AT500782A4 - METHOD FOR SEPARATING LAYERS FROM IONIC LIQUIDS - Google Patents

Description

METHOD FOR SEPARATING LAYERS FROM IONIC LIQUIDS

The invention relates to a method for depositing layers of metallic or semiconducting elements and / or their compounds on substrates, by means of chemical, electrochemical and / or thermally induced chemical reactions, of non-aqueous solution as a carrier liquid, which at least one, a cation and an anion , organic, ionic liquid, as well as containing the / the layer element (s) containing precursor substance (s) and wherein the deposition takes place at temperatures below the decomposition point of the carrier liquid.

The electrochemical deposition of layers by means of electroplating processes from aqueous and nonaqueous solution as the electrolyte is just as widespread a method as thermal vapor deposition from the gas phase by evaporation of volatile compounds on highly heated substrates to be coated.

However, the applicability of these methods is limited to certain coating materials. 9 ·································································································································································································································· · »· · ··········· ·

In electrochemical or galvanic processes in aqueous electrolytes, the choice of possible coating materials is limited by the potential of hydrogen evolution, the availability of suitable reactants for the electrolyte and suitable materials for the electrode pair. The limitation applies more to the requirement for well-adhering, non-porous layers and, in particular, relates to the galvanic production of elements whose deposition potential is more cathodic than the potential of hydrogen evolution in the particular electrolyte.

Layer deposits from the gas phase are known in the material field of thermally and mechanically highly stable metal compounds, in individual cases also for the metals themselves. The number of suitable reaction systems is relatively small and, in addition, many desirable substrate materials have too low thermal and corrosion stability. Such, known as CVD, PVD or sputtering, thermal deposition can be carried out at relatively high reaction temperatures of up to about 1000 ° C.

Likewise, there are known electrodeposition processes of layers of electrolytes composed of a nonaqueous organic solvent in combination with conducting salts, such as lithium or sodium compounds, e.g. Acetonitrile, propylene carbonate, dimethyl sulfoxide and tetrahydrofuran exist. Such electrolytes usually have not only a low electrical conductivity and low solubility for oxides and salts, but are also very difficult to keep anhydrous. They often tend to form undefined complex compounds as unwanted consequence of anodic and / or cathodic degradation reactions, whose properties greatly alter or impede the entire deposition process. 3: ··············································································································································································································

Inorganic molten salts of metal salts or oxides and alkali halides with eutectic melting points far below the melting points of the individual pure compounds are prior art, but usually work at temperatures above 400 ° C.

For some years organic ionic liquids, so-called "ILs", have also been tested as constituents of electrolytes or carrier liquids for electrochemical deposition processes of layers of nonaqueous solution, in particular of aluminum and aluminum alloys. Corresponding publications have been made by G. R. Stafford and Ch. L. Hussey, Advances in Electrochemical Science and Engineering, 7 (2002), p. 275, ed. Wiley-VCH, Weinheim; also by M. Zhang, V. Kamavaram, R.G. Reddy, JOM, 55 (2003), p. 54.

In addition to the salt-like character of " ILs ", which is important for the electrolyte conductivity, it is above all their broadly usable electrochemical potential range which makes them appear as an electrolyte for electrochemical layer depositions.

However, organic, ionic liquids, or mixtures of solvents with organic, ionic liquids, are only useful as carrier liquids in electrochemical systems when the electroactive component containing the element to be deposited is introduced into the electrochemical system in sufficient concentration and in the course of the electrochemical deposition reaction In accordance with the conversion can be supplemented in sufficient quantity and homogeneous concentration distribution.

In addition, the reaction taking place at the respective counterelectrode (in the case of metal deposits usually being an anode) should also be able to take place continuously in the electrochemical system. Furthermore, the following must be specified for • ········································ ······ ····· · commercial applications should be given a sufficiently high reaction rate at suitable temperatures of the electrochemical system.

The previously known electrochemical systems using organic, ionic liquids as electrolyte meet these conditions only very inadequate. The number of application-oriented pre-publications on the subject of metallic film deposition is therefore very small.

DE 101 08 893 A1 describes a process for the electrochemical deposition of metals, alloys and semiconductors from organic, ionic liquids and low-melting salt mixtures. The layer material disclosed are metals of the second to fifth main or subgroup of the periodic table and their alloys with average crystallite size in the range of 1 to 2000 nm.

According to the invention, these materials are deposited galvanically in an apparatus equipped with a cathode and an anode from an ionic liquid or a suitable molten salt at temperatures below 200 ° C., preferably between 20 and 100 ° C.

Preferably, the electrolyte consists of one or more metal salts and one or more organic components. As metal salt components, metal or semiconductor halides, nitrates, perchlorates, fluorophosphates, sulfonates, acetylacetonates or mixtures thereof are explicitly mentioned. The explicitly mentioned components of organic ionic liquids consist of halides, fluorophosphates or sulfonates of substituted imidazolium or pyridinium salts or mixtures thereof. The substituents are selected from methyl, ethyl, butyl, decyl, dodecyl substituents. Further mentioned are mixtures of NaCl, AICI3 and a metal salt as electrolytes, i. Combinations Μ · «* · · · Μ ·····························································································. ···································································································································································· For the adjustment of the desired Kristaliitgröße additives from the group of carboxylic acids, amines and aromatic compounds in a proportion of 1-10 wt.%, Based on the total amount of electrolyte, added to the electrolyte. For example, galvanic precipitation reactions with a pulsed current characteristic are described.

This process shows a wealth of weaknesses and disadvantages.

The use of a, the metal to be deposited nacherfernden in the electrolyte, thereby sacrificing sacrificial electrode is not provided or not satisfactorily possible. The use of the metal to be deposited as the anode material would, as already described for lithium [Y. Katayama, T. Morita, M. Yamagata and T. Miura, Electrochemistry (Tokyo, Japan) 71 (2003), 1033], severely limited by the formation of passivating layers. However, if the use of soluble anodes to maintain the metal ion concentration is not possible, there is a significant disadvantage of the method described above when using the organic and inorganic components mentioned therein. The reason for this is the concentration of the individual chemical components in the electrolyte and at the electrodes, which otherwise changes greatly with the duration of the process. The electrochemical reactions slow down and come to a halt, in part also via passivation effects, as detailed by Y. Katayama, T. Morita, M. Yamagata, and T. Miura, Electrochemistry (Tokyo, Japan) 71 (2003), 1033. The method does not allow economical layer deposition. Furthermore, there is often formation of unwanted, deposition-inert complex compounds with the compounds to be deposited and / or their ♦ ··· ···· ··· ····

• · · · · · · · · I · · · · • · · ··· # · • * ···· «·· I« »*« ·

Ingredients. This has serious disadvantages for the mobility of the ions in the electrolyte.

Further disadvantages of the above-cited method are the uncontrolled decomposition of electrolyte components at the anode and the uncontrolled accumulation of decomposition products in the electrochemical system. Finally, corrosive oxidation products, such as elemental gaseous halogens, can form.

US Pat. No. 5,827,602 describes hydrophobic organic ionic liquids for use in the fields of nonaqueous batteries, electrochemical capacitors, electrodeposition, catalysis and chemical separation.

Specifically, there are listed on differently substituted heterocycles, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, thiazole, oxazole or triazole, hydrophobic organic ionic liquids, which are composed of a cationic and an anionic component, where according to the invention Anions are non-Lewis acid containing polyatomic anions with a van der Waals volume greater than 100 Å3 (Angstrom to cube).

Process details for layer deposition in the use of these ionic liquids are not carried out there. The above-mentioned, to methods according to the prior art disadvantages also arise when using the aforementioned ionic liquids.

Object of the present invention is therefore to provide a method which does not have the disadvantages of the previously published layer deposition method with the previously proposed, organic ionic liquids as electrolyte or in the carrier liquid. For the deposition of dense, homogeneous • · · · · · · · · · · · · · ·········································································· * ···· ·· ···· ··· · «« · «·

Layers of useful solid state structure, consisting of metals, semiconductors and their compounds are suitable to propose organic ionic liquids which allow in combination with selected, the / the layer element (s) containing precursor substances the appropriate deposition conditions.

It is also an object of the present invention to provide methods of the type initially mentioned which either permit a substantially continuous deposition or which, when using sequential deposition cycles, bring about at most only a small change in the composition of the carrier liquid.

This object is solved by the features of the characterizing part of claim 1.

The subclaims contain preferred embodiments of the present invention.

As used herein, the term carrier liquid refers to all the substances provided to the process in non-aqueous solution. In addition to the organic ionic liquid essential to the invention, or a mixture of organic ionic liquids and the precursor substances to be provided for the layer materials to be deposited, the carrier liquid may contain further additives. These can be used, for example, to increase the electrical conductivity, the solubility of added substances, as an additive to accelerate desired, or to prevent other undesirable reactions in the process according to the invention. They may be in the form of a molten salt or in the form of other organic, ionic and non-ionic liquids. ♦ · · · · · · · · · · · · · · · · · «·· ···· ··· ·· ··· #

The farther from the stated reasons for the previous use of organic ionic liquids in processes according to this invention are still valid. Nonetheless, the many hitherto encountered difficulties in the use of ionic liquids which can not be calculated individually or in terms of their interweaving have rather prevented the person skilled in the art from continuing to search for suitable such substance systems as carrier electrolyte.

The inventively newly proposed group of organic ionic liquids with reducing organic or inorganic components as anion include, in particular, the azides, further cyanoboranates, boranates and alanates, as well as germanates, silicates and gallates of the present in these compounds jeweis divalent elements germanium , Silcium and Gallium. This group of organic ionic liquids resulted in the process according to the invention particularly great progress in overcoming the disadvantages mentioned in the prior art.

The term reducing agent in the present document is not primarily to classify the classification of individual substance components according to their redox potential or their place in the electrochemical series, but the ability of the respective component with other, provided as oxidation components components of the carrier liquid to respond reliably to the desired reactions , without being subject to unwanted secondary or subsequent reactions. This also applies, in particular, to the anions of organic ionic liquids in the carrier liquid (in the case of electrochemical processes, where appropriate, also of the electrode materials), in combination with .alpha .. selected according to the invention. ··············································

Counterions. Not only do the reducing anions not cause undesirable secondary and subsequent reactions in the carrier liquid, they also ensure that any layer deposits which may be useful for a short period are not obstructed or reversed in the further sequence. The ionic liquids with reducing anions and the cations selected in each case differ from those known to those skilled in the art as related substances or solids in that they form stable electrolytes or electrolyte components well below their decomposition temperature and also without the addition of solvents, or pure can be used according to the invention as reactants. For a classification as a reducing anion, according to the invention, therefore, not its redox potential alone is decisive; then almost inevitably all ionic components with hydrogen strongly negative redox potential would belong to the substance components according to the invention, regardless of the controllability or non-controllability of a total in a Schichtabscheideverfahren running reactions. Rather, the organic ionic liquids with inventively reducing anions must meet the above-mentioned additional selection criteria. Already the recognition of these selection criteria per se, was not suggested by the state of the art. Without doubt, however, it exceeds the knowledge of the average person skilled in the art to select and provide the ionic liquids mentioned in the invention as being preferred for the process mentioned at the outset.

Azide ions represent the strongest reducing agents known in solution (E ° = -3.608 V (neutral), -3.334 (acid) [H.J. Quadbeck-Seeger, Chemie-Rekord,

Wiley-VCH (1997), p.41; ISBN 3-527-29452-X]. They are known to the skilled person as usually highly explosive components - except the alkali compounds. He will therefore not include the use of azides among the selection candidates. To date, it has not been known to the person skilled in the art and it has surprisingly been found that certain groups of ionic azides, beyond which the alkali metal azides are known to be safe, can be handled safely under suitable conditions and, when used in the process according to the invention, fulfill the stated additional selection criteria.

The reaction scheme shown below shows the inventive electrochemical deposition of palladium from non-aqueous solution as the carrier liquid or electrolyte. The electrolyte is an organic ionic liquid composed of a palladium complex compound which contains the counterions of a component of the electrolyte, and an azide as the anodically active or reducing anion component. This anodically active component ensures the charge transfer at the anode in the galvanic deposition process while avoiding uncontrolled formation of reactive degradation products of the electrolyte. . · · · 9 ·· ···· ··· ·· ··· # +

Cathode + 4 H3C-C = N as needed removable cosolvent \ (ligand exchange)

+ 2 BF4, anion = identical to anion carrier electrolyte

N- ^ n- * pWn = - T " N precipitable complex salt 2 ©

-N BF4 · > - -N Θ

supporting electrolyte

.N * N Θ I β β 'N = N = N ^

Anode (no deposition) 3 N2 f (gas) 2g Q.® v® 2 'N = N = N ^

Reduction cycle of anodic active species of carrier electrolyte " oxidation cycle

The use according to the invention of cyanoboranates, boranates and alanates in the present process was likewise not obvious. Their formal redox potential does not make these substances appear as preferred components. Decisive for their use, however, is the recognition of their ability to transfer hydrides or alkyl radicals to the reactants, without causing unwanted side reactions.

For example, alanates and boranates react with salts of Group 4 elements to bidentate hydride-bridged neutral complexes (T.J. Marks, J.R. Kolb, Chem. Rev. 77/2 (1977), p.263). In the case of Ti (IV) halides, e.g. under diborane and hydrogen evolution to a prereduction to neutral Ti (III) complexes or tetrakis (tetrahydridoboranato) titanate (III) anions.

The latter reducing anion group is also excellently suitable as a precursor substance for the thermally induced low-temperature CVD deposition........ Layers (JA Jensen, JE Gozum, DM Pollina, GS Girolami, J. Am. Chem. Soc., 110 (1988), p.1643).

The reactions proceed according to the following scheme:

TiCl4 + 4 [BH4] ® Θ4 Cl + V2 H2 + B2H6 + Ti (BH4) 3-CH2 (OCH3) 2

Ti (BH4) 3 · thenn. Decomposition r

TiB21 + / 2 B2H6 + / 2 H2 +. Ό "

The use of organic ionic liquids with divalent germanium, silicon and gallium in germanates, silicates and gallates as a reducing anion has also not been suggested by the prior art.

It was previously known (D. Obendorf, H. Schottenberger, C. Rieker, Organometallics 10 (1991), p 1293), that in non-aqueous, organometallic electrolyte systems with reducible (precursor) substances in different possible starting oxidation states the use of low valency substances which can be prevented in electrochemistry well known Komproportionierungsreaktionen.

If this finding is consistently transferred to the object of the present invention, organic ionic liquids according to the invention are obtained, correspondingly also to the trichlorogermanate (II) shown in the following reaction scheme as the starting compound to be reduced for the Ge deposits. When used, or in the presence of Ge (IV) compounds in the presence of already deposited Ge (0) would regularly be a Komproportionierung occur. ················································································································································································································································

In the method for the deposition of metallic germanium according to the inventive method, the following partial reactions take place, or not from:

low-valency chlorogermanate in the form of an ionic liquid (according to the invention) reduction q 2e + GeCl 2 -► Ge + 2 Cl

Reduction q 2e + GeCl 2 -► Ge + 2 CI

Partial reduction 2e '+ GeCl4 -► GeCl2 + 2Cl® -► GeCl2

Ge in the presence of Ge (IV) unwanted Komproportionierung

A very significant advantage of the organic ionic liquids which can be used according to the invention over the explicitly described systems as a carrier liquid for depositing metallic and semiconductive layers is their freedom from unwanted, e.g. bridging complex forming side reactions. The ionic liquids with a comparatively narrow electrochemical window already described for such use belong to the dialkylimidazolium salts with dicyanamide anions (MacFarlane, J. Golding, S. Forsyth, M. Forsyth, GB Deacon, Chem. Commun. (2001), p. , However, dicyanamide, as well as its postulated dimer formed in the counter-oxidation, act as strong, multidentate complexing agents and lead to the formation of coordination polymers for solidification of the carrier liquid. In contrast to the present invention, those ionic liquids are only of limited use for electrochemical applications. II «· · · · ·····

• * * II «· I · # ···· ··· ·· ···«

Reducing inorganic or organic components as anion in organic ionic liquids generally have the great advantage of occupying the role of a so-called sacrificial electrolyte in the layer deposition method according to the invention and in this function to no, in deposition process highly undesirable composition and in particular concentration shift within to carry the carrier liquid, ie, these anions are reacted without any disadvantage to the overall reaction system, or used up.

For the sake of illustration, reference is made to the above-described reaction scheme using azide anions.

In this and the comparable material and reaction systems according to the invention, it is therefore possible to achieve optimized layer thickness distributions by means of alternating current methods (modified "Pulseplating" in which pulses in the cathodic potential range are combined with pulses in the anodic potential range or by eddy current method) and both working electrodes to use as a layer-deposition electrodes, because at a potential reversal occurs no simultaneous total reversal of the electrochemical reactions. Already deposited metal can not dissolve again thus; the oxidative counterreaction of the anion or the anion complex system becomes effective. In the preferential use of azide as a sacrificial anion, the destruction is without trace in the sense of the dimerization reaction: 2 N3 "-> 2e ~ + [N6]. The not-stable pseudohalogen N6 decomposes spontaneously and irreversibly into inert elemental nitrogen: [N6] - »3 N2T.

By means of the additional choice of homoleptic azidometallates or metal azides (A. Konrath, Angew. Chem. 2002, 1313/17, p. 3231) as preferred for a layer deposition organic cations of the carrier liquid (conducting salt ILs), according to the above azide example in which the azide complexes are also prepared in situ, the electrolysis can be formally operated as a total traceless process, ie without a net change in the composition of the carrier liquid.

As already known in the prior art for the layer deposition from electrochemical carrier liquids, the morphology or solid state structure of the layers can also be influenced by the addition of additives in the method according to the invention. By additions, a mechanistic influence of the redox potentials in the sense of a controllable sequence, or an overall facilitated separability is still possible.

The anionic components used in the present invention, in combination with known organic cations, form stable ionic liquids which are completely water-free or sufficiently freewheelable and are readily electrochemically oxidizable (e.g., to neutral, volatile di- or oligomers). This has particular advantages when using "Pulseplating" techniques, such as the "Reverse-Pulse-Plating", because the anodic sacrificial reactions lead to no net change in the Leitelektrolytzusammensetzung and Fremdsalzakkumulationen can be avoided.

With the ionic liquids according to the invention as the carrier liquid, unlike methods using the specifically described ionic liquids, the production of compact, pore-free metallic layers of unalloyed titanium in variable thickness succeeded. So far, only the deposition of titanium alloy layers or non-contiguous titanium microlayers has been described (W. Freyland et al., Langmuir, 19 (2003), p.1951).

As precursor substances, i. as metal-containing and semiconductor-containing neutral complexes, salts and solvate salts, preference is given to using hexafluorophosphates, hexafluorosilicates, pentafluorosilicates, tetrafluoroborates, tetraphenylborates, trifluoroacetates, triflates, bis (trifluoromethyl) amides, dicyanamides, tetrachloroborates, tetrachloroaluminates, bis [(trifluoromethyl) sulfonyl] amides, saccharates , Trifluoroacetates, carboxylates, propiolates, tris (trifluoromethyl) sulfonylmethanides, tosylates, sulfonates, fluorosulfonates, monoalkyl sulfates, hydrogen sulfates, alkali azides, alkaline earth metal azides, technically safe, dilute solutions of transition metal azides in benzonitrile, acetonitrile, aromatic hydrocarbons and halogenated hydrocarbons and azidometalates.

However, it is also possible to use other salts soluble in the carrier liquid, such as halides, pseudohalides, propiolates, oxalates, fluorometallates, chlorometallates, cyanometallates, oxalatometallates, 1,3-diaryltriazenides, or 1,3-pentanedionates, and also their solvates.

Exemplary representatives here are 1-butyl-2,3-dimethylimidazolium tetraazidocuprate (I), tetrakis (acetonitrile) palladium (II) bis (tetrafluoroborate), tetrakis (acetonitrile) iridium (I) tetrafluoroborate, 1-butyl-2,3- dimethylimidazolium hexachlorotitanate (IV), 1-butyl-2,3-dimethylimidazolium tetrachlorocerate (III),

Bis [(1,2,3,4,5,6-η) -1,3,5-trimethylbenzene] iron (II) tris [(trifluoromethyl) sulfonylmethanide], bisfa6-benzene) chromium (I) tetrafluoroborate, trichloro [ (1,2,3,4,5,6-η) -1,3,5-trimethylbenzene] titanium (I) tetrachloroaluminate, ···· ··· ····· ········· ··· »··« μ · · · «· ·

Tetrabutylammonium hexaazidoferrat (III), tetrabutylammonium hexaazidochromat (III) and titanium tetraazide listed in acetonitrile.

As starting material for the production of ionic liquids with non-reducing, organic and inorganic anion components as constituents which are only optionally optionally contained in a carrier liquid, preference is given to halides, pseudohalides, hexafluorosilicate, pentafluorosilicate, hexafluorophosphate, hexafluoroarsenate, hexafluorotantalates, hexafluorotitanates, perfluoroalkyltrifluoroborates, tetrafluoroborate, Tetrachloroborate, chlorotrifluoroborate, tetrachloroaluminate, tetraaryl borates, fluorinated tetraaryl borates, fluorinated halotriaryl borates, fluorinated pseudohalogenotriaryl borates, trifluoroacetate, triflate, nonaflate, tosylate, sulfonates, fluorosulfonate, saccharate, monoalkyl sulfates, hydrogen sulfate, bis [(trifluoromethyl) sulfonylamide,

Tris (trifluoromethyl) sulfonylmethanide, bis (trifluoromethyl) amide, dicyanamide, dicyanomethanide, tricyanomethanide, tetrakis (trifluoromethanesulfonato-0) borate or propiolate and its complex compounds. For the production or provision of redoxinerten cation components according to the invention in organic ionic liquids, with also according to the invention reducing acting, organic and / or inorganic anions and in the function (the ionic liquid) as a carrier, conduction and / or sacrificial electrolyte come preferably used: C- and N-alkyl-substituted imidazolium, triazolium, thiazolium, oxazolium, pyridinium ions, and dialkylpyrrolidinium, trialkylsulfonium, Tetralkylphosphonium-, Hexaalkylguanidinium-, tetraalkylammonium, orTetraalkyl-hydroxylammoniumionen. Besides alkyl- ························································································································· ·············· , Cyanoalkyl, alkenyl and alkynyl substituents, as well as their combinations and complex derivatives are used.

Particularly preferred redoxinerte, cationic organic components are 1,2,3-trialkyl-imidazolium salts, and among these in particular the 1-butyl-2,3-dimethylimidazoliumsalze, since in these components by the substitution of the hydrogen atom in position 2, a deprotonation to the blocked known carbenoid complexing agents.

The abovementioned preferred cationic organic components are in turn preferred in organic ionic liquids according to the invention in conjunction with the following reducing inorganic and / or organic anion components azide, cyanoboranates, boranates, cyanoalanates, alanates, azidoalanates, azidogermanates, azidogallates , as well as germanates and gallates in their unpreferred, low-valent 2-valent oxidation states, eg as trichlorogermanate (II) and dimeric trichloro-gallate (II).

As organic and inorganic additives to the carrier liquid can be used: mono- or oligodentate donor systems such as olefins, dienes, ethers, thioethers, sulfoxides, sulfones, nitriles, amines, imines, amides, Carbonsaureamide, sulfonamides, phosphites, phosphine oxides, Phosphoranimine, phosphines, Azidliganden , Boranatliganden, Cyanoboranatometall neutral complexes, Boranatometall neutral complexes, cyanoalanatometall neutral complexes, Alanatometall neutral complexes or aromatic π-donor compounds such as benzene, Durol, mesitylene, hexaethylbenzene or hexamethylbenzene as reduction-supporting ligands, and Lewis acids such Silicon tetrafluoride, hexachlorodisilane,

Hexabromdisilan, titanium trifluoride, titanium tetrafluoride, boron trifluoride and boron trichloride, as well as halogen and Pseudohalogenakzeptoren as Haloborane.Cyanotrimethylsilan, Azidotrimethylsilan, Anionenakzeptoren such as Calixpyrrole, and / or Haloaryl-, Perfluoroaryl- and Perfluoroalkylborane, which are able to identical counterions to the anions of form ionic liquids used.

The ionic liquids according to the invention containing the reducing organic and inorganic anion components azide, azidoboranates, cyanoboranates, boranates, cyanoalanates, alanates, azidoalanates, azidogermanates, azidogallates and germanates, silicates and gallates in their unpreferred, low-valent 2-valent oxidation states (eg trichlorogermanate (II), dimeric trichloro-gallate (II) and complex anions of silicon dibromide are used in the use cases of an electroless or partially electroless, purely chemical deposition of layers as reducing supportive systems covered by the invention.

In addition to the use according to the invention in processes for layer deposition, the abovementioned anion-cation combinations of organic ionic liquids can also be used for organic-synthetic, for inorganic-synthetic purposes, as catalysts and for the preparation of catalytically active materials, furthermore as a solvent with selective dissolution properties especially for extraction processes, as electrolytes with adaptable potential window for batteries and fuel cells, as ion-conducting media in membranes (eg for fuel cells), as viscosity and heat conduction media with high resistance and with controllable ignition behavior also as safety explosives (eg for use in airbags) or use as a propellant.

Moreover, because of the high thermal stability (decomposition temperatures above 220 ° C) of the ionic liquids of the present invention, corresponding azides can be used as a source of thermal nitrogen and nitride and used in their electrochemical oxidation readiness as systems for controlled, controllable continuous or discontinuous nitrogen delivery.

The present invention will be further described by the following embodiments, which by no means limit the invention.

Examples 1 to 8 describe in brief the preparation or synthesis of organic ionic liquids preferably used in the deposition process according to the invention, and their structure and material properties are characterized.

Example 9 describes the preparation of a precursor substance for the preferred use in the process according to the invention.

In the following Examples 10-15, process examples for the electrochemical or galvanic deposition of metal layers which were previously not representable from carrier liquids are described.

example 1

The example describes the synthesis of 1-butyl-2,3-dimethylimidazolium azide (BuMM N3) for later use as an organic ionic liquid in the process according to the invention.

To a suspension of 49.7 g of 1-butyl-2,3-dimethylimidazolium chloride [98892-75-2], (Acros Organics, http://www.acros.be), (0.26 mol) in 250 ml of acetone 17.1 g of sodium azide (0.26 mol) were added. The reaction mixture was stirred for 24 hours by occasional sonication to give a white precipitate of sodium chloride. The reaction solution was filtered through a sintered G4 ceramic sinter, dried over Na 2 SO 4 and the solvent removed under high vacuum at 80 ° C. There were 49.7 g of a light yellow, viscous liquid, or at room temperature for months stable, supercooled melt obtained (96.6% theoretical yield). The compound shows no impact-shock or thermal explosion sensitivity. Also by electrostatic sparking could not be caused explosive decomposition. When the compound is ignited, it burns lazily with a yellow flame, similar to a little volatile organic solvent. This ionic liquid is therefore suitable as a carrier liquid, or as part of such a liquid. Analytical data for 1-butyl-2,3-dimethylimidazolium azide (BuMM + N3 ~): cyclic voltammetric data. D. elektrochem. Window: see Fig. B in the appendix. Zers, from 240 ° C (see Fig. A in the Annex); Residual chloride content (CE) 0.55 ± 0.022%. Structural analysis data: FAB-MS (glycerol, pos m / z C9Hi8N2 + = 153.1 (theoretical value for CgHi7N2 +: 153.12), cluster [C9Hi7N2 ++ CgHi7N2 + N3] + = 348.3 (theoretical [C9Hi7N2 ++ C9H17N2 + N3 '] +: 348.29); 1H NMR (acetonitrile-d3 δ 0.90 (3H, t, J 7.43 Hz), 1.30 (2H, m), 1.71 (2H, m), 2.55 (3H, s), 3.75 (3H , s), 4.09 (2H, t, J 7.4 Hz), 7.46 (1H, m), 7.49 ppm (1H, m), 13C NMR (acetonitrile-d3 δ 9.8, 13.5, 19.7, 32.0, 35.4, 48.5, 121.6 , 123.0, 145.0 ppm. IR (KBr) 2958, 2935, 2873, 2015vs (azide vibration), 1639, 1587, 1536, 1465, 1421, 1380, 1253, 1135, 755 cm-1.

The ionic liquid thus obtained was analyzed for its electrochemical potential. 1 shows a graph of the CV determination of the electrochemical

As a dashed curve, the component BuMM + BF4 ', at an electrolyte temperature of 65 ° C and a voltage change of 50mV / s against a Pt reference electrode - as a solid curve, the component BuMM + BF4 / N3 'under the aforementioned boundary conditions.

Due to the pronounced oxidation state above 500 mV, it can be seen that BuMM + N3 'is reduced earlier than, for example, BuMM + BF4. From this potential on, a significant gas bubble formation (N2) can be observed for the former component.

Example 2

The example describes the synthesis of 1-butyl-3-methylimidazolium azide.

To a suspension of 33.6 g of 1-butyl-3-methylimidazolium chloride (0.192 mol) in 250 mL of acetone was added 12.5 g of sodium azide (0.192 mol). The reaction mixture was stirred for 24 hours with occasional sonication to give a white precipitate of sodium chloride. The reaction solution was filtered through a G4 frit, dried over Na 2 SO 4 and the solvent was removed by high vacuum connection (40 ° C.). There were obtained 32.8 g of a reddish, viscous liquid (94% theoretical yield). Structural analytical data for 1-butyl-3-methylimidazolium azide: MS: FAB, glycerol 139.1 [C8Hi5N2r 1H NMR (benzened d6 capillary delta 0.71 (3H), 1.13 (2H, m), 1.76 (2H, m), 4.06 (3H, s), 4.34 (2H), (4.49 traces HN3I), 7.99 (1H, m), 8.10 ppm (1H, m), 9.64 (1H, s). 13C NMR (benzene-d6 capillary delta 13.4 , 19.4, 32.3, 36.0, 49.3, 122.9, 124.1, 137.6 ppm IR (KBr) 3145, 3085, 2960, 2935, 2873, 2015 (azide oscillation), 1643, 1571, 1463, 1678, 755, 622 cm'1. ·· ♦ · · · t * '· · · • # · ····· ·· ···········

Note: The compound prepared in an analogous manner to Example 1 from 1-butyl-3-methylimidazolium chloride is also a pure, liquid at room temperature azide. By unsubstituted proton in position 2 formed on prolonged storage under Eliminative Carbenblildung but continuously highly toxic and explosive hydrazoic acid (HN3), Therefore, the production and use of this derivative in larger quantities is foreseeable.

Also, the addition of broth-containing reagents (e.g., HCl from wet titanium tetrachloride) to the inherently stable azides (see Example 1) of this class of compounds directly results in the formation of hydrazoic acid (HN3), which in undiluted form is known to detonate.

Example 3

The example describes the synthesis of 1-butyl-2,3-dimethylimidazolium cyanide (BuMM + CN) as a precursor to other ionic liquids according to the invention. To a suspension of 3.91 g of 1-butyl-2,3-dimethylimidazolium chloride [98892-75-2] in 40 ml of acetone was added 1.02 g of sodium cyanide. The mixture was stirred for 2 h and occasionally sonicated, whereupon NaCl turbidity was observed. MgSC> 4 was added to the mixture for drying, filtered through a G4 frit and freed from the solvent by connection to a high vacuum at 60 ° C.

There was obtained 3.0 g of a white solid (81% theoretical yield). Structural Analytical Data: IR (KBr) 3073, 2961, 2873, 2066 (cyanide vibration), 1587, 1540, 1465, 1420, 1380, 125, 1184, 1336, 1078, 756 cm-1.

Synthesis of 1-butyl-2,3-dimethylimidazolium trichlorogermanate (II) is described. 8.3 g of 1-butyl-2,3-dimethylimidazolium chloride and 10.2 g of germanium (II) chloride dioxane complex were combined in a Schlenk tube. The solid starting materials immediately began to collapse to a liquid. The reaction mixture was briefly immersed in ultrasound and then stirred for 1 h at 30 ° C. Subsequently, the dioxane was removed at 50 ° C under high vacuum (2 h at 60 ° C). 13.8 g of a yellowish, moderately viscous liquid were obtained (94.3% of theory).

Structural Analytical Data: 1H NMR (benzene-d6 capillary): delta 0.86 (3H, t, J 7.1 Hz), 1.30 (2H, m), 1.75 (2H, m), 2.65 (3H, s), 3.52 ( Dioxane), 3.81 (3H, s), 4.10 (2H, t, J 7.1Hz), 7.42 (1H, m), 7.44ppm (1H, m). 13C NMR (benzene d6 capillary): delta 11.27, 14.18, 19.7, 31.8, 36.4, 48.7, 67.15 (dioxane), 121.3, 122.7, 144.2.

From the integrals in the H-NMR results in a residual content of 1.5% dioxane.

Example 5

The example describes the synthesis of 1-butyl-2,3-dimethylimidazolium chlorohydridodiisobutylaluminate.

In a Schlenk tube, 2.0 g of 1-butyl-2,3-dimethylimidazolium chloride (0.011 mol, 1 eq.) Was initially charged and 11 ml of a 1 M DIBAH solution in hexane (0.011 mol, 1 eq.) By means of a syringe added. Immediately afterwards, the formation of a second, more difficult phase began. The mixture was further stirred for 1 h, the orange-red colored hexane phase was removed by syringe, and the orange-red liquid salt phase was washed twice with hexane (5 ml each). The · · · · · · · · · · · ·. ···························································································································································································································· ° C removed via connection to high vacuum (2h). There was obtained 1.5 g of a yellow, moderately viscous liquid (41% theoretical yield). Upon standing at room temperature, the product gradually took on a dark red color. At -20 ° C, the liquid was stable for weeks.

Structural Analytical Data: 1 H NMR (benzene-d6 capillary): delta -0.24 (1H, hydride), -0.14 (4H, m), 0.8-1 (alkyl region, isopropyl radicals: 12H, imidazolium: 3H), 1.41 (2H, m ), 1.81 (4H, m), 2.69 (3H, s), 3.87 (3H, s), 4.15 (2H, m), 7.47 (1H, m), 7.49 ppm (1H, m). 13C NMR (benzene d6 capillary): delta 10.8,14.0,19.9,26.7, 27.2,28.5,32,1,36,0,49.0,121.5, 122.9, 144.2.

Example 6

Preparation of 1-butyl-2,3-dimethylimidazolium azidohydridodiisobutylaluminate.

3.38 g of 1-butyl-2,3-dimethylimidazolium azide (0.018 mol, 1 eq.) Were placed in a Schlenk tube and 17.85 ml of a 1 M DIBAH solution in hexane (0.018 mol, 1 eq.) Were added dropwise , whereupon the reaction mixture began to boil. The formation of a second, heavier phase was observed. The mixture was stirred for a total of h, the lower phase was taken by syringe and washed twice with hexane (5 ml each). The residual solvent was removed at 60 ° C via high vacuum connection (2 h). There was obtained 2.6 g of a red, moderately viscous liquid (43.3% theoretical yield).

Structural analysis data:

1H NMR (benzene-d6 capillary): delta -0.18 (1H, hydride), -0.10 (4H, m), 0.9-1.1 (alkyl region, isopropyl radicals: 12H, imidazolium: 3H), 1.55 (2H, m), 1.95 (4H, m), 2.79 (3H, s), 3.96 (3H, s), 4.25 (2H, m), 7.45 (1H, m), 7.47 ppm (1H, m). 13C NMR (benzene d6 capillary): delta 9.6, 13.9, 0.20, 6.26, 6.28.4, 29.0, 32.1, 35.4, 49.0, 121.4, 122.9, 144.3.

Example 7

The example shows the synthesis of 1-butyl-2,3-dimethylimidazolium cyanohydridodiisobutylaluminat.

1.89 g of 1-butyl-2,3-dimethylimidazolium cyanide (0.011 mol, 1 eq.) Were initially charged in a Schlenk tube and 10.5 ml of a 1 M DIBAH solution in hexane (0.011 mol, 1 eq.) Were used added to a syringe. The formation of a second, heavier phase began immediately. The mixture was stirred for 1 h, the lower phase was taken by syringe and washed twice with hexane (5 ml each).

The residual solvent was removed at 60 ° C via high vacuum connection (2 h). There was obtained 1.45 g of a yellow-red, medium-viscosity liquid (43.0% theoretical yield).

Structural Analytical Data: 1 H NMR (benzene-d6 capillary): delta -0.30 (1H, hydride), -0.18 (4H, m), 0.6-1.0 (alkyl region, isopropyl radicals: 12H, imidazolium: 3H), 1.38 (2H, m ), 1.80 (4H, m), 2.71 (3H, s), 3.92 (3H, s), 4.20 (2H, m), 7.71 (1H, m), 7.76 ppm (1H, m). 13C NMR (benzene d6 capillary): delta 10.7,13.9,19.8, 26.7, 28.5,29.1,32.2, 35.9, 48.8, 121.6,123.0,144.1.

Example 8

The example describes the synthesis of 1-butyl-2,3-dimethylimidazolium cyanoborohydride. 1.11 g of sodium cyanoborohydride and 3.3 g of 1-butyl-2,3-dimethylimidazolium chloride were suspended in a Schlenk tube with 15 ml of CH 2 Cl 2 abs. dissolved / suspended. It also occurred after 10 min. ♦. Ultrasound treatment no reaction. Thereafter, the reaction mixture with 10 ml of THF abs. shifted and placed again in the ultrasonic bath (1/2 h). A milky turbidity was observed (finely divided NaCl). The suspension was stirred for 2 h and then filtered through a G4 Schlenk frit. The filtrate was freed from the solvent after connection to a high vacuum (at 50 ° C.). There was obtained 3.12 g of a clear, nearly colorless room temperature ionic liquid (91% theoretical yield).

Structural Analytical Data: 1H NMR (benzene-d6 capillary): delta -0.3 to 0.75 (3H, BH3), 0.98 (3H, t, J 7.1 Hz), 1.45 (2H, m), 1.88 (2H, m), 2.78 (3H, s), 3.95 (3H, s), 4.27 (2H, t, J 7.1 Hz), 7.66 (1H, m), 7.68 ppm (1H, m). 13C NMR (benzene-d6 capillary): delta 10.5,14.0,19.8,32.0, 35.7, 48.6,121.5,122.8,142.6,150.0. IR (KBr) 3565, 3428, 3139, 2961, 2936, 2875, 2339 (broad, BH vibrations), 2220, 2167, 1589, 1539, 1465, 1421, 1250, 1262, 868, 756, 666 cm'1.

Example 9

The example describes the synthetic preparation of 1-butyl-2,3-dimethylimidazolium tetrachlorocerate (III) as a precursor substance. 7.0 g of 1-butyl-2,3-dimethylimidazolium chloride and 9.1 g of anhydrous CeCl 3 were dissolved in a 50 ° Schlenk tube 1 ml of a mixture of acetone / ethanol dried over Na 2 SO 4. After stirring for 1 h, yellowing was observed, which increased over 5 days. The resulting suspension was filtered from the solvent and dried by applying an oil pump vacuum (60 ° C). There was obtained 13.5 g of a pale yellow powder (84% theoretical yield).

Relative element ratio (electron beam microprobe): CI: Ce = 4: 1TG / DSC: 3% residual solvent content, phase transition: 68 ° C.

Structural Analytical Data: 1H NMR (acetonitrile-d3): delta 0.92 (3H, t, J 7.3 Hz), 1.32 (2H, m), 1.72 (2H, m), 2.50 (3H, s), 3.71 (3H, s) , 4.04 (2H, t, J 7.43 Hz), 7.31 (1H, m), 7.33 ppm (1H, m). 13C NMR (acetonitrile-d3): delta 10.0, 13.5, 19.9, 32.0, 35.7, 48.8, 121.6, 123.1, 145.0 .; 1H NMR (CD 2 Cl 2): delta 0.91 (3H, t, J 7.1 Hz), 1.30 (2H, m), 1.69 (2H, m), 2.41 (3H, s), 3.58 (3H, s), 3.96 (2H, t), 7.08 (1H, m), 7.29 ppm (1H, m). 13 C NMR (CD 2 Cl 2): delta 10.6, 13.6, 19.9, 31.9, 36.3, 48.8, 121.0, 123.3, 143.8. IR (KBr): 2961.2936, 2874.1636, 1540, 1465, 1420, 1249, 1136, 754, 664 cm -1.

Example 10

The example describes the electrochemical deposition of a layer of titanium. The deposition is carried out according to 3 experimental variants using different organic ionic liquids in the support electrolyte.

In a first test variant, the layer deposition from non-aqueous solution was first carried out with hexamethylbenzene trichlorotitan (IV) tetrachloroborate in BuMM + BF4 (Ti complex salt with reduction-supporting π-aromatic ligand in the coordination sphere of the precursor cation.

The substrate used for the deposition was a gold electrode.

The deposition of the Ti layer took place potentiostatically at a voltage of -2.8 V.

From the solution of HMB-TiCl3 + BCI4 " in BuMM tetrachloroborate, a covering, compact titanium layer can be deposited at an electrolyte temperature of 135 ° C. ·· ···· Μ · Μ · | ··· ·······························································································

In a second test variant, Ti deposition from TiCl4 into BuMM + BF47 N3 "

Even at an electrolyte temperature of 65 ° C. and at an electrolysis voltage from -2800 mV, a Ti deposition with a compact layer structure could be achieved.

In a third experiment variant, the layer deposition of (BuMM +) 2 [Ti CI4 (N3) 2] 2 ~ in BuMM + BF4 ~ (= complex anion of azide and TiCl4) as an ionic liquid and precursor substance in one.

It was possible to achieve a Ti deposition as in test variant 2 at 65 ° C. and from -2800 mV. The deposits according to Experimental Variant 2 and 3 satisfy the claim that in the oxidation of the sacrificial anion azide no traces, i. E. specifically, to leave no corrosive Gegenoxidationssprodukte such as elemental chlorine in the carrier liquid.

The associated figures 2-4 prove the advantages mentioned above of the method according to the invention.

FIG. 2 shows in a graph, separated for substeps 1-3, the current-voltage curve of the respective electrochemical system, measured at a CV of 50 mV / s, measured against an Ag / AgBF4 reference electrode. The curve, plotted with the indication of the potential in volts as abscissa and with the indication of the current density in mA / cm 2 as ordinate, shows the favorable electrochemical window for the partial steps 2 and 3.

An associated FIG. 3 shows in a SEM image the large-area, compact deposition of titanium in dense metallic form. • • • • • • • • • • • • • • • • • • · • · · ·

Place · · · · · · · · · · · · · · · ·························· »»

The graph of an EDX analysis shown as FIG. 4 confirms the compact, high-purity deposition of titanium in the layer.

Example 11

The example describes the galvanic deposition of iron.

The carrier liquid or the electrolyte consists essentially of [BuMM +] 2 [Fe (III) (N3 ') 5] 2' in BuMM + BF4 "/ BuMM + N3".

The homoleptic azidometalate bis-1-butyl-2,3-dimethylimidazolium pentaazidoferrat (III) (= salt complex compound from formal azide metathesis of BuMM azide and iron (III) azide, prepared in analogy to the above-described synthesis of bis-tetraethylammonium pentaazidoferrat (III) (W Becketal., Chem. Ber. 100, (1967) pp. 2235-2361), with complete preservation of the carrier electrolyte (BuMM + BF4 ") results in reconstitution of the sacrificial electrolyte BuMM + N3 ".

At an electrolyte temperature of 65 ° C and from a cathode potential of -1.80 V, the deposition of a black iron layer on a gold substrate is used as the cathode material. The layer is dense and well adhesive.

Example 12

This example shows the preparation of a galvanic layer of palladium. While under a / the method according to the invention is successfully carried out in the use of an azide as a reducing anion in the ionic liquid with BuMM + as a cation, as a counterexample the non-inventive method according to b / shows no success because there, under otherwise identical conditions the use of a reducing anion in the ionic liquid has been omitted in the form of an azide.

Specifically, the process conditions are as follows: a) [Pd (II) - (CH3CN) 4] 2+ (BF4 ') ············································· 2 in BuMM + BF47BuMM + N3 "(5: 1)] as the carrier liquid.

Concentration of Precursor Substance: (CH 3 CN) 4Pd (BF 4) 2; c = 6g / l CV: 50 mV / s, vs. Pt-reference; 65 ° C, potentiostatic deposition from -1.2 V; Substrate: gold.

Forming a shiny metallic, polishable layer.

Electrolyte remains stable without separation of Pd-Black. b) [Pd (II) - (CH 3 CN) 4] 2+ (BF 4 -) 2 in BuMM + BF 4 "alone as a carrier liquid. Deposition of Pd at 65 ° C, from about -1500 mV. In the absence of the reducing anion from the sacrificial electrolyte (BuMM azide), however, a shiny Pd layer forms only shortly after bath start / start of the test. After a short time, the electrolyte becomes dark and Pd salts still remaining in the electrolyte are reduced without precipitation to elemental Pd.

Example 13

The example describes the galvanic deposition of a layer of germanium in the form of two process variants with differently composed carrier liquid.

The carrier liquid can contain both BuMM + BF4 "and BuMM + BF47BuMM + N3" (5: 1) as ionic liquid and BuMM + Ge (II) Cl3 'in a concentration of 10% by volume as precursor substance. The latter case is a gel electrolyte in which azide acts as a non-tracer sacrificial species to prevent the formation of elemental halogen in the course of the oxidative counterreaction and its possible reverse reaction.

The electrochemical characterization by CV: 50 mV / s; vs Pt reference at 100 ° C is shown as Fig.5. Substrate: gold electrode.

The Ge deposition occurs potentiostatically from -1.3 V.

It forms a covering Ge layer.

In an alternative experimental procedure, due to the presence of a reducing anion in the form of the low valent Ge (II), CI3 " a stable, opaque layer even without additional presence of azide as sacrificial anion.

FIG. 6 shows the associated EDX analysis of the layer and documents the compact deposition of a pure Ge layer.

Example 14

The example describes a method for the electrodeposition of a copper layer.

The galvanic deposition of copper from aqueous solution, for example in the use of CuCl 2, is considered largely problem-free. Similarly, the galvanic process is basically possible also from non-aqueous solution with a variety of ionic liquids in the carrier liquid.

Subsequent experiment a) shows the process parameters for a non-inventive counter example, i. ionic liquid without reducing anion and no mode of action as a sacrificial electrolyte.

In contrast, sub-experiment b) shows the reduction-promoting effect of an azide, as an example of a reducing anion in the ionic liquid, in the process of copper deposition. 9 9 9 9 9 9 9 9 9 9 9 999 9 99 9 9 99 9 9999 ··· · · 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

The alternative process parameters in detail: a) ionic liquid in the carrier liquid: BuMM + BF4 ~ (without azide as sacrificial electrolyte). Precursor substance: CuCl 2 in a concentration of 5 g / l. Electrolyte temperature 65 ° C. Substrate: Au.

As expected, Cu deposition took place from a potential of -1.8 V.

This countermeasure was only proof of the stratabilty as such and was aborted after a short time without an investigation of the long-term effects. b) Carrier / sacrificial electrolyte: BuMM + BF47BuMM + N3 ~ (5: 1); Precursor substance: CuCl 2, c = 5 g / l; Substrate: Au; Cu deposition potentiostatic from -0.9 V.

A coppery glossy opaque layer resulted at a potential that is nearly 1 volt less cathodic than in the absence of BuMM azide.

Claims (32)

Claims 1. A method for depositing layers of metallic or semiconductive elements and / or their connections on substrates by means of chemical, electrochemical and / or thermally induced chemical reactions, of non-aqueous solution as the carrier liquid which contains at least one organic ionic liquid having a cation and an anion and the precursor substance (s) containing the layer element (s) and wherein the deposition takes place at temperatures below the decomposition point of the carrier liquid, characterized in that for this purpose one or more organic ionic liquids are used, based on the remaining carrier liquid in the starting state, redoxinerter component as a cation and reducing, organic or inorganic component as the anion. 2. A method for depositing layers according to claim 1, characterized in that as redox-stable cation components of the ionic liquids C- and N-alkyl-substituted or alkoxyalkyl, cyanoalkyl, alkenyl and AIkinyIsubstituierte imidazolium, triazolium, thiazolium, oxazolium, pyridinium and dialkylpyrrolidinium, trialkylsulfonium, tetralkylphosphonium, hexaalkylguanidinium, tetraalkylammonium or tetraalkylhydroxylammonium ions and their combinations and complex derivatives can be used. IC ············································································ « 3. A method for depositing layers according to claim 2, characterized in that the compounds listed there as redox-stable cations of the ionic liquids are used simultaneously as cation components of precursor substances. 4. A method for depositing layers according to claim 1 - 3, characterized in that in addition to ionic liquids with reducing anion one or more ionic liquids are used with reduction-stable anions. 5. A method for depositing layers according to claim 4, characterized in that the compounds listed there as redox-stable anions of the ionic liquids are simultaneously used as anion components of precursor substances. 6. A method for depositing layers according to claim 1-5, characterized in that an azide is used as ionic liquid with reducing anion. 7. A method for depositing layers according to claim 1-5, characterized in that a cyanoboranate, boronate and / or an alanate is used as the ionic liquid having a reducing anion. 8. A method for depositing layers according to claim 1 - 5, characterized in that as an ionic liquid with reducing anion ···· •·················································································· "A germanate of the divalent germanium, a silicate of the divalent silicon and / or a Gaiiat of 2-valent gallium is used. 9. A method for depositing layers according to claim 1-8, characterized in that ionic liquids are used, the reducing anion of which is identical to the anion or a complex anion of an ionic or charge-neutral precursor substance. 10. A method for depositing layers by means of electrochemical reaction according to claim 1-9, characterized in that an ionic liquid is used, the reducing anion is converted in the electrochemical partial reaction at the anode in a gaseous component. 11. A process for depositing layers according to claim 10, characterized in that a 1-butyl-2,3-dimethylimidazolium azide and / or a 1-butyl-3-methylimidazolium azide is used as the ionic liquid. 12. A method for depositing layers according to claim 1-11, characterized in that the carrier liquid are added as precursor substances organometallic, organic and / or inorganic metal compounds. 13. A method for depositing layers according to claim 12, characterized in that as metal compounds metal-containing or semiconductor element-containing salts and / or solvate salts of hexafluorophosphates, tetrafluoroborates, tetraphenylborates, fluorinated tetraarylborates, fluorinated • · ♦ · ♦ · ·· ··· «· · Halotriaryl borates, trifluoroacetates, triflates, bis (trifluoromethyl) sulfonylamides, tris (trifluoromethyl) sulfonylmethanides, alkali azides or azidometalates trifluoromethylsulfonyloxyborates , Azidoborates, tetraazido borates, hexaazidogermanates, and reducing anions from the cyanoborate, boranate, alanant, gallium gallate, divalent silicon silicates, and divalent germanium germanates (ie, complex anions of Ge, Si, and Ga in their non-preferred low valent oxidation states ) be used. 14. A method for depositing layers according to claim 12, characterized in that as metal compounds such soluble in the carrier liquid salts from the groups of halides, pseudohalides, fluorometallates, chlorometalates, cyanometalates, Azidometallate, Oxalatometallate, 1.3-diaryltriazenides and / or 1, 3-pentanedionates, triflates, trifluoroacetates and / or their solvates can be used. 15. A method for depositing layers according to claim 1-14, characterized in that are used as redoxinerte cations in the ionic liquid, 1,2,3-trialkylimidazoliumsalze and / or 1-butyl-2,3-dimethylimidazoliumsalze, in which by substitution the hydrogen atom in position 2 is blocked from deprotonation to carbenoid complexing agents in the carrier liquid. 16. A method for depositing layers according to claim 1-15, characterized in that the carrier liquid reaction-controlling additives are added. 17. A method for depositing layers according to claim 16, characterized in that as additives azide ligands and / or boranate ligands, alanates, germanates, boron atom neutral complexes, Alanatometall neutral complexes and / or mono- or oligodentate donor compounds such as olefins, dienes, ethers, thioethers , Sulfoxides, sulfones, phosphites, phosphanes, nitriles, amides, amines, and / or imines, may be added as complexing agents. 18. A method for depositing layers according to claim 16, characterized in that are added as additives aromatic π-donor compounds such as benzene, Duren, mesitylene, hexaethylbenzene and / or hexamethylbenzene. 19. A method for depositing layers according to claim 16, characterized in that as additives halogen and / or pseudohalogen acceptors, such as haloaryl, Perfluoroaryl- and Perfluoroalkylborane, calixpyrroles, triarylboranes, fluorinated triarylboranes as anion acceptors, titanium trifluoride, titanium tetrafluoride, silicon tetrafluoride, hexachlorodisilane, Hexabromosilane, boron trifluoride, boron trifluoride adducts, mixed boron trihalides and / or boron trihalide adducts that form identical ions to the anions of the ionic liquids used. • · · · 74) · · · ··························································································· 20. A method for depositing layers by means of electrochemical reactions according to claim 1-19, characterized in that the current density, electrode surfaces and carrier liquid are coordinated so that when using reverse pulse method, the concentration of the reducing anions in the ionic liquid at both electrodes simultaneous deposition of the respective layer allows. 21.The method for depositing layers according to claim 1 - 20, characterized in that the current density, electrode surfaces and composition of the carrier liquid are coordinated so that the anodic partial reaction takes place at a constant net concentration of the components of the carrier liquid. 22. A method for depositing layers according to claim 1 - 21, characterized in that one or more of the metals Ti, Zr, V, Nb, Ta, Cr, Mo, W and Hf and / or their hard material compounds are deposited. 23. A method for depositing layers according to claim 1 - 21, characterized in that elements from the group of rare earths and / or their compounds are deposited. 24. A method for depositing layers according to claim 1 - 23, characterized in that this is carried out at temperatures between -30 ° C and 200 ° C. 25. A method for depositing layers according to claim 1 - 23, characterized in that this is carried out at a temperature of the carrier liquid between room temperature and 140 ° C. 26. A method for depositing layers according to claim 1 - 25, characterized in that 0.001 - 50 wt.% Additives, based on the carrier liquid, are added. 27. A method for electrochemical deposition of layers according to claim 1 - 26, characterized in that this is carried out potentiostatically at 0.1 - 50 V electrode voltage. 28. A method for the electrochemical deposition of layers according to claim 1-26, characterized in that this is carried out galvanostatically at a current density of 0.01-2000mA / cm2. 29. A method for electrochemical deposition of layers according to claim 1 - 28, characterized in that the control of the crystallite size in the layer material, the deposition is pulsed, with temporally modulated, rectangular or sinuidalen current profile. 30. A method for electrochemical deposition of layers according to claim 29, characterized in that the layer deposition by means of pulsed deposition with 0.1 -100 ms pulse duration, 1 -1000 ms off-time and at current densities of 0.01 to 2000 mA / cm2. ··· · Μ · ···· · # · · · · · «···· * * t ····· • ι * ··· ··« ·· ··· · 31 .The method for the electrochemical deposition of layers according to claim 1 - 30, characterized in that two electrodes are used, one of which as a substrate for the deposited layer of metal or a metal compound, the other such as corresponding, resolving, metallic sacrificial anode is formed so that the metal ion concentration in the carrier liquid remains constant. 32. A method for the electrochemical deposition of layers according to claim 1 - 31, characterized in that components are used in the carrier liquid whose concentration regenerates itself.