HYDROXYAMINOPHOSPHINIC ACID DERIVATIVES

Abstract

The present invention relates to hydroxyamino phosphinic acid derivatives of formula I

##STR00001##

in which the occurring groups and parameters have the meanings defined in claim 1, to a method for their preparation and to their use for the fabrication of self-assembled monolayers (SAM), in particular for the fabrication of switchable SAM for electronic devices. The invention further relates to electronic devices comprising said SAM, preferably in the field of organic electronics, in particular for use in memory, sensors, furthermore in organic light-emitting diodes (OLEDs), photovoltaics (OPVs), field-effect transistors (OFETs) and Josephson junctions, very particularly in memristive components such as memristive crossbar-arrays.

Claims

1. A compound of formula I ##STR00058## in which T is selected from the group of radicals consisting of the following groups: a) straight chain or branched alkyl or alkoxy each having 1 to 20 C atoms, where one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by CC, CHCH, ##STR00059## O, S, CF.sub.2O, OCF.sub.2, COO, OCO, SiR.sup.0R.sup.00, NH, NR.sup.0 or SO.sub.2 in such a way that O atoms are not linked directly to one another, and in which one or more H atoms may be replaced by halogen, CN, SCN or SF.sub.5, wherein R.sup.0 and R.sup.00, identically or differently, denote an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, one or more H atoms may be replaced by halogen, b) a three- to ten-membered saturated or partially unsaturated aliphatic ring, in which at least one CH.sub.2 group is replaced with O, S, S(O), SO.sub.2, NR.sup.x or N(O)R.sup.x, or in which at least one CH group is replaced with N, c) a diamondoid radical, Z.sup.T, Z.sup.1, Z.sup.2, and Z.sup.4, on each occurrence, identically or differently, denote a single bond, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CH.sub.2O, OCH.sub.2, C(O)O, OC(O), C(O)S, SC(O), (CH.sub.2).sub.n1, (CF.sub.2).sub.n2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CHCH, CFCF, CFCH, CHCF, (CH.sub.2).sub.n3O, O(CH.sub.2).sub.n4, CC, O, S, CHN, NCH, NN, NN(O), N(O)N or NCCN, wherein n1, n2, n3, n4, identically or differently, are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, Z.sup.3 denotes O, S, CH.sub.2, C(O), CF.sub.2, CHF, C(R.sup.x).sub.2, S(O) or SO.sub.2, ##STR00060## on each occurrence, identically or differently, denote an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain condensed rings and which may be mono- or polysubstituted by Y, ##STR00061## denotes an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain condensed rings and which may be mono- or polysubstituted by R.sup.C, Y on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, ##STR00062## denotes a group ##STR00063## ##STR00064## wherein the groups may be oriented in both directions, L.sup.1 to L.sup.5, identically or differently, denote H, F, Cl, Br, I, CN, SF.sub.5, CF.sub.3, OCF.sub.3, or OCHF.sub.2, where at least one of the present radicals L.sup.1 to L.sup.5 in the respective groups is not H, R.sup.L on each occurrence, identically or differently, denotes H, alkyl having 1 to 6 C atoms, alkenyl having 2 to 6 C atoms or alkoxy having 1 to 5 C atoms, R.sup.C on each occurrence, identically or differently, denotes straight-chain 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 denotes a spacer group or a single bond, R.sup.0, R.sup.00, R.sup.x denote straight-chain or branched alkyl having 1 to 6 C atoms, R.sup.1 denotes H or straight chain or branched alkyl having 1 to 12 C atoms, R.sup.2 and R.sup.3 identically or differently denote H or straight chain or branched or cyclic alkyl having 1 to 12 C atoms, r, s, t, u and v, identically or differently, are 0, 1 or 2, where r+s+t+u+v is 0, 1, 2, 3 or 4.

2. The compound according to claim 1, in which R.sup.2 and R.sup.3 denote H.

3. The compound according to claim 1, wherein the compound is selected from the compounds of the formulae Ia-1a to Ia-1d ##STR00065## in which T, Z.sup.T, ##STR00066## Z.sup.1, Z.sup.2, Sp, and R.sup.1 have the meanings given for formula I, r is 1 or 2, and s is 1 or 2.

4. The compound according to claim 1, wherein T denotes H, ##STR00067## or straight chain or branched alkyl or alkoxy each having 1 to 7 C atoms or straight chain or branched alkenyl having 2 to 7 C atoms, Z.sup.T denotes CH.sub.2O, OCH.sub.2, CH.sub.2CH.sub.2, or a single bond, Z.sup.1 and Z.sup.2, identically or differently, denote CH.sub.2O, OCH.sub.2, CH.sub.2CH.sub.2, CF.sub.2O, OCF.sub.2, C(O)O, OC(O) or a single bond, ##STR00068## identically or differently, denote ##STR00069## Y.sup.1 and Y.sup.2, on each occurrence, identically or differently, denote H, F of Cl, Sp denotes branched or unbranched 1,-alkylene having 1 to 12 C atoms, in which one or more non-adjacent CH.sub.2-groups may be replaced by O, R.sup.1 denotes H, and ##STR00070## has the meanings defined for formula I.

5. The compound according to claim 1, wherein the compound is selected from the compounds of the formula Ia-2 ##STR00071## in which T, Z.sup.T, ##STR00072## Z.sup.1, Z.sup.3, Z.sup.4, Sp, R.sup.1, r and u have the meanings given for formula I.

6. The compound according to claim 5, wherein ##STR00073## identically or differently, denote ##STR00074## A.sup.3-Z.sup.3 denotes ##STR00075## ##STR00076## Z.sup.T denotes a single bond, CH.sub.2O, OCH.sub.2 or CH.sub.2CH.sub.2, Y.sup.1 and Y.sup.2 denote H, F or Cl, Y.sup.3 and Y.sup.4 denote methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, Z.sup.3 denotes CH.sub.2 or O, Z.sup.1 and Z.sup.4, independently of one another, denote a single bond, C(O)O, OC(O), CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CH.sub.2CH.sub.2, r and u independently are 0, 1 or 2.

7. The compound according to claim 1, wherein the group ##STR00077## denotes ##STR00078##

8. A process for the preparation of a compound of formula Ib comprising the steps of a) reaction of a phosphonochloridate of formula II with an O-(trialkylsilyl)hydroxylamine in the presence of a base to give N-[(alkoxy)phosphoryl]hydroxylamines of formula Ia, and b) ester cleavage of the compound of formula Ia to give the compounds of the formula Ib ##STR00079## in which T is selected from the group of radicals consisting of the following groups: a) straight chain or branched alkyl or alkoxy each having 1 to 20 C atoms, where one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by CCCHCH, ##STR00080## O, S, CF.sub.2O, OCF.sub.2, COO, OCO, SiR.sup.0R.sup.00, NH, NR.sup.0 or SO.sub.2 in such a way that O atoms are not linked directly to one another, and in which one or more H atoms may be replaced by halogen, CN, SCN or SF.sub.5, wherein R.sup.0 and R.sup.00, identically or differently, denote an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, one or more H atoms may be replaced by halogen, b) a three- to ten-membered saturated or partially unsaturated aliphatic ring, in which at least one CH.sub.2 group is replaced with O, S, S(O), SO.sub.2, NR.sup.x or N(O)R.sup.x, or in which at least one CH group is replaced with N, c) a diamondoid radical, Z.sup.T, Z.sup.1, Z.sup.2, and Z.sup.4, on each occurrence, identically or differently, denote a single bond, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CH.sub.2O, OCH.sub.2, C(O)O, OC(O), C(O)S, SC(O), (CH.sub.2).sub.n1, (CF.sub.2).sub.n2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CHCH, CFCF, CFCH, CHCF, (CH.sub.2).sub.n3O, O(CH.sub.2).sub.n4, CC, O, S, CHN, NCH, NN, NN(O), N(O)N or NCCN, wherein n1, n2, n3, n4, identically or differently, are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, Z.sup.3 denotes O, S, CH.sub.2, C(O), CF.sub.2, CHF, C(R.sup.x).sub.2, S(O) or SO.sub.2, ##STR00081## on each occurrence, identically or differently, denote an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain condensed rings and which may be mono- or polysubstituted by Y, ##STR00082## denotes an aromatic or heteroaromatic ring having 5 to 25 ring atoms, which may also contain condensed rings and which may be mono- or polysubstituted by R.sup.C, Y on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, ##STR00083## denotes a group ##STR00084## wherein the groups may be oriented in both directions, L.sup.1 to L.sup.5, identically or differently, denote H, F, Cl, Br, I, CN, SF.sub.5, CF.sub.3, OCF.sub.3, or OCHF.sub.2, where at least one of the present radicals L.sup.1 to L.sup.5 in the respective groups is not H, R.sup.L on each occurrence, identically or differently, denotes H, alkyl having 1 to 6 C atoms, alkenyl having 2 to 6 C atoms or alkoxy having 1 to 5 C atoms, R.sup.C on each occurrence, identically or differently, denotes straight-chain 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 denotes a spacer group or a single bond, R.sup.0, R.sup.00, R.sup.x denote straight-chain or branched alkyl having 1 to 6 C atoms, r, s, t, u and v, identically or differently, are 0, 1 or 2, where r+s+t+u+v is 0, 1, 2, 3 or 4, and R.sup.11 denotes straight chain alkyl having 1 to 12 C atoms or branched alkyl having 3 to 12 C atoms.

9. An electronic switching device (100) which comprises, in this sequence, 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), identically or differently, preferably comprise a material selected from Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, Si, W, CrN, HfN, MoN, NbN, TiN, TaN, Ta.sub.3N.sub.5, TaNx, TaON, WN, WCN, VN, ZrN, Ta.sub.2O.sub.5, SiO.sub.2, ZrO.sub.2, HfO.sub.2, WO.sub.3, RuO.sub.2, Cu.sub.2O, TiO.sub.2, Co.sub.2O.sub.3, and niobium-doped strontium titanate, characterised in that the molecular layer (103) is essentially formed from one or more compounds of formula I according to claim 1.

10. Electronic switching device (100) according to claim 9, wherein an interlayer (105) is arranged between the first electrode (102) and the molecular layer (103), where the interlayer (105) comprises an oxidic material and where the molecular layer (103) is bonded to said oxidic material, and where the first electrode (102) and the interlayer (105) are operable as a first electrode (102).

11. Electronic switching device (100) according to claim 9, wherein the one or more compounds of the formula I are bonded to the first electrode (102) by chemisorption or covalently.

12. Electronic switching device (100) according to claim 9, wherein the molecular layer (103) is a molecular monolayer.

13. Electronic component comprising one or more switching devices (100) according to claim 9.

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

15. Electronic component according to claim 13, wherein the switching devices (100) are configured to change between a state having high electrical resistance and a state having low electrical resistance, where the quotient between high electrical resistance and low electrical resistance is between 10 and 100,000.

16. A method for the fabrication of a self-assembled monolayer, comprising achieving such a monolayer by a compound of formula I according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0056] FIG. 1A shows a schematic illustration of the layer structure of a first embodiment of the electronic switching device according to the invention.

[0057] FIG. 1B shows a schematic illustration of the layer structure of a second embodiment of the electronic switching device according to the invention.

[0058] FIG. 2A shows current-voltage curves of an electronic switching device fabricated using a compound of the state of the art.

[0059] FIG. 2B shows a current-voltage curve of an electronic switching device according to the invention fabricated using a compound of formula I.

[0060] The term diamondoid refers to substituted and unsubstituted cage compounds of the adamantane series including adamantane, diamantane, triamantane, tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, and the like, including all isomers and stereoisomers thereof.

[0061] The compounds have a diamondoid topology, which means their carbon atom arrangement is superimposable on a fragment of a face centered cubic diamond lattice. Substituted diamondoids from the first of the series are preferable with 1 to 4 independently-selected alkyl or alkoxy substituents. Diamondoids include lower diamondoids and higher diamondoids, as these 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 show no isomers or chirality and are readily synthesized, distinguishing them from higher diamondoids. The term higher diamondoids refers to any and/or all substituted and unsubstituted tetramantane components; to any and/or all substituted and unsubstituted pentamantane components; to any and/or all substituted and unsubstituted hexamantane components; to any and/or all substituted and unsubstituted heptamantane components; to any and/or all substituted and unsubstituted octamantane components; as well as mixtures of the above and isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane, and octamantane. Adamantane chemistry 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 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 there is only one isomeric form of adamantane, diamantane, and triamantane, there are four different isomers of tetramantane, (two of which represent an enantiomeric pair), i.e., four different possible ways or arranging the four adamantane subunits. The number of possible isomers increases non-linearly with each higher member of the diamondoid series, pentamantane, hexamantane, heptamantane, octamantane, etc. Adamantane, which is commercially available, has been studied extensively. The studies have been directed toward a number of areas, such as thermodynamic stability, functionalization, and the properties of adamantane-containing materials. For instance, Schreiber et al., New J. Chem., 2014, 38, 28-41 describes the synthesis and application of functionalized diamondoids to form large area SAMs on silver and gold surfaces. In K. T. Narasimha et al., Nature Nanotechnology 11, March 2016 page 267-273, monolayers of diamondoids are described to effectively confer enhanced field emission properties to metal surfaces due to a significant reduction of the work function of the metal.

[0062] As used herein, an anchor group is a functional group by means of which a compound is adsorbed onto or bonded to the surface of the substrate or electrode by physisorption, chemisorption or by chemical reaction. This chemical reaction includes the transformation of a precursor of an anchor group in situ, for example on the surface of a substrate or electrode.

[0063] A spacer group in the sense of the present invention is a flexible chain between dipolar moiety and anchor group which causes a separation between these sub-structures and, owing to its flexibility, at the same time improves the mobility of the dipolar moiety after bonding to a substrate.

[0064] The spacer group can be branched or straight chain. Chiral spacers are branched and optically active and non-racemic.

[0065] Herein, alkyl is straight-chain or branched and has 1 to 15 C atoms, is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.

[0066] Herein, an alkoxy radical is straight-chain or branched and contains 1 to 15 C atoms. It is preferably straight-chain and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.

[0067] Herein, an alkenyl radical is preferably an alkenyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one CC double bond. It is preferably straight-chain and has 2 to 7 C atoms. Accordingly, 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 the two C atoms of the CC double bond are substituted, the alkenyl radical can be in the form of E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred. Of the alkenyl radicals, prop-2-enyl, but-2- and -3-enyl, and pent-3- and -4-enyl are particularly preferred.

[0068] Herein alkynyl is taken to mean an alkynyl radical having 2 to 15 C atoms, which is straight-chain or branched and contains at least one CC triple bond. 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.

[0069] In the formula I, preferred aryl groups are derived, for example, from the parent structures benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophen-anthrene, fluorene, indene and indane.

[0070] In the formula I, preferred heteroaryl groups are, for example, five-membered rings, such as, for example, 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, six-membered rings, such as, for example, pyridine, pyri-dazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine, or condensed rings, such as, for example, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, benzoxazole, naphthoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothio-phene, dibenzothiophene, benzothiadiazothiophene, 2H-chromen (2H-1-benzopyran), 4H-chromene (4H-1-benzopyran) and coumarin (2H-chromen-2-one), or combinations of these groups.

[0071] In the 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.

[0072] Preferred spacer groups Sp are selected from the formula Sp-X in which X is bonded to a ring A.sup.1, A.sup.2, A.sup.3, A.sup.4 or B of formula I. [0073] in which [0074] Sp denotes straight-chain or branched alkylene having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or poly-substituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by O, S, NH, NR.sup.0, SiR.sup.00R.sup.000, CO, COO, OCO, OCOO, SCO, COS, NR.sup.0COO, OCONR.sup.0, NR.sup.0CONR.sup.0, CHCH or CC in such a way that 0 and/or S atoms are not linked directly to one another, [0075] X denotes O, S, CO, COO, OCO, OCOO, CONR.sup.0, NR.sup.00CO, NR.sup.00CONR.sup.00, OCH.sub.2, CH.sub.2O, SCH.sub.2, CH.sub.2S, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2, CHN, NCH, NN, CHCR.sup.00, CY.sup.xCY.sup.x, CC, CHCHCOO, OCOCHCH or a single bond, [0076] R.sup.0, R.sup.00 [0077] and R.sup.000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, and [0078] Y.sup.x and Y.sup.x each, independently of one another, denote H, F, C or CN. [0079] X is preferably O, S, CO, COO, OCO, OCOO, CONR.sup.0, NR.sup.0CO, NR.sup.0CONR.sup.0 or a single bond.

[0080] Preferred groups Sp are (CH.sub.2).sub.p1, (CF.sub.2).sub.p1, (CH.sub.2CH.sub.2O).sub.q1CH.sub.2CH.sub.2, (CF.sub.2CF.sub.2O).sub.q1CF.sub.2CF.sub.2, CH.sub.2CH.sub.2SCH.sub.2CH.sub.2, CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2 or (SiR.sup.00R.sup.000O).sub.p1, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R.sup.00 and R.sup.000 have the meanings indicated above.

[0081] Particularly preferred groups X-Sp- are (CH.sub.2).sub.p1, O(CH.sub.2).sub.p1, (CF.sub.2).sub.p1, O(CF.sub.2).sub.p1, OCO(CH.sub.2).sub.p1 and OC(O)O(CH.sub.2).sub.p1, in which p1 has the meaning indicated above.

[0082] Particularly preferred groups 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, ethenylene, propenylene and butenylene.

[0083] Particularly preferred groups X are O or a single bond.

[0084] The compounds of the general formula I can be prepared as illustrated below by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), and under reaction conditions which are known and suitable for the said reactions. Use can be made here of variants known per se which are not mentioned here in greater detail.

[0085] 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 the compounds of the general formula I.

[0086] The syntheses of compounds of the general formula I according to the invention are described in illustrative terms in the examples. The starting substances can be obtained by generally accessible literature procedures or are commercially available.

[0087] A process according to the invention for the preparation of a compound of formula I in which R.sup.1, R.sup.2 and R.sup.3 denote H (formula Ib) via the compound of formula I in which R.sup.1 denotes alkyl and R.sup.2 and R.sup.3 denote H (formula Ia) comprises the steps of [0088] a) reaction of a phosphonochloridate of formula II with an O-(trialkylsilyl)hydroxylamine in the presence of a base, to give N-[(alkoxy)phosphoryl]hydroxylamines of formula Ia, and [0089] b) ester cleavage of the compound of formula Ia for example with a trialkylsilylhalide, preferably trimethylsilylbromide or trimethylsilyliodide to give the compounds of the formula Ib; [0090] as shown in scheme 1. In step a) a preferred trialkylsilylhydroxylamine is O-(trimethylsilyl)hydroxylamine, and the base is preferably an amine, preferably a tertiary amine, very preferably triethylamine, ethyl diisopropylamine, or diazabicyclooctane.

##STR00010##

[0091] In scheme 1, R.sup.11 denotes straight chain alkyl having 1 to 12 C atoms or branched alkyl having 3 to 12 C atoms and the remaining groups and parameters occurring have the meanings defined above for formula I.

[0092] The phosphonochloridates II are obtainable from dialkyl phosphonates III by known processes, e.g., treatment with an acid chloride, for example with oxalyl chloride, thionyl chloride, phosphorous pentachloride, phosphorous oxychloride, dichlorotriphenyl-phosphorane or phosgene, optionally in the presence of a base, for example pyridine, diazabicyclooctane, or triethylamine. (scheme 2).

[0093] The 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.

##STR00011##

in which R denotes straight chain alkyl having 1 to 12 C atoms or branched alkyl having 3 to 12 C atoms, and the remaining groups and parameters have the same meanings as in scheme 1.

[0094] Preferably, in formula I and its sub-formulae, the radical T denotes

##STR00012##

very preferably

##STR00013##

in which R.sup.x denotes alkyl having 1 to 6 C atoms, preferably methyl.

[0095] In another preferred embodiment, in formula I and its sub-formulae the radical T denotes straight chain or branched alkyl having 1 to 12 C atoms, where one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by CC, CHCH,

##STR00014##

or O, in such a way that O atoms are not linked directly to one another, and in which one or more H atoms may be replaced by halogen, preferably by F.

[0096] In a preferred embodiment, the compounds of the formula I are selected from the compounds of the formulae Ia-1a to Ia-1d

##STR00015## [0097] in which T, Z.sup.T,

##STR00016##

Z.sup.1, Z.sup.2, Sp, and R.sup.1 have the meanings given above for formula I, and r is 1 or 2, and s is 1 or 2, and preferably [0098] T denotes H,

##STR00017##

or straight chain or branched alkyl or alkoxy each having 1 to 7 C atoms or straight chain or branched alkenyl having 2 to 7 C atoms, preferably straight chain alkyl or alkoxy each having 1 to 7 C atoms, [0099] Z.sup.T denotes CH.sub.2O, OCH.sub.2, CH.sub.2CH.sub.2, or a single bond, preferably a single bond Z.sup.1 and Z.sup.2, identically or differently, denote CH.sub.2O, OCH.sub.2, CH.sub.2CH.sub.2, CF.sub.2O, OCF.sub.2, C(O)O, OC(O) or a single bond, preferably a single bond, [0100] A.sup.1 and A.sup.2, identically or differently, denote

##STR00018## [0101] Y.sup.1 and Y.sup.2, on each occurrence, identically or differently, denote H, F of Cl, preferably H or F, and [0102] Sp denotes branched or unbranched 1,-alkylene having 1 to 12 C atoms, in which one or more non-adjacent CH.sub.2-groups may be replaced by O, and [0103] R.sup.1 denotes H.

[0104] Very preferred are the compounds of the formulae Ia-1b and Ia-1c, in particular Ia-1c.

[0105] In another preferred embodiment, the compounds of the formula I are selected from the compounds of the formula Ia-2

##STR00019##

in which the occurring groups and parameters have the meanings given above for formula I and preferably

##STR00020##

identically or differently, denote

##STR00021##

##STR00022##

denotes

##STR00023##

##STR00024## [0106] Z.sup.T denotes a single bond, CH.sub.2O, OCH.sub.2 or CH.sub.2CH.sub.2, [0107] Y.sup.1 and Y.sup.2 denote H, F or Cl, [0108] Y.sup.3 and Y.sup.4, identically or differently, denote methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, [0109] Z.sup.3 denotes CH.sub.2 or O, [0110] Z.sup.1 and Z.sup.4, independently of one another, denote a single bond, C(O)O, OC(O), CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CH.sub.2CH.sub.2, [0111] r and u independently are 0, 1 or 2, very preferably u is 0 and r is 0 or 1, and [0112] R.sup.1 denotes H.

[0113] In formula I and its sub-formulae, the group

##STR00025##

preferably denotes

##STR00026##

[0114] In a preferred embodiment, the compounds of the formula I are chiral.

[0115] The molecular layers obtained from chiral compounds of the formula I enable memristic devices with significantly further reduced stochastic noise and faster switching, reducing the read and write error rate, which has a positive effect on energy-efficiency. In addition, increased tunnel current are observed allowing for the integration to smaller junction sizes.

[0116] Preferably, the chiral compound has an enantiomeric excess (ee) of above 50%, preferably above 80%, 90%, or 95%, more preferably above 97%, in particular above 98%.

[0117] Chirality is achieved by a branched chiral group Sp of formula I above having one or more, preferably one or two, very preferably one, asymmetrically substituted carbon atom (or: asymmetric carbon atom, C*), hereinafter referred to as Sp*. In Sp* 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 with 1 to 5 carbon atoms in each case, and CN.

[0118] The chiral organic radical Sp* preferably has the formula in which

##STR00027## [0119] X has the meanings defined above and preferably denotes COO, OCO, OCOO, CO, O, S, CHCH, CHCHCOO or a single bond, more preferably COO, OCO, O or a single bond, very preferably O or a single bond, [0120] Q and Q identically or differently, denote a single bond or optionally fluorinated alkylene having 1 to 10 carbon atoms, in which a CH.sub.2 group not linked with X can also be replaced by O, CO, OCO, COO or CHCH, preferably alkylene having 1 to 10 carbon atoms or a single bond, particularly preferably (CH.sub.2).sub.n5 or a single bond, [0121] n5 is 1, 2, 3, 4, 5, or 6, [0122] Y denotes optionally fluorinated alkyl having 1 to 15 carbon atoms, in which one or two non-adjacent CH.sub.2 groups can also be replaced by O, CO, OCO, COO and/or CHCH, further CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, CN or C, particularly preferably CH.sub.3, C.sub.2H.sub.5, CF.sub.3 or C,

[0123] In addition, chirality is achieved by a chiral group T of formula I above having one or more, preferably one or two, very preferably one asymmetrically substituted carbon atom (or: asymmetric carbon atom, C*), hereinafter referred to as R*.

[0124] 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 with 1 to 5 carbon atoms in each case, and CN.

[0125] The chiral organic radical preferably has the formula in which

##STR00028## [0126] X has the meanings defined above for formula I and preferably denotes COO, OCO, OCOO, CO, O, S, CHCH, CHCHCOO or a single bond, more preferably COO, OCO, O, or a single bond, very preferably O or a single bond, [0127] Q denotes a single bond or optionally fluorinated alkylene having 1 to 10 carbon atoms, in which a CH.sub.2 group not linked with X can also be replaced by O, CO, OCO, COO or CHCH, preferably alkylene having 1 to 5 carbon atoms or a single bond, particularly preferably CH.sub.2, CH.sub.2CH.sub.2 or a single bond, [0128] Y denotes optionally fluorinated alkyl having 1 to 15 carbon atoms, in which one or two non-adjacent CH.sub.2 groups can also be replaced by O, CO, OCO, COO and/or CHCH, further CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, CN or C, particularly preferably CH.sub.3, C.sub.2H.sub.5, CF.sub.3 or C, [0129] R.sup.Ch denotes an alkyl group having 1 to 15 carbon atoms that is different from Y, in which one or two non-adjacent CH.sub.2 groups can also be replaced by O, CO, OCO, COO and/or CHCH, preferably denotes straight-chain alkyl having 1 to 10, in particular 1 to 7, carbon atoms, in which the CH.sub.2 group linked to the asymmetric carbon atom can be replaced by O, OCO or COO.

[0130] In the memory cell according to the invention, preferably, the first electrodes and/or second electrodes are made from a metal, a conductive alloy, a conductive ceramic, a semiconductor, a conductive oxidic material, conductive or semi conductive organic molecules or a layered conductive 2D material. The first and/or second electrode may comprise combinations of more than one of said materials, for example in form of a multi-layer system. The material of the first and the second electrode may be chosen identically or differently.

[0131] Suitable metals include Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, W, Pd, Pt, wherein Al, Cr and Ti are preferred.

[0132] Suitable conductive ceramic materials include CrN, HfN, MoN, NbN, TiO.sub.2, RuO.sub.2, VO.sub.2, NSTO (niobium-doped strontium titanate), TaN and TiN, WN, WCN, VN and ZrN, wherein TiN is preferred.

[0133] Suitable semiconductor materials include indium tin oxide (ITO), indium gallium oxide (IGO), InGa--ZnO (IGZO), aluminium-doped zinc oxide (AZO), tin-doped zinc oxide (TZO), fluorine-doped tin oxide (FTO) and antimony tin oxide.

[0134] Suitable element semiconductors include Si, Ge, C (diamond, graphite, graphene, fullerene), -Sn, B, Se and Te. Suitable compound semiconductors include group III-V semiconductors, in particular GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN, Al.sub.x Ga.sub.1-xAs and In.sub.xGa.sub.1-x Ni, group II-VI semiconductors, in particular ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg.sub.(1-x)Cd.sub.(x) Te, BeSe, BeTex and HgS; and group III-VI semiconductors, in particular GaS, GaSe, GaTe, InS, InSex and InTe, group I-III-VI semiconductors, in particular CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, group IV-IV semiconductors, in particular SiC and SiGe, group IV-VI semiconductors, in particular SeTe.

[0135] Suitable highly doped semiconductor materials include p+Si, n+Si.

[0136] An example of a suitable layered conductive 2D material is graphene.

[0137] Suitable semiconductive organic molecules include polythiophene, tetracene, pentacene, phthalocyanines, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flavanthrone, perinone, AlQ3, and mixed systems, in particular PEDOT:PSS and polyvinylcarbazole/TLNQ complexes.

[0138] 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, Ta.sub.3N.sub.5, TaNx, TaON, WN, WCN, VN, ZrN, Ta.sub.2O.sub.5, SiO.sub.2, ZrO.sub.2, HfO.sub.2, WO.sub.3, RuO.sub.2, Cu.sub.2O, TiO.sub.2, Co.sub.2O.sub.3, and niobium-doped strontium titanate.

[0139] More preferably, the first and second electrodes, identically or differently, comprise, preferably consist of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN and ZrN.

[0140] In particular, the first electrode consist of a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN, and the second electrode consists of TiN.

[0141] Very particularly, the first and the second electrode both consist of TiN.

[0142] In another preferred embodiment, the first electrode on which the SAM is formed from the compounds of the formula I comprises a material selected from the group consisting of TiN, Ta.sub.3N.sub.5, TaNx, TaON, Ta.sub.2O.sub.5, SiO.sub.2, ZrO.sub.2HfO.sub.2, WO.sub.3, RuO.sub.2, Cu.sub.2O, TiO.sub.2, Co.sub.2O.sub.3, 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.

[0143] In the following description of the illustrative embodiments of the invention, identical or similar components and elements are denoted by identical or similar reference numbers, where repeated description of these components or elements is avoided in individual cases. The figures only depict the subject-matter of the invention schematically.

[0144] FIG. 1A illustrates a nanoscale non-volatile solid state resistive device 100 having a molecular switching layer 103 according to an embodiment of the present invention. Device 100 is a two-terminal memory in the present 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 the present embodiment but may be other types of device in other embodiments. The molecular switching layer can be selectively set to various resistance values by applying a voltage to the electrodes and reset, using appropriate control circuitry. The resistance of the device 100 changes according to the orientation of the molecular dipoles of the molecular switching layer 103. Device 100 is formed over an outer semiconductor substrate 101. The semiconductor substrate may be a silicon substrate, or a compound substrate of a III-V or II-VI type. In an embodiment, the substrate is not made of semiconductor material, e.g., made of plastic.

[0145] Particularly suitable substrates are selected from: [0146] element semiconductors, such as Si, Ge, C (diamond, graphite, graphene, fullerene), -Sn, B, Se and Te; [0147] compound semiconductors, preferably [0148] group III-V semiconductors, in particular GaAs, GaP, InP, InSb, InAs, GaSb, GaN, TaN, TiN, MoN, WN, AlN, InN, Al.sub.xGa.sub.1-xAs and In.sub.xGa.sub.1-xNi, [0149] group II-VI semiconductors, in particular ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Hg.sub.(1-X)Cd.sub.(x)Te, BeSe, BeTex and HgS; [0150] group III-VI semiconductors, in particular GaS, GaSe, GaTe, InS, InSex and InTe, [0151] group I-III-VI semiconductors, in particular CuInSe.sub.2, CuInGaSe.sub.2, CuInS.sub.2 and CuInGaS.sub.2, [0152] group IV-IV semiconductors, in particular SiC and SiGe, [0153] group IV-VI semiconductors, in particular SeTe; [0154] organic semiconductors, in particular polythiophene, tetracene, pentacene, phthalocyanines, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flavanthrone, perinone, AlQ.sub.3, and mixed systems, in particular PEDOT:PSS and polyvinylcarbazole/TLNQ complexes; [0155] metals, in particular Ta, Ti, Co, Mo, Pt, Ru, Au, Ag, Cu, Al, W and Mg; [0156] conductive oxidic materials, in particular indium tin oxide (ITO), indium gallium oxide (IGO), InGa--ZnO (IGZO), aluminium-doped zinc oxide (AZO), tin-doped zinc oxide (TZO), fluorine-doped tin oxide (FTO) and antimony tin oxide.

[0157] Preference is given to the use of crystalline silicon as substrate 101, where silicon wafers having a (100) surface are particularly preferred. Silicon wafers whose surface is oriented at (100) are employed as conventional substrate in microelectronics and are available in high quality and with a low proportion of surface defects.

[0158] In the switching devices according to the invention, the molecules of formula I forming the molecular layer 103 are bonded to the first electrode 102 by means of the hydroxyaminophosphinic acid anchor group as defined above in formula I.

[0159] The molecular layer may optionally be bonded to a relatively thin (preferably 0.5-5 nm thick) oxidic interlayer 105, for example TiO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2, HfO.sub.2, or SiO.sub.2, which is located on the first electrode 102, thus in this embodiment, the first electrode comprises a first layer comprising the material defined in claim 1 and a second oxidic layer to which the molecular layer 103 is bonded (FIG. 1B). Hence, first electrode 102 and interlayer 105 are operable as an alternative first electrode 102.

[0160] The molecular layer of the present invention is a layer of electrically insulating, non-conducting and non-semiconducting organic compounds.

[0161] The molecular layer is essentially formed from precursors of the formula I.

[0162] Preferably, the precursors used for the formation of the molecular layer consist of compounds of the formula I.

[0163] 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.

[0164] The molecular layer may consist of one, two, three or more molecule layers comprising compounds of the formula I.

[0165] The molecular layer employed in accordance with the invention is preferably a molecular monolayer.

[0166] In an embodiment, the molecular layer is a self-assembled monolayer (SAM).

[0167] The production of self-assembled monolayers is known to the person skilled in the art; a review is given, for example, in A. Ulman, Chem. Rev. 1996, 96, 1533-1554.

[0168] The degree of coverage of the substrate is preferably 90% to 100%, particularly preferably 95% to 100%, very particularly preferably 98% to 100%.

[0169] Preferably, the second electrode 104 consists of TiN.

[0170] In an embodiment, first electrodes 102, which in the embodiment of FIG. 1A are implemented in the form of conductor tracks which run perpendicular to the drawing plane, are arranged on the substrate 101.

[0171] A 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, so that a cross-shaped arrangement arises. This arrangement is also called a crossbar array, where the 90 angle is selected here as an example and arrangements in which second electrodes 104 and first electrodes 102 cross at an angle deviating from the right angle are also conceivable. A switching device 100, which is formed from a layer system having, in this sequence, a second electrode 104, a molecular layer 103 and a first electrode 102, is arranged at each crossing point between a second electrode 104 and a first electrode 102. In an embodiment a diode is also assigned to each switching device 100.

[0172] The crossbar array enables each switching device 100 to be addressed electrically by applying a voltage between the corresponding first electrode 102 and second electrode 104.

[0173] The production and structuring of the electrodes is carried out by means of processes known to the person skilled in the art and is explained in greater detail below with reference to the working examples.

[0174] The structures of the electrodes 102, 104 can be produced by means of structuring methods known to the person skilled in the art from microelectronics. For example, a lithography method can be employed for the production of the first electrodes 102. In this, a metal layer is applied to the substrate 101 by means of vapour deposition. The metal layer is subsequently coated with a photoresist, which is exposed with the structures to be produced. After development and, where necessary, baking of the resist, the parts of the metal layer that are not required are removed, for example, by wet-chemical etching. The remaining resist is subsequently removed, for example using a solvent.

[0175] A further possibility for the production of the electrodes 102, 104 is vapour 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 a metal is subsequently applied by vapour deposition. The metal vapour is only able to precipitate and form the electrode 102, 104 on the component in the areas not covered by the mask.

[0176] Suitable and preferred processes for the fabrication of the switching device according to the invention are published in EP 3 813 132 A1, paragraph [0113] to [0126], which is incorporated by reference. The compounds according to the invention can be used as described therein.

[0177] A substrate 101 whereon a plurality of devices 100 is to be defined is provided. The substrate is silicon (p doped, resistivity <0.001 cm.sup.1, prime grade) in the present embodiment. In a preferred embodiment, the silicon substrate comprises a SiO.sub.2 layer which serves as an isolating 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 a back-end process depending on implementation. Accordingly, substrate 101 may include one or more layers of material formed and patterned thereon when the substrate is provided for the present process.

[0178] A first electrode is formed over substrate 101 using any deposition process, such as, for example, 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 misted chemical deposition (LSMCD), and/or sputtering, or another deposition or growth process to form at least a top portion of the first electrode. The bottom electrode preferably should comprise a material having a high voltage threshold for ion migration, and it can be blanket or structured by photolithography or other advanced lithography processes known to a person skilled in the art, e.g. nano-imprint lithography or dip-pen lithography.

[0179] Optionally, the first electrode is treated with oxygen, argon or nitrogen plasma or UV/ozone in order to obtain a hydrophilic oxidic surface which is populated with hydroxyl groups. It is clear that an oxidic surface of this type merely serves for surface modification with the aim of possible derivatisation via condensation reactions and does not represent an insulator layer or interlayer in the true sense. Sufficiently large tunnel currents through this oxidic surface are possible owing to the low thickness in the order of 1 nm.

[0180] A molecular layer 103 is formed over the first electrode 102.

[0181] The deposition of the molecular layer onto the first electrode is carried out with the pure substance or from solution, preferably from solution. Suitable deposition methods and solvents are known to the person skilled in the art; examples are spin coating or dip coating.

[0182] The molecules of the molecular layer are preferably bonded to the first electrode by chemisorption or covalently, more preferably covalently. The bonding is carried out by known methods which are familiar to the person skilled in the art, for example by condensation with hydroxyl groups located on the surface of the substrate.

[0183] In an alternative embodiment, the molecular layer 103 can also be linked to a first electrode not directly but via a thin oxidic adhesion layer 105 derived from a metal different from that of the first electrode (e.g. Al.sub.2O.sub.3, ZrO.sub.2) and which is deposited onto the first electrode using the deposition techniques mentioned above for the first electrode, preferably CVD.

[0184] Preferred is grafting of a molecular layer directly onto a titanium nitride first electrode 102 by means of molecules of formula I in which the anchor group is a group P(O)(OH)(NHOH).

[0185] In a preferred embodiment, the device is annealed after deposition of the monolayer. The annealing is carried out at a temperature of greater than 20 C. and less than 300 C., preferably at greater than 50 C. and less than 200 C., particularly preferably at greater than 90 C. and less than 150 C. The time duration of the annealing is 1 to 48 h, preferably 4 to 24 h, particularly preferably 8 to 16 h.

[0186] The first electrode 102 is patterned to obtain an electrode extending along a direction (e.g., horizontal direction). A plurality of first electrodes extending along the first direction in parallel is formed at this step.

[0187] Patterned second electrodes are formed on the molecular layer 103 by a lift-off process using a known processing sequence including a lift-off photoresist, patterning step, electrode deposition, and lift off, or using a photoresist.

[0188] The second electrode 104 can be deposited, e.g., by sputtering or atomic layer deposition, preferably by sputtering.

[0189] According to another aspect of the present invention, a plurality of cells is arranged in a three dimensional array of cells. Accordingly, the array extends in two directions of a plane, which may be defined by a substrate onto which the electronic element is formed and may also extend in a vertical direction perpendicular to this plane. A number of cells arranged in the each of the two directions or dimensions of the plane may be very high, ranging from at least two to several thousands, millions or even billions of cells. For example, in a configuration of 1024 cells in an x-direction and 1024 cells in a y-direction, a single two dimensional layer of cells comprises 1048576 cells. Such a two-dimensional arrangement of cells, wherein each of the cells is located at a crossing of two orthogonal electrode lines is known as crossbar array.

[0190] The number of levels or layers of cells arranged in the vertical direction or dimension is typically lower and ranges from 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 and most preferred at least 64 levels of cells. Such a three-dimensional arrangement of cells is known as a 3D crossbar array or 3D cross point device.

EXAMPLES

[0191] The present invention is illustrated in detail by the following non-restrictive working 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

##STR00029##

[0192] 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) is added and the resultant mixture is stirred at room temperature for 1 hour. Then 1,4-dibromobutane (7.3 g, 4.0 ml, 34 mmol) is added, followed by the addition of potassium iodide (0.2 g, 1 mmol). After 18 h of stirring at room temperature, the mixture is filtered off and the filtrate is concentrated in vacuo. The residue is taken up with diethyl ether (100 ml), washed with brine (350 ml), dried over sodium sulfate and concentrated under reduced pressure to give white solid which is suspended in cold n-pentane, filtered off and washed three times with cold pentane to give 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene as white solid, m.p. 47-48 C.

[0193] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.83 (dd, J=9.2, 2.3 Hz, 1H), 6.68 (dd, J=7.33, 1.9 Hz, 1H), 4.04 (t, J=5.7 Hz, 2H), 3.49 (t, J=6.1 Hz, 2H), 2.82 (tt, J=12.1, 2.9 Hz, 1H), 2.31 (q, J=5.9 Hz, 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, .sup.3J.sub.HH=7.3 Hz, 3H) .sup.13C NMR (101 MHz, CDCl.sub.3): 149.0 (dd, J=245.1, 10.2 Hz), 145.6 (dd, J=8.2, 2.9 Hz), 141.0 (dd, J=246.9, 15.3 Hz), 128.2 (dd, J=12.5, 1.3 Hz), 120.3 (dd, J=5.7, 4.6 Hz), 109.2 (d, J=3.3 Hz), 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).

Step 2: Diethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphonate

##STR00030##

[0194] To a solution of diethyl phosphite (0.69 g, 0.64 ml, 5 mmol) in 80 ml of dry THE cooled to 0 C. sodium hydride (0.24 g, 6 mmol, 60% dispersion in oil) is added portionwise. It is stirred 30 min at 0 C. and then a solution of 1-(4-bromobutoxy)-2,3-difluoro-4-(4-pentylcyclohexyl)benzene (2 g, 5 mmol) in 5 ml of anhydrous THE is added. The resultant mixture is then stirred at 66 C. for 4 h. The reaction is quenched with 1 M solution of HCl (100 ml), organic phase is separated and water phase is extracted with diethyl ether (330 ml). Organic phase is then dried over Na.sub.2SO.sub.4, 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.

[0195] .sup.1H NMR (401 MHz, CDCl.sub.3): 6.81 (t, J=8.2 Hz, 1H), 6.63 (t, J=8.1 Hz, 1H), 4.15-4.02 (m, 4H), 4.01 (dd, J=11.7, 5.9 Hz, 2H), 2.70 (tt, J=12.1, 1.1 Hz, 1H), 1.85 (dt, J=21.4, 11.1 Hz, 9H), 1.50-1.11 (m, 16H), 1.05 (dd, J=17.1, 6.4 Hz, 2H), 0.87 (t, J=6.7 Hz, 3H); .sup.19F NMR (377 MHz, CDCl.sub.3): -143.15 (dd, J=19.6, 7.4 Hz, 1F), 159.47 (ddd, J=19.6, 7.6, 2.1 Hz, 1F); .sup.31P NMR (162 MHz, CDCl.sub.3): 32.42 (s, 1P).

Step 3: Ethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)phosphono-chloridate

##STR00031##

[0196] Oxalyl chloride (200 mg, 1.6 mmol) is 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 dry dichloromethane at room temperature. When addition is complete, the mixture is stirred for another 4 h under reflux. Afterwards all volatiles are removed in vacuo to give ethyl (4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-phosphonochloridate as a yellow oil.

[0197] .sup.1H NMR (401 MHz, CDCl.sub.3): 6.83 (td, J=8.3, 2.6 Hz, 1H), 6.64 (td, J=7.7, 1.9 Hz, 1H), 4.37-4.27 (m, 1H), 4.27-4.18 (m, 1H), 4.03 (t, J=5.4 Hz, 2H), 2.80-2.66 (m, 1H), 2.23 (dt, J=15.1, 6.5 Hz, 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=6.6 Hz, 3H); .sup.19F NMR (377 MHz, CDCl.sub.3): 143.15 (dd, J=19.6, 7.4 Hz, 1F), 159.47 (dd, J=19.6, 7.6, 1F); .sup.31P NMR (162 MHz, CDCl.sub.3): 44.62 (s, 1P)

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

##STR00032##

[0198] 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 at 0 C. 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). After further 5 h at room temperature, volatile matter is evaporated, ether (10 ml) is added and the solid (Et.sub.3NHCl) is filtered off. The filtrate is treated with methanol (3 ml) for 10 min to effect desilylation and is then evaporated to dryness to give an oily residue which is purified by column chromatography eluting with ethyl acetate to give the ethyl P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidate. 1H NMR (401 MHz, CDCl3): 6.82 (t, J=8.2 Hz, 1H), 6.62 (t, J=8.2 Hz, 1H), 4.16-4.10 (m, 4H), 3.90 (t, J=5.9 Hz, 2H), 2.71 (t, J=12.3 Hz, 1H), 1.76-1.96 (m, 4H), 1.48-1.32 (m, 9H), 1.26 (ddd, J=22.9, 13.6, 6.0 Hz, 4H), 1.04 (q, J=11.8 Hz, 2H), 0.88 (t, J=6.8 Hz, 3H); 19F NMR (377 MHz, CDCl3): 143.06 (d, J=19.6 Hz, 1F), 159.37 (d, J=20.2 Hz, 1F); 31P NMR (162 MHz, CDCl3): 26.91 (s, 1P)

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

##STR00033##

[0199] Bromotrimethylsilane (3.5 g, 3 ml, 22 mmol) is added to neat ethyl P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidate (0.33 g, 0.77 mmol)) under argon. The resulting solution is stirred at room temperature for 24 h. Volatile materials are removed in vacuo and the residue is treated with methanol (2 ml). After stirring for 12 h at room temperature the solvent is evaporated under reduced pressure to give P-(4-(2,3-difluoro-4-(4-pentylcyclohexyl)phenoxy)butyl)-N-hydroxyphosphonamidic acid as a solid. 1H NMR (401 MHz, DMSO-d6): 10.36 (s, 3H), 6.81 (t, J=8.2 Hz, 1H), 6.63 (t, J=8.2 Hz, 1H), 3.99 (t, J=5.9 Hz, 2H), 2.71 (t, J=12.3 Hz, 1H), 1.76-1.96 (m, 4H), 1.48-1.32 (m, 9H), 1.26 (ddd, J=22.9, 13.6, 6.0 Hz, 4H), 1.04 (q, J=11.8 Hz, 2H), 0.88 (t, J=6.8 Hz, 3H); 19F NMR (377 MHz, DMSO-d6): 143.06 (d, J=19.6 Hz, 1F), 159.37 (d, J=20.2 Hz, 1F); 31P NMR (162 MHz, DMSO-d6): 26.91 (s, 1P); 13C NMR (101 MHz, DMSO-d6): 149.4 (dd, J=245.1, 10.2 Hz), 146.0 (dd, J=8.2, 2.9 Hz), 141.5 (dd, J=246.9, 15.3 Hz), 128.7 (dd, J=12.5, 1.3 Hz), 121.5 (dd, J=5.7 Hz, 4.6 Hz), 110.3 (d, J=2.0 Hz), 69.29 (s), 33.48 (s), 32.99 (s), 30.12 (s), 29.86 (s), 28.51 (d, J=135.8 Hz), 27.10 (s), 26.51 (s), 22.60 (s), 19.99 (s), 19.95 (s), 14.49 (s).

Application Tests

Comparative Characterization of SAMs

##STR00034##

Preparation of Test Chips

[0200] Test chips are prepared by the following steps in this order using the acids compound A (Synthesis Example 1) and for comparison with compound B from the state of the art: [0201] 1. Preparation of N-hydroxylamidophosphonic acid A and phosphonic acid B (as reference) solution in THE (c=1 mmol/l) [0202] 2. UV ozone treatment 15 min of test chips: 1) 88 mm p++Si (525 m)/Al.sub.2O.sub.3 (2-3 nm, deposited by ALD), and 2) 88 mm p++Si (525 m)/Ti (10 nm, sputtered)/TiN (30 nm, sputtered) [0203] 3. Immersion of chip 1 or 2 into N-hydroxylamidophosphonic or phosphonic acid solution for 72 h to give chips 1A, 1B, 2A and 2B [0204] 4. Drying in a stream of N.sub.2 gas [0205] 5. Bake (T=120 C.) in N.sub.2 atmosphere for 1 h [0206] 6. Cleaning by short rinsing with THE [0207] 7. Drying in a stream of N.sub.2 gas

Water Contact Angle (WCA) Measurement:

TABLE-US-00001 Test chip Compound WCA 1A A 105.3 1B B 104.7 2A A 115.0 2B B 115.8

[0208] The WCAs for A are at approx. on the same level as the reference compounds B on Al.sub.2O.sub.3 (1) as well as on TiN (2) substrates.

[0209] Comparative current-voltage (IV) characteristics are recorded using a standard setup as described for example in EP 3 481916 A1.

[0210] FIG. 2A shows the IV characteristics (200, absolute current density vs. voltage) of reference compound B on a TiN substrate (88 mm p++Si (525 m)/Ti (10 nm, sputtered)/TiN (30 nm, sputtered); contacted by a Hg droplet with ca. 160 mm diameter. FIG. 2B shows the IV characteristics (300, absolute current density vs. voltage) of compound A according to the invention on a TiN substrate (88 mm p++Si (525 m)/Ti (10 nm, sputtered)/TiN (30 nm, sputtered); contacted by a Hg droplet with ca. 160 mm diameter. The upper curves 200 show the result of four sweeps 201, 202, 203 and 204. The lower curves 300 show the result of four sweeps 301, 302, 303 and 304. The result indicates that N-hydroxyphosphonamide compound A is more stable against dielectric breakdown than the phosphonic acid compound B (1.5 V and 1.0 V, respectively). The IV curves 300 show a pronounced hysteretic behaviour with a high-resistive state (HRS) to low resistive state (LRS) ratio of about one order of magnitude.

[0211] In analogy to Synthesis Example 1 the following compounds are obtained:

##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039##

##STR00040## ##STR00041## ##STR00042## ##STR00043##

##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050##

##STR00051## ##STR00052## ##STR00053## ##STR00054##

##STR00055## ##STR00056## ##STR00057##