Electronic Switching Devices

Abstract

The present invention relates to electronic switching devices, in particular tunnel junctions, comprising organic molecular layers for use in memories, sensors, field effect transistors or Josephson junctions. More particularly, the present invention is encompassed in the field of random access non-volatile memristor memories (RRAMs). Another aspect of the present invention relates to compounds for use in molecular layers of formula I, in which the resulting radicals have the meanings defined in claim 1. The present invention further relates to the use of said molecular layers, as well as processes for the manufacture and operation of electronic switching elements and components based thereon.

Description

[Technical field]

[0001] The present invention relates to electronic switching devices, in particular tunnel junctions, comprising organic molecular layers for use in memories, sensors, field effect transistors or Josephson junctions. More particularly, the present invention is encompassed in the field of random access non-volatile memristor memories (RRAMs). Further aspects of the present invention relate to compounds for use in molecular layers, the use of the molecular layers, and processes for the manufacture and operation of electronic switching elements and components based thereon. [Background technology]

[0002] Tunnel junctions are used for many applications in the electronics industry, ranging from superconducting Josephson junctions to tunnel diodes. They require extremely thin dielectric materials as insulators. One of the most cost-effective ways to create such insulating layers with single-digit nanometer thicknesses is by using self-assembled monolayers (SAMs).

[0003] In computer technology there is a need for storage media which allow fast writing and reading access to the stored information. Solid-state or semiconductor memories allow a particularly fast and reliable storage medium to be achieved, since no moving parts are required. At present, use is mainly made of dynamic random access memories (DRAMs). DRAMs allow fast access to the stored information, but this means that this information must be regularly updated and that the stored information is lost if the power supply is switched off.

[0004] The prior art also discloses non-volatile semiconductor memories, such as flash memories or magnetoresistive random access memories (MRAMs), whose information is retained even after the power supply is switched off. The drawback of flash memories is that write access occurs relatively slowly and the memory cells of flash memories cannot be erased indefinitely. The lifespan of flash memories is usually limited to a maximum of one million read / writes. MRAMs can be used in a similar manner to DRAMs and have a long lifespan, but this type of memory has not been able to establish itself due to difficult manufacturing processes.

[0005] A further alternative is a memory based on a memristor. The term memristor is a contraction of "memory" and "resistor" and describes a component whose electrical resistance can be reproducibly changed between high and low electrical resistance. The respective state (high or low resistance) is retained even without the supply of voltage, meaning that non-volatile memory can be achieved by a memristor. Memristor crossbar arrays may be used in a variety of applications including non-volatile solid-state memory, programmable logic, signal processing, control systems, pattern recognition and other applications. The memristor crossbar array includes a number of row lines, a number of column lines that cross the row lines to form a number of junctions, and a number of resistive memory devices coupled between the row lines and the column lines at the junctions.

[0006] For example, WO 2012 / 127542 A1 and US 2014 / 008601 A1 disclose organic molecular memories having two electrodes and an active area arranged between the two electrodes. The active area has a molecular layer of an electrically conductive aromatic alkyne, the conductivity of which can be changed under the influence of an electric field. A similar component based on redox-active bipyridinium compounds is proposed in US 2005 / 0099209 A1.

[0007] Known memories based on a change in conductivity or resistance have the drawback that the free radical intermediates formed by passing an electric current through the molecules of the molecular layer are in principle susceptible to degradation processes, which have a detrimental effect on the lifetime of the component.

[0008] In WO 2018 / 007337 A2 an improved switching layer is described which utilizes a non-redox-active molecular layer comprising dipolar compounds linked to a substrate via an aliphatic spacer group, where the compounds are reversibly switched by application of an electric field which causes reorientation of the molecular dipoles and thus enables low and high resistance states depending on the respective orientation of the molecules.

[0009] To obtain electrically switchable tunnel junctions from organic compounds with structurally flexible dipoles, a molecular layer sandwiched between two conducting electrodes is required. The deposition of this molecular layer onto the electrodes is achieved either by spin-coating or by dip-coating from an organic solvent. The basic principle of the resulting memory device is described in WO 2016 / 110301 A1 and WO 2018 / 007337 A2.

[0010] Information storage devices based on electrically switchable tunnel barriers made from self-assembled bipolar monolayers are required to have long retention times of selected states, even at high temperatures, for example up to 85° C. Long retention times enable memory devices that require fewer refresh cycles. There remains a need in the art for devices with long retention times. Summary of the Invention

[0011] It is an object of the present invention to provide new compounds for the fabrication of improved electronic components comprising a molecular layer attached to a first electrode, suitable for example for use in memristor devices, which do not have the above mentioned drawbacks and in particular provide improvements with regard to improved retention times.

[0012] To achieve this goal, compounds of formula I are provided, [ka] During the ceremony U and V are the same or different and are CF, C-Cl, C-CF 3 , C-CN or N; L represents a linear, branched or cyclic alkyl or alkenyl having 1 to 8 C atoms, each of which may have one or more non-adjacent CH 2 each group may be independently replaced by -O- or -S-, and one or more H atoms may be replaced by F; T is selected from the group of radicals consisting of: a) linear or branched alkyl or alkoxy, each having 1 to 20 C atoms, where in these radicals one or more CH 2 The groups are, independently of one another, -C≡C-, -CH=CH, [ka] -O-, -S-, -CF 2 O-, -OCF 2 -, -CO-O-, -O-CO-, -SiR 0 R 00 -, -NH-, -NR 0 -OR-SO 2 - may be substituted with each other such that the O atoms are not directly linked to each other, and where one or more H atoms are halogen, CN, SCN or SF 5 may be replaced by Here, R 0 , R 00 are identical or different and represent 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) at least one -CH 2- groups are -O-, -S-, -S(O)-, -SO 2 -, -NR x -or-N(O)R x or at least one -CH= group is replaced by -N=; x represents a linear or branched alkyl group having 1 to 6 carbon atoms, c) diamondoid radicals, preferably those derived from lower diamondoids, very preferably lower diamondoids selected from the group consisting of adamantyl, diamantyl and triamantyl, in which one or more H atoms may be replaced by F, in each case optionally fluorinated, alkyl, alkenyl or alkoxy having up to 12 C atoms, in particular [ka] Z T , Z 1 , Z 2 , and Z 4 are the same or different in each occurrence and are 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 ) n4represents -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, wherein n1, n2, n3 and n4 are the same or different and each represents 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 - [ka] which are identical or different in each occurrence and represent an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain 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 contain fused rings, and Y C may be mono- or polysubstituted by Y is the same or different in each occurrence and is F, Cl, CN, SCN, SF 5 or linear or branched, in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F or Cl, Y C has one of the meanings of Y or represents cycloalkyl or alkylcycloalkyl, each with 3 to 12 C atoms, preferably methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, methoxy or trifluoromethoxy, Sp represents a spacer group or a single bond; R 0 , R 00 , R x represents a linear or branched alkyl group having 1 to 6 C atoms, G is -OH, -SH, -SO 2 OH, -OP(O)(OH) 2 , -PO(OH) 2 , -C(OH)(PO(OH) 2 ) 2 , -COOH, -Si(OR x ) 3 , -SiCl 3 , -CH=CH 2 , -POCl 2 , -COH(PO(OH) 2 ) 2 , -CO(NHOH), -CO(NR 0 -OH), -Si(NMe 2 ) 3 or a straight-chain or branched alkyl having 1 to 12 C atoms, in which 1, 2 or 3 non-geminal H atoms are replaced by OH; or -OC(O)-OR V , -OC(O)-Si(OR x ) 3 , PO(OR V ) 2 , S.O. 2 OR V represents a group selected from R V represents a linear or branched alkyl having 1 to 12 C atoms, and r, s, t and u are the same or different and are 0, 1 or 2.

[0013] According to another aspect of the invention, in this order: A first electrode, a molecular layer coupled to the first electrode; and A second electrode, wherein the molecular layer is formed essentially of one or more, preferably one, of the compounds represented by formula I as defined above and below.

[0014] 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 defined above; iii. Application of a second electrode.

[0015] The invention furthermore relates to a method for operating an electronic component according to the invention, characterized in that a switching device of the electronic component is switched to a high electrical resistance state by setting a corresponding first electrode to a first potential and a corresponding second electrode to a second potential, where the value of the voltage between the two electrodes is greater than the first switching voltage and the first potential is greater than the second potential, and a switching device of the electronic component is switched to a low electrical resistance state by setting the corresponding first electrode to a third potential and the corresponding second electrode to a fourth potential, where the value of the voltage between the two electrodes is greater than the second switching voltage and the fourth potential is greater than the third potential and the value of the voltage between the corresponding electrodes is smaller than the first and second switching voltages, and determining the state of the switching device by applying a read voltage between the corresponding electrodes and measuring the current flowing.

[0016] According to another aspect of the invention, there is provided an electronic component, wherein the component is a memristor crossbar array comprising a number of switching devices according to the invention. The crossbar array can be integrated into a three-dimensional array of cells comprising a stack of two or more crossbar arrays. Such a configuration is known as a 3D crosspoint or 3D X-point memory device.

[0017] The present invention further relates to the use of a molecular layer obtained from one or more compounds as indicated in claim 1 in a memristor electronic component. The resulting devices can be used in memories, sensors, field effect transistors or Josephson junctions, preferably in resistive memory devices. The invention further relates to the use of the switching device in a memory, a sensor, a field effect transistor or a Josephson junction.

[0018] 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 especially in memristor components such as memristor crossbar arrays exhibiting the advantageous properties indicated above.

[0019] The compounds of formula I according to the invention enable switching devices that are distinguished by an order of magnitude improved retention compared to the state of the art. Tunnel junctions based on the SAM precursors of formula I above exhibit significantly higher current densities in their current-voltage characteristics, enabling faster read operations and higher integration densities.

[0020] The switching voltage of the switching device according to the invention is advantageously low. The switching device exhibits high reliability and durability. Furthermore, the memory window is advantageously large and is improved over devices known from the prior art.

[0021] The electrode materials that can be used in the device according to the invention are highly compatible with semiconductor industry device and fabrication processes, and are surprisingly well suited for the formation of stable, homogeneous molecular monolayers. [Brief description of the drawings]

[0022] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] Figure 1A shows a schematic diagram of the layer structure of a first embodiment of an electronic switching device, and Figure 1B shows a schematic diagram of the layer structure of a second embodiment of an electronic switching device according to the invention.

[0023] [Diagram 2] FIG. 2 shows the current-voltage curves of an electronic switching device according to the invention compared to a similar device made using state-of-the-art compounds. [Diagram 3] FIG. 3 shows the HRS and LRS decay of an electronic switching device according to the invention compared to a similar device made using state-of-the-art compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In claim 8, the expression "essentially formed from" is understood to mean that among the compounds used to form the molecular layer, certain further compounds may be present, i.e. those that do not significantly affect the essential properties of the molecular layer.

[0025] As used herein, the term "RRAM" or "resistive memory device" is understood to mean a memory device that uses a molecular switching layer whose resistance can be controlled by applying a voltage.

[0026] The low resistance state (LRS) or ON state of a resistive memory device is understood to mean a state in which the resistive memory device has a low electrical resistance. The high resistance state (HRS) or OFF state of a resistive memory device is understood to mean a state in which the resistive memory device has a high resistance.

[0027] A memory window is understood to mean an interval of resistance values ​​having a lower bound and an upper bound. A state having a resistance below the lower limit of this interval is considered an ON state. A state having a resistance value higher than the upper limit of this interval is considered an OFF state.

[0028] The term "diamondoid" refers to substituted and unsubstituted cage compounds of the adamantane series, such as adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, etc., including all isomers and stereoisomers thereof. The compounds have a "diamondoid" topology, meaning that the arrangement of their carbon atoms superimposes a fragment of a face-centered cubic diamond lattice. Substituted diamondoids from the first series preferably have from one to four independently selected alkyl or alkoxy substituents.

[0029] 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 any and / or all of adamantane, diamantane and triamantane, and unsubstituted and substituted derivatives of adamantane, diamantane and triamantane. These lower diamondoid components do not exhibit isomerism or chirality and are easily synthesized, distinguishing them from the "higher diamondoids." The term "higher diamondoids" refers to any and / or all of the substituted and unsubstituted tetramantane components; any and / or all of the substituted and unsubstituted pentamantane components; any and / or all of the substituted and unsubstituted hexamantane components; any and / or all of the substituted and unsubstituted heptamantane components; any and / or all of the substituted and unsubstituted octamantane components; and mixtures of the above, as well as isomers and stereoisomers of tetramantane, pentamantane, hexamantane, heptamantane, and octamantane. Adamantane chemistry is reviewed in "Adamantane: Consequences of the Diamondoid Structure", Chem.Rev. 64, pp., by Fort, Jr. et al. Adamantane is the smallest member of the diamondoid series and may be considered as a single cage crystal subunit. Diamantane contains two subunits, triamantane three, tetramantane four, and so on. While adamantane, diamantane, and triamantane have only one isomeric form, tetramantane has four different isomers (two of which represent enantiomeric pairs), i.e., four different possible ways or arrangements of the four adamantane subunits. The number of possible isomers increases non-linearly with each higher member of the diamondoid series, such as pentamantane, hexamantane, heptamantane, octamantane, etc.Commercially available adamantane has been extensively studied. Research has been directed in a number of areas, including thermodynamic stability, functionalization, and properties of adamantane-containing materials. As an 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 page 267-273, describe that monolayers of diamondoids effectively impart enhanced field emission properties to metal surfaces due to a significant reduction in the work function of the metal.

[0030] As used herein, an anchoring group is a functional group that allows a compound to adsorb or bind to the surface of a substrate or electrode by physisorption, chemisorption, or chemical reaction, including the conversion of a precursor of the anchoring group in situ, e.g., at the surface of the substrate or electrode.

[0031] In the sense of the present invention, a spacer group is a flexible chain between the dipolar moiety and the anchor group, which creates a distance between these moieties and at the same time, its flexibility improves the mobility of the dipolar moiety after binding to the substrate. The spacer group can be branched or linear. Chiral spacers are branched and optically active and non-racemic.

[0032] 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.

[0033] In the present 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.

[0034] In the present specification, an alkenyl radical is preferably an alkenyl radical having 2 to 15 C atoms, is linear or branched and contains at least one CC double bond. It is preferably linear and has 2 to 7 C atoms. It is therefore preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, 4-, -5- or -6-enyl. If two C atoms of the CC double bond are substituted, the alkenyl radical may be in the form of E and / or Z isomers (trans / cis). In general, the respective 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.

[0035] 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.

[0036] The compounds of general formula I are prepared in a manner known per se and under reaction conditions known and suitable for the reaction, as described in the literature (e.g. in standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart). A preferred synthesis route is similar to the synthesis of similar compounds 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. Use can be made here in the variants which are known and described in the literature and which are exemplified below by way of examples.

[0037] In formula I, preferred aryl groups are derived, for example, from the parent structures benzene, naphthalene, tetrahydronaphthalene, 9,10-dihydrophenanthrene, fluorene, indene and indane.

[0038] In formula I, preferred heteroaryl groups are 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, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine, or Examples of fused rings include 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.

[0039] 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.

[0040] Preferred spacer groups Sp are selected from the formula Sp'-X', such that the radical G-Sp- of formula I corresponds to the formula G-Sp'-X'-, During the ceremony, Sp' represents a straight-chain or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and in addition, which may contain one or more non-adjacent CH 2The 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 be substituted, respectively, such that the O and / or S atoms are not directly linked to each other; X' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 00 -,-NR 00 -CO-, -NR 00 -CO-NR 00 -, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-,-CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY x =CY x '-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; 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 of one another, represents H, F, Cl or CN, X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0-,-NR 0 -CO-, -NR 0 -CO-NR 0 - or a single bond.

[0041] A preferred group Sp' is -(CH 2 ) p1 -, -(CF 2 ) p1 -, -(CH 2 CH 2 O) q1 -CH 2 CH 2 -, -(CF 2 CF 2 O) q1 -CF 2 CF 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH 2 -NH-CH 2 CH 2 -or-(SiR 00 R 000 -O) p1 where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 00 and R 000 has the meaning indicated above.

[0042] Particularly preferred groups -X'-Sp'- are -(CH 2 ) p1 -, -O-(CH 2 ) p1 -, -(CF 2 ) p1 -,-O(CF 2 ) p1 -, -OCO-(CH 2 ) p1 - and -OC(O)O-(CH 2 ) p1 - where p1 has the meaning indicated above. Particularly preferred radicals Sp' are, for example, in each case linear 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.

[0043] An especially preferred group X' is --O-- or a single bond. In a preferred embodiment in formula I, the radical T is preferably [ka] represents Here, R x represents alkyl having 1 to 6 C atoms, preferably methyl.

[0044] In another preferred embodiment of the formula I, the radical T represents a linear or branched alkyl having 1 to 12 C atoms, in which one or more CH 2 The groups are independently -CC-, -CH=CH-, [ka] or -O-, each of which may be replaced by an --O-- such that the O atoms are not directly linked to each other, and one or more H atoms may be replaced by a halogen, preferably by F. In formula I and subformulas thereof, U and V preferably independently represent C-Cl or CF, most preferably CF.

[0045] In formula I and its subformulas, the radical L is preferably Me, Et, n-Pr, iPr, CF 3 , O.C.H. 3 , OCF 3 , S.C.H. 3 , SCF 3 , cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, more preferably Me, Et, or OCH 3 , in particular Me or Et.

[0046] In a preferred embodiment, the compound of formula I is selected from the compounds of formulae IA-1a to IA-1f, [ka] Here, T and Z T , [ka] , Z 1 , Z 2 , U, V, L, Sp and G have the meanings given above in formula I and preferably T is H, [ka] or linear or branched alkyl or alkoxy having 1 to 7 C atoms or linear or branched alkenyl having 2 to 7 C atoms, 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, and CH 2 O, OCH 2 , C.H. 2 CH 2 , C.F. 2 O, O.C.F. 2 , C(O)O, OC(O) or a single bond; A 1 and A2 are the same or different, [ka] represents Y 1 and Y 2 are identical or different and represent H, F or Cl, preferably H or F, Sp represents a branched or unbranched 1,ω-alkylene having 1 to 12 C atoms, where one or more non-adjacent CH 2 - group may be replaced by O, G is -OP(O)(OH) 2 , -PO(OH) 2 , -COH(PO(OH) 2 ) 2 OR-PO(OR V ) 2 represents R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms, and U, V, and L have the meanings given above for formula I.

[0047] In another preferred embodiment, the compound of formula I is selected from the compounds of formula IA-2: [ka] The groups and parameters occurring herein have the meanings given in formula I above and are preferably A 1 and A 4 are the same or different, [ka] represents A 3 -Z 3 teeth, [ka] represents; ZT is a single bond, -CH 2 O-, -OCH 2 -or-CH 2 CH 2 - represents L 1 and L 2 are the same or different, F, CF 3 or Cl, Y 1 and Y 2 are identical or different and represent H or have one of the meanings given above for Y and preferably represent H, F or Cl, Y 3 and Y 4 are the same or different, and Y 1 and Y 2 and preferably denotes methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, Z 3 is CH 2 or O, Z 1 , Z 4 are each independently 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 G is -OP(O)(OH) 2 , -PO(OH) 2 , -COH(PO(OH) 2 ) 2 OR-PO(OR V ) 2 represents R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms, and r and u are independently 0, 1 or 2.

[0048] According to another aspect of the invention, the molecular layer comprises one or more chiral non-racemic compounds selected from the compounds represented by formula I.

[0049] Molecular layers derived from the chiral compounds of formula I enable memristor devices to significantly reduce stochastic noise and switch faster, reducing the read and write error rate and having a definite effect on energy efficiency. In addition, an increase in tunneling current is observed, allowing integration into smaller junction sizes.

[0050] 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%.

[0051] Chirality can be achieved by one or more, preferably one or two, very preferably one asymmetrically substituted carbon atoms (or: asymmetric carbon atoms, C * ) having a branched chiral group Sp (hereinafter Sp * This is achieved by the Sp * In the formula (I), the asymmetric carbon atom is preferably linked to a substituent selected from the group of two differently substituted carbon atoms, a hydrogen atom, and halogen (preferably F, Cl, or Br), alkyl or alkoxy having in each case 1 to 5 carbon atoms, and CN.

[0052] Chiral organic radical Sp * is preferably of the formula [ka] wherein 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, where CH 2 The radicals may also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH=CH-, preferably having 1 to 10 carbon atoms or a single bond, particularly preferably (CH 2 ) n5 - or alkylene having a single bond, n5 is 1, 2, 3, 4, 5, or 6; Y represents an optionally fluorinated alkyl having 1 to 15 carbon atoms, where one or two non-adjacent CH 2 The radicals can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, further by CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH 3 , -C 2 H 5 , -CF 3 Or Cl.

[0053] In addition, chirality can be achieved by one or more, preferably one or two, very preferably one, asymmetrically substituted carbon atoms (or: asymmetric carbon atoms, C * ) of formula I above, * This is achieved by the

[0054] R *In the formula (I), the asymmetric carbon atom is preferably linked to a substituent selected from the group of two differently substituted carbon atoms, a hydrogen atom and halogen (preferably F, Cl, or Br), alkyl or alkoxy having in each case 1 to 5 carbon atoms, and CN.

[0055] The chiral organic radical is preferably of the formula [ka] wherein 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 is a single bond or an optionally fluorinated alkylene having 1 to 10 carbon atoms, where CH 2 The radicals may 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 2 -, -CH 2 CH 2 - or a single bond, Y represents an optionally fluorinated alkyl having 1 to 15 carbon atoms, where one or two non-adjacent CH 2 The radicals can also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, furthermore by CN or halogen, preferably optionally fluorinated alkyl or alkoxy having 1 to 7 C atoms, -CN or Cl, particularly preferably -CH 3 , -C 2 H 5 , -CF 3 Or Cl. R Ch represents an alkyl group having 1 to 15 carbon atoms different from Y, wherein one or two non-adjacent CH2 The group may also be replaced by -O-, -CO-, -O-CO-, -CO-O- and / or -CH=CH-, preferably representing a straight-chain alkyl having 1 to 10, in particular 1 to 7, carbon atoms, in which the CH 2 The groups may also be replaced by -O-, -O-CO- or -CO-O-.

[0056] Preferably, the first and / or second electrodes of each cell are made of metals, conductive alloys, conductive ceramics, semiconductors, conductive oxide materials, conductive or semiconductive organic molecules, or layered conductive two-dimensional materials. The first and / or second electrodes may comprise a combination of more than one of said materials, for example in the form of a multilayer system. The materials of the first and second electrodes may be selected to be the same or different.

[0057] Suitable metals include Ag, Al, Au, Co, Cr, Cu, Mo, Nb, Ni, Pt, Ru, W, Pd, Pt, where Al, Cr and Ti are preferred. Suitable conductive ceramic materials are CrN, HfN, MoN, NbN, TiO 2 , RuO 2 , V.O. 2 , NSTO (niobium doped strontium titanate), TaN and TiN, WN, WCN, VN and ZrN, with TiN being preferred.

[0058] 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.

[0059] 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, Alx Ga1-x As and Inx Ga1-x Ni, II-VI semiconductors, in particular ZnO, ZnS, ZnSe, ZnTe, CdS, CdTe, Hg(1-x) Cd(x)Te, BeSe, BeTex and HgS; and III-VI semiconductors, in particular GaS, GaSe, GaTe, InS, InSex and InTe, I-III-VI semiconductors, in particular CuInSe2, CuInGaSe2, CuInS2 and CuInGaS2, IV-IV semiconductors, in particular SiC and SiGe, IV-VI semiconductors, in particular SeTe.

[0060] Suitable highly doped semiconductor materials include p+Si, n+Si. One example of a suitable layered conductive two-dimensional material is graphene.

[0061] Suitable semiconducting organic molecules include polythiophenes, tetracene, pentacene, phthalocyanine, PTCDA, MePTCDI, quinacridone, acridone, indanthrone, flamenthrone, perinone, AlQ3, and mixed systems, particularly PEDOT:PSS and polyvinylcarbazole / TLNQ composites.

[0062] In a preferred embodiment, the first electrode and the second electrode are the same or different and 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, WN, WCN, VN and ZrN.

[0063] More preferably, the first electrode and the second electrode are the same or different and comprise, preferably consist of, a metal nitride selected from CrN, HfN, MoN, NbN, TiN, TaN, WN, tungsten carbide nitride (WCN), VN and ZrN.

[0064] In particular, 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 particularly, the first electrode and the second electrode both consist of TiN.

[0065] In the following description of exemplary embodiments of the present invention, identical or similar components and elements are represented by identical or similar reference numbers, and repeated description of these components or elements is avoided in individual cases. The figures only diagrammatically depict the subject matter of the present invention.

[0066] FIG. 1A illustrates a nanoscale nonvolatile solid-state resistance device 100 with a molecular switching layer 103 according to an embodiment of the present invention. The device 100 is a two-terminal memory in this embodiment. The device 100 includes a first electrode 102, a molecular switching layer 103, and a second electrode 104. The device 100 is a resistive memory device in this embodiment, but may be other types of devices in other embodiments. 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 value of the device 100 varies depending on the orientation of the molecular dipoles of the molecular switching layer 103. The 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 compound substrate. In one embodiment, the substrate is not made of a semiconductor material, but is made of, for example, plastic.

[0067] 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, InSe x and InTe, -I-III-VI semiconductors, especially CuInSe 2 , CuInGaSe 2 , CuInS 2 and CuInGaS 2 , -IV-IV semiconductors, especially SiC and SiGe, -IV-VI semiconductors, especially SeTe; - organic semiconductors, in particular polythiophenes, tetracene, pentacene, phthalocyanines, PTCDA, MePTCDI, quinacridones, acridones, indanthrones, flavanthrones, perinones, AlQ 3 , and mixed systems, especially PEDOT:PSS and polyvinylcarbazole / TLNQ complexes; - metals, in particular 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 zinc oxide (FTO), and antimony tin oxide.

[0068] The use of crystalline silicon as substrate 101 is preferred, whereby surface-textured silicon wafers (100) are particularly preferred. Surface-textured silicon wafers (100) are employed as conventional substrates in microelectronics and are available with high quality and a low percentage of surface defects.

[0069] In a switching device according to the invention, the molecules of the molecular layer 103 are attached to the first electrode 102 by anchor groups G as defined above.

[0070] A molecular layer is optionally disposed on the first electrode 102, e.g., TiO 2 , A l2 O 3 , ZrO 2 , HfO 2 , or SiO 2 and thus in this embodiment the first electrode comprises a first layer comprising the material 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 the intermediate layer 105 can act as an alternative first electrode 102'.

[0071] The molecular layers of the present invention are layers of electrically insulating, non-conductive, and non-semiconductive organic compounds. The molecular layer is essentially formed from a precursor of general formula I. Preferably, the precursor used to form the molecular layer consists of a compound represented by general formula I.

[0072] The thickness of the molecular layer is preferably less than or equal to 10 nm, particularly preferably less than or equal to 5 nm, very particularly preferably less than or equal to 3 nm. The molecular layer may consist of one, two, three or more molecular layers comprising the compound of formula I.

[0073] The molecular layers employed in accordance with the present invention are preferably molecular monolayers. In one embodiment, the molecular layer is a self-assembled monolayer (SAM).

[0074] The preparation of self-assembled monolayers is known to those skilled in the art; a review is given, for example, in A. Ulman, Chem. Rev. 1996, 96, 1533-1554. The degree of coverage of the substrate is preferably between 90% and 100%, particularly preferably between 95% and 100%, very particularly preferably between 98% and 100%.

[0075] Preferably, the second electrode 104 is made of TiN. In one embodiment, that of FIG. 1A, a first electrode 102 implemented in the form of a conductor track running perpendicular to the drawing plane is arranged on a substrate 101 .

[0076] Like the first electrode 102, the second electrode 104 in the form of a conductor track is arranged on the side of the molecular layer 103 facing outwards of the substrate 101. However, the second electrode 104 is rotated by 90° with respect to the first electrode 102, resulting in a cross-shaped arrangement. This arrangement is also called a crossbar array, where an angle of 90° is chosen here as an example, and arrangements in which the second electrode 104 and the first electrode 102 cross at an angle deviating from a right angle can also be envisaged. At each crossing point between the second electrode 104 and the first electrode 102, a switching device 100 is arranged, formed from a layer system having, in this order, the second electrode 104, the molecular layer 103 and the first electrode 102. In one embodiment, a diode is also assigned to each switching device 100.

[0077] 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 .

[0078] The manufacture and structuring of the electrodes is carried out by processes known to those skilled in the art and is explained in more detail below with reference to the examples.

[0079] The structures of the electrodes 102, 104 can be produced by structuring methods known to the person skilled in the art from microelectronics. For example, lithographic methods can be employed for the production of the first electrode 102. In this, a metal layer is applied to the substrate 101 by vapor deposition. This metal layer is then covered with a photoresist and exposed to the structure to be produced. After development and, if necessary, baking of the resist, the unnecessary parts of the metal layer are removed, for example by wet chemical etching. The remaining resist is then removed, for example using a solvent.

[0080] A further possibility for the manufacture of the electrodes 102, 104 is vapor deposition with the aid of a shadow mask. In this method, a mask with openings corresponding to the shape of the electrodes 102, 104 to be manufactured is placed on the part and the metal is subsequently applied by vapor deposition. The metal vapor is able to precipitate on the part only in the areas not covered by the mask and form the electrodes 102, 104.

[0081] Suitable and preferred processes for the fabrication of switching devices according to the invention are disclosed in EP 3813132, paragraphs

[0113] to

[0126] . The compounds according to the invention may be used as described therein.

[0082] A substrate 101 is provided on which a plurality of devices 100 are defined. The substrate, in this embodiment, is silicon (p-doped, resistivity <0.001 Ω cm -1 In a preferred embodiment, the silicon substrate is a SiO 2 substrate, which acts as an insulator layer and improves derivatization. 2 In other embodiments, other semiconductor materials, such as III-V and II-VI 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 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.

[0083] 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), radio frequency CVD (RFCVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular beam deposition (MBD), pulsed laser deposition (PLD), and / or liquid source mist chemical deposition (LSMCD), and / or sputtering, or another deposition or growth process that forms at least the top portion of the first electrode. The bottom electrode should preferably comprise 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, such as nanoimprint lithography or dip pen lithography.

[0084] Optionally, the first electrode is treated with oxygen, argon or nitrogen plasma or UV / ozone to obtain a hydrophilic oxidized surface with hydroxyl groups. It is clear that this type of oxidized surface serves merely for surface modification with a view to possible derivatization by condensation reactions, and does not represent a real insulating or intermediate layer. Sufficiently large tunneling currents through this oxidized surface are possible for thicknesses as small as 1 nm. On top of the first electrode 102, a molecular layer 103 is formed.

[0085] The deposition of the molecular layer on the first electrode is carried out either by pure substance or from solution, preferably from solution. Compilation Deposition methods and solvents are known to those skilled in the art, examples are spin coating or dip coating. In one embodiment, the anchor group G of the compounds forming the molecular layer, in particular of the compounds of formula I and its subformulas, is OH, [ka] -CH(CH 2 OH) 2, -COOH, and -OC(O)-OR 2 wherein R is selected from 2 stands for primary or secondary or tertiary alkyl having 1 to 6 C atoms, preferably tert-butyl, preferably the anchor group G is OH, [ka] -CH(CH 2 OH) 2 and -COOH, and wherein the molecular layer is formed in an ALD process as described in WO 2021 / 083934. According to another aspect of the invention, an ALD process is provided, wherein a first reactant in said ALD process has an associated fluorine atom, and wherein the anchor group G of the compounds that form the molecular layer, particularly compounds represented by formula I and its subformulas, is selected from the group consisting of -OSiR 3 , -COOSiR 3 , -CH(CH 2 OSiR 3 ) 2 , [ka] and -OC(O)-OSiR 3 is selected from wherein R, identical or different, in each occurrence, represents alkyl having 1 to 6 C atoms, preferably methyl, ethyl or isopropyl, very preferably methyl.

[0086] The molecules of the molecular layer are preferably attached to the first electrode by chemisorption or covalent bonding, more preferably by covalent bonding, by known methods familiar to those skilled in the art, for example by condensation with hydroxyl groups located on the surface of the substrate.

[0087] In an alternative embodiment, the molecular layer 103 may also be formed not directly from a metal different from that of the first electrode (e.g., Al 2 O 3 , ZrO 2) and which is deposited on the first electrode using the deposition techniques mentioned above for the first electrode, preferably CVD.

[0088] Preference is given to grafting a molecular layer directly onto the first electrode 102 of titanium nitride with molecules of formula I in which the anchor group G is a phosphonic acid group.

[0089] In a preferred embodiment, the device is annealed after deposition of the monolayer. The annealing is carried out 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 between 1 and 48 hours, preferably between 4 and 24 hours, particularly preferably between 8 and 16 hours.

[0090] In accordance with another aspect of the invention, a monolayer is fabricated from one or more compounds of formula I, wherein the anchor group G is -SO 2 OR V , OP(O)(OR V ) 2 , -PO(OR V ) 2 , C(OH)(PO(OR V ) 2 ) 2 , -COOR V Or Si(OR V ) 3 where R V denotes alkyl having 1 to 20 C atoms, preferably secondary or tertiary alkyl having up to 20 C atoms. These compounds are distinguished by particularly high solubility and are well suited to industrial processes such as spin-coating. In addition, it is possible to process these compounds by vapor deposition methods. The compounds act as precursors of the corresponding free acids and are obtained in situ by heat treatment of the compounds after deposition on the first electrode. The first electrode is then heated to a temperature between 60 ° C and 300 ° C, preferably between 100 ° C and 250 ° C, in particular between 140 ° C and 180 ° C.

[0091] The first electrode 102 is patterned to obtain electrodes extending along a direction (eg, horizontal direction). In this step, a plurality of first electrodes extending in parallel along the first direction are formed.

[0092] A patterned second electrode is formed on molecular layer 103 using a known processing sequence involving lift-off photoresist, a patterning step, electrode deposition, and lift-off, or by a lift-off process using photoresist.

[0093] The second electrode 104 may be deposited, for example, by sputtering or atomic layer deposition, preferably by sputtering.

[0094] According to another aspect of the invention, a plurality of cells are arranged in a three-dimensional array of cells. Thus, the array may extend in two directions in a plane, defined by the substrate on which the electronic device is formed, and in a vertical direction perpendicular to the plane. The number of cells arranged in each of the two directions or dimensions of the plane may be very high, ranging from at least two to thousands of cells, millions of cells, or even billions of cells. For example, in an arrangement of 1024 cells in the x direction and 1024 cells in the y direction, a single two-dimensional layer of cells contains 1048576 cells. Such a two-dimensional arrangement of cells, where each cell is located at the intersection of two orthogonal electrode lines, is known as a crossbar array.

[0095] The number of levels or layers of cells arranged in a vertical or dimensional fashion is typically less, ranging from 2 to at least 64, preferably at least 1024, or even higher. 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 array of cells is known as a 3D crossbar array or a 3D crosspoint device.

[0096] example Synthesis Example Example 1: 11-(4-cyclohexyl-2,3-difluoro-5-methyl-phenoxy)undecylphosphonic acid Step 1: 1-Benzyloxy-4-bromo-2,3-difluoro-5-methyl-benzene [ka] 1-Benzyloxy-2,3-difluoro-5-methyl-benzene (20.0 g, 85.38 mmol) is dissolved in acetonitrile (200 ml) under nitrogen. N-Bromosuccinimide (19.8 g) is added and the mixture is heated at reflux for 2 h. The reaction is cooled and then concentrated to dryness leaving a waxy solid. Heptane (200 ml) is added and the mixture is warmed to 40° C. then filtered, washing the retained solid with heptane. The filtrate is concentrated to dryness leaving a pale yellow waxy solid. The material is dissolved in heptane (5 vol) and filtered through silica eluting with heptane. The product containing fractions are combined and concentrated to dryness leaving an off-white solid which is recrystallized from isopropanol to give 1-benzyloxy-4-bromo-2,3-difluoro-5-methyl-benzene as a white solid; mp. 71-73° C.

[0097] 1 H NMR (400 MHz, CDCl 3 ) δ ppm 2.35 (3 H, m), 5.14 (2 H, s), 6.73 (1 H, dd, J=7.6, 1.8 Hz), 7.32 - 7.47 (5 H, m).

[0098] Step 2: 1-benzyloxy-4-(cyclohexen-1-yl)-2,3-difluoro-5-methyl-benzene [ka] 1-Benzyloxy-4-bromo-2,3-difluoro-5-methyl-benzene (11.7 g) is dissolved in THF (117 ml) and n-butyllithium (2.5 M, 16.4 ml) is added over 25 min at -74°C and the reaction mixture is stirred at <-70°C for 1 h. Cyclohexanone (4.6 ml) is added dropwise and allowed to warm to room temperature overnight. The solution is cooled to 0°C and quenched with water (20 ml). The reaction mixture is diluted with CH 2 Cl 2 (75 ml) and water (50 ml), 2 Cl 2 (2x50 ml). The combined organics are washed with water and then dried (MgSO 4 ), filtered and concentrated to dryness to leave a yellow oil. The crude oil was dissolved in CH 2 Cl 2 The mixture is purified on silica eluting with an increasing gradient of 0-100% CH. The product containing fractions are combined and concentrated to dryness to give a yellow solid which is not further purified. The crude cyclohexanol intermediate is dissolved in toluene (92 ml) and p-toluenesulfonic acid monohydrate (0.53 g, 10 mol%) is added. The mixture is heated at reflux for 90 min and concentrated to dryness to leave a brown oil. The material is purified by elution with 10% CH. 2 Cl 2 Dissolve in DCM / heptane (5 vol) and filter through silica, eluting with 20% DCM / heptane. Combine product containing fractions and concentrate to dryness to a nearly colorless oil (8.2 g) which slowly crystallizes on standing. Recrystallize the solid from methanol to give 1-benzyloxy-4-(cyclohexen-1-yl)-2,3-difluoro-5-methyl-benzene as a white solid; mp. 57-60°C.

[0099] 1 H NMR (400 MHz, CDCl 3) δ ppm 1.66 - 1.83 (4 H, m), 2.07 - 2.25 (7 H, m), 5.13 (2 H, s), 5.59 (1 H, m), 6.62 (1 H, dd, J=7.5, 1.5 Hz), 7.32 - 7.49 (5 H, m).

[0100] Step 3: 4-Cyclohexyl-2,3-difluoro-5-methyl-phenol [ka] A solution of 1-benzyloxy-4-(cyclohexen-1-yl)-2,3-difluoro-5-methyl-benzene (5.0 g) in methanol (100 ml) is added to 5% Pd / C (0.29 g, 0.50% wet, 5 wt%) and heated at 100 °C under 10 bar hydrogen pressure overnight. The reaction is cooled to room temperature, filtered and concentrated to dryness to give 4-cyclohexyl-2,3-difluoro-5-methyl-phenol as an off-white solid; mp. 71-74 °C. 1 H NMR (400 MHz, DMSO-d 6 )δ ppm 1.11~1.38(3H, m), 1.53~1.84(7H, m), 2.08~2.25(3H, s), 2.66(1H, t, J=11.4Hz), 6.54(1H, d, J=8.2Hz), 9.92(1H, s)

[0101] Step 4: 4-Cyclohexyl-1-(11-diethoxyphosphorylundecoxy)-2,3-difluoro-5-methyl-benzene [ka] 4-Cyclohexyl-2,3-difluoro-5-methyl-phenol (4.4 g) is dissolved in butanone (57 ml). Diethyl (11-bromodecyl)phosphonate (9.4 g, 1.30 eq) and sodium iodide (0.15 g, 5 mol%) are added, potassium carbonate (10.8 g, 4.0 eq) is added and the mixture is heated at reflux under nitrogen overnight. The reaction is cooled and filtered, washing the solid with acetone. The filtrate is concentrated to dryness and the raw material is eluted with CH. 2 Cl 2 and filtered through silica and washed with 10% ethyl acetate / CH 2 Cl 2 Filtration by eluting with (9 x 200 ml) gives 4-cyclohexyl-1-(11-diethoxyphosphorylundecoxy)-2,3-difluoro-5-methyl-benzene as a colourless oil. 1 H NMR (400 MHz, CDCl 3 ) δ ppm 1.20 - 1.49 (24 H, m), 1.50 - 1.89 (12 H, m), 2.25 (3 H, s), 2.67 (1 H, t, J=11.9 Hz), 3.97 (2 H, t, J=6.5 Hz), 4.00 - 4.17 (4 H, m), 6.49 (1 H, d, J=7.6 Hz).

[0102] Step 5: 11-(4-Cyclohexyl-2,3-difluoro-5-methyl-phenoxy)undecylphosphonic acid [ka] 4-Cyclohexyl-1-(11-diethoxyphosphorylundecoxy)-2,3-difluoro-5-methyl-benzene (7.0 g) is dissolved in dichloromethane (105 ml). Trimethylsilyl bromide (18 ml, 10.0 eq) is added and the solution is stirred at room temperature overnight. The reaction mixture is concentrated to dryness to a yellow oil, then methanol is added and concentrated to dryness again to a yellow oil. Methanol is added and stored at -20°C overnight. The solid is filtered, washed with cold methanol and dried. The crude product is recrystallized from dichloromethane and acetonitrile to give 11-(4-cyclohexyl-2,3-difluoro-5-methyl-phenoxy)undecylphosphonic acid as a white solid.

[0103] 1 H NMR (400 MHz, THF) δ ppm 1.23 - 1.52 (17 H, m), 1.53 - 1.92 (13 H, m combined with residual THF), 2.26 (3 H, s), 2.75 (1 H, t, J=11.9 Hz), 3.99 (2 H, t, J=6.5 Hz), 6.63 (1 H, d, J=7.7 Hz). 19 F NMR (376MHz, THF) δ ppm -165.69 (d, J=19.1Hz), -142.45 (d, J=19.1Hz). 31 P NMR (162 MHz, THF) δ ppm 30.66.

[0104] Analogously to the above synthesis, the following compounds are obtained: Compounds of formula IA-1a: [ka] [ka] [ka] [ka] [ka]

[0105] Compounds represented by formula IA-1b: [ka] [ka] [ka]

[0106] Compounds represented by formula IA-2 (wherein r=1 and u=0) [ka] [ka] [ka]

[0107] Device fabrication Test chips are prepared with compound A of Synthesis Example 1 and compound B known from the prior art, respectively: [ka]

[0108] Preparation of test chips A 45x45 mm silicon wafer with a 4 nm TiO top layer deposited by ALD is treated with ozone for 15 min and then immersed in a 1 mM solution of compound A or B in THF for 72 h. The chip is dried in a nitrogen stream and then tempered at 120° C. for 1 h. The chip is washed with THF and dried in a stream of nitrogen gas.

[0109] The water contact angle measurements give the following results: Compound A: 106.6° Compound B: 104.8°

[0110] Electrical characterization Silicon wafers A and B, obtained by treatment with compounds A or B, respectively, are glued to a copper plate that has been cleaned by immersion in 1M HCl with silver conductive paste. The silver conductive paste is annealed at 80° C. for 10 min under a flow of nitrogen. The sample is then introduced into a nitrogen glove box and contacted by a capillary of Hg at the bottom and top of the copper contact. For each measurement, a new Hg drop is produced. The size of the drop is measured by a camera system for the determination of the contact area.

[0111] Four cycles of current-voltage (IV) measurements between -3 and +3 V in 40 mV steps are performed per contact area. For retention measurements, half a cycle of IV measurements from 0 to 3 V and back to 0 V for a set operation (low resistance state, LRS) is performed. For reset, IV measurements from 0 to -3 V and back to 0 V are performed (high resistance state, HRS). After a certain time interval, a short constant voltage measurement at 1 V is performed. The results for both wafers are shown in FIG. 2. Curve 201 shows the results for wafer A made with compound A according to the invention. A higher current density is shown (curve 202) than for wafer B from the comparative compound.

[0112] For both wafers A and B, retention is determined at a voltage of 1 V. Figure 3 shows the current density versus time. Line 301 shows the change in current density over time for wafer A in the LRS. Line 302 shows the change in current density over time for wafer A in the HRS. Line 303 shows the change in current density over time for wafer B in the LRS. Line 304 shows the change in current density over time for wafer B in the HRS.

[0113] The retention of a device is defined as the intersection of the respective HRS and LRS trendlines. As a result, the retention of compound A is approximately 10,000 min (approximately one week), which is improved by three orders of magnitude compared to the unmethylated reference compound B, which has a retention of 10-15 min.

Claims

1. A compound of formula I, 【Chemistry 1】 During the ceremony, U and V are the same or different and are selected from CF, C-Cl, C-CF 3 , C-CN or N, L represents a linear, branched or cyclic alkyl or alkenyl, each having 1 to 8 C atoms, and one or more non-adjacent CH 2 the groups may each be replaced independently by -O- or -S-, and one or more H atoms may be replaced by F; T is selected from the group of radicals consisting of: a) linear or branched alkyl or alkoxy, each having 1 to 20 C atoms, where 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 - so 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 may be replaced by where R 0 , R 00 are identical or different and represent alkyl or alkoxy radicals having 1 to 15 C atoms, where, in addition, one or more H atoms may be replaced by halogen, b) at least one -CH 2 - group is -O-, -S-, -S(O)-, -SO 2 -, -NR x -or-N(O)R x a 3- to 10-membered saturated or partially unsaturated aliphatic ring, wherein R is replaced by - or at least one -CH= group is replaced by -N=; x represents a straight-chain or branched alkyl having 1 to 6 C atoms, c) diamondoid radicals; Z T , Z 1 , Z 2 , and Z 4 are the same or different in each occurrence and are 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 -, -C≡C-, -O-, -S-, -CH=N-, -N=CH-, -N=N-, -N=N(O)-, -N(O)=N- or -N=CC=N-, wherein n1, n2, n3, and n4 are the same or different and 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 【Transformation 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 contain 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 contain fused rings, and Y C may be mono- or polysubstituted by Y is the same or different in each occurrence and is F, Cl, CN, SCN, SF 5 or a linear or branched, in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, Y C has one of the meanings of Y or denotes 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 straight-chain or branched alkyl having 1 to 6 C atoms, G is -OH, -SH, -SO 2 OH, -OP(O)(OH) 2 , -PO(OH) 2 , -C(OH)(PO(OH) 2 ) 2 , -COOH, -Si(OR x ) 3 , -SiCl 3 , -CH=CH 2 , -POCl 2 , -COH(PO(OH) 2 ) 2 , -CO(NHOH), -CO(NR 0 -OH), -Si(NMe 2 ) 3 or a straight-chain or branched alkyl having 1 to 12 C atoms, in which one, two or three non-geminal H atoms are replaced by OH; or -OC(O)-OR V , -OC(O)-Si(OR x ) 3 , PO(OR V ) 2 , SO 2 OR V represents a group selected from R V represents a linear or branched alkyl having 1 to 12 C atoms, and The compound wherein r, s, t and u are the same or different and are 0, 1 or 2.

2. the compound is selected from the group consisting of formulas IA-1a to IA-1f, 【Transformation 5】 In the formula, T, Z T , 【Transformation 6】 Z 1 , Z 2 2. The compound according to claim 1, wherein U, V, L, Sp and G have the meanings given in claim 1.

3. T, H, 【Transformation 7】 or linear or branched alkyl or alkoxy, each having 1 to 7 C atoms, or linear or branched alkenyl having 2 to 7 C atoms, Z T is -CH 2 O-, -OCH 2 -, -CH 2 CH 2 - or a single bond, Z 1 and Z 2 are the same or different, and -CH 2 O-, -OCH 2 -, -CH 2 CH 2 -, -CF 2 O-, -OCF 2 represents -, -C(O)O-, -OC(O)- or a single bond; A 1 and A 2 are the same or different, 【Transformation 8】 represents Y 1 and Y 2 are the same or different 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 being optionally replaced by O, G is -OP(O)(OH) 2 , -PO(OH) 2 , -COH(PO(OH) 2 ) 2 or-PO(OR V ) 2 represents R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms, and 3. A compound according to claim 1 or 2, wherein U, V and L have the meanings given in claim 1.

4. The compound has the formula IA-2 【Chemistry 9】 and In the formula, T and Z T , 【Chemistry 10】 Z 1 , Z 3 , Z 4 2. The compound according to claim 1, wherein U, V, L, Sp, G, r and u have the meanings given in claim 1.

5. A 1 and A 4 are the same or different, 【Chemistry 11】 represents A 3 -Z 3 teeth, 【Chemistry 12】 represents Z T is a single bond, -CH 2 O-, -OCH 2 -or-CH 2 CH 2 - represents Y 1 and Y 2 are identical or different and have one of the meanings given above for Y or denote H, Y 3 and Y 4 are the same or different, and Y 1 and Y 2 has one of the meanings given above for and preferably denotes methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, Z 3 But -CH 2 - or -O-, Z 1 , Z 2 are independently a single bond, -C(O)O-, -OC(O)-, -CF 2 O-, -OCF 2 -, -CH 2 O-, OCH 2 -or-CH 2 CH 2 - represents G is -OP(O)(OH) 2 , -PO(OH) 2 , -COH(PO(OH) 2 ) 2 or-PO(OR V ) 2 represents R V represents methyl, ethyl or secondary or tertiary alkyl having 1 to 6 C atoms, r and u are independently 0, 1 or 2, and 5. The compound of claim 4, wherein L, U, and V have the meanings given in claim 1.

6. The radical L is Me, Et, n-Pr, i-Pr, CF 3 , OCH 3 , OCF 3 , S.C.H. 3 , SCF 3 6. A compound according to any one of claims 1, 2, 4 and 5, wherein R represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

7. 6. A compound according to any one of claims 1, 2, 4 and 5, wherein U and V are the same or different and represent CF or C-Cl.

8. An electronic switching device (100) comprising, in order: a first electrode (102); a molecular layer (103) bonded to the first electrode; and a second electrode (104); Including, 10. The electronic switching device (100), wherein the molecular layer is formed essentially of one or more compounds of formula I according to any one of claims 1, 2, 4 and 5.

9. 9. The electronic switching device (100) of claim 8, wherein an intermediate layer (105) is disposed between the first electrode (102) and the molecular layer (103), wherein the intermediate layer (105) comprises an oxidizable material, and wherein the molecular layer (103) is bonded to the oxidizable material, and wherein the first electrode (102) and the intermediate layer (105) are operable as a first electrode (102').

10. The oxidizing intermediate layer is TiO 2 , Al 2 O 3 , ZrO 2 , HfO 2 , or SiO 2 10. The electronic switching device (100) of claim 9, comprising:

11. 9. The electronic switching device (100) of claim 8, wherein the group G of the compound of formula I, as defined in claim 1, is bonded to the first electrode (102) by chemisorption or covalently.

12. 9. The electronic switching device (100) of claim 8, wherein the molecular layer (103) is a molecular monolayer.

13. An electronic component comprising one or more switching devices (100) according to claim 8.

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

15. 14. The electronic component of claim 13, 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, the quotient between the high and low electrical resistances being between 10 and 100,000.

16. 14. The electronic component of claim 13, wherein the component is a resistive memory device, a sensor, a field effect transistor, or a Josephson junction.

17. 14. A method for operating an electronic component according to claim 13, characterized in that a switching device (100) of the electronic component is switched to a state of high electrical resistance by setting a corresponding first electrode (102) to a first potential and a corresponding second electrode (104) to a second potential, wherein a value of the voltage between the two electrodes (102, 104) is greater than a first switching voltage and the first potential is greater than the second potential; and a switching device (100) of the electronic component is switched to a state of low electrical resistance by setting the corresponding first electrode (102) to a third potential and the corresponding second electrode (104) to a fourth potential, wherein a value of the voltage between the two electrodes (102, 104) is greater than the second switching voltage and the fourth potential is greater than the third potential, and the state of the switching device is determined by applying a read voltage between the corresponding electrodes (102, 104) having a value less than the first and second switching voltages and measuring the current flow.

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