IP Library Granted Patent US 11,063,227
Granted Patent B2
US 11,063,227 · App. 16/315,827 · Granted Jul 13, 2021

Electronic switching element

Inventors: Peer Kirsch (Seeheim-Jugenheim, DE); Andreas Ruhl (Rossdorf, DE); Marc Tornow (Munich, DE); Achyut Bora (Munich, DE)
Assignee: MERCK PATENT GMBH
H01L51/0076C07C43/29C07C59/125C07F9/386C07F9/3808C07F9/3839C09K19/12C09K19/3003C09K19/60G11C13/0016G11C13/0069H01L27/285C07C2601/14C09K2019/122C09K2019/301G11C2013/009G11C2213/35G11C2213/52H01L51/0591H01L51/105Y10T428/1114
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Quick Facts
Patent No.
US 11,063,227
App. No.
16/315,827
Granted
Jul 13, 2021
Kind
B2
Abstract

An electronic switching element is described having, in sequence, a first electrode, a molecular layer bonded to a substrate, and a second electrode. The molecular layer contains compounds of formula I, R 1 -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp-G, wherein A 1 , A 2 , B 1 , Z 1 , Z 2 , Sp, G, r, and s are as defined herein, in which a mesogenic radical is bonded to the substrate via a spacer group, Sp, by means of an anchor group, G. The switching element is suitable for production of components that can operate as a memristive device for digital information storage.

Claims (70)

1. A memristive electronic component comprising one or more switching elements, wherein each switching element comprises, in sequence, the following:

a first electrode,

a molecular layer of mesogenic compounds bonded to a substrate, said molecular layer having negative dielectric anisotropy, and

a second electrode,

wherein said component is able to function as a memristor,

where the substrate consists of the first electrode and optionally one or more layers lying on top of the first electrode, and

where the molecular layer is a monolayer comprising one or more mesogenic compounds of formula I, as defined below:

R 1 -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp-G  (I)

in which

R 1 denotes H or an alkyl or alkoxy radical having 1 to 15 C atoms, wherein one or more CH 2 groups may each be replaced, independently of one another, by —C≡C—, —CH═CH—,

—O—, —S—, —CF 2 O—, —OCF 2 —, —CO—O—, or —O—CO—, —SiR 0 R 00 —, —NH—, —NR 0 — or —SO 2 — in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may each be replaced by halogen, CN, SCN or SF 5 ,

R 0 , R 00 , identically or differently, denote an alkyl or alkoxy radical having 1 to 15 C atoms, wherein one or more H atoms may each be replaced by halogen,

A 1 , A 2 on each occurrence, identically or differently, denote an aromatic, heteroaromatic, alicyclic or heteroaliphatic ring having 4 to 25 ring atoms, which may also contain one or more condensed rings and which may be mono- or polysubstituted by Y,

Y on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF 5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms,

B 1 denotes

where the groups may be oriented in either direction,

L 1 to L 5 , independently of one another, denote F, Cl, Br, I, CN, SF 5 , CF 3 or OCF 3 , where L 3 may alternatively also denote H,

Z 1 , Z 2 on each occurrence, identically or differently, denote 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 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —CF 2 —, —CF 2 —CF 2 —, —CF 2 —CH 2 —, —CH 2 —CF 2 —, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —(CH 2 ) 3 O—, —O(CH 2 ) 3 —, —C≡C—, —O—, —S—, —C═N—, —N═C—, —N═N—, —N═N(O)—, —N(O)═N— or —N═C—C═N—,

Sp denotes a spacer group or a single bond,

G denotes —CH═CH 2 , —SO 2 OH, —OP(O)(OH) 2 , —PO(OH) 2 , —C(OH)(PO(OH) 2 ) 2 , —COOH, —Si(OR X ) 3 or —SiCl 3 ,

R X denotes straight-chain or branched alkyl having 1 to 6 C atoms, and

r and s, independently of one another, denote 0, 1, 2 or 3,

where r+s≤4;

wherein group G of each of the one or more compounds of formula I is bonded to the substrate by chemisorption or by a covalent bond.

2. The memristive electronic component according to claim 1 , wherein the first electrode is the substrate for the molecular layer.

3. The memristive electronic component according to claim 1 , wherein a diode, which is the substrate for the molecular layer, is arranged between the first electrode and the molecular layer.

4. The memristive electronic component according to claim 3 , wherein the diode comprises an n+-doped layer and a p+-doped layer, where the n+-doped layer or the p+-doped layer is designed as a combined electrode together with a semiconducting first electrode.

5. The memristive electronic component according to claim 1 , wherein a diode is arranged between the second electrode and the molecular layer.

6. The memristive electronic component according to claim 1 , wherein an interlayer is arranged between the substrate and the molecular layer, where the interlayer is selected from an oxidic or fluoridic material and the molecular layer is bonded to the interlayer.

7. The memristive electronic component according to claim 6 , wherein the oxidic or fluoridic material is TiO 2 , Al 2 O 3 , HfO 2 , SiO 2 or LiF.

8. The memristive electronic component according to claim 1 , wherein group G of each of the one or more compounds of formula I is bonded to the substrate by chemisorption.

9. The memristive electronic component according to claim 1 , wherein group G of each of the one or more compounds of formula I is bonded to the substrate by a covalent bond.

10. The memristive electronic component according to claim 1 , wherein group G of each of the one or more compounds of formula I is selected from —CH═CH 2 , —PO(OH) 2 and —C(OH)(PO(OH) 2 ) 2 .

11. The memristive electronic component according to claim 1 , wherein the first electrode consists of a material selected from element semiconductors, compound semiconductors from groups III-V, compound semiconductors from groups II-VI, metals, and conductive, oxidic materials.

12. The memristive electronic component according to claim 11 , wherein the first electrode consists of a material selected from the element semiconductors Si, Ge, C, Sn (alpha modification) and Se, the compound semiconductors GaAs, InAs, InP, GaSb, TaN, TiN, MoN, WN and GaN, CdSe and ZnS, the metals Au, Ag, Cu, Al, W, Ta, Ti, Co, Mo, Pt, Ru and Mg, and the conductive oxidic materials ITO, IGO, IGZO, AZO and FTO.

13. The memristive electronic component according to claim 1 , wherein the second electrode consists of a conducting or semiconducting material, or combination of a plurality of conducting or semiconducting materials selected from Hg, In, Ga, InGa, Ag, Au, Cr, Pt, Pd, Au, Pb, Al, Mg, Zn, Yb, W, CNT, graphene and conductive polymers.

14. The memristive electronic component according to claim 1 , wherein the first electrode and the second electrode are metallic conductors, or the first electrode is semiconducting and the second electrode is a metallic conductor.

15. The memristive electronic component according to claim 1 , wherein the component has a multiplicity of switching elements, where the first electrodes and second electrodes of the switching elements form a crossbar array.

16. The memristive electronic component according to claim 1 , wherein the one or more switching elements are set up 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.

17. A method for operating the memristive electronic component according to claim 1 , said method comprising:

switching a switching element of the memristive electronic component into a state of high electrical resistance by setting a corresponding first electrode to a first electrical potential and setting a corresponding second electrode to a second electrical potential, where the value of the voltage between the two electrodes is greater than a first switching voltage and the first potential is greater than the second potential,

switching a switching element of the memristive electronic component into a state of low electrical resistance by setting a corresponding first electrode to a third electrical potential and setting a corresponding second electrode to a fourth electrical potential, where the value of the voltage between the two electrodes is greater than a second switching voltage and the fourth potential is greater than the third potential, and

determining the state of a switching element by applying a reading voltage whose value is smaller than the first and second switching voltages between corresponding electrodes and measuring the current flowing.

18. A process for production of the memristive electronic component according to claim 1 , said method comprising:

producing the switching element by:

production of a first electrode,

deposition of a monolayer comprising one or more compounds of the formula I onto a substrate and bonding said one or more compounds to the substrate by chemisorption or by a covalent bond, and

application of a second electrode; and

incorporating said switching element into the memristive electronic component.

19. The memristive electronic component according to claim 1 , wherein group G of each of the one or more compounds of formula I is selected from —OP(O)(OH) 2 , —P(O)(OH) 2 , or —C(OH)(P(O)(OH) 2 ) 2 .

20. The memristive electronic component according to claim 1 , wherein Sp denotes —(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 —, in which p1 denotes an integer from 1 to 12.

21. The memristive electronic component according to claim 1 , wherein Sp denotes —O(CF 2 ) p1 — or —(CF 2 ) p1 —, and p1 denotes an integer from 1 to 12.

22. The memristive electronic component according to claim 1 , wherein one or more compounds of formula I are selected from sub-formulae Ia to If:

R 1 —B 1 -Sp-G  Ia

R 1 -(A 1 -Z 1 )—B 1 -Sp-G  Ib

R 1 -(A 1 -Z 1 ) 2 —B 1 -Sp-G  Ic

R 1 —B 1 —(Z 2 -A 2 )-Sp-G  Id

R 1 —B 1 —(Z 2 -A 2 ) 2 -Sp-G  Ie

R 1 -(A 1- -Z 1 )—B 1 —(Z 2 -A 2 -)-Sp-G  If

wherein

A 1 and each independently denote

B 1 denotes

where the groups may be oriented in either direction,

R 1 denotes alkyl having 1-15 C atoms,

L 1 and L 2 , independently of one another, denote Cl or F, where at least one of the radicals L 1 and L 2 denotes F,

L 3 denotes F,

Y 1 and Y 2 independently of one another, denote H, Cl or F,

Z 1 and Z 2 independently of one another, denote a single bond, —CF 2 O—, —OCF 2 —, —CH 2 O—, OCH 2 — or —CH 2 CH 2 —,

Sp denotes unbranched 1, ω-alkylene having 1 to 12 C atoms, and

G denotes —CH═CH 2 , —OH, —SH, —SO 2 OH, —OP(O)(OH) 2 , —PO(OH) 2 , —COH(PO(OH) 2 ) 2 , —COOH, —Si(OR) 3 or —SiCl 3 .

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 7, 2019
From: KIRSCH, PEER; RUHL, ANDREAS; TORNOW, MARC; BORA, ACHYUT
To: MERCK PATENT GMBH
Reel/Frame 048268/0279 →
Priority Claims (1)
DE 10 2016 008 207.0 · Jul 7, 2016 · national
Continuity (1)
Related Publication 20190312216A1 · Oct 10, 2019
Cited By (6)
US 12,193,328 US 12,320,802 US 12,336,362 US 12,424,277 US 12,451,821 US 12,549,114