Hydroxyaminophosphinic acid derivatives

Abstract

The present invention relates to hydroxyaminophosphinic acid derivatives of formula I, in which the groups and parameters occurring have the meanings defined in claim 1, to processes for the preparation of said compounds, and to the use thereof in the production of self-assembled monolayers (SAM), in particular in the production of switchable SAMs for electronic devices. The invention also relates to an electronic device comprising said SAM, preferably in the field of organic electronics, in particular for memories, sensors, in addition for organic light emitting diodes (OLEDs), photovoltaics (OPVs), field effect transistors (OFETs) and Josephson junctions, very particularly for memristive components such as memristive crossbar arrays. # imgabs0 #

Description

[0001] The present invention relates to hydroxyaminophosphinic acid derivatives, methods for preparing the same and their use in preparing self-assembled monolayers (SAMs), in particular in preparing switchable SAMs for electronic devices. The present invention also relates to electronic devices comprising the SAMs.

[0002] Compounds for preparing self-assembled monolayers are known in the prior art and are widely used, for example, for the derivatization of electrodes of electronic components. These monolayers are ordered arrays of rod-shaped molecules, which are bound to a substrate via suitable anchoring groups and carry functional groups at the other end of the molecular backbone. Such monolayers can be used to control the physical and chemical properties of surfaces and interfaces. Self-assembled monolayers are often used in organic electronics to electrostatically engineer interfaces by controlling the arrangement of interfacial energy levels. The performance and lifetime of these devices, such as organic light emitting diodes (OLEDs), photovoltaic devices (OPVs) and field effect transistors (OFETs), depend critically on the properties of the active materials and their interfaces. The interfacial properties can be controlled from simple wettability or adhesion between different materials to direct changes in the electronic structure of the materials.

[0003] Recently, switchable SAMs have been proposed for use in computer memories. In computer technology, storage media are required which allow fast read and write access to the information stored therein. Solid-state memories or semiconductor memories allow particularly fast and reliable storage media to be implemented, since absolutely no moving parts are required. Currently, dynamic random access memories (DRAM) are mainly used. DRAM allows fast access to stored information, but this information must be refreshed regularly, which means that the stored information is lost when the power is turned off.

[0004] The prior art also discloses non-volatile semiconductor memories, such as flash memories or magnetoresistive random access memories (MRAM), in which information is retained even after the power supply has been switched off. A disadvantage of flash memories is that write access occurs relatively slowly and the memory cells of flash memories cannot be erased indefinitely. The life of flash memories is generally limited to a maximum of one million read / write cycles. MRAM can be used in a similar manner to DRAM and has a long life, but this type of memory has not yet been able to establish itself due to difficult production methods.

[0005] Another alternative is a memory based on memristor operation. The term memristor is an abbreviation of the words "memory" and "resistor" and refers to a component that can repeatedly change its resistance between high and low resistance. The corresponding state (high resistance or low resistance) is retained even without a power supply voltage, which means that non-volatile memory can be implemented with memristors. Crossbar arrays of memristors can be used in various applications, including non-volatile solid-state memory, programmable logic, signal processing, control systems, pattern recognition and other applications. The memristor crossbar array includes many column lines, many row lines that intersect with the column lines to form many junctions, and many resistive memory devices coupled at these junctions between the column lines and the row lines.

[0006] WO 2016 / 110301 A1 and WO 2018 / 007337 A2 disclose electronic components suitable for memristive devices. Thus, a non-redox-active molecular layer comprising dipolar compounds attached to a substrate via aliphatic spacer groups is proposed, wherein these compounds are reversibly switched by applying an electric field, which causes a reorientation of the molecular dipoles and thus enables a low-resistance state and a high-resistance state depending on the respective orientation of the molecules.

[0007] The compound used to prepare the SAM includes an organic residue and a group suitable for binding to the surface of the substrate and thereby fixing the organic residue to the surface. Suitable anchor groups include thiols, phosphonic acids, phosphoric acids, sulfuric acids, sulfonic acids, carboxylic acids or siloxanes.

[0008] The choice of anchoring groups depends largely on the chemical nature of the substrate. The anchoring groups and the substrate together determine the nature and stability of the bonds between the molecules forming the monolayer and substates.

[0009] The deposition of SAM on a suitable substrate is preferably carried out by spin coating or organic solvent dip coating. The amphiphilicity of the SAM precursor and the high polarity of the anchoring group usually result in poor solubility of the precursor. The solubility of these compounds in most polar aprotic solvents is very low, and SAM can only be applied by quite dilute solutions in toxic solvents (such as THF or dioxane). They cannot be dissolved in sufficient concentrations in typical semiconductor industry solvents.

[0010] There is a need in the art for materials that form SAMs of acceptable quality with very short deposition times and convenient deposition processes. To obtain high quality SAMs, it is important that the formation of the SAM first proceeds through a thermodynamically reversible physical adsorption step and then is fixed in place by an annealing step that initiates an irreversible condensation reaction.

[0011] In particular, widely used phosphonic acids form high-quality SAMs on substrates such as Al2O3, but it is notoriously difficult to obtain good SAMs on materials with lower isoelectric points.

[0012] The present invention is proposed in view of the above problems, and the object of the present invention is to provide an anchoring group, which can make the SAM precursor not show the above disadvantages or at least show the above disadvantages to a lesser extent. Another object is to find a novel compound suitable for producing electronic components using conventional methods of the storage industry.

[0013] In order to solve this problem, a compound of formula I is provided:

[0014]

[0015] in

[0016] T is selected from the group consisting of the following groups:

[0017] a) straight-chain or branched alkyl or alkoxy radicals each having 1 to 20 C atoms, wherein one or more CH2 radicals in these radicals can each independently of one another be replaced by -C≡C-, -CH=CH-, -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is substituted in such a way that the O atoms are not directly connected to each other, and one or more H atoms may be replaced by halogen, CN, SCN or SF5, wherein R 0 , R 00 represent, identically or differently, alkyl or alkoxy radicals having 1 to 15 C atoms, in which one or more H atoms may additionally be replaced by halogen,

[0018] b) a 3-10 membered saturated or partially unsaturated aliphatic ring, wherein at least one -CH2- group is replaced by -O-, -S-, -S(O)-, -SO2-, -NR x -or-N(O)R x -, or wherein at least one -CH= group is replaced by -N=,

[0019] c) diamondoid radicals, preferably derived from lower adamantyl radicals, very preferably selected from adamantyl, diamantyl and triamantyl radicals, in which one or more H atoms may be replaced by F, in each case optionally fluorinated alkyl, alkenyl or alkoxy radicals having up to 12 C atoms, in particular

[0020] Z T , Z 1 , Z 2 and Z 4represents, identically or differently on each occurrence, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(CH2) n1 -、-(CF2) n2 -, -CF2CH2-, -CH2CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4 -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, wherein n1, n2, n3, n4 are the same or different and are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10,

[0021] Z 3 Indicates -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-, represents, identically or differently on each occurrence, an aromatic, heteroaromatic, cycloaliphatic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain condensed rings and may be mono- or polysubstituted by Y,

[0022] represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain condensed rings and may be replaced by R C Single or multiple substitutions,

[0023] Y represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5 or a linear or branched chain,

[0024] alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F or Cl,

[0025] Representation group

[0026]

[0027]

[0028] These groups can be oriented in two directions,

[0029] L 1 -L 5Identically or differently represent H, F, Cl, Br, I, CN, SF5, CF3, OCF3 or OCHF2, preferably Cl or F, very preferably F, wherein the radical L present in the corresponding radical 1 -L 5 At least one of them is not H,

[0030] R L represents, identically or differently on each occurrence, H, alkyl having 1 to 6 C atoms, alkenyl having 2 to 6 C atoms or alkoxy having 1 to 5 C atoms, preferably H or alkyl having 1 to 4 C atoms, very preferably H, methyl or ethyl,

[0031] R C represents, identically or differently on each occurrence, in each case optionally fluorinated, straight-chain or branched alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy radicals having 1 to 12 C atoms or cycloalkyl or alkylcycloalkyl radicals having 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, trifluoromethoxy or trifluoromethylthio,

[0032] Sp represents a spacer group or a single bond,

[0033] R 0 , R 00 , R x represents a straight-chain or branched alkyl group having 1 to 6 C atoms,

[0034] R 1 denotes H or a straight-chain or branched alkyl group having 1 to 12 C atoms in each case, preferably H or a tert-alkyl group, very preferably H or tert-butyl, in particular H,

[0035] R 2 and R 3 represents, identically or differently, H or a linear, branched or cyclic alkyl radical having 1 to 12 C atoms, preferably H, methyl or cyclohexyl, very preferably H or methyl, in particular H,

[0036] r, s, t, u and v are identical or different and are 0, 1 or 2, wherein r+s+t+u+v=0, 1, 2, 3 or 4.

[0037] The present invention also relates to a method for preparing the compound of formula I.

[0038] According to another aspect of the present invention, there is provided a switching device comprising, in this order:

[0039] The first electrode,

[0040] a molecular layer bonded to the first electrode, and

[0041] The second electrode,

[0042] Therein the molecular layer is essentially formed by one or more, preferably one, compounds of the formula I as defined above and below.

[0043] Furthermore, the present invention relates to a method for producing a switching device according to the present invention, comprising at least the following steps:

[0044] i. producing a first electrode having a surface;

[0045] ii. depositing a molecular layer comprising one or more compounds selected from the compounds of formula I defined above on the surface of the first electrode;

[0046] iii. Applying a second electrode.

[0047] According to another aspect of the present invention, an electronic component is provided, wherein the component is a memristive crossbar array comprising a plurality of switching devices of the present invention. The crossbar array can be integrated into a three-dimensional array of cells comprising a stack of two or more crossbar arrays. Such a configuration is known as a 3D crosspoint or 3D X-point memory device.

[0048] The invention further relates to the use of a molecular layer obtained from one or more compounds according to claim 1 in a memristive electronic component.

[0049] The resulting device can be used in a memory, a sensor, a field effect transistor or a Josephson junction, preferably in a resistive memory device.

[0050] The invention further relates to the use of the switching device in a memory, a sensor, a field effect transistor or a Josephson junction.

[0051] The switching device of the invention is suitable for use in electronic components, especially in memories, sensors, field effect transistors or Josephson junctions, very particularly in memristive components such as memristive crossbar arrays, which electronic components exhibit the advantageous properties shown above.

[0052] Surprisingly, compounds of the formula I containing hydroxyaminophosphonic acid or hydroxyaminophosphonic acid-derived anchoring groups dissolve very well in solvents used in the storage industry, in particular in halogenated hydrocarbons (chlorobenzene, trichloroethylene, Solkan-365 (HFC-365mfc, 1,1,1,3,3-pentafluorobutane) or weakly polar esters, ethers and ketones (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), methyl amyl ketone (MAK), ethyl acetate, methyl tert-butyl ether (MTBE), cyclohexanone), as well as in common solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), tetrahydrofuran (THF), toluene, anisole, chlorobenzene or CH2Cl2.

[0053] The compounds of formula I show improvements in SAM quality and SAM formation rate on more acidic substrates with lower isoelectric points (e.g., TiN, Ta3N5, TaN x , TaON, Ta2O5, SiO2, ZrO2, HfO2, WO3, RuO2, Cu2O, TiO2, Co2O3) and on metals (e.g. Si, Co, Ni, W, Ru, Cu, Pt via their native oxides or surface oxidized by oxygen plasma, UV / O3 treatment or similar methods).

[0054] The SAM precursors of formula I and the electronic components obtained from the compounds of formula I have surprisingly high chemical and thermal stability. The switchable electronic components obtained from the compounds of formula I only require low voltage and low electric field strength to switch the device and show long-term retention of the resistance state. The switching device exhibits high reliability and durability and high stability against dielectric breakdown. In addition, the memory window is advantageously large.

[0055] The electrode materials that can be used in the devices according to the invention are highly compatible with the devices and manufacturing processes of the semiconductor industry and are surprisingly well suited to forming stable and uniform molecular monolayers. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1A Schematic illustration showing the layer structure of a first embodiment of an electronic switching device according to the invention.

[0058] Figure 1B Schematic illustration showing the layer structure of a second embodiment of an electronic switching device according to the invention.

[0059] Figure 2A Shown is a current-voltage curve for an electronic switching device fabricated using prior art compounds.

[0060] Figure 2B The current-voltage curve of an electronic switching device according to the invention fabricated using a compound of formula I is shown.

[0061] The term "adamantanes" refers to substituted and unsubstituted cage compounds of the adamantane series, including adamantane, diamantane, triamantane, tetraamantane, pentamantane, hexamantane, heptamantane, octamantane, etc., including all isomers and stereoisomers. These compounds have an "adamantanes" topology, which means that their carbon atoms are arranged to be superimposed on a fragment of a face-centered cubic diamond lattice. Substituted adamantane from the first series preferably has 1-4 independently selected alkyl or alkoxy substituents.

[0062] Adamantanes include "lower adamantanes" and "higher adamantanes", as these terms are defined herein, as well as mixtures of any combination of lower and higher adamantanes. The term "lower adamantanes" refers to adamantane, diamantane and triamantane and any and / or all unsubstituted and substituted derivatives of adamantane, diamantane and triamantane. These lower adamantane components do not show isomers or chirality and are easy to synthesize, which distinguishes them from "higher adamantanes". The term "higher adamantanes" refers to any and / or all substituted and unsubstituted tetramantane components; any and / or all substituted and unsubstituted pentamantane components; any and / or all substituted and unsubstituted hexamantane components; any and / or all substituted and unsubstituted heptamantane components; any and / or all substituted and unsubstituted octamantane components; and mixtures thereof and isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane and octamantane. The chemistry of adamantane has been reviewed by Fort, Jr. et al. in "Adamantane: Consequences of the Diamondoid Structure", Chem. Rev., Vol. 64, pp. 277-300 (1964). Adamantane is the smallest member of the adamantane family and can be considered a single cage crystalline subunit. Diamantane contains two subunits, triamantane contains three, tetraamantane contains four, and so on. Although adamantane, diamantane, and triamantane have only one isomeric form, tetraamantane has four different isomers (two of which represent enantiomeric pairs), i.e., four different possible ways or arrangements of the four adamantane subunits. The number of possible isomers increases nonlinearly with each of the higher members of the adamantane family - pentamantane, hexamantane, heptamantane, octamantane, etc. Commercially available adamantane has been extensively studied. These studies have been directed to many areas, such as the thermodynamic stability, functionalization, and performance of adamantane-containing materials. For example, Schreiber et al., New J. Chem., 2014, 38, 28-41 describe the synthesis and application of functionalized adamantane to form large area SAMs on silver and gold surfaces. KT Narasimha et al., Nature Nanotechnology 11, March 2016, pp. 267-273 describe that a monolayer of adamantane effectively imparts enhanced field emission properties to metal surfaces due to a significant reduction in the work function of the metal.

[0063] As used herein, an anchoring group is a functional group by which a compound is adsorbed or bound to a substrate or electrode surface by physical adsorption, chemical adsorption or by chemical reaction. The chemical reaction includes the in situ conversion of a precursor of the anchoring group, for example, on the substrate or electrode surface.

[0064] A spacer group in the sense of the invention is a flexible chain between the dipole moiety and the anchoring group which brings about a separation between these substructures and at the same time improves the mobility of the dipole moiety after binding to the substrate due to its flexibility.

[0065] The spacer group can be branched or straight chain.Chiral spacers are branched and are optically active and non-racemic.

[0066] Alkyl here is straight-chain or branched and has 1 to 15 C atoms, preferably straight-chain and, unless otherwise specified, has 1, 2, 3, 4, 5, 6 or 7 C atoms, thus preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0067] Alkoxy here is straight-chain or branched and contains 1 to 15 C atoms. It is preferably straight-chain and, unless otherwise specified, has 1, 2, 3, 4, 5, 6 or 7 C atoms, and is therefore preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy.

[0068] Herein, alkenyl is preferably an alkenyl having 2 to 15 C atoms, which is straight or branched and contains at least one C-C double bond. It is preferably straight chain and has 2 to 7 C atoms. Therefore, it is preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl. If two C atoms of the C-C double bond are substituted, the alkenyl may be in the form of E and / or Z isomers (trans / cis). The corresponding E isomer is usually preferred. Among the alkenyls, prop-2-enyl, but-2- and -3-enyl and pent-3- and -4-enyl are particularly preferred.

[0069] Alkynyl here refers to alkynyl groups having 2 to 15 C atoms, which are straight-chain or branched and contain at least one CC triple bond. Preference is given to 1- and 2-propynyl and 1-, 2- and 3-butynyl.

[0070] In formula I, preferred aryl groups are derived, for example, from the parent structures benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophenanthrene, fluorene, indene and indane.

[0071] In formula I, preferred heteroaryl groups are, for example, 5-membered rings, such as furan, thiophene, selenophene, Azoles, Isopropylamine Azoles, 1,2-thiazoles, 1,3-thiazoles, 1,2,3- Oxadiazole, 1,2,4- Oxadiazole, 1,2,5- Oxadiazole, 1,3,4- oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine, or condensed rings such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, benzotriazole Azoles, naphtho oxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazolothiophene, 2H-chromene (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran) and coumarin (2H-chromen-2-one) or a combination of these groups.

[0072] In formula I, preferred cycloaliphatic groups are cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, decahydronaphthalene, bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, spiro[3.3]heptane and octahydroindane.

[0073] The preferred spacer group Sp is selected from the formula Sp'-X', wherein X' is bound to ring A of formula I 1 , A 2 , A 3 , A 4 or B, where

[0074] Sp' denotes a straight-chain or branched alkylene radical having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which one or more non-adjacent CH2 groups may furthermore each independently of one another be substituted by -O-, -S-, -NH-, -NR- 0 -、-SiR 00 R 000 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 0 -CO-O-, -O-CO-NR 0 -、-NR 0 -CO-NR 0 -, -CH=CH- or -C≡C- are substituted in such a way that the O and / or S atoms are not directly connected to each other,

[0075] X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 00 -、-NR 00 -CO-, -NR 00 -CO-NR 00-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -、-CY x =CY x' -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond,

[0076] R 0 , R 00 and R 000 each independently represents H or an alkyl group having 1 to 12 C atoms, and Y x and Y x' Each independently represents H, F, Cl or CN.

[0077] X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-, -NR 0 -CO-NR 0 - or single key.

[0078] A preferred group Sp' is -(CH2) p1 -、-(CF2) p1 -、-(CH2CH2O) q1 -CH2CH2-, -(CF2CF2O) q1 -CF2CF2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR 00 R 000 -O) p1 -, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 00 and R 000 Has the meaning indicated above.

[0079] A particularly preferred group -X'-Sp'- is -(CH2) p1 -、-O-(CH2) p1 -、-(CF2) p1 -、-O(CF2) p1 -、-OCO-(CH2) p1 - and -OC(O)O-(CH2) p1 -, where p1 has the meaning shown above.

[0080] Particularly preferred radicals Sp′ are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, perfluoroethylene, perfluoropropylene, perfluorobutylene, perfluoropentylene, perfluorohexylene, perfluoroheptylene, perfluorooctylene, perfluorononylene, perfluorodecylene, perfluoroundecylene, perfluorododecylene, perfluorooctadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene and butenylene.

[0081] Particularly preferred groups X' are -O- or a single bond.

[0082] The compounds of the general formula I can be prepared as shown below by methods known per se as described in the literature (e.g. standard works such as Houben-Weyl, Methoden der organischen Chemie [Organic Chemistry Methods], Georg-Thieme-Verlag, Stuttgart) and under reaction conditions known and suitable for the described reactions. Variants known per se which are not mentioned in greater detail here can be used here.

[0083] If desired, it is also possible to form the starting materials in situ by not isolating them from the reaction mixture but converting them immediately further into compounds of the formula I.

[0084] The synthesis of compounds of the general formula I of the present invention is described in illustrative terms in the Examples. The starting materials can be obtained by generally available literature procedures or are commercially available.

[0085] In the method of preparing the compound of formula I of the present invention, wherein R 1 , R 2 and R 3 Represents H (Formula Ib), which is prepared by the following formula I compound, wherein R 1 represents an alkyl group, R 2 and R 3 Representing H (Formula Ia), the method comprises the following steps:

[0086] a) reacting a phosphonyl chloride of formula II with O-(trialkylsilyl)hydroxylamine in the presence of a base to obtain an N-[(alkoxy)phosphoryl]hydroxylamine of formula Ia, and

[0087] b) subjecting a compound of formula Ia to ester cleavage, for example with a trialkylsilyl halide, preferably trimethylsilyl bromide or trimethylsilyl iodide, to give a compound of formula Ib;

[0088] As shown in Scheme 1. In step a), the preferred trialkylsilylhydroxylamine is O-(trimethylsilyl)hydroxylamine, and the base is preferably an amine, preferably a tertiary amine, very preferably triethylamine, ethyldiisopropylamine or diazabicyclooctane.

[0089] Scenario 1:

[0090]

[0091] In Scheme 1, R 11 represents a straight-chain alkyl radical having 1 to 12 C atoms or a branched alkyl radical having 3 to 12 C atoms, and the remaining radicals and parameters occurring have the meanings defined above for formula I.

[0092] Phosphonyl chloride II can be obtained by known methods from dialkyl phosphonate III, for example, by treatment with an acyl chloride, for example, oxalyl chloride, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, dichlorotriphenylphosphine or phosgene, and the base is for example pyridine, diazabicyclooctane or triethylamine (Scheme 2). Dialkylphosphonate (III) can be prepared as described in WO2018 / 007337 A2, WO 2019 / 238649A2, WO 2020 / 225270 A2, WO 2020 / 225398 A2, WO 2021 / 078699A2, WO 2021 / 078714 A2 and WO 2021 / 083934 A2.

[0093] Scenario 2:

[0094]

[0095] Where R 11 represents a straight-chain alkyl group having 1 to 12 C atoms or a branched alkyl group having 3 to 12 C atoms, and the remaining groups and parameters have the same meanings as in Scheme 1.

[0096] In formula I and its subformulae, the radical T preferably represents Very preferred Where R x represents an alkyl group having 1 to 6 C atoms, preferably a methyl group.

[0097] In another preferred embodiment, the radical T in formula I and its subformulae represents a straight-chain or branched alkyl radical having 1 to 12 C atoms, wherein one or more CH2 groups in these radicals can each be independently replaced by -C≡C-, -CH=CH-, or -O- in such a way that the O atoms are not directly connected to one another, and wherein one or more H atoms may be replaced by halogen, preferably F.

[0098] In a preferred embodiment, the compound of formula I is selected from the group consisting of compounds of formula Ia-1a to Ia-1d:

[0099]

[0100] Among them, T, Z T , Z 1 , Z 2 , Sp and R 1 has the meanings given above for formula I, r is 1 or 2 and s is 1 or 2, and

[0101] Preferably, T represents H, or linear or branched alkyl or alkoxy groups each having 1 to 7 C atoms or linear or branched alkenyl groups having 2 to 7 C atoms, preferably linear alkyl or alkoxy groups each having 1 to 7 C atoms,

[0102] Z T represents CH2O, OCH2, CH2CH2 or a single bond, preferably a single bond,

[0103] Z 1 and Z 2 Identically or differently represent CH2O, OCH2, CH2CH2, CF2O, OCF2, C(O)O, OC(O) or a single bond, preferably a single bond,

[0104] A 1 and A 2 Same or different

[0105] Y 1 and Y 2 represents, identically or differently on each occurrence, H, F or Cl, preferably H or F, and

[0106] Sp represents a branched or unbranched 1,ω-alkylene radical having 1 to 12 C atoms, in which one or more non-adjacent CH2 groups may be replaced by O, and

[0107] R 1 Indicates H.

[0108] Very particular preference is given to compounds of the formulae Ia-1b and Ia-1c, especially Ia-1c.

[0109] In another preferred embodiment, the compound of formula I is selected from the compounds of formula Ia-2:

[0110]

[0111] The radicals and parameters occurring therein have the meanings given above for formula I, and preferably Same or different express

[0112] Z T represents a single bond, -CH2O-, -OCH2- or -CH2CH2-,

[0113] Y 1 and Y 2 represents H, F or Cl,

[0114] Y 3 and Y 4 represents, identically or differently, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

[0115] Z 3 represents CH2 or O,

[0116] Z 1 and Z 4 independently represent a single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, OCH2- or -CH2CH2-,

[0117] r and u are independently 0, 1 or 2, very preferably u is 0 and r is 0 or 1, and R 1 Indicates H.

[0118] In formula I and its subformulae, the group Preferred representation Very preferred

[0119] In a preferred embodiment, the compounds of formula I are chiral.

[0120] The molecular layer obtained from the chiral compound of formula I enables memristive devices to significantly further reduce random noise and switch faster, thereby reducing read and write error rates, which has a positive impact on energy efficiency. In addition, an increase in tunnel current is observed, which allows integration into smaller junction sizes.

[0121] Preferably the chiral compound has an enantiomeric excess (ee) of higher than 50%, preferably higher than 80%, 90% or 95%, more preferably higher than 97%, especially higher than 98%.

[0122] Chirality is achieved by branched chiral groups Sp of the above formula I, hereinafter referred to as Sp*, having one or more, preferably one or two, very preferably one asymmetrically substituted carbon atoms (or: asymmetric carbon atom, C*). In Sp*, the asymmetric carbon atom is preferably connected to two differently substituted carbon atoms, a hydrogen atom and a substituent selected from halogen (preferably F, Cl or Br), alkyl or alkoxy groups having in each case 1 to 5 carbon atoms and CN.

[0123] The chiral organic group Sp* preferably has the following formula:

[0124]

[0125] in

[0126] X′ has the meaning defined above and preferably represents —CO—O—, —O—CO—, —O—CO—O—, —CO—, —O—, —S—, —CH═CH—, —CH═CH—COO— or a single bond, more preferably —CO—O—, —O—CO—, —O— or a single bond, very preferably —O— or a single bond,

[0127] Q and Q' identically or differently represent a single bond or an optionally fluorinated alkylene group having 1 to 10 carbon atoms,

[0128] The CH2 group not connected to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-, preferably an alkylene group having 1 to 10 carbon atoms or a single bond, particularly preferably -(CH2) n5 - or single key,

[0129] n5 is 1, 2, 3, 4, 5 or 6,

[0130] Y represents an optionally fluorinated alkyl radical having 1 to 15 carbon atoms, wherein one or two non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, further represents CN or halogen, preferably an optionally fluorinated alkyl radical or alkoxy radical having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl,

[0131] Furthermore, the chirality is achieved by a chiral group T of the above formula I, hereinafter referred to as R*, having one or more, preferably one or two, very preferably one asymmetrically substituted carbon atoms (or: asymmetric carbon atom, C*).

[0132] In R*, the asymmetric carbon atom is preferably bonded to two differently substituted carbon atoms, a hydrogen atom and a substituent selected from halogen (preferably F, Cl or Br), alkyl or alkoxy having in each case 1 to 5 carbon atoms and CN.

[0133] The chiral organic group preferably has the formula:

[0134]

[0135] in

[0136] X′ has the meaning defined above for formula I and preferably represents —CO—O—, —O—CO—, —O—CO—O—, —CO—, —O—, —S—, —CH═CH—, —CH═CH—COO— or a single bond, more preferably —CO—O—, —O—CO—, —O— or a single bond, very preferably —O— or a single bond,

[0137] Q represents a single bond or an optionally fluorinated alkylene group having 1 to 10 carbon atoms, wherein the CH2 group not connected to X may also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-, preferably an alkylene group having 1 to 5 carbon atoms or a single bond, particularly preferably -CH2-, -CH2CH2- or a single bond,

[0138] Y represents an optionally fluorinated alkyl radical having 1 to 15 carbon atoms, wherein one or two non-adjacent CH2 groups may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, further represents CN or halogen, preferably an optionally fluorinated alkyl radical or alkoxy radical having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl,

[0139] R Ch It represents an alkyl group having 1 to 15 carbon atoms, which is different from Y, in which one or two non-adjacent CH2 groups can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, preferably a straight-chain alkyl group having 1 to 10, in particular 1 to 7 carbon atoms, in which the CH2 group attached to the asymmetric carbon atom can be replaced by -O-, -O-CO- or -CO-O-.

[0140] In the memory cell of the present invention, the first electrode and / or the second electrode are preferably made of a metal, a conductive alloy, a conductive ceramic, a semiconductor, a conductive oxide material, a conductive or semiconductive organic molecule or a layered conductive 2D material. The first and / or second electrode may comprise a combination of more than one of the materials, for example in the form of a multilayer system. The materials of the first and second electrodes may be selected identically or differently.

[0141] Suitable metals include Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, W, Pd, Pt, among which Al, Cr and Ti are preferred.

[0142] Suitable conductive ceramic materials include CrN, HfN, MoN, NbN, TiO2, RuO2, VO2, NSTO (niobium doped strontium titanate), TaN and TiN, WN, WCN, VN and ZrN, among which TiN is preferred.

[0143] Suitable semiconductor materials include indium tin oxide (ITO), indium gallium oxide (IGO), InGa-α-ZnO (IGZO), aluminum doped zinc oxide (AZO), tin doped zinc oxide (TZO), fluorine doped tin oxide (FTO), and antimony tin oxide.

[0144] Suitable elemental semiconductors include Si, Ge, C (diamond, graphite, graphene, fullerenes), α-Sn, B, Se and Te. Suitable compound semiconductors include III-V semiconductors, especially GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN, Al x Ga 1-x As and In x Ga 1-x Ni, II-VI semiconductors, especially ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg(1-x)Cd(x)Te, BeSe, BeTex and HgS; and III-VI semiconductors, especially GaS, GaSe, GaTe, InSex and InTe, I-III-VI semiconductors, especially CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, IV-IV semiconductors, especially SiC and SiGe, IV-VI semiconductors, especially SeTe.

[0145] Suitable highly doped semiconductor materials include p+Si, n+Si.

[0146] An example of a suitable layered conductive 2D material is graphene.

[0147] Suitable semiconducting organic molecules include polythiophenes, tetracene, pentacene, phthalocyanine, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flavanthrinone, peronone, AlQ3 and mixed systems, especially PEDOT:PSS and polyvinylcarbazole / TLNQ complexes.

[0148] In a preferred embodiment, the first and second electrodes identically or differently comprise a material selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, Ta3N5, TaNx, TaON, WN, WCN, VN, ZrN, Ta2O5, SiO2, ZrO2, HfO2, WO3, RuO2, Cu2O, TiO2, Co2O3 and niobium-doped strontium titanate.

[0149] More preferably, the first and second electrodes identically or differently comprise, preferably consist of, a metal nitride selected from the group consisting of CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN, and ZrN.

[0150] Specifically, the first electrode is composed of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN, and ZrN, and the second electrode is composed of TiN.

[0151] Very particularly, the first and second electrodes are both composed of TiN.

[0152] In another preferred embodiment, the first electrode on which the SAM is formed by the compound of formula I comprises a material selected from the group consisting of TiN, Ta3N5, TaNx, TaON, Ta2O5, SiO2, ZrO2HfO2, WO3, RuO2, Cu2O, TiO2, Co2O3, Si, Co, Ni, W, Ru, Cu and Pt, and the second electrode comprises a material selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN.

[0153] In the following description of illustrative embodiments of the invention, identical or similar components and elements are denoted by identical or similar reference numerals, wherein a repeated description of these components or elements is avoided in individual cases.The figures depict the inventive subject matter only schematically.

[0154] Figure 1AA nanoscale nonvolatile solid-state resistive device 100 having a molecular switching layer 103 according to an embodiment of the present invention is described. Device 100 is a two-terminal memory in this embodiment. Device 100 includes a first electrode 102, a molecular switching layer 103, and a second electrode 104. Device 100 is a resistive memory device in this embodiment, but can be other types of devices in other embodiments. The molecular switching layer can be selectively set to various resistance values ​​by applying a voltage to the electrodes and resetting using a suitable control circuit. The resistance of device 100 varies depending on the orientation of the molecular dipoles of the molecular switching layer 103. Device 100 is formed on an external semiconductor substrate 101. The semiconductor substrate can be a silicon substrate or a composite substrate of III-V or II-VI type. In one embodiment, the substrate is not made of a semiconductor material, for example, made of plastic.

[0155] Particularly suitable substrates are selected from:

[0156] - Elemental semiconductors such as Si, Ge, C (diamond, graphite, graphene, fullerene), α-Sn, B, Se and Te;

[0157] - Compound semiconductors, preferably

[0158] -III-V semiconductors, especially GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN, Al x Ga 1-x As and In x Ga 1-x Ni,

[0159] -II-VI semiconductors, especially ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg (1-x) Cd (x) Te, BeSe, BeTe x and HgS;

[0160] -III-VI semiconductors, especially GaS, GaSe, GaTe, InS, InSe x and InTe,

[0161] - Group I-III-VI semiconductors, in particular CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2,

[0162] - Group IV-IV semiconductors, especially SiC and SiGe,

[0163] - Group IV-VI semiconductors, especially SeTe;

[0164] - organic semiconductors, in particular polythiophene, tetracene, pentacene, phthalocyanine, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flavanone, peronone, AlQ3 and mixed systems, in particular PEDOT:PSS and polyvinylcarbazole / TLNQ complexes;

[0165] - metals, in particular Ta, Ti, Co, Mo, Pt, Ru, Au, Ag, Cu, Al, W and Mg;

[0166] - Conductive oxide materials, in particular indium tin oxide (ITO), indium gallium oxide (IGO), InGa-α-ZnO (IGZO), aluminum-doped zinc oxide (AZO), tin-doped zinc oxide (TZO), fluorine-doped tin oxide (FTO) and antimony tin oxide.

[0167] Preferably, crystalline silicon is used as substrate 101, wherein silicon wafers with a (100) surface are particularly preferred. Silicon wafers whose surfaces are oriented in (100) are used as conventional substrates in microelectronics and are available with high quality and a low proportion of surface defects.

[0168] In the switching device of the present invention, the molecules of formula I forming the molecular layer 103 are bound to the first electrode 102 via the hydroxyaminophosphinic acid anchoring groups as defined in formula I above.

[0169] The molecular layer may optionally be bonded to a thinner (preferably 0.5-5 nm thick) oxide interlayer 105, such as TiO2, Al2O3, ZrO2, HfO2 or SiO2, located on the first electrode 102, so that in this embodiment, the first electrode comprises a first layer comprising a material as defined in claim 1 and a second oxide layer, wherein the molecular layer 103 is bonded to the second oxide layer ( Figure 1B ). Therefore, the first electrode 102 and the interlayer 105 may operate as an alternative first electrode 102'.

[0170] The molecular layer of the present invention is a layer of electrically insulating, non-conductive and non-semiconducting organic compounds.

[0171] The molecular layer is essentially formed from the precursor of formula I. Preferably, the precursor used to form the molecular layer consists of the compound of formula I.

[0172] The thickness of the molecular layer is preferably 10 nm or less, particularly preferably 5 nm or less, very particularly preferably 3 nm or less.

[0173] The molecular layer may be composed of 1, 2, 3 or more molecular layers comprising the compound of formula I.

[0174] The molecular layer used according to the invention is preferably a molecular monolayer.

[0175] In one embodiment, the molecular layer is a self-assembled monolayer (SAM).

[0176] The production of self-assembled monolayers is known to the person skilled in the art; an overview is given, for example, in A. Ulman, CHem. Rev. 1996, 96, 1533-1554.

[0177] The degree of coverage of the substrate is preferably from 90 to 100%, particularly preferably from 95 to 100%, very particularly preferably from 98 to 100%.

[0178] The second electrode 104 is preferably made of TiN.

[0179] In one embodiment, Figure 1A In an embodiment of the present invention, a first electrode 102 embodied in the form of a conductor track running perpendicular to the drawing surface is arranged on the substrate 101 .

[0180] The second electrode 104, which is in the form of a conductor track like the first electrode 102, is arranged on the side of the molecular layer 103 facing away from the substrate 101. However, the second electrode 104 is rotated 90° relative to the first electrode 102, thereby producing a cross-shaped arrangement. This arrangement is also called a crossbar switch array, where the 90° angle is selected as an example here, and an arrangement in which the second electrode 104 and the first electrode 102 cross at an angle deviating from a right angle can also be imagined. The switching device 100 formed by the layer system having the second electrode 104, the molecular layer 103 and the first electrode 102 in this order is arranged at each intersection between the second electrode 104 and the first electrode 102. In one embodiment, a diode is also assigned to each switching device 100.

[0181] The crossbar switch array allows each switching device 100 to be electrically addressed by applying a voltage between a corresponding first electrode 102 and a second electrode 104 .

[0182] The production and structuring of the electrodes is carried out by means of methods known to the person skilled in the art and are explained in more detail below with reference to working examples.

[0183] The structures of the electrodes 102, 104 can be produced by structuring methods known from microelectronics by those skilled in the art. For example, a lithographic method can be used to produce the first electrode 102. In this case, a metal layer is applied to the substrate 101 by means of vapor deposition. The metal layer is then coated with a photoresist, which is exposed together with the structure to be produced. After development and, if necessary, baking of the resist, the unwanted parts of the metal layer are removed, for example, by wet chemical etching. The remaining resist is then removed, for example, using a solvent.

[0184] Another possibility for producing electrodes 102, 104 is vapor deposition with the aid of a shadow mask. In this method, a mask whose openings correspond to the shape of the electrodes 102, 104 to be produced is placed on the component and the metal is subsequently applied by vapor deposition. The metal vapor can only precipitate on the component in the areas not covered by the mask and form electrodes 102, 104.

[0185] Suitable and preferred methods for producing the switching device of the present invention are disclosed in EP3813132A1 paragraphs

[0113] to

[0126] , which is incorporated by reference. The compounds of the present invention can be used as described therein.

[0186] A substrate 101 is provided on which a plurality of devices 100 are to be defined. The substrate in this embodiment is silicon (p-doped, resistivity <0.001Ωcm -1 , high quality). In a preferred embodiment, the silicon substrate comprises a SiO2 layer used as an isolation layer and improved derivatization. In other embodiments, other semiconductor materials such as III-V and II-VI type semiconductor compounds can be used as the substrate. Depending on the implementation, the device 100 can be formed as part of the front-end process or the back-end process. Therefore, when providing a substrate for the method of the present invention, the substrate 101 can include one or more layers of material formed and patterned thereon.

[0187] The first electrode is formed on the substrate 101 using any deposition process, such as chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), radio frequency CVD (RFCVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular beam deposition (MBD), pulsed laser deposition (PLD) and / or liquid source mist chemical deposition (LSMCD) and / or sputtering, or other deposition or growth methods are used to form at least the top portion of the first electrode. The bottom electrode should preferably contain a material with a high voltage threshold for ion migration and it can be covered or structured by photolithography or other advanced lithography methods known to those skilled in the art, such as nanoimprint lithography or dip pen lithography.

[0188] Optionally, the first electrode is treated with oxygen, argon or nitrogen plasma or UV / ozone to obtain a hydrophilic oxide surface full of hydroxyl groups. It is clear that this type of oxide surface is only used for surface modification, with the purpose of possible derivatization via condensation reactions and does not represent an insulator layer or interlayer in the true sense. Due to the low thickness of about 1 nm, a sufficiently large tunnel current through this oxide surface becomes possible.

[0189] A molecular layer 103 is formed on the first electrode 102 .

[0190] The deposition of the molecular layer on the first electrode is carried out with pure substances or from solution, preferably from solution. Suitable deposition methods and solvents are known to those skilled in the art; examples are spin coating or dip coating.

[0191] The molecules of the molecular layer are preferably bonded to the first electrode by chemical adsorption or covalent bonding, more preferably covalent bonding, by known methods well known to those skilled in the art, for example, by condensation with hydroxyl groups on the surface of the substrate.

[0192] In an alternative embodiment, the molecular layer 103 may also be connected to the first electrode not directly, but via a thin oxide adhesion layer 105 (e.g., Al2O3, ZrO2) derived from a metal different from the first electrode, and the thin oxide adhesion layer 105 is deposited on the first electrode using the deposition technique mentioned above for the first electrode, preferably CVD.

[0193] The molecular layer is preferably grafted directly onto the titanium nitride first electrode 102 by means of a molecule of formula I in which the anchoring group is a group -P(O)(OH)(NHOH).

[0194] In a preferred embodiment, the device is annealed after the deposition of the monolayer. The annealing is carried out at a temperature of greater than 20° C. and less than 300° C., preferably greater than 50° C. and less than 200° C., particularly preferably greater than 90° C. and less than 150° C. The duration of the annealing is 1-48 hours, preferably 4-24 hours, particularly preferably 8-16 hours.

[0195] The first electrode 102 is patterned to obtain an electrode extending in a certain direction (eg, horizontal direction). In this step, a plurality of first electrodes extending in parallel along a first direction are formed.

[0196] A patterned second electrode is formed on the molecular layer 103 by a lift-off process using a known processing sequence including stripping of the photoresist, a patterning step, electrode deposition and lift-off, or using photoresist.

[0197] The second electrode 104 may be deposited, for example, by sputtering or atomic layer deposition, preferably by sputtering.

[0198] According to another aspect of the present invention, multiple units are arranged in a three-dimensional array of units. Therefore, the array extends in two directions of a plane defined by the substrate on which electronic components are formed and can also extend in a vertical direction perpendicular to the plane. The number of units arranged in the two directions or dimensions of the plane can be very high, ranging from at least two to thousands, millions or even billions of units. For example, in a configuration of 1024 units in the x direction and 1024 units in the y direction, a single two-dimensional layer of units comprises 1048576 units. This two-dimensional arrangement of units is known as a crossbar array, in which each unit is located at the intersection of two orthogonal electrode lines.

[0199] The number of levels or layers of cells arranged in the vertical direction or dimension is typically low and in the range of 2 to at least 64, preferably up to at least 1024 or even higher. Preferably the array comprises at least 16 levels of cells, more preferably at least 32 levels of cells, most preferably at least 64 levels of cells. This three dimensional arrangement of cells is known as a 3D crossbar array or a 3D crosspoint device. Example

[0200] The present invention is described in detail by the following non-limiting working examples.

[0201] Synthesis Example 1: P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxy-phosphonamidic acid

[0202] Step 1: 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene

[0203]

[0204] To a solution of 2,3-difluoro-4-(4-pentylcyclohexyl)phenol (5 g, 17 mmol) in 60 ml of anhydrous DMF was added potassium carbonate (3.6 g, 26 mmol) and the resulting mixture was stirred at room temperature for 1 hour. 1,4-dibromobutane (7.3 g, 4.0 ml, 34 mmol) was then added followed by potassium iodide (0.2 g, 1 mmol). After stirring at room temperature for 18 hours, the mixture was filtered off and the filtrate was concentrated in vacuo. The residue was treated with ether (100 ml), washed with brine (3 x 50 ml), dried over sodium sulfate, and concentrated under reduced pressure to give a white solid, which was suspended in cold n-pentane, filtered, and washed three times with cold pentane to give 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene as a white solid, melting point 47-48°C.

[0205] 1 H NMR (400MHz, CDCl3): δ6.83 (dd, J=9.2, 2.3Hz, 1H), 6.68 (dd, J=7.33, 1.9Hz, 1H), 4.04 (t, J=5.7Hz, 2H), 3.49 (t, J=6.1Hz, 2H), 2.82 (tt,J=12.1,2.9Hz,1H),2.31(q,J=5.9Hz,2H),1.88-1.78(m,6H),1.46-1.36(m,2H),1.35-1.17(m,2H),1.09-0.99(m,9H),0.86(t, 3 J HH =7.3Hz,3H)

[0206] 13 C NMR (101MHz, CDCl3): δ149.0(dd,J=245.1,10.2Hz), 145.6(dd,J=8.2,2.9Hz), 141.0(dd,J=246.9,15.3Hz), 128.2(dd,J=12.5,1.3Hz), 120.3( dd,J=5.7,4.6Hz),109.2(d,J=3.3Hz),67.1(s),40.1(s),36.7(s),33. 3(s),33.1(s),32.4(s),31.7(s),31.5(s),27.7(s),23.4(s),14.1(s).

[0207] Step 2: Diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphate

[0208]

[0209] To a solution of diethyl phosphite (0.69 g, 0.64 ml, 5 mmol) in 80 ml of anhydrous THF cooled to 0 ° C, sodium hydride (0.24 g, 6 mmol, 60% dispersion in oil) was added in batches. It was stirred at 0 ° C for 30 minutes, and then a solution of 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene (2 g, 5 mmol) in 5 ml of anhydrous THF was added. The resulting mixture was then stirred at 66 ° C for 4 hours. The reaction was quenched with 1M HCl solution (100 ml), the organic phase was separated, and the aqueous phase was extracted with ether (3x30 ml). The organic phase was then dried with Na2SO4, filtered and the solvent was evaporated to obtain an oily residue, which was purified by column chromatography, eluted with ethyl acetate, to obtain diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonate as a pale yellow oil.

[0210] 1 H NMR (401MHz, CDCl3): δ6.81(t,J=8.2Hz,1H),6.63(t,J=8.1Hz,1H),4.15-4.02(m,4H),4.01(dd,J=11.7,5.9Hz,2H),2.70(tt ,J=12.1,1.1Hz,1H),1.85(dt,J=21.4,11.1Hz,9H),1.50-1.11(m,16H),1.05(dd,J=17.1,6.4Hz,2H),0.87(t,J=6.7Hz,3H); 19 F NMR (377MHz, CDCl3): δ-143.15 (dd, J=19.6, 7.4Hz, 1F), -159.47 (ddd, J=19.6, 7.6, 2.1Hz, 1F); 31 P NMR (162MHz, CDCl3): δ32.42 (s, 1P).

[0211] Step 3: (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonyl chloride ethyl ester

[0212]

[0213] Oxalyl chloride (200 mg, 1.6 mmol) was added dropwise to a stirred solution of diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonate (780 mg, 1.6 mmol) dissolved in 5 ml of anhydrous dichloromethane at room temperature. When the addition was complete, the mixture was stirred at reflux for an additional 4 hours. All volatiles were then removed in vacuo to give (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-ethyl phosphonate chloride as a yellow oil.

[0214] 1 H NMR (401MHz, CDCl3): δ6.83 (td, J=8.3, 2.6Hz, 1H), 6.64 (td, J=7.7, 1.9Hz, 1 H),4.37-4.27(m,1H),4.27-4.18(m,1H),4.03(t,J=5.4Hz,2H),2.80-2.66(m ,1H),2.23(dt,J=15.1,6.5Hz,2H),2.00-1.88(m,3H),1.49-1.39(m,4H),1. 41-1.37(m,6H),1.35-1.17(m,9H),1.12-0.98(m,2H),0.88(t,J=6.6Hz,3H); 19 F NMR (377MHz, CDCl3): δ-143.15 (dd, J=19.6, 7.4Hz, 1F), -159.47 (dd, J=19.6, 7.6, 1F); 31 P NMR (162MHz, CDCl3): δ44.62 (s, 1P)

[0215] Step 4: P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamide ethyl ester

[0216]

[0217] A solution of (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-phosphonyl chloride (760 mg, 1.6 mmol) in 1 ml of dry dichloromethane was added to a stirred mixture of O-trimethylsilylhydroxylamine (180 mg, 1.8 mmol) and triethylamine (159 mg, 0.22 ml, 1.8 mmol) in dry dichloromethane (20 ml) at 0°C. After a further 5 hours at room temperature, the volatiles were evaporated, ether (10 ml) was added and the solid (Et3NHCl) was filtered off. The filtrate was treated with methanol (3 ml) for 10 minutes for desiliconization and then evaporated to dryness to give an oily residue which was purified by column chromatography eluting with ethyl acetate to give P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidoethyl ester.

[0218] 1H NMR (401MHz, CDCl3): δ6.82(t,J=8.2Hz,1H),6.62(t,J=8.2Hz,1H),4.16-4.10(m,4H),3.90(t,J=5.9Hz,2H),2.71(t,J=12.3Hz, 1H),1.76-1.96(m,4H),1.48-1.32(m,9H),1.26(ddd,J=22.9,13.6,6.0Hz,4H),1.04(q,J=11.8Hz,2H),0.88(t,J=6.8Hz,3H); 19F NMR (377MHz, CDCl3): δ-143.06 (d, J=19.6Hz, 1F), -159.37 (d, J=20.2Hz, 1F); 31P NMR (162MHz, CDCl3): δ26.91 (s, 1P)

[0219] Step 5: P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxy-phosphonamidic acid

[0220]

[0221] Bromotrimethylsilane (3.5 g, 3 ml, 22 mmol) was added to neat P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidoethyl ester (0.33 g, 0.77 mmol) under argon. The resulting solution was stirred at room temperature for 24 hours. The volatiles were removed in vacuo and the residue was treated with methanol (2 ml). After stirring at room temperature for 12 hours, the solvent was evaporated under reduced pressure to give P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonimidic acid as a solid.

[0222] 1H NMR (401MHz, DMSO-d6): δ10.36(s,3H),6.81(t,J=8.2Hz,1H),6.63(t,J=8.2Hz,1H),3.99(t,J=5.9Hz,2H),2.71(t,J=12.3Hz,1 19F 13C NMR (101MHz, DMSO-d6): δ149.4 (dd, J=245.1, 10.2Hz), 146.0 (dd, J=8.2, 2.9Hz), 141.5(dd,J=246.9,15.3Hz),128.7(dd,J=12.5,1.3Hz),121.5(dd,J=5.7Hz,4.6H z),110.3(d,J=2.0Hz),69.29(s),33.48(s),32.99(s),30.12(s),29.86(s),28.5 1(d,J=135.8Hz),27.10(s),26.51(s),22.60(s),19.99(s),19.95(s),14.49(s).

[0223] Application Testing

[0224] Comparative characterization of SAMs

[0225]

[0226] Preparation of test chip:

[0227] A test chip was prepared using acid compound A (Synthesis Example 1) by the following steps in this order and compared with compound B in the prior art:

[0228] 1. Preparation of THF solutions of N-hydroxyamidophosphonic acid A and phosphonic acid B (as reference) (c = 1 mmol / l)

[0229] 2. Treat the test chip with UV ozone for 15 minutes: 1) 8x8 mm p ++ Si (525 μm) / Al2O3 (2-3 nm, deposited by ALD), and 2) 8x8 mm p++ Si (525 μm) / Ti (10 nm, sputtering) / TiN (30 nm, sputtering)

[0230] 3. Immerse chip 1 or 2 in N-hydroxyamide phosphonic acid or phosphonic acid solution for 72 hours to obtain chips 1A, 1B, 2A and 2B

[0231] 4. Drying in a nitrogen stream

[0232] 5. Bake in nitrogen atmosphere (T = 120 ° C) for 1 hour

[0233] 6. Clean with a short rinse in THF

[0234] 7. Drying in N2 flow

[0235] Water Contact Angle (WCA) Measurement:

[0236] Test chip Compound WCA 1A A 105.3° 1B B 104.7° 2A A 115.0° 2B B 115.8°

[0237] On Al2O3(1) and TiN(2) substrates, the WCA of A is roughly at the same level as the reference compound B.

[0238] Comparative current-voltage (IV) characteristics were recorded using a standard setup as described, for example, in EP 3 481 916 A1.

[0239] Figure 2A The results show that the reference compound B is ++ IV characteristics (200, absolute current density vs. voltage) on Si (525 μm) / Ti (10 nm, sputtered) / TiN (30 nm, sputtered); in contact with a Hg droplet of approximately 160 mm diameter. Figure 2B The results show that the compound A of the present invention is deposited on a TiN substrate (8x8 mm p ++ IV characteristics (300, absolute current density vs. voltage) on Si (525 μm) / Ti (10 nm, sputtered) / TiN (30 nm, sputtered); in contact with a Hg droplet of approximately 160 mm in diameter. The upper curve 200 shows the results of four scans 201, 202, 203, and 204. The lower curve 300 shows the results of four scans 301, 302, 303, and 304. The results show that N-hydroxyphosphonamide compound A is more stable to dielectric breakdown than phosphonic acid compound B (1.5 V and 1.0 V, respectively). The IV curve 300 shows a clear hysteresis behavior, where the ratio of the high resistance state (HRS) to the low resistance state (LRS) is approximately one order of magnitude.

[0240] Similar to Synthesis Example 1, the following compound was obtained:

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[0247]

[0248]

[0249]

[0250]

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Claims

1. Compounds of formula I: in T is selected from the group consisting of the following groups: a) straight-chain or branched alkyl or alkoxy radicals each having 1 to 20 C atoms, wherein one or more CH2 radicals in these radicals can each independently of one another be replaced by -C≡C-, -CH=CH-, -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -、-NH-、-NR 0 - or -SO2- is substituted in such a way that the O atoms are not directly connected to each other, and wherein one or more H atoms may be replaced by halogen, CN, SCN or SF5, R 0 , R 00 represent, identically or differently, alkyl or alkoxy radicals having 1 to 15 C atoms, in which one or more H atoms may additionally be replaced by halogen, b) a 3-10 membered saturated or partially unsaturated aliphatic ring, wherein at least one -CH2- group is replaced by -O-, -S-, -S(O)-, -SO2-, -NR x -or-N(O)R x -, or wherein at least one -CH= group is replaced by -N=, c) an adamantane group, Z T , Z 1 , Z 2 and Z 4 represents, identically or differently on each occurrence, a single bond, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2O-, -OCH2-, -C(O)O-, -OC(O)-, -C(O)S-, -SC(O)-, -(CH2) n1 -、-(CF2) n2 -, -CF2CH2-, -CH2CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4 -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, wherein n1, n2, n3, n4 are the same or different and are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, Z 3 Indicates -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-, represents, identically or differently on each occurrence, an aromatic, heteroaromatic, cycloaliphatic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain condensed rings and which may be mono- or polysubstituted by Y, represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain condensed rings and may be replaced by R C Single or multiple substitutions, Y, identically or differently on each occurrence, represents F, Cl, CN, SCN, SF5 or linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, Representation group These groups can be oriented in two directions, L 1 -L 5 Identically or differently represent H, F, Cl, Br, I, CN, SF5, CF3, OCF3 or OCHF2, wherein the radical L present in the corresponding radical 1 -L 5 At least one of them is not H, R L represents, identically or differently on each occurrence, H, alkyl having 1 to 6 C atoms, alkenyl having 2 to 6 C atoms or alkoxy having 1 to 5 C atoms, R C represents, identically or differently on each occurrence, in each case optionally fluorinated, straight-chain or branched alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy radicals having 1 to 12 C atoms or cycloalkyl or alkylcycloalkyl radicals having 3 to 12 C atoms, Sp represents a spacer group or a single bond, R 0 , R 00 , R x represents a straight-chain or branched alkyl group having 1 to 6 C atoms, R 1 represents H or a straight-chain or branched alkyl group each having 1 to 12 C atoms, R 2 and R 3 identically or differently represent H or a linear, branched or cyclic alkyl group having 1 to 12 C atoms, r, s, t, u and v are identical or different and are 0, 1 or 2, wherein r+s+t+u+v=0, 1, 2, 3 or 4.

2. The compound according to claim 1, wherein R 2 and R 3 Indicates H.

3. The compound according to claim 1 or 2, wherein the compound is selected from the compounds of formula Ia-1a to Ia-1d: Among them, T, Z T , Z 1 , Z 2 , Sp and R 1 has the meaning given to it in claim 1, r is 1 or 2, and s is 1 or 2.

4. A compound according to one or more of claims 1 to 3, wherein T stands for H, or a straight-chain or branched alkyl or alkoxy radical each having 1 to 7 C atoms or a straight-chain or branched alkenyl radical having 2 to 7 C atoms, Z T represents CH2O, OCH2, CH2CH2 or a single bond, Z 1 and Z 2 represent, identically or differently, CH2O, OCH2, CH2CH2, CF2O, OCF2, C(O)O, OC(O) or a single bond, Same or different Y 1 and Y 2 represents H, F or Cl, identically or differently on each occurrence, Sp represents a branched or unbranched 1,ω-alkylene radical having 1 to 12 C atoms, in which one or more non-adjacent CH2 groups may be replaced by O, R 1 represents H, and Has the meaning defined in claim 1.

5. The compound according to claim 1 or 2, wherein the compound is selected from the group consisting of compounds of formula Ia-2: Among them, T, Z T , Z 1 , Z 3 , Z 4 ,Sp,R 1 , r and u have the meanings given in claim 1.

6. A compound according to claim 5, wherein Same or different A 3 -Z 3 express Z T represents a single bond, -CH2O-, -OCH2- or -CH2CH2-, Y 1 and Y 2 represents H, F or Cl, Y 3 and Y 4 represents a methyl group, an ethyl group, an isopropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, a methoxy group, a trifluoromethyl group, a trifluoromethoxy group or a trifluoromethylthio group, Z 3 represents CH2 or O, Z 1 and Z 4 independently represent a single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -CH2O-, OCH2- or -CH2CH2-, r and u are independently 0, 1 or 2.

7. A compound according to one or more of claims 1 to 6, wherein the group express 8. A method for preparing a compound of formula Ib, comprising the steps of: a) reacting a phosphonyl chloride of formula II with O-(trialkylsilyl)hydroxylamine in the presence of a base to obtain an N-[(alkoxy)phosphoryl]hydroxylamine of formula Ia, and b) ester cleavage of the compound of formula Ia to obtain a compound of formula Ib; Among them, T, Z T , Z 1 , Z 2 , Z 3 , Z 4 , Sp, r, s, t, u and v have the meanings given in claim 1, and R 11 represents a straight-chain alkyl group having 1 to 12 C atoms or a branched alkyl group having 3 to 12 C atoms.

9. An electronic switching device (100) comprising, in this order: a first electrode (102), a molecular layer (103) bonded to the first electrode, and a second electrode (104), wherein the first and second electrodes (102, 104) are identical or different, and preferably comprise a material selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, Ta3N5, TaNx, TaON, WN, WCN, VN, ZrN, Ta2O5, SiO2, ZrO2, HfO2, WO3, RuO2, Cu2O, TiO2, Co2O3 and niobium-doped strontium titanate, It is characterized in that the molecular layer (103) is essentially formed by one or more compounds of the formula I according to one or more of claims 1 to 7.

10. An electronic switching device (100) according to claim 9, wherein the interlayer (105) is arranged between the first electrode (102) and the molecular layer (103), wherein the interlayer (105) comprises an oxide material and wherein the molecular layer (103) is bonded to the oxide material, and wherein the first electrode (102) and the interlayer (105) can operate as a first electrode (102').

11. An electronic switching device (100) according to claim 9 or 10, wherein the one or more compounds of formula I are bound to the first electrode (102) by chemical adsorption or covalent bonding.

12. An electronic switching device (100) according to one or more of claims 9-11, wherein the molecular layer (103) is a molecular monolayer.

13. Electronic assembly comprising one or more switching devices (100) according to one or more of claims 9-12.

14. An electronic component according to claim 13, wherein the component has a plurality of switching devices (100), wherein the first electrodes (102) and the second electrodes (104) of the switching devices (100) form a crossbar array.

15. An electronic assembly according to claim 13 or 14, wherein the switching device (100) is configured to change between a high resistance state and a low resistance state, wherein the quotient of the high resistance and the low resistance is 10-100,000.

16. Use of a compound of formula I according to claim 1 in the preparation of a self-assembled monolayer.

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