EP2926384A1 - Dünnschichtkondensatoren mit hoher integrationsdichte - Google Patents

Dünnschichtkondensatoren mit hoher integrationsdichte

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Publication number
EP2926384A1
EP2926384A1 EP14702496.2A EP14702496A EP2926384A1 EP 2926384 A1 EP2926384 A1 EP 2926384A1 EP 14702496 A EP14702496 A EP 14702496A EP 2926384 A1 EP2926384 A1 EP 2926384A1
Authority
EP
European Patent Office
Prior art keywords
guanidinium
compounds
layer
nch
dielectric layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14702496.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
David Hartmann
Andreas Kanitz
Willi Kantlehner
Gerhard Maas
Günter Schmid
Dan Taroata
Maria ARKHIPOVA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP2926384A1 publication Critical patent/EP2926384A1/de
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/07—Dielectric layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/181—Printed circuits structurally associated with non-printed electric components associated with surface mounted components
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10015—Non-printed capacitor

Definitions

  • the present invention relates to a two-layer, dielekt ⁇ generic layer for a thin film capacitor, characterized in that a) the lower first position a self orga ⁇ n Budapestde monolayer containing phosphoroxo compounds and b) the upper second layer, a planarization layer containing guanidinium Compounds includes.
  • a "3D assembly” in particular passive components such as Wi resistors and capacitors in the circuit board inte ⁇ grated be.
  • This also takes into account that with increasing frequency in Commodity products such as computer motherboards or mobile circuit boards, increasingly broad data buses for reliable communication between the components (signal-to-noise ratio) are used, which increasingly require capacitive sinks Due to the changed requirements, the ratio has now risen to a 3: 1 ratio and, in addition, "3D placement” is particularly suitable for boards with integrated capacitors of high capacitance in DC or low frequency applications, where the integrated Use capacitors as back-up capacitors or for voltage smoothing.
  • the integrated capacitor is very robust and reliable
  • a dielectric layer for an electric Bauele- ment with organic dielectric on a Porterplattensub ⁇ strat is disclosed and wherein the dielectric layer comprises an ionic liquid.
  • this construction can be such as to provide, for example, capacitive construction ⁇ elements which strat on a Porterplattensub-, a prepreg or a printed circuit board are arranged electrical components.
  • the inventors have now found that two-layer thin-film capacitors having a planarization layer which contains a guanidinium compound have significantly improved properties in comparison to the prior art.
  • the guanidinium compounds generally belong to the class of ionic liquids (IL). These liquids are particularly suitable for the construction of the planarization layer.
  • the guanidinium compounds are distinguished from the other members of the IL by improved properties.
  • the compound should be liquid at the application temperature range and have a smallest possible visco sity ⁇ at operating temperature. This allows a higher mobility of the charge carriers and thus leads to a faster response. Furthermore, there is a wider processing window.
  • An effective means for adapting the phase behavior of the IL is generally given by the choice of the substituents of the guanidinium compound. For example, the attachment of bulky organic side groups on the cation usually leads to a lower IL melting point. b) the residual moisture
  • the guanidinium compound should not be hygroscopic as a compound. Furthermore, the residual moisture of the guanidinium compound should not be hygroscopic as a compound. Furthermore, the residual moisture of the guanidinium compound should not be hygroscopic as a compound. Furthermore, the residual moisture of the guanidinium compound should not be hygroscopic as a compound. Furthermore, the residual moisture of the guanidinium compound should not be hygroscopic as a compound. Furthermore, the residual moisture of the
  • Guanidinium compounds are kept as low as possible during processing and best be vanishingly small. This can be done, for example, by pre-drying the Guanidinium compound or by the use of a
  • the guanidine compound should have high electrochemical stability and, consequently, a wide elektrochemi ⁇ MOORISH window. This reduces the possibility of undesirable side reactions in the component and the decomposition of the planarization layer. Less unwanted by-products are accumulated, which increases the life of the thin-film capacitor. d) chemical stability
  • the guanidinium compound should be chemically inert. In addition to the loss of the electrolyte by electrochemical processes, the loss of the guanidinium compound by reactions with the other components of the thin film capacitor should be excluded. This avoids too short a lifetime and capacity losses of the thin-film capacitor.
  • a defined class of compounds results, which is particularly suitable as a planarization layer for the production of thin-film capacitors. especially the
  • Guanidinium compounds are characterized by an extraordinary electrochemical stability (Trans.
  • Nonferrous Met. Soc. China 19 (2009) It is therefore the object of the present invention, a particular class of compounds for the construction of a Planarisie ⁇ approximately location of a two layer thin film capacitor be ⁇ riding determine which improved to a capacity, a extended life and a more cost-effective production of the capacitors contributes.
  • a two-layer dielectric layer for a thin-film capacitor is characterized in that a) the lower first layer comprises a self-assembling monolayer containing phosphoroxo compounds and b) the upper second layer comprises a planarization layer containing guanidinium compounds.
  • SAM self-organizing monolayer
  • Guanidinium compounds may also have a partial electrical conductivity.
  • SAM self-assembling monolayer
  • the term self-assembling monolayer (SAM) refers to a layer consisting of only one molecule layer which adheres to a substrate by means of an anchor group. Interactions with the substrate and intermolecular interactions are the focus of the individual
  • Dielectric layer this possibly also with an approaching ⁇ parallel alignment of the individual molecules.
  • the off ⁇ choice of the compounds of the monolayer determines utzsumble- borrowed the leakage current characteristics and the reliability of the thin ⁇ layer capacitor.
  • the Phosphoroxo- show compounds on the usual substrates of printed circuit board production, such as copper, an extremely good orientation.
  • Phosphoroxo compounds according to the invention are organic phosphoric or phosphonic acid derivatives with at least ⁇ least an organic radical which connected in the case of phosphoric acid compounds over the oxygen and in the case of the phosphonic acid compounds across the phosphor and from the group of linear, branched or cyclic C5 - C25 alkyl, aryl, heteroalkyl, heteroaryl is selected.
  • planarization layer according to the invention comprises a
  • planarleiterslage fulfilled at this point two functions.
  • the planarization layer improves rule dielektri ⁇ properties of the thin film capacitor and resistors ⁇ ren the second layer leads to a reduction of the upper psychrauaught of the substrate. For this reason, less rough surface structures are obtained by this structure on which a further metal electrode is easier from ⁇ divorce.
  • the surface roughness is determined in ⁇ We sentlichen about the roughness of the substrate.
  • the guanidinium compounds according to the invention in the planarization layer can contain guanidinium cations and the anions required for charge neutrality.
  • the Guanidinium cations can correspond to the following general formula (I)
  • substituents Ri - R6 in this case from the group of li ⁇ linear, branched or cyclic C1 - C25 alkyl, aryl, heteroalkyl, heteroaryl, oligoethers (eg, [- CH 2 -CH 2 -O-] n , oligoesters (eg [-CH 2 -CO-O-] n ), oligoamides,
  • Oligoacrylamiden or hydrogen may be selected.
  • substituents may also be bridged together via cyclic or heterocyclic compounds.
  • planarization situation can only one
  • Guanidinium compound or a mixture of guanidinium compounds according to the invention are used.
  • the two-layer dielectric layer may contain guanidinium compounds, the guanidinium compounds being selected from the group comprising guanidinium salts, bis-guanidinium salts and guanidinium betaines. Just the loaded ones
  • Guanidinium compounds which moreover have the structures according to the invention, can contribute both to an increase in the dielectric constant of the two-layered dielectric layer and to a very good processability.
  • the substituents Ri - R H can independently of one another and from the group of the linear, branched or cyclic C 1 -C 25 -alkyl, aryl, heteroalkyl, heteroaryl, oligoethers (eg [-CH 2 -CH 2 -O-] n, oligoesters (eg [-CH 2 -CO-0-] n), oligoamides, Oligoacrylamiden or hydrogen can be selected.
  • oligoethers eg [-CH 2 -CH 2 -O-] n, oligoesters (eg [-CH 2 -CO-0-] n)
  • Oligoamides Oligoacrylamiden or hydrogen
  • more of the substituents may also be bridged over cyclic or heterocyclic compounds MITEI ⁇ Nander.
  • the substituent X may be selected from the group comprising halogen, -OH, -CN, -COOH.
  • at least one of the substitution patterns of a nitrogen of the bis-guanidinium cation is different from the other two
  • the planarization layer of the two-layer dielectric layer may comprise a guanidinium salt whose cation has the following formula (IV):
  • R p branched, unbranched or cyclic C 1 -C 20 -alkyl, heteroalkyl, aromatics, heteroaromatics and R 1 --R 4 independently of one another may be selected from the group of branched or unbranched C 1 -C 20 -alkyl, Heteroalkyl, oligoether, oligoester, oligoamide, oligoacrylamide.
  • ⁇ sondere the use of a guanidine compound with a guanidinium cation, in which one of the nitrogens are integrated within one 6-membered heterocycle shows ei ⁇ ne special chemical and electrochemical stability and significant improvement in the dielectric constant of the two ⁇ layered dielectric layer.
  • oligoethers are understood as meaning, for example, substituents having the structure [-CH 2 -CH 2 -O-] n , where n may be chosen to be integer and between 1 and 10.
  • Oligoesters as substituents have one or more structural units according to [-CH 2 -CO-O-] n, n being integer and between 1 and 10. Analogously, the structures of the oligoamide substituents result in [-CO-NR-] n and the structures of the oligoacrylamide substituents [-CH 2 - CHCONH2-] n.
  • At least two of the substituents of Ri-R 4 of the formula (IV) may be selected from the group of C 10 -C 20 -alkyl, heteroalkyl, oligoether, oligoester, oligoamides, oligoacrylamides.
  • These longer-substituents can be an especially good stability of the planarization layer and a high ⁇ The lektrizticianskonstanten contribute.
  • the longer-chain variants also have good solubility, so that they can be processed more easily into solution-processable, in particular printable formulations.
  • R p may be further substituted on the backbone.
  • the substituents of the R p Kgs be ⁇ NEN selected from the group consisting of furan, thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole, Isothazol,
  • the guanidinium compounds of the planarization layer may contain anions which are selected from the group of fluorophosphates, fluoroborates, phenylborates, sulfonylimides, trifluoromethanesulfonates, bis (trifluoromethylsulfonyl) imides, sulfonates, sulfates, chlorides, bromide
  • the melting point and thus the processability of the guanidinium compound can be influenced to a great extent by the choice of the anion of the guanidinium compounds.
  • the anions listed above lead to chemically and electrochemically very stable guanidinium compounds with low melting points and a large electrochemical window.
  • the guanidinium compound contains anions which are selected from the group consisting of hexafluorophosphate (PF6-), tetrafluoroborate (BF 4 ⁇ ) and bis-trifluoromethylsulfonic amide (TF 2 N ").
  • PF6- hexafluorophosphate
  • BF 4 ⁇ tetrafluoroborate
  • TF 2 N bis-trifluoromethylsulfonic amide
  • the two-layered dielectric layer may comprise a planarization layer, wherein the thickness of the planarization layer is less than or equal to 10000 nm.
  • the thickness of the planarization layer can be in principle be ⁇ arbitrarily be selected and should be determined by the roughness of the substrate.
  • the layer thickness according to the invention of the planarization layer is less than 10000 nm, preferably less than 1000 nm, more preferably less than 500 nm.
  • the lower layer thickness limit may take place before ⁇ geous enough, greater than or equal to 10 nm, preferably greater or equal to 50 nm and particularly preferably greater than or equal to 100 nm.
  • the two-layer, dielectric layer phosphoroxo compounds have, wherein the phosphoroxo compounds of the self-assembling monolayer are selected from the group of orga ⁇ African phosphonic acids, organic phosphonic acid esters or phosphonic acid amides.
  • Phosphonic ester anchor group has proved to be the best suited for the different support materials ⁇ here, in particular for copper. This anchor group can be deposited directly on the support material, the
  • Phosphonic acid are hydrolyzed in the deposition and bind as phosphonate to the surface.
  • the surface must therefore be particularly not specially functionalized via an additional ⁇ From divorce with aluminum or titanium (such as in DE10 2004 005 082 B4 described for silane anchor groups). Such a functionalization step of the surface can be completely eliminated in the case of the dielectric layer according to the invention.
  • Phosphonic acid compounds according to the invention are substances having a structure according to the following formula (V)
  • O is formula (V) wherein R is an organic radical.
  • the organic radical R can be selected from the group of linear, branched or cyclic C 5 -C 30 -alkyl, aryl, heteroalkyl, heteroaryl.
  • the phosphonic acid compounds may be uncharged as well as anions during the deposition of the SAM. A conversion of the uncharged phosphonic acid derivatives into the corresponding anions can be effected by addition of the corresponding bases within the solution and deposition process.
  • the alkyl chain may also contain a head group selected from aromatics or heteroarmonates eg phenyl or phenoxy. The pi pi interaction of this head group can enhance the stability of the self-assembled monolayer.
  • the two-layered dielectric layer can have a SAM with phosphonic acid compounds in which the phosphonic acid compounds correspond to the self-assembling monolayer of general formula (VI)
  • n is greater than or equal to 2 and less than or equal to 25.
  • n may be greater than or equal to 8 and less than or equal to 25 and particularly preferably greater than or equal to 14 and less than or equal to 20.
  • These longer-chain phosphonic acid compounds can contribute to the construction of low-leakage layers.
  • n 18 or 14.
  • the molecular chain for the construction of the SAM can also be formed as a polyether chain (-O-CH 2 -CH 2 -O-) m , where m between 1 and 20, preferably between 2 and 10.
  • the alkyl chains of the phosphonic acid compounds may also be completely or partially fluorinated.
  • the deposition can also be carried out via the phosphonic acid esters or their salts or other derivatives such as amides.
  • the salts can be obtained directly in solution by adding lesser or equivalent amounts of caustic (NaOH, KOH, ammonia or ammonium hydroxides).
  • the two-layered dielectric layer may contain a planarization layer, where ⁇ additionally has polymeric substances in the planarization layer.
  • ⁇ additionally has polymeric substances in the planarization layer.
  • particularly high me ⁇ chanical stability or chemical inertness of Planarisie ⁇ approximate location may be desired. This eg in the case in which the surface of the carrier is particularly rough and a particularly thick planarization layer is applied.
  • the layer thickness of the planarization layer can also serve as a parame ter ⁇ laying down the condenser capacity or integration be used onsêt. In these cases, the planarization layer can be mixed with other polymeric substances in addition to the guanidinium compounds.
  • the mass ratio of polymer: guanidinium compound can be used, for example, from 1: 1000 to 1000: 1. If the melting point of the guanidinium compound is sufficiently high, these can also be used purely.
  • the two-ply dielectric layer may comprise polymeric substances, the polymeric substances being selected from the group comprising epoxides, polyacrylates, polyurethanes, polycarbonates, polyesters, polyamides, polyimides, polybenzoxazoles,
  • polycarbazoles and phenol / formaldehyde compounds show on the one hand together with the inventive guanidinium compounds sufficient viscosity to provide a mechanical extremely stable planarization layer to form and are sufficiently chemically and electrochemically inert to the other to any Ne ⁇ benre syndrome with the other layers of the Dünn fürkonden- to show sators. Furthermore, it is in the polyme ⁇ ren compounds are substances which form shear-thinning fluids. This can simplify the processing out of a solution and contribute to the production of the most uniform possible planarization. It is also possible to use mixtures of the abovementioned polymeric compounds.
  • the molecular weight of the polymers can be in the range between 1000 and 1 000 000 g / mol.
  • co-polymers or block co-polymers such as acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile (SAN), polyethylene oxide-b-polypropylene oxide (PEO-b-PPO), Pluronic,
  • Brij, and / or Poloxamine be used as polymeric admixtures to build the planarization.
  • a method of manufacturing a thin film capacitor with a two-layer, dielekt ⁇ generic layer comprising the steps of:
  • the pickling of a copper plate can be carried out as usual by degreasing the copper plate with organic solvents and subsequent etching with
  • ⁇ acted surface can, in a subsequent working step (ii), the monolayer containing phosphoroxo compounds are deposited.
  • This is preferably carried out by a wet-chemical or solvent process.
  • This process can be monitored by measuring the contact angle to water analy ⁇ table.
  • the contact angle with respect to water may increase to> 130 ° after deposition of, for example, an alkylphosphonic acid.
  • the SAM can be dried in a subsequent process, for example by a thermal process.
  • the application of the planarization layer (step (iii)) can also take place via a wet-chemical or solvent process.
  • the guanidinium compound can be used alone or dissolved in a solvent. Furthermore, polymeric substances can be added at this point. Examples of suitable organic solvents include propylene glycol monoethyl ether acetate (PGMEA), Tetrahydrofuran, dioxane, chlorobenzene,
  • PMEA propylene glycol monoethyl ether acetate
  • Tetrahydrofuran dioxane
  • chlorobenzene chlorobenzene
  • planarization layer can then be dried analogously to step ii) in a subsequent process, for example via a thermal process.
  • the substances used in the solvent processes are anhydrous, which means they essentially have a water content of ⁇ 0.1% by weight.
  • the water content can be determined by the usual methods in the prior art. Called at this point is the determination of water according to Karl Fischer.
  • any metal or its alloy or conductive metal-containing printing pastes can be used.
  • the Deckelekt ⁇ rode may also consist of conductive oxides such as tin doped indium oxide or consist aluminiumdotiertem zinc oxide.
  • organic conductors such as PEDOT (polystyrenesulfonic acid-doped polydiethoxythiophene) or PANI (champersulfonic acid-doped polyaniline).
  • PEDOT polystyrenesulfonic acid-doped polydiethoxythiophene
  • PANI champersulfonic acid-doped polyaniline
  • Full-surface applied metal counterelectrodes can be subsequently structured by the etching and mechanical ablation method (laser) known to the person skilled in the art. If a plurality of thin film capacitors are provided with a common counterelectrode, the deposition of the counterelectrode can also take place from the gas phase by means of shadow masks .
  • the counterelectrodes can also be applied by electroless metallization after local or full-surface germination. In principle, all methods of the printed circuit board industry can be used in this step.
  • the application can the self-assembling monolayer and / or the application of the planarization layer by spin coating, slot coating, printing, spin coating, dipping, curtain coating or doctoring done.
  • spin coating slot coating, printing, spin coating, dipping, curtain coating or doctoring done.
  • These processes are particularly suitable in the specified thickness range of the SAM and the planarization layer to form a uniform and hole-free layer.
  • the pseudoplastic solutions or pure guanidinium compound can effectively penetrate the rough surfaces of the printed circuit boards and thus form an effective dielectric surface layer.
  • the planarization layer may additionally comprise crosslinkable compounds and in a further method step the crosslinkable compounds are crosslinked with one another.
  • the crosslinkable compounds can be polymers having reactive side chains or reactive sites in the polymer backbone, which can be thermally or photochemically crosslinked. Crosslinking is optional, with possible crosslinkers being photoacids, for example. For example, melamine-co-formaldehyde can be used as crosslinker for novolac-like systems.
  • the Vernet ⁇ wetting the crosslinkable compounds may be preferably carried out in the temperature range between 180 ° C and 230 ° C.
  • the subject matter further includes electrical components having a first electrode layer, a two-layer dielectric layer comprising a self-assembling monolayer comprising phosphoroxo compounds and a planarization layer
  • the gate dielectric consists of the layer according to the invention.
  • the transistor is supplemented by its further electrodes (source, drain, gate) and by the deposition of a semiconductor.
  • These capacitors have a higher integration density (capacitance / area) than the thin-film capacitors mentioned in the prior art, are robust and can be produced easily and inexpensively.
  • the electronic device may be a storage capacitor in an electronic circuit.
  • the use of the layer according to the invention can therefore not be limited to integrated thin-film capacitors. The advantages according to the invention therefore also arise in the context of the construction of storage capacitors.
  • the electronic component can be arranged on a printed circuit board substrate, egg ⁇ nem prepreg or a printed circuit board.
  • the dielectric layer of the invention and that he ⁇ method according to the invention can lead to more effective, durable, and economically producible components.
  • Fig. 1 An embodiment of a capacitor according to the invention with the prepreg (1) on which the metal for the lower first electrode (2) with the terminal (3) is located.
  • the insulating SAM layer (4) is located according to the Phosphoroxo- OF INVENTION ⁇ dung containing compounds on the planarization layer (5) containing guanidinium compounds is applied.
  • the counter electrode (6) is applied.
  • the arrows (7) indicate locations where critical E fields in the capacitor are possible;
  • Fig. 2 Cyclo voltammogram of the guanidine compounds M7a / b, M8 compared to the reference BMIMPF6;
  • Fig. 3a Cyclo-voltammogram of the guanidine compound K6 compared to the reference BMIMPF6
  • Fig. 3b Cyclo-voltammogram of the guanidine compound K8 compared to the reference BMIMPF6;
  • Fig. 4a Cyclo-voltraph of the guanidine compound K2 in acetonitrile and the solvent acetonitrile compared to the reference BMIMPF6;
  • Fig. 4b Cyclo-voltammogram of the guanidine compound K3 in acetonitrile and the solvent acetonitrile compared to the reference BMIMPF6;
  • Fig. 5a Cyclo-voltraph of the guanidine compound K6, K6 in acetonitrile, K6 in anisole and the solvent acetonitrile;
  • FIG. 5b Cyclo-voltraph of the solvents acetonitrile, anisole and MEK
  • FIG. 6 Cyclo voltammogram of the reference substance BMIMPF6 in anisole and as pure IL and the solvent anisole
  • Fig. 7 Cyclo-voltammogram of the guanidine compound K3 dissolved in acetonitrile and in the molten state at 140 ° C and the solvent acetonitrile.
  • N, N, N ', N', N ", N" -hexabutylguanidinium trifluoromethanesulfonate has already been described in H. Kunkel et al. , Eur. J. Org. Chem. 2007, 3746-3757.
  • N, N-dimethyl-phosgeniminium chloride (3.25 g, 20 mmol) in tro ⁇ ckenem dichloromethane (40 mL) at 0 ° C with stirring, a solution of di-n-hexylamine (4.6 mL, 20 mmol) and triethylamine (2.8 mL, 20 mmol) in anhydrous dichloromethane (10 mL). After 1 h of stirring at RT, a solution of piperidine (2.0 mL, 20 mmol) and triethylamine (2.8 mL, 20 mmol) in anhydrous dichloromethane (10 mL) was added dropwise at 0 ° C with stirring.
  • the mixture was stirred for 3 h at room temperature and the precipitated solid (triethylammonium chloride) filtered off. After removal of the solvent de ⁇ first given to the residue 0.1 M NaOH until the pH weakly ba- was.
  • the aqueous phase was extracted three times with 15 mL diethyl ether gewa ⁇ rule.
  • the aqueous phase was saturated with sodium chloride and extracted three times with 15 mL dichloromethane each time.
  • the or- ganic phases were combined and dried ⁇ ge over sodium sulfate, and the solvent was removed.
  • the product was dried for 6 h at 40 ° C / 0.05 mbar. Yield: 5.0 g (70%), orange oil. Glass transition temp.
  • NCH 2 CH 2 CH 2 , Pip 26.37 and 26.52 (N (CH 2 ) 3 CH 2 CH 2 CH 3 ), 27.36 and 27.46 (N (CH 2 ) 2 CH 2 (CH 2 ) 2 CH 3 ), 31.33 and 31.37 (NCH 2 CH 2 (CH 2 ) 3 CH 3), 40.49 and 40.51 (NCH 3 ), 49.4 and 49.6
  • Triethylamine stirred for 16 h and then heated for 2 h at reflux. The mixture is stirred for 1 h at room temperature and then removed the volatiles in a rotary evaporator under reduced pressure.
  • To the resulting salt mixture is about as much grams of water as the residue present, covered with diethyl ether and then added with vigorous stirring 2.0 equivalent sodium hydroxide solution (1 mol in 75 ml of water). The mixture is then stirred for 1 h, the organic phase is separated after 30 min, washed three times with water and dried over sodium sulfate. The resulting solution is Evaporator evaporated and then recrystallized either from a ge ⁇ suitable solvent or fractionally distilled via a 30 cm Vigreux column. I.G1 ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-N''- [2- ( ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylguanidino) ethyl] guanidine
  • N, N-diethyl-N ', N'-dipropyl-N' '- [2- (N, N-diethyl-N', N'-dipropylylguanidino) ethyl] -guanidine are obtained as a yellowish oil. Yield: 43.5 g (68%).
  • guanidines 1-4 required as starting materials have already been described in W. Kantlehner, J. Mezger, R. Kreß, H. Hartmann, T. Moschny, I. Tiritiris, B. Hiev, 0. Scherr, G. Ziegler, B. Souley , W. Frey, IC Ivanov, MG Bogdanov, U. Jaeger, G. Dospil, T. Viefhaus, Z. Natural science. 210, 656, 873-906.
  • Trifluoromethanesulfonic acid (150.08 g / mol) 20 mmol 3.0 g 4.4 g (10 mmol) of N-butyl- ', N', N 1 1 , N 1 '-tetramethyl-N- [2- (N-butyl- ⁇ ', ⁇ ', ⁇ 1 VN 1' tetramethyl-guanidino) ethyl] -guanidinium- dichloride (I.V1) are dissolved in 50 ml of water and then (3.0 g 20 mmol) was added trifluoromethane sulfonic acid in 20 ml of water.
  • N ethylguanidinio propanesulfonate (K7): colorless solid of mp 253 ° C.
  • Trifluoromethanesulfonic acid (150.08 g / mol) 9.3 mmol 1.4 g
  • Potassium hydroxide (56.11 g / mol) 8.9 mmol 0.5 g 3.0 g (4.4 mmol) N, NO ⁇ et yl-N ', N'-dipropyl-''-methyl-''- [2- (N, N-diethyl- N ', N'-dipropylyl-N''-methyl-guanidino) ethyl] guanidinium bis (methylsulfate) (I.V2) are dissolved in 30 ml of water and then treated with a solution of 2.5 g (8.9 mmol) of bis- (Trifluoromethanesulfonyl) imide and 0.5 g (8.9 mmol) of potassium hydroxide in 20 ml of water.
  • guanidinium betaines made.
  • BMIMPF6 (1-butyl-3-methyl-imidazolium hexafluorophosphate) was used.
  • a platinum wire with an area of 0.1 cm 2 served as working ⁇ electrode.
  • Platinum wires also served as reference and counter electrodes.
  • the internal standard used was ferrocene.
  • FIG. 2 shows a cyclovoltagram of the compounds M7a / b
  • Betaines are ionic compounds in which the anion and cation are linked together by a covalent bond, so that they can not be separated by electric fields, but can be addressed from ⁇ .
  • the molecules are electrically neut ral ⁇ but have hardly delocalized, spatially separated charges.
  • the betaines K2, K3, K6, K7, K8 and K9, which are characterized by a covalently-bound sulfonate anion to an alkyl radical of a hexaalkyl guanidinium cation from ⁇ were tested.
  • the Betaine K6 and K8 ionic at room tempera ture ⁇ liquids remaining on the other hand are present as solids at room temperature.
  • the results of the cyclic voltammetry measurements on compound K6 are shown in Figure 3a and the results of
  • FIGS. 4a-4d show the cyclic voltammetry measurements for the solid betaines K2, K3, K7 and K9. In addition, the corresponding spectrum for pure acetonitrile and the BMIMPF6 standard reference is shown.
  • FIG. 5a shows the cyclic voltammetry data of the compound K6 in different solvents.
  • Figure 5b shows the cyclic voltammetry behavior of only the solvents. It is found that the measured solvent anisole, MEK and acetonitrile reduce the electrochemical stability ⁇ window of the material. The observed Reduzie ⁇ tion of electrochemical stability in the case of anisole smallest. Significant differences between acetonitrile and MEK could not be observed.
  • BMIMPF6 Measurements on the reference material BMIMPF6 ( Figure 6) show that, compared to pure BMIMPF6, a combination of anisole and BMIMPF6 has a significantly reduced size elektrochemi ⁇ ULTRASONIC window.
  • anisole is electrochemically oxidized to bis-4,4'-dimethoxy-biphenyl in the presence of this IL.
  • Lawesson's reagent ie an oxidatively formed insertion compound of anisole and phosphorus-V-sulfide, can form extremely easily (see also author collective, Organikum, 20. Aufläge (1996)). 481-482). It can also be seen from FIG. 6 that pure anisole behaves in an insulating manner and does not initiate any RedOx processes.

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US5726856A (en) * 1996-02-28 1998-03-10 General Electric Company Hexasubstituted guanidinium salts and ultracapacitors employing them as electrolytes
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