Hydroxyaminophosphinic acid derivatives

Abstract

The present invention relates to hydroxyaminophosphinic acid derivatives of formula I, in which the occurring radicals and parameters have the meanings defined in claim 1, to their preparation process and to the formation of self-assembled monolayers ( s elf- a assembled m The present invention further relates to electronic devices comprising said SAMs, preferably in the field of organic electronics, in particular for use in memories, sensors, and also in memristive components such as organic light-emitting diodes (OLEDs), photovoltaics (OPVs), field-effect transistors (OFETs), and Josephson junctions, and very particularly memristive crossbar arrays.

Description

[Technical Field]

[0001] The present invention relates to a hydroxyaminophosphinic acid derivative, a method for producing the same, and a self-assembled monolayer ( s elf- a assembled m The present invention relates to their use for the fabrication of switchable monolayers (SAMs), in particular for the fabrication of switchable SAMs for electronic devices. The present invention further relates to electronic devices comprising said SAMs. [Background technology]

[0002] Compounds for preparing self-assembled monolayers are known from the prior art and are widely used, for example, for the derivatization of electrodes in electronic components. These monolayers are ordered arrays of rod-like molecules that are attached to a substrate via suitable anchoring groups and harbor functional groups at the other end of the molecular backbone. Such monolayers are useful for controlling the physical and chemical properties of surfaces and interfaces. In organic electronics, self-assembled monolayers are frequently used for electrostatic modification of interfaces by controlling interfacial-level alignment. The performance and lifetime of these devices, such as organic light-emitting diodes (OLEDs), photovoltaics (OPVs), and field-effect transistors (OFETs), depend heavily on the properties of both the active material and its interface. Interfacial properties can be controlled by simple wettability and adhesion between different materials, thereby modifying the electronic structure of the materials.

[0003] Switchable SAMs have been proposed for use in computer memory in recent years. Computer technology requires storage media that allow rapid write and read access to the information stored therein. Solid-state memory, or semiconductor memory, is a particularly fast and reliable storage medium because it requires no moving parts. Currently, dynamic random access memory (DRAM) is the predominant type used. DRAM allows rapid access to stored information, but this information must be periodically refreshed, meaning 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 memory and magnetoresistive random access memory (MRAM), which retain information even after power is turned off. A drawback of flash memory is that write access occurs relatively slowly and flash memory memory cells cannot be erased indefinitely. The lifespan of flash memory is typically limited to a maximum of one million read / write cycles. MRAM can be used in a manner similar to DRAM and has a long lifespan, but this type of memory has not yet become established due to difficult manufacturing processes.

[0005] A further alternative is memory based on memristors. The term memristor is a contraction of the words "memory" and "resistance" and describes a component whose electrical resistance can be reproducibly changed between high and low resistance. Each state (high or low resistance) is maintained even in the absence of a power supply voltage, meaning that memristors can realize nonvolatile memory. Memristor crossbar arrays can be used in a variety of applications, including nonvolatile solid-state memory, programmable logic, signal processing, control systems, pattern recognition, and other applications. A memristive crossbar array includes a number of row lines, a number of column lines that intersect the row lines to form a number of intersections, and a number of resistive memory devices coupled between the row and column lines at the intersections.

[0006] WO 2016 / 110301 A1 and WO 2018 / 007337 A2 disclose electronic components suitable for use in memristive devices. Herein, a non-redox-active molecular layer is proposed, which comprises a dipolar compound linked to a substrate via an aliphatic spacer group, and in which the compound is reversibly switched by application of an electric field that causes a reorientation of the molecular dipoles, thereby enabling low and high resistance states to be achieved depending on the respective orientation of the molecules.

[0007] Compounds for preparing SAMs include an organic residue and a group suitable for binding to the substrate surface and thereby anchoring the organic residue to the surface. Suitable anchor groups include thiol, phosphonate, phosphate, sulfate, sulfonate, carboxylic acid, or siloxane.

[0008] The choice of anchor group depends largely on the chemical nature of the substrate, which together determine the nature and stability of the bonds between the individual molecules that form the monolayer and the substrate.

[0009] Deposition of SAMs onto suitable substrates is preferably carried out by either spin-coating or dip-coating from organic solvents. The amphiphilic nature of the SAM precursors and the high polarity of the anchoring groups often lead to poor precursor solubility. These compounds exhibit extremely low solubility in most polar aprotic solvents, and SAMs can only be applied from fairly dilute solutions in toxic solvents such as THF or dioxane. They do not dissolve in sufficient concentrations in typical semiconductor industry solvents.

[0010] There is a need in the art for materials that form SAMs of acceptable quality in extremely short deposition times and convenient deposition processes. To achieve high-quality SAMs, it is important that the formation of the SAM first proceeds via a thermodynamically reversible physisorption step, which is then locked into place by an annealing step that initiates an irreversible condensation reaction.

[0011] In particular, the 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. Summary of the Invention

[0012] The present invention has been made in view of the above problems, and it is an object of the present invention to provide anchoring groups that make it possible to obtain SAM precursors that do not exhibit the above drawbacks, or at least to a lesser extent. A further object is to search for new compounds that are suitable for the manufacture of electronic components using conventional methods in the memory industry.

[0013] To solve this problem, compounds of formula I are provided: [ka] In that formula T is the group: a) linear or branched alkyl or alkoxy having 1 to 20 C atoms each, in which one or more CH2 groups in these radicals are independently -C≡C-, -CH=CH-, [ka] -O-, -S-, -CF2O-, -OCF2-, -CO-O-, -O-CO-, -SiR 0 R 00 -, -NH-, -NR 0 - or -SO2-, each in such a way that the O atoms are not directly linked to each other, and wherein one or more H atoms may be replaced by halogen, CN, SCN or SF5, wherein R 0 , R 00 are identical or different and represent alkyl or alkoxy radicals having 1 to 15 C atoms, in which, in addition, one or more H atoms may be replaced by halogen, b) A 3- to 10-membered saturated or partially unsaturated aliphatic ring in which at least one -CH2- group is -O-, -S-, -S-, -S(O)-, -SO2-, or -NR x -or-N(O)R x or at least one -CH= group is replaced by -N=; c) diamondoid radicals, which are preferably derived from lower diamondoid radicals, very preferably those selected from the group consisting of adamantyl, diamantyl and triamantyl (in which one or more H atoms can be replaced by F, alkyl, alkenyl or alkoxy having up to 12 C atoms, in each case optionally fluorinated), in particular [ka] is selected from the group of radicals consisting of Z T , Z 1 , Z 2 , and Z 4 are the same or different in each occurrence and represent a single bond, CFO-, OCF-, -CFS-, -SCF-, -CHO-, -OCH-, -C(O)O-, -OC(O)-, C(O)S-, -SC(O)-, (CH) n1 -, -(CF2) n2 -, -CF2CH2-, -CH2CF2-, -CH=CH-, CF=CF-, -CF=CH-, -CH=CF-, -(CH2) n3 O-, -O(CH2) n4 represents -, -C≡C-, -O-, -S-, CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, and n1, n2, n3 and n4 may be the same or different and each represent 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; Z 3 -O-, -S-, -CH2-, -C(O)-, -CF2-, -CHF-, -C(R x )2-, -S(O)- or -SO2-; [ka] are the same or different in each occurrence and represent an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also include fused rings, and which may be mono- or polysubstituted by Y; [ka] represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also include fused rings, and which is C may be mono- or polysubstituted by Y in each occurrence is identical or different and 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, preferably F or Cl, [ka] is the base [ka] [ka] where the groups may be oriented in both directions, L 1 ~L 5 are the same or different and represent H, F, Cl, Br, I, CN, SF5, CF3, OCF3 or OCHF2, preferably Cl or F, very preferably F, and the radicals L present in each group 1 ~L 5 At least one of them is not H, R Lare identical or different in each occurrence and represent 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, R C are identical or different in each occurrence and represent a straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a cycloalkyl or alkylcycloalkyl each having 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy, trifluoromethoxy or trifluoromethylthio, Sp represents a spacer group or a single bond; R 0 , R 00 , R x represents a linear or branched alkyl having 1 to 6 carbon atoms, R 1 stands for H or linear or branched alkyl having 1 to 12 C atoms, preferably for H or tert-alkyl, very preferably for H or tert-butyl, in particular for H, R 2 and R 3 are the same or different and represent H or linear, branched or cyclic alkyl having 1 to 12 C atoms, preferably H, methyl or cyclohexyl, very preferably H or methyl, in particular H, r, s, t, u and v are the same or different and are 0, 1 or 2; where r+s+t+u+v is 0, 1, 2, 3, or 4.

[0014] The present invention further relates to a process for the preparation of compounds of formula I. According to another aspect of the present invention, a first electrode: a molecular layer attached to the first electrode; and 2nd electrode in this order, There is now provided a switching device, wherein the molecular layer is formed essentially of one or more, preferably one, compound of formula I as defined above and below.

[0015] The invention further relates to a process for the manufacture of a switching device according to the invention, comprising at least the following steps: i. preparing a first electrode having a surface; ii. depositing on the surface of the first electrode a molecular layer comprising one or more compounds selected from the group of compounds of formula I as defined above; iii. Application of a second electrode.

[0016] According to another aspect of the present invention, there is provided an electronic component, wherein the component is a memristive crossbar array comprising a number of switching devices according to the present invention. The crossbar arrays 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.

[0017] The invention further relates to the use of a molecular layer obtained from one or more compounds as set out in claim 1 in a memristive electronic component. The resulting devices can be used in memories, sensors, field effect transistors or Josephson junctions, preferably in resistive memory devices.

[0018] The invention further relates to the use of the switching device in a memory, a sensor, a field effect transistor or a Josephson junction. The switching device according to the invention is suitable for use in electronic components, in particular in memories, sensors, field effect transistors or Josephson junctions, very particularly in memristive components such as memristive crossbar arrays, which exhibit the advantageous properties set out above.

[0019] The compounds of formula I containing hydroxyaminophosphinic acid or hydroxyaminophosphinic acid-derived anchor groups are surprisingly well soluble in solvents used in the memory industry, in particular 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), but also common solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), tetrahydrofuran (THF), toluene, anisole, chlorobenzene or CHCl.

[0020] Compounds of formula I have been shown to improve SAM quality and the speed of SAM formation, especially on more acidic and lower isoelectric substrates (e.g., TiN, Ta3N5, TaN X , TaON, TaN, Ta2O5, SiO2, ZrO2, HfO2, WO3, RuO2, Co2O3) and for metals (e.g., Si, Co, Ni, W, Ru, Cu, Pt via their native oxides or via surface oxidation by oxygen plasma, UV / O3 treatment or similar methods).

[0021] The SAM precursors of formula I and the electronic components obtained from the compounds of formula I are distinguished by surprisingly high chemical and thermal stability. The switchable electronic components obtained from the compounds of formula I require only small voltages and small field strengths to switch the devices and exhibit long-term retention of the resistance state. The switching devices exhibit high reliability and durability, as well as high stability against dielectric breakdown. Furthermore, they have an advantageously large memory window.

[0022] The electrode materials that can be used in the devices according to the invention are highly compatible with semiconductor industry device and fabrication processes and are surprisingly suitable for the formation of stable and homogeneous molecular monolayers. A brief description of the drawings. [Brief explanation of the drawings]

[0023] [Figure 1] Figure 1A shows a schematic diagram of the layer structure of a first embodiment of an electronic switching device according to the present invention, and Figure 1B shows a schematic diagram of the layer structure of a second embodiment of an electronic switching device according to the present invention. [Figure 2] Figure 2A shows the current-voltage curves of an electronic switching device fabricated using a state-of-the-art compound, and Figure 2B shows the current-voltage curves of an electronic switching device fabricated using a compound of Formula I according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] The term "diamondoid" refers to substituted and unsubstituted cage compounds of the adamantane series, including adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, etc., including all isomers and stereoisomers thereof. The compounds have "diamondoid" topology, meaning that their carbon atom arrangement can be superimposed onto a fragment of a face-centered cubic diamond lattice. Substituted diamondoids from the first in the series are preferred, bearing one to four independently selected alkyl or alkoxy substituents.

[0025] Diamondoids encompass "lower diamondoids" and "higher diamondoids," as those terms are defined herein, as well as mixtures of any combination of lower and higher diamondoids. The term "lower diamondoids" refers to adamantane, diamantane, and triamantane, and any and / or all unsubstituted and substituted derivatives of adamantane, diamantane, and triamantane. These lower diamondoid components do not exhibit isomerism or chirality, are easily synthesized, and are distinct from "higher diamondoids."

[0026] The term "higher diamondoid" 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 of the above, as well as isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane, and octamantane.

[0027] The chemistry of adamantane is 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 diamondoid series and may be thought of as a single-cage crystalline subunit. Diamantane contains two subunits, triamantane three, tetramantane four, and so on. While adamantane, diamantane, and triamantane each have only one isomer, tetramantane has four different isomers (two of which represent enantiomeric pairs), i.e., four different possible ways of arranging the four adamantane subunits. The number of possible isomers increases nonlinearly with higher members of the diamondoid series, such as pentamantane, hexamantane, heptamantane, octamantane, etc.

[0028] Commercially available adamantane has been extensively studied. Research has focused on many areas, including thermodynamic stability, functionalization, and properties of adamantane-containing materials. For example, Schreiber et al., New J. Chem., 2014, 38, 28-41, describe the synthesis and application of functionalized diamondoids to form large-area SAMs on silver and gold surfaces. KT Narasimha et al., Nature Nanotechnology, 11, March 2016, pp. 267-273, describe how a monolayer of diamondoids significantly reduces the metal's work function, effectively imparting enhanced field emission properties to metal surfaces.

[0029] As used herein, an anchor group is a functional group by means of which a compound is adsorbed or attached onto the surface of a substrate or electrode by physisorption, chemisorption or by chemical reaction, which involves the transformation of a precursor of the anchor group in situ, for example on the surface of the substrate or electrode.

[0030] A spacer group in the sense of the present invention is a flexible chain between the dipole moiety and the anchor group, which creates a separation between these substructures and at the same time, due to its flexibility, improves the mobility of the dipole moiety after binding to the substrate. The spacer group may be branched or linear. A chiral spacer is branched and optically active and non-racemic.

[0031] In this specification, alkyl is linear or branched and has 1 to 15 C atoms, preferably linear, and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0032] In this specification, an alkoxy radical is linear or branched and contains 1 to 15 C atoms. It is preferably linear and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is therefore preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.

[0033] In this specification, the alkenyl radical is preferably an alkenyl radical having 2 to 15 carbon atoms, which is linear or branched and contains at least one C-C double bond. It is preferably linear and has 2 to 7 carbon 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 carbon atoms of the C-C double bond are substituted, the alkenyl radical may be in the form of an E and / or Z isomer (trans / cis). Generally, each E isomer is preferred. Of the alkenyl radicals, prop-2-enyl, but-2- and -3-enyl, and pent-3- and -4-enyl are especially preferred.

[0034] In the present specification, alkynyl is understood to mean an alkynyl radical having 2 to 15 C atoms, which is linear or branched and contains at least one C-C triple bond. 1- and 2-propynyl, and 1-, 2- and 3-butynyl are preferred.

[0035] In Formula I, preferred aryl groups are derived, for example, from the parent structures benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophenanthrene, fluorene, indene, and indane.

[0036] In formula I, preferred heteroaryl groups are, for example, 5-membered rings such as furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 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 , fused groups such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthymidazole, benzoxazole, naphthoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, 2H-chromene (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran) and coumarin (2H-chromen-2-one), or combinations of these groups.

[0037] 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 octahydro-4,7-methanoindane.

[0038] A preferred spacer group Sp is ring A of formula I 1 , A 2 , A 3 , A 4 or the formula Sp'-X', where X' is attached to B, In the formula, Sp' represents a straight-chain or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which may optionally be mono- or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH groups are, independently of one another, -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- may each be replaced by O and / or S atoms in such a way that they are not directly linked to one another; X' is -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’ represents -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R 0 , R 00 and R 000 each, independently of one another, represents H or alkyl having 1 to 12 C atoms, and Y X and Y X’ each independently represent H, F, Cl or CN. X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 0- or a single bond.

[0039] 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 given above. Particularly preferred groups -X'-Sp'- are -(CH2) p1 -, -O-(CH2) p1 -, -(CF2) p1 -, -O(CF2) p1 -, -OCO-(CH2) p1 - and -OC(O)O-(CH2) p1 -, where p1 has the meaning given above.

[0040] Particularly preferred radicals Sp are, for example, in each case linear, ethylene, propylene, butylene, pentylene, 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, ethenylene, propenylene and butenylene. Particularly preferred groups X' are -O- or a single bond.

[0041] The compounds of general formula I can be prepared by methods known per se, as described in the literature (for example in standard treatises such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), and under reaction conditions known and suitable for the reaction, as exemplified below, whereby variants known per se, but not mentioned in more detail here, can also be used.

[0042] If desired, the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into compounds of general formula I.

[0043] The synthesis of compounds of general formula I according to the invention is illustrated in illustrative terms in the examples. The starting materials are obtained from generally accessible literature procedures or are commercially available.

[0044] A compound of formula I, wherein R 1 , R 2 and R 3 Compounds of formula I, in which R represents H (formula Ib), 1 represents alkyl and R 2 and R 3 represents H (formula Ia), the process according to the invention comprises the following steps, as shown in Scheme 1: a) reaction of a phosphonochloridate salt of formula II with an O-(trialkylsilyl)hydroxylamine in the presence of a base to give an N-[(alkoxy)phosphoryl]hydroxylamine of formula Ia; and b) Ester cleavage of a compound of formula Ia using, for example, a trialkylsilyl halide, preferably trimethylsilyl bromide or trimethylsilyl iodide, to give a compound of formula Ib. 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.

[0045] Scheme 1: [ka]

[0046] In Scheme 1, R 11 represents a linear alkyl having 1 to 12 C atoms or a branched alkyl having 3 to 12 C atoms, and the remaining occurring radicals and parameters have the meanings defined above for formula I.

[0047] Phosphonochloridates II can be obtained from dialkylphosphonates III by known processes, for example, treatment with acid chlorides such as oxalyl chloride, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, dichlorotriphenylphosphorane or phosgene, optionally in the presence of a base such as pyridine, diazabicyclooctane, or triethylamine (Scheme 2). Dialkylphosphonates (III) can be prepared as described in WO 2018 / 007337 A2, WO 2019 / 238649 A2, WO 2020 / 225270 A2, WO 2020 / 225398 A2, WO 2021 / 078699 A2, WO 2021 / 078714 A2, and WO 2021 / 083934 A2.

[0048] Scheme 2: [ka] In the formula, R 11represents a linear alkyl having 1 to 12 C atoms or a branched alkyl having 3 to 12 C atoms, and the remaining groups and parameters have the same meaning as in formula I.

[0049] Preferably, in formula I and its subformulas, the radical T is [ka] Highly preferably [ka] where R X represents alkyl having 1 to 6 carbon atoms, preferably methyl.

[0050] In another preferred embodiment, in formula I and its subformulae, the radical T represents a linear or branched alkyl having 1 to 12 carbon atoms, in which one or more CH groups are, independently of one another, -C≡C-, -CH=CH-, [ka] or by —O—, each in such a way that the O atoms are not directly linked to one another, and wherein one or more H atoms may be replaced by a halogen, preferably by F.

[0051] In a preferred embodiment, the compound of formula I is selected from the compounds of formulae Ia-1a to Ia-1d: [ka] In the formula, T, Z T , [ka] Z 1 , Z 2 , Sp, and R 1has the meaning given above for formula I, and r is 1 or 2, and s is 1 or 2, and preferably T is H, [ka] or represents a linear or branched alkyl or alkoxy having 1 to 7 C atoms, or a linear or branched alkenyl having 2 to 7 C atoms, preferably a linear or branched alkyl or alkoxy having 1 to 7 C atoms, Z T represents CH2O, OCH2, CH2CH2 or a single bond, preferably a single bond; Z 1 and Z 2 are the same or different and represent CH2O, OCH2, CH2CH2, CF2O, OCF2, C(O)O, OC(O) or a single bond, preferably a single bond; A 1 and A 2 are the same or different, [ka] represents Y 1 and Y 2 is the same or different in each occurrence and represents H, F or Cl, preferably H or F, and Sp represents a branched or unbranched 1,ω-alkylene having 1 to 12 C atoms, in which one or more non-adjacent CH groups may be replaced by O, and R 1 represents H.

[0052] Highly preferred are compounds of formula Ia-1b and Ia-1c, especially Ia-1c.

[0053] In another preferred embodiment, the compound of formula I is selected from the compounds of formula Ia-2: [ka] In that formula, the occurring groups and parameters have the meanings given above for formula I and preferably [ka] are the same or different, [ka] or [ka] represents [ka] teeth, [ka] represents 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 are the same or different and represent methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio; Z 3 represents CH2 or O, Z 1 and Z 4 represent, independently of one another, a single bond, -C(O)O-, -OC(O)-, -CF2O-, -OCF2-, -C2O-, OCH2- or -CH2CH2-, r and u are independently 0, 1 or 2, most preferably u is 0 and r is 0 or 1, and R 1 represents H.

[0054] In formula I and its subformulas, the group [ka] is preferably [ka] and most preferably [ka] Represents.

[0055] In a preferred embodiment, the compound of formula I is chiral. Molecular layers derived from chiral compounds of Formula I enable memronic devices with significantly reduced stochastic noise and faster switching, reducing read and write error rates, which has a positive effect on energy efficiency. In addition, increased tunneling currents are observed, allowing integration into smaller junction sizes.

[0056] Preferably, the chiral compounds have an enantiomeric excess (ee) of greater than 50%, preferably greater than 80%, 90%, or 95%, more preferably greater than 97%, especially greater than 98%.

[0057] Chirality is achieved by a branched chiral group Sp (hereinafter referred to as Sp*) of the above formula I, which has one or more, preferably one or two, and very preferably one, asymmetrically substituted carbon atoms (or asymmetric carbon atoms, C*), in which the asymmetric carbon atom is preferably linked to two differently substituted carbon atoms, a hydrogen atom, and a substituent selected from the group: halogen (preferably F, Cl, or Br), alkyl or alkoxy in each case having 1 to 5 carbon atoms, and CN.

[0058] The chiral organic radical Sp* preferably has the formula: [ka] In that formula 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, Q and Q' are the same or different and represent a single bond or an optionally fluorinated alkylene having 1 to 10 carbon atoms (in which the CH group not connected to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-), preferably an alkylene having 1 to 10 carbon atoms or a single bond, particularly preferably -(CH) n5 - or a single bond, n5 is 1, 2, 3, 4, 5, or 6, Y represents optionally fluorinated alkyl having 1 to 15 C atoms (in which one or two non-adjacent CH groups can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-), furthermore CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl.

[0059] Additionally, chirality is achieved by the chiral group T (hereinafter referred to as R*) of formula I above having one or more, preferably one or two, and very preferably one, asymmetrically substituted carbon atoms (or asymmetric carbon atoms, C*).

[0060] In R*, the asymmetric carbon atom is preferably linked to two differently substituted carbon atoms, a hydrogen atom and a substituent selected from the group: halogen (preferably F, Cl, or Br), alkyl or alkoxy in each case having 1 to 5 carbon atoms, and CN.

[0061] The chiral organic radical preferably has the formula: [ka] In that formula 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, Q represents a single bond or optionally fluorinated alkylene having 1 to 10 carbon atoms (in which the CH group not linked to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-), preferably alkylene having 1 to 5 carbon atoms or a single bond, particularly preferably -CH-, -CHCH- or a single bond, Y represents optionally fluorinated alkyl having 1 to 15 C atoms (in which one or two non-adjacent CH groups can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-), furthermore CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH3, -C2H5, -CF3 or Cl, R Chrepresents alkyl having 1 to 15 C atoms different from Y (in which one or two non-adjacent CH groups can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-), preferably linear alkyl having 1 to 10, in particular 1 to 7 carbon atoms (in which a CH group linked to an asymmetric carbon atom can also be replaced by -O-, -O-CO- or -CO-O-).

[0062] In the memory cell according to the invention, the first and / or 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 said materials, for example in the form of a multilayer system. The materials chosen for the first and second electrodes may be the same or different.

[0063] Suitable metals include Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, W, Pd, Pt, with Al, Cr and Ti being preferred. 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, with TiN being preferred.

[0064] 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.

[0065] Suitable elemental semiconductors include Si, Ge, C (diamond, graphite, graphene, fullerenes), α-Sn, B, Se, and Te. Suitable compound semiconductors include III-V semiconductors, in particular 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, and Hg (1-X) CD (X) Te, BeSe, BeTe X and HgS; and III-VI semiconductors, in particular GaS, GaSe, GaTe, InS, InSe X and InTe, I-III-VI semiconductors, particularly CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, IV-IV semiconductors, particularly SiC and SiGe, IV-VI semiconductors, particularly SeTe.

[0066] Suitable highly doped semiconductor materials include p+Si, n+Si. An example of a suitable layered conductive 2D material is graphene. Suitable semiconducting organic molecules include polythiophenes, tetracenes, pentacenes, phthalocyanines, PTCDA, MePTCDI, quinacridones, acridones, indanthrones, flavanthrones, perinones, AlQ3, and mixed systems, particularly PEDOT:PSS and polyvinylcarbazole / TLNQ complexes.

[0067] In a preferred embodiment, the first and second electrodes, the same or different, 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.

[0068] More preferably, the first and second electrodes comprise, preferably consist of, the same or different metal nitrides selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN and ZrN.

[0069] Specifically, the first electrode is made of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN, and the second electrode is made of TiN. Most specifically, the first and second electrodes are both made of TiN.

[0070] In another preferred embodiment, the first electrode on which a SAM is formed from the compound of Formula I comprises a material selected from the group consisting of TiN, TaN, Ta3N5, TaNx, TaON, Ta2O5, SiO2, ZrO2, HfO2, 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.

[0071] In the following description of exemplary embodiments of the present invention, identical or similar parts and elements are represented by identical or similar reference numerals, and repeated description of these parts or elements in individual instances is avoided. The figures only schematically depict the subject matter of the present invention.

[0072] 1A illustrates a nanoscale nonvolatile solid-state resistive device 100 having a molecular switching layer 103 according to one embodiment of the present invention. 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 may be other types of devices in other embodiments.

[0073] The molecular switching layer can be selectively set to various resistance values ​​by applying and resetting voltages to the electrodes using appropriate control circuitry. The resistance of device 100 varies depending on the orientation of the molecular dipoles in molecular switching layer 103. Device 100 is formed on an outer semiconductor substrate 101. The semiconductor substrate may be a silicon substrate or a III-V or II-VI type composite substrate. In one embodiment, the substrate is not made from a semiconductor material, but is made from, for example, plastic.

[0074] Particularly suitable substrates are selected from: ·Elemental semiconductors such as Si, Ge, C (diamond, graphite, graphene, fullerenes), α-Sn, B, Se and Te; Compound semiconductors, preferably - 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, BeTe X and HgS; - III-VI semiconductors, especially GaS, GaSe, GaTe, InS, and InSe X and InTe, - I-III-VI semiconductors, in particular CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, - IV-IV semiconductors, in particular SiC and SiGe, - IV-VI semiconductors, especially SeTe; Organic semiconductors, in particular polythiophenes, tetracenes, pentacenes, phthalocyanines, PTCDA, MePTCDI, quinacridones, acridones, indanthrones, flavanthrones, perinones, AlQ3, and mixed systems, in particular PEDOT:PSS and polyvinylcarbazole / TLNQ complexes; Metals, especially Ta, Ti, Co, Mo, Pt, Ru, Au, Ag, Cu, Al, W and Mg; Conductive oxide materials, especially 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.

[0075] It is preferred to use crystalline silicon as the substrate 101, with silicon wafers having a (100) surface being particularly preferred. Silicon wafers with a (100) oriented surface are employed as conventional substrates in microelectronics and are available with high quality and a low rate of surface defects.

[0076] In a switching device according to the present invention, the molecules of formula I forming the molecular layer 103 are attached to the first electrode 102 by means of hydroxyaminophosphinic acid anchor groups as defined above in formula I.

[0077] The molecular layer may optionally be bonded to a relatively thin (preferably 0.5-5 nm thick) oxidative intermediate layer 105, such as TiO2, Al2O3, ZrO2, HfO2, or SiO2, located on the first electrode 102; thus, in this embodiment, the first electrode comprises a first layer comprising a material as defined in claim 1 and a second oxidative layer to which the molecular layer 103 is bonded (FIG. 1B). Thus, the first electrode 102 and intermediate layer 105 can operate as an alternative first electrode 102'.

[0078] The molecular layer of the present invention is a layer of an electrically insulating, non-conductive and non-semiconductive organic compound. The molecular layer is formed essentially from a precursor represented by formula I. Preferably, the precursor used to form the molecular layer consists of a compound represented by formula I.

[0079] The thickness of the molecular layer is preferably 10 nm or less, particularly preferably 5 nm or less, and very particularly preferably 3 nm or less. The molecular layer may consist of one, two, three or more molecular layers comprising the compound of formula I. The molecular layer employed in accordance with the present invention is preferably a molecular monolayer.

[0080] In one embodiment, the molecular layer is a self-assembled monolayer (SAM). The preparation of self-assembled monolayers is known to those skilled in the art and is reviewed, for example, in A. Ulman, Chem. Rev. 1996, 96, 1533-1554.

[0081] The coverage of the substrate is preferably 90% to 100%, particularly preferably 95% to 100%, very particularly preferably 98% to 100%. Preferably, the second electrode 104 is made of TiN.

[0082] In one embodiment, a first electrode 102, which in the embodiment of FIG. 1A is implemented in the form of a conductor track running perpendicular to the plane of the drawing, is arranged on a substrate 101.

[0083] The second electrode 104, which, like the first electrode 102, is in the form of a conductor track, is arranged on the side of the molecular layer 103 facing away from the substrate 101. However, the second electrode 104 is rotated by 90° relative to the first electrode 102, resulting in a cross-shaped arrangement. This arrangement is also called a crossbar array; here, an angle of 90° is chosen as an example, although arrangements in which the second electrode 104 and the first electrode 102 intersect at an angle other than a right angle are also conceivable. A switching device 100 formed from a layer system comprising, in this order, the second electrode 104, the molecular layer 103, and the first electrode 102 is arranged at each cross point between the second electrode 104 and the first electrode 102. In one embodiment, each switching device 100 is also assigned a diode.

[0084] The crossbar array allows each switching device 100 to be electrically addressed by applying a voltage between the corresponding first electrode 102 and second electrode 104 .

[0085] The production and structuring of the electrodes is carried out by means of processes known to those skilled in the art, which are explained in more detail below with reference to the examples.

[0086] The structures of the electrodes 102, 104 can be produced by means of structuring methods known to those skilled in the art of microelectronics. For example, lithographic methods can be used to produce the first electrode 102. In this case, a metal layer is applied to the substrate 101 by means of evaporation. The metal layer is then covered with a photoresist that is exposed to the structures to be produced. After resist application and, if necessary, baking, the unnecessary parts of the metal layer are removed, for example by wet chemical etching. The remaining resist is then removed, for example with a solvent.

[0087] Another possibility for the production of the electrodes 102, 104 is evaporation 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 part, and the metal is subsequently applied by evaporation. The metal vapor can deposit only on the areas of the part not covered by the mask to form the electrodes 102, 104.

[0088] Suitable and preferred processes for producing switching devices according to the present invention are disclosed in paragraphs

[0113] to

[0126] of EP 3813132 A1, which is incorporated by reference. The compounds according to the present invention can be used as described therein.

[0089] A substrate 101 is provided on which a plurality of devices 100 are defined. In this embodiment, the substrate is silicon (p-doped, resistivity <0.001 Ω cm -1 , prime grade). In a preferred embodiment, the silicon substrate includes a SiO2 layer that acts as an insulating layer and improves derivatization. In other embodiments, other semiconductor materials, such as III-V and II-VI type semiconductor compounds, may be used as the substrate. Device 100 may be formed as part of a front-end process or as part of a back-end process, depending on the implementation. Thus, substrate 101 may include one or more layers of material formed and patterned thereon when the substrate is provided for the process.

[0090] The first electrode is formed on the substrate 101 using any deposition process, such as, for example, chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), radiofrequency 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, or another deposition or growth process to form at least a top portion of the first electrode. The bottom electrode preferably comprises a material with a high voltage threshold for ion migration, and it can be blanketed or structured by photolithography or other advanced lithography processes known to those skilled in the art, for example, by nanoimprint lithography or dip pen lithography.

[0091] Optionally, the first electrode is treated with oxygen, argon, or nitrogen plasma, or UV / ozone to obtain a hydrophilic oxide surface with a high concentration of hydroxyl groups. It is clear that this type of oxide surface merely serves as a surface modification for possible derivatization via condensation reactions and does not represent a true insulating or intermediate layer. Due to its small thickness, on the order of 1 nm, a sufficiently large tunneling current can flow through this oxide surface.

[0092] The molecular layer 103 is formed on the first electrode 102 . The deposition of the molecular layer onto the first electrode can be carried out using pure material or from solution, preferably from solution. Suitable deposition methods and solvents are known to those skilled in the art, examples being spin coating or dip coating.

[0093] The molecules of the molecular layer are preferably attached to the first electrode by chemisorption or covalently, more preferably covalently, by known methods familiar to those skilled in the art, for example by condensation with hydroxyl groups located on the surface of the substrate.

[0094] In an alternative embodiment, the molecular layer 103 can also be connected to the first electrode not directly, but via a thin oxidative adhesion layer 105 made of a metal different from that of the first electrode (e.g., Al2O3, ZrO2) and deposited onto the first electrode using a deposition technique described above for the first electrode, preferably CVD.

[0095] Preferably, a molecular layer is directly grafted onto the first electrode 102 of titanium nitride by means of molecules of formula I in which the anchor group is a -P(O)(OH)(NHOH) group.

[0096] In a preferred embodiment, the device is annealed after deposition of the monolayer at a temperature above 20° C. and below 300° C., preferably above 50° C. and below 200° C., particularly preferably above 90° C. and below 150° C. The duration of the annealing is 1 to 48 hours, preferably 4 to 24 hours, particularly preferably 8 to 16 hours.

[0097] The first electrode 102 is patterned to obtain an electrode extending along a certain direction (for example, the horizontal direction). A plurality of first electrodes extending in parallel along the first direction are formed in this step. A patterned second electrode is formed on molecular layer 103 by a lift-off process using a known processing sequence involving lift-off photoresist, a patterning step, electrode deposition, and lift-off, or using photoresist. The second electrode 104 can be deposited by, for example, sputtering or atomic layer deposition, preferably by sputtering.

[0098] According to another aspect of the present invention, a plurality of cells are arranged in a three-dimensional array of cells. Thus, the array extends in two directions in a plane, which may be defined by the substrate on which the electronic device is formed, and may also extend in a vertical direction, perpendicular to this plane. The number of cells arranged in each of the two directions or dimensions of the plane can be extremely large, ranging from at least two to thousands, millions, or even billions of cells. For example, in a configuration with 1024 cells in the X direction and 1024 cells in the Y direction, a single two-dimensional cell layer contains 1,048,576 cells. Such a two-dimensional arrangement of cells, each located at the intersection of two orthogonal electrode lines, is known as a crossbar array.

[0099] The number of levels or layers of cells arranged in a vertical or dimensional manner is typically smaller, ranging from 2 to at least 64, preferably up to at least 1024, or even greater. Preferably, the array contains at least 16 levels of cells, more preferably at least 32 levels of cells, and most preferably at least 64 levels of cells. Such a three-dimensional arrangement of cells is known as a 3D crossbar array or 3D crosspoint device.

[0100] example The present invention is further illustrated by the following non-limiting examples. Synthesis Example 1: P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidic acid Step 1: 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene [ka]

[0101] To a solution of 2,3-difluoro-4-(4-pentylcyclohexyl)phenol (5 g, 17 mmol) in 60 ml of dry DMF, potassium carbonate (3.6 g, 26 mmol) was added, 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 the addition of potassium iodide (0.2 g, 1 mmol). After stirring at room temperature for 18 hours, the mixture was filtered, and the filtrate was concentrated in vacuo. The residue was taken up in diethyl ether (100 ml), washed with brine (3×50 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, mp 47-48°C.

[0102]

number

[0103] Step 2: Diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonate [ka]

[0104] To a solution of diethyl phosphite (0.69 g, 0.64 mL, 5 mmol) in 80 mL of dry THF cooled to 0° C., sodium hydride (0.24 g, 6 mmol, 60% dispersion in oil) is added portionwise. This is 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 is added. The resulting mixture is then stirred at 66° C. for 4 hours. The reaction is quenched with a 1 M solution of HCl (100 mL), the organic phase is separated, and the aqueous phase is extracted with diethyl ether (3×30 mL). The organic phase is then dried over Na2SO4, filtered off, and the solvent is evaporated to give an oily residue, which is purified by column chromatography eluting with ethyl acetate to give diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonate as a yellowish oil.

[0105]

number

[0106] Step 3: Ethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonochloridate [ka]

[0107] 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 dry dichloromethane at room temperature, oxalyl chloride (200 mg, 1.6 mmol) is added dropwise. After the addition is complete, the mixture is stirred under reflux for an additional 4 hours. All volatiles are then removed in vacuo to give ethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonochloridate as a yellow oil.

[0108]

number

[0109] Step 4: Ethyl P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidate [ka]

[0110] A solution of ethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-phosphonochloridate (760 mg, 1.6 mmol) in 1 ml of dry dichloromethane is 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 h at room temperature, the volatiles are evaporated, ether (10 ml) is added, and the solid (EtNHCl) is filtered off. The filtrate is treated with methanol (3 ml) for 10 minutes to effect desilylation, which is then evaporated to dryness to give an oily residue, which is purified by column chromatography eluting with ethyl acetate to give ethyl P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidate.

[0111]

number

[0112] Step 5: P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidic acid [ka]

[0113] Bromotrimethylsilane (3.5 g, 3 mL, 22 mmol) was added to pure ethyl P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidate (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-hydroxyphosphonamidic acid as a solid.

[0114]

number

[0115] Applicable Test Comparative characterization of SAMs [ka]

[0116] Preparation of test chips: A test chip is prepared using acidic compound A (Synthesis Example 1) and for comparison with compound B from the state of the art by the following steps in this order: 1. Preparation of N-hydroxylamidophosphonic acid A and phosphonic acid B (reference values) solutions in THF (c = 1 mmol / l) 2. UV ozone treatment of test chips for 15 minutes: 1) 8x8mm p ++ Si (52 μm) / Al2O3 (2–3 nm, deposited by ALD), and 2) 8 × 8 mm p ++ Si (525 μm) / Ti (10 nm, sputtered) / TiN (30 nm, sputtered) 3. Immersion of Chip 1 or 2 in N-hydroxylamidophosphonic acid or phosphonic acid solution for 72 hours to obtain Chips 1A, 1B, 2A, and 2B 4. Drying in a stream of N2 gas 5. Baked in N2 atmosphere for 1 hour (T=120℃) 6. Cleaning with a short rinse in THF 7. Drying in a stream of N2 gas

[0117] Water Contact Angle (WCA) Measurement: [Table 1] The WCA for A is at approximately the same level as the reference compound B on Al2O3(1) as well as on TiN(2) substrates. Comparative current-voltage (IV) characteristics are recorded using standard settings, for example as described in EP 3481916 A1.

[0118] FIG. 2A shows the IV characteristics (200, absolute current density vs. voltage) of reference compound B on a TiN substrate (8 × 8 mm p++Si (525 μm) / Ti (10 nm, sputtered) / TiN (30 nm, sputtered) contacted by a Hg droplet with a diameter of approximately 160 mm. FIG. 2B shows the IV characteristics (300, absolute current density vs. voltage) of compound A according to the invention on a TiN substrate (8 × 8 mm p++Si (525 μm) / Ti (10 nm, sputtered) / TiN (30 nm, sputtered) contacted by a Hg droplet with a diameter of approximately 160 mm.

[0119] The upper curve 200 shows the results of four sweeps: 201, 202, 203, and 204. The lower curve 300 shows the results of four sweeps: 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). IV curve 300 shows significant hysteresis behavior, with the ratio between the high resistance state (HRS) and the low resistance state (LRS) being approximately one order of magnitude.

[0120] The following compounds can be obtained in the same manner as in Synthesis Example 1: [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4] [Table 2-5] [Table 2-6] [Table 2-7] [Table 2-8] [Table 2-9] [Table 2-10] [Table 2-11] [Table 2-12] [Table 2-13] [Table 2-14] [Table 2-15] [Table 2-16]

Table 2-17

Table 2-18

Table 2-19

Table 2-20

Table 2-21

Table 2-22

Table 2-23

Table 2-24

Table 2-25

Table 2-26

Table 2-27

Table 2-28

Table 2-29

Claims

1. A compound of formula I: 【Chemical 1】 In that formula T is the group: a) linear or branched alkyl or alkoxy having 1 to 20 C atoms each, with one or more CH 2 The groups are, independently of one another, -C≡C-, -CH=CH-, 【Chemistry 2】 -O-, -S-, -CF 2 O-, -OCF 2 -, -CO-O-, -O-CO-, -SiR 0 R 00 -, -NH-, -NR 0 -or- SO 2 - may each be replaced by - in such a way that the O atoms are not directly linked to each other, and wherein one or more H atoms are halogen, CN, SCN or SF 5 where R 0 and R 00 are identical or different and represent alkyl or alkoxy radicals having 1 to 15 C atoms, in which, in addition, one or more H atoms may be replaced by halogen, b) a 3- to 10-membered saturated or partially unsaturated aliphatic ring containing at least one -CH 2 -groups are -O-, -S-, -S-, -S(O)-, and -SO 2 -, -NR x -or-N(O)R x or at least one -CH= group is replaced by -N=; c) Diamondoid radicals is selected from the group of radicals consisting of Z T , Z 1 , Z 2 , and Z 4 are the same or different in each occurrence and represent a single bond, CF 2 O-, OCF 2 -, -CF 2 S-, -SCF 2 -, -CH 2 O-, -OCH 2 -, -C(O)O-, -OC(O)-, C(O)S-, -SC(O)-, (CH 2 ) n1 -, -(CF 2 ) n2 -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CH=CH-, CF=CF-, -CF=CH-, -CH=CF-, -(CH 2 ) n3 O-, -O(CH 2 ) n4 represents -, -C≡C-, -O-, -S-, CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, and n1, n2, n3 and n4 may be the same or different and each represent 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; Z 3 -O-, -S-, -CH 2 -, -C(O)-, -CF 2 -, -CHF-, -C(R x ) 2 -, -S(O)- or -SO 2 - represents 【Chemistry 3】 are the same or different in each occurrence and represent an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also include fused rings, and which may be mono- or polysubstituted by Y; 【Chemistry 4】 represents an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also include fused rings, and which is C may be mono- or polysubstituted by Y may be the same or different in each occurrence and may be F, Cl, CN, SCN, SF 5 or a linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, 【Chemistry 5】 is the base 【Chemistry 6-1】 【Chemistry 6-2】 where the groups may be oriented in both directions, L 1 ~L 5 are the same or different and are H, F, Cl, Br, I, CN, SF 5 , CF 3 , OCF 3 , or OCHF 2 and the radicals L present in each group 1 ~L 5 At least one of them is not H, R L are identical or different in each occurrence and represent 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 in each occurrence, linear or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or cycloalkyl or alkylcycloalkyl, each having 3 to 12 C atoms, Sp represents a spacer group or a single bond; R 0 , R 00 , R x represents a linear or branched alkyl having 1 to 6 C atoms, R 1 represents H or linear or branched alkyl having 1 to 12 C atoms, R 2 and R 3 are the same or different and represent H or linear, branched or cyclic alkyl having 1 to 12 carbon atoms, r, s, t, u and v are the same or different and are 0, 1 or 2; where r+s+t+u+v is 0, 1, 2, 3 or 4; The compound.

2. R 2 and R 3 2. The compound of claim 1, wherein represents H.

3. 3. The compound according to claim 1 or 2, wherein the compound is selected from the compounds of formulae Ia-1a to Ia-1d: 【Chemistry 7】 In the formula, T, Z T , 【Chemistry 8】 Z 1 , Z 2 , Sp, and R 1 has the meaning according to claim 1, r is 1 or 2 and s is 1 or 2, The compound.

4. A compound according to any one of claims 1 to 3, T is H, 【Chemistry 9】 or linear or branched alkyl or alkoxy having 1 to 7 C atoms each, or linear or branched alkenyl having 2 to 7 C atoms each, Z T is CH 2 O, OCH 2 , C.H. 2 CH 2 , or a single bond, Z 1 and Z 2 are the same or different, CH 2 O, OCH 2 , C.H. 2 CH 2 , CF 2 O, OCF 2 , C(O)O, OC(O) or a single bond; 【Chemistry 10】 are the same or different, 【Chemistry 11-1】 or 【Chemistry 11-2】 represents Y 1 and Y 2 are the same or different in each occurrence and represent H, F or Cl; Sp is one or more non-adjacent CH 2 represents a branched or unbranched 1,ω-alkylene having 1 to 12 C atoms, the group of which may be replaced by O, R 1 represents H, and 【Chemistry 12】 has the meaning defined in claim 1, The compound.

5. 3. The compound according to claim 1 or 2, wherein the compound is selected from the compounds of formula Ia-2: 【Chemistry 13】 In the formula, T, Z T , 【Chemistry 14】 Z 1 , Z 3 , Z 4 , Sp, R1, r and u have the meanings set forth in claim 1; The compound.

6. 6. The compound of claim 5, 【Chemistry 15】 are the same or different, 【Chemistry 16-1】 or 【Chemistry 16-2】 represents A 3 -Z 3 teeth, 【Chemistry 17】 represents Z T is a single bond, -CH 2 O-, -OCH 2 -or-CH 2 CH 2 - represents Y 1 and Y 2 represents H, F or Cl, Y 3 and Y 4 represents methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio; Z 3 is CH 2 or O, Z 1 and Z 4 are, independently of each other, a single bond, -C(O)O-, -OC(O)-, or -CF 2 O-, -OCF 2 -, -CH 2 O-, OCH 2 -or-CH 2 CH 2 - represents r and u are independently 0, 1 or 2; The compound.

7. base 【Chemistry 18】 but, 【Chemistry 19】 The compound according to any one of claims 1 to 6, wherein

8. A process for the preparation of compounds of formula Ib, comprising the steps of: a) reaction of a phosphonochloridate salt of formula II with an O-(trialkylsilyl)hydroxylamine in the presence of a base to give an N-[(alkoxy)phosphoryl]hydroxylamine of formula Ia; and b) ester cleavage of a compound of formula Ia to give a compound of formula Ib; 【Chemistry 20】 where T, Z T , 【Chemical 21】 Z 1 , Z 2 , Z 3 , Z 4 , Sp, r, s, t, u and v have the meanings according to claim 1, and R 11 represents a linear alkyl having 1 to 12 C atoms or a branched alkyl having 3 to 12 C atoms, The process.

9. first electrode (102), a molecular layer (103) attached to the first electrode; and 2nd electrode (104) in this order, Here, the first and second electrodes (102, 104) may be the same or different, and are preferably made of Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, Ta 3 N 5 , TaNx, TaON, WN, WCN, VN, ZrN, Ta 2 O 5 , SiO 2 , ZrO 2 , HfO 2 , WO 3 , RuO 2 , Cu 2 O, TiO 2 , Co 2 O 3 and niobium-doped strontium titanate, the molecular layer (103) is essentially formed from one or more compounds of formula I according to any one of claims 1 to 7, The electronic switching device (100).

10. 10. The electronic switching device (100) of claim 9, wherein an intermediate layer (105) is disposed between the first electrode (102) and the molecular layer (103), the intermediate layer (105) comprising an oxidizable material, and the molecular layer (103) is bonded to the oxidizable material, and the first electrode (102) and the intermediate layer (105) are operable as a first electrode (102').

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

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

13. An electronic component comprising one or more switching devices (100) according to any one of claims 9 to 12.

14. 14. The electronic component of claim 13, comprising a number of switching devices (100), the first electrodes (102) and second electrodes (104) of the switching devices (100) forming a crossbar array.

15. 15. The electronic component of claim 13 or 14, wherein the switching device (100) is configured to change between a state having a high electrical resistance and a state having a low electrical resistance, wherein the quotient between the high and low electrical resistances is between 10 and 100,000.

16. 10. Use of a compound of formula I according to claim 1 for the fabrication of a self-assembled monolayer.

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