boating Guide from the NC Department of Transportation. If you prefer, you can also download a digital copy.
Order Link
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Escape door first horse. Drop feed doors.
Manual single leg jack. Spare.
Finished dressing room. Dinette. Heater. Bed.
Portapottie. Carpeted wall.
Double rear doors. Butterfly latches. Sliding window/s.
Rear tack. Heavy duty floor, wall mats.
3 tier saddle rack
Aluminum dividers. Pads.
Escape door first horse, interior.
Stock# 13701 - $10,995.00 - Located in Wicksburg, AL


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Former White House Official: Obama Really Needs Another Campaign, Because He's Not So Good At Governing
CNN's Peter Hamby reveals that it has dawned on at least one of Barack Obama's former aides, that the president isn't very good at his job.
"I talked to a former Obama White House person, just before Christmas, when Obama was sort of adrift, figuring out what to do, his poll numbers were pretty low," Hamby said. "And he said, 'Look, the president needs to find an issue to campaign on. This is what he's good at. He's really good at campaigning. Maybe not governing,' according to this Democrat."
That Democrat must have been the Deputy Senior Undersecretary for the Bleeding Obvious.
These comments came just before Christmas, at a time when President Obama and some Democrats had already started to try to push Obamacare's rolling disaster out of the headlines by pushing for a national minimum wage hike. So, message received and acted upon.


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What exactly does a slackbuild do (aside from installing a package)?
I mean like, what does it do differently from just installing something from source? Check to make sure you have the required dependencies before compiling the .tgz package? something else?
Normally a SlackBuild will just Build a package from source.
It's just a script that is written to automate all the steps to create a package.
It can set compiler options and other environmental variables and sometimes even download the source but does not resolve dependencies (unless someone hard codes this in).
More interesting reading to be found here. http://www.slackwiki.org/Writing_A_SlackBuild_Script
Another thing the slackbuild does is: document the build process. Though that's more of a soft benefit.
I recently had an epiphany and discovered that it's not automated dependency checking, but automated dependency resolution that I object too. :)
Besides, making it easy to compile a package (it isn't always easy), using a Slackbuild allows you to uninstall the program.
Actually using a Package allows the un-installing =)
Also, the SlackBuild does not *install* the program -it just creates the package. As GazL pointed out, the script provides the most concise documentation of the build, which to me is the *biggest* benefit.
A SlackBuild can also be used to adapt an install to suit the standard Slackware structure. An example of this is the SlackBuild for OpenOffice by rworkman. It actually unpacks the compiled binary rpm package and makes changes to suit Slackware.
Most usually a slackbuild script actually does dependency checking. That is: if the build process performs a "./configure --parameters"
What most of the SlackBuild scripts do:
1) unpack the source
2) run configure
3) make the software
4) "install" it in a safe location which allows for creation of the package
5) add the documentation and other useful resources (like config files) to the package
6) create the package so that it is easy to install, uninstall and upgrade, allowing you to keep the rest of your system clean.
This is, however, NOT what _all_ SlackBuild scripts do; in essence what they do in one line is this:
put together the files into a (compressed) archive in a format that is understood by the package application so that it may be installed, upgraded or un-installed.
When building from source, the commonly stated last step of "su make install" does not do it for me because not only do I want to be able to uninstall (and there is no "make uninstall") but I want a record of what is installed and where, That only takes place with packages. Additionally SlackBuilds, for me, fills a hole left by "checkinstall" when it failed to keep up and was dropped from Slackware Extras. For those newer to Slack or who never used it, "su checkinstall" took the place as a direct substitute for "make install" and it could create packages, slacpakcks, debs and/or rpms. It was great while it lasted.
Slackpkg isn't bad but I have yet to learn how to control the configure process the way I want with it. SlackBuilds generally lay it all out and make it easy to set any options you want and I never needed debs or rpms anyway. The dependencies are generally listed from the same place you get the SlackBuild so before you even download it you know what you need. That means you don't have to sit and watch as configure runs for the tenth time stopping on some missing library you must then go fetch and install first. With SlackBuilds you can plan ahead and make compiling all but effortless and go fix a cup of coffee while the build script runs unattended and return ready to go.
Does it mean that if I install the VLC player slackbuild, it won't install ALL the codecs on its own? Do I have to download 100 codecs from different websites individually?
For mplayer though, yes, you'd need to hunt down some dependencies if you're unhappy with the build that ships with Slackware. ffmpeg is another one that can make good use of codecs that may not be included with Slackware. I have a list of codecs from SBo that I generally build before anything else (and I recompile mplayer to take advantage of them). This lets me include support for the codecs that I plan on using without burdening my system with added optional dependencies that will never be used. sbopkg makes preparing queues for these multimedia dependencies relatively painless while still providing you with control over which optional dependencies are to be included.
For those arguing about dependency resolution, in *my* mind the only dependency resolution I would accept would be something akin to Gentoo's portage system with USE flags allowing me to enable/disable optional dependencies at will. Right now I essentially prepare sbopkg queues manually which takes slightly longer than a USE flag-like system but is still reasonable.
|All times are GMT -5. The time now is 03:09 PM.


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SAO PAULO, June 24 (Reuters) - OSX Brasil SA, the shipbuilding company of billionaire Eike Batista, on Monday denied a report it failed to make payments on debt held by Spanish infrastructure group Acciona.
The local Folha da S.Paulo newspaper reported on Sunday that Batista's OSX Brasil was struggling to avoid bankruptcy after it defaulted on some 500 million reais ($222 million) in debt held by Acciona.
"The story on the supposed debt with supplier Acciona that OSX CN failed to honor is false," OSX said in a market filing with regulator CVM on Monday.
Representatives of Acciona in Spain had no comment.
OSX said its debt payments were up to date.
OSX shares have sunk 85 percent since the beginning of the year as a series of missed targets and project delays eroded investor confidence in Batista's ability to deliver on his promises. Markets were not yet open in Sao Paulo on Monday.
Batista became Brazil's richest man in recent years after raising billions of dollars amid booming demand for commodity-related investments in the country, but lost his standing after the selloff helped slash more than $20 billion from his fortune in the past year.
OSX Brasil is a holding company involved in the oil and gas sector. The Company provides equipment and services to the offshore oil and gas industries.


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This part of the memorial shows the Spanish towns and battle locations where Hungarian volunteers fought in the civil war.
Thanks to William Barletta for enhancing this image for me!
All photos copyright © by Helen Betts. All rights reserved. Please do not use or copy without written permission of owner.


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During the Peasants' War the abbey lost all its properties and became subject to secular regulations as a result of the introduction of the Reformation in the county of Schwarzburg. Eight years after the Benedictine abbey was dissolved in 1534 and the monks displaced, the estate passed into the ownership of Count Gunther XL of Schwarzburg. This spelt the gradual decline of the entire abbey complex and stones from the ruins were used to construct other buildings.
Johann Wolfgang von Goethe was highly impressed by the picturesque ruins of the abbey. Although in those days, as he wrote himself, it was 'unfashionable to view these monastic ruins as being highly significant and sacred', they had been 'extolled as a spectacular sight' and so he spent his 68th birthday there.
Today the ruins of the abbey are some of the most significant Romanesque constructions in Germany and are an insider's tip for all fans of this architectural style.
Crossing the Rennsteig, the most famous hiking trail in Germany, you continue up to the ridge of the Thuringian Forest to Frauenwald. Located right on the main trading route between Erfurt and Nuremburg – which itself was part of the long-distance road between Denmark and Italy – crossing the Rennsteig Trail was considered the major route here in Frauenwald due to the long, gentle incline. Luther took this route via Frauenwald eleven times on his journeys to Rome and twice he is said to have stayed overnight in a nearby monastery.
In Gehren, the Schlossparkfest (Castle Gardens Festival) takes place every year in August.
As this section is quite long, it is also suitable for a two-day trip. Spend the night in the heart of the countryside at the Waldhotel near Gehren.
This tour is conveniently accessible by public transport.Paulinzella is easily accessible on the regional trains from Arnstadt. The station is not far from the start of the trip.
This functionality is only avaliable for members of the outdooractive plattform.
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September 8, 2017
May 17, 2017
May 9, 2017
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April 28, 2017
In partnership with Pike Place Market and 4Culture, "One Market for All" weaves the voices of the Pike Place Market through history, linking the past, present and the future while celebrating the uniqueness of the Market through oral tradition.
April 12, 2017
In partnership with BECU, this special section will provide middle and high school students with tools for building financial literacy.
February 23, 2017
This publication commemorates the 75th anniversary of executive order 9066 – which ordered the removal of Japanese Americans from Seattle during World War II. This supplement highlights the seldom told story of the incarceration of Japanese Americans during World War II to provide students with the opportunity to learn from a challenging time in our country's history – and to apply lessons learned to issues of today.
April 7, 2016
Boost your brand awareness and connect with consumers on a whole new level. NIE partners with corporations and community businesses to make our program available to educators at no cost.
Sponsor a program or publication, adopt a classroom, or make a donation.


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More Reasons Why Evolution Is Stupid Trailer (2004)
This past school year was my freshman year in college and I had to take Biology. My teacher taught me all these things about evolution and eventually, I accepted them. Then in June, I saw the YouTube video of "100 Reasons Why Evolution is SO Stupid!" I watched that and realized that nearly everything my teacher had taught me was disproved lies. It was so entertaining as well as informative and educational, that I stayed up nearly all night watching more videos. You got me to realize that Genesis is true! I can EVER repay you for saving me! When we see each other in Heaven, I will be standing along with the hundreds of thousands of people you won to Christ! I myself have already won a friend to Christ with your material! I want to save more people. God bless you!–Eric June 2013
Watch the official More Reasons Why Evolution Is Stupid 2004 trailer in HD below or find more More Reasons Why Evolution Is Stupid videos on Vidimovie.