Electronic switching device

Patent metadata

Field	Value
Publication number	US-12424277-B2
Application number	US-202017770311-A
Country	US
Kind code	B2
Filing date	Oct 20, 2020
Priority date	Oct 21, 2019
Publication date	Sep 23, 2025
Grant date	Sep 23, 2025

Abstract

The present invention relates to an electronic switching device comprising an organic molecular layer in contact with a metal nitride electrode for use in memory, sensors, field-effect transistors or Josephson junctions. More particularly, the invention is included in the field of random access non-volatile memristive memories (RRAM). The invention thus further relates to an electronic component comprising a crossbar array comprising a multitude of said electronic switching devices.

First claim

The invention claimed is:

1. An electronic switching device ( 100 ) comprising, in this sequence,
a first electrode ( 102 ),
a molecular layer ( 103 ) bonded to the first electrode, and
a second electrode ( 104 ),
where the first and second electrodes comprise a metal nitride, and
where the molecular layer is formed from one or more compounds selected from formulae IA, IB and IC:
R 1A -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp A -G  (IA)

D 1 -Z D -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp-G  (IB)

R 1C -(A 1 -Z 1 ) r —B 1 —Z L -A 2C -(Z 3 -A 3 ) s -G  (IC)

in which
R 1A , R 1C denote straight chain or branched alkyl or alkoxy each having 1 to 20 C atoms, where one or more CH 2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CH═CH—,

 —O—, —S—, —CF 2 O—, —OCF 2 —, —CO—O—, —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 one or more H atoms may be replaced by halogen, CN, SCN or SF 5 , where R 1C alternatively denotes a group D 1 -Z D ,
Z D has one of the meanings of Z 1 , Z 2 and Z 3 or denotes a spacer group,
Z 1 , Z 2 , Z 3 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 ) 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═C—C═N—,
n1, n2, n3, n4 identically or differently, are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10,
Z L denotes —O—, —S—, —CH 2 —, —C(O)—, —CF 2 —, —CHF—, —C(R x ) 2 —, —S(O)— or —SO 2 —,
R 0 , R 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,
D 1 denotes a diamondoid radical,
A 1 , A 2 , A 3 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,
A 2C 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 Y C ,
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 1 to 12 C atoms,
Y C 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 1 to 12 C atoms, or cycloalkyl or alkylcycloalkyl each having 3 to 12 C atoms,
B 1 denotes

in which R 0 and R 00 denote F or alkyl having 1 to 6 C atoms,

where the groups may be oriented in both directions,

L 1 to L 3 , 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,
Sp A denotes a spacer group or a single bond,
Sp denotes a spacer group,
G denotes —OH, —CH(CH 2 OH) 2 , —C(CH 2 OH) 3 , —SH, —SO 2 OH, —OP(O)(OH) 2 , —PO(OH) 2 , —C(OH)(PO(OH) 2 ) 2 , —COOH, —Si(OR x ) 3 , —SiCl 3 , 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 ,
R V denotes secondary or tertiary alkyl having 1 to 20 C atoms,
R x denotes straight-chain or branched alkyl having 1 to 6 C atoms, and
r, s on each occurrence, identically or differently, are 0, 1 or 2,

wherein at least one of the groups Sp A and R 1A of the compounds of formula IA, or at least one of the groups Z D and Sp of the compounds of formula IB, or the group R 1C of the compounds of formula IC, respectively, is chiral.

2. The electronic switching device ( 100 ) according to claim 1 , wherein the first electrode ( 102 ) and the second electrode ( 104 ), identically or differently, comprise a metal nitride selected from the group consisting of CrN, HfN, MoN, NbN, TiN, TaN, WN, WCN, VN and ZrN.

3. The electronic switching device ( 100 ) according to claim 1 , wherein the second electrode ( 104 ) consists of TiN.

4. The electronic switching device ( 100 ) according to claim 1 , 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 ′).

5. The electronic switching device ( 100 ) according to claim 4 , wherein the oxidic interlayer comprises TiO 2 , Al 2 O 3 , ZrO 2 , HfO 2 , or SiO 2 .

6. The electronic switching device ( 100 ) according to claim 1 , wherein the group G in formula IA, IB or IC denotes —PO(OH) 2 or —C(OH)(PO(OH) 2 ) 2 .

7. The electronic switching device ( 100 ) according to claim 1 , wherein the group G of the compounds of the formulae IA, IB or IC is bonded to the first electrode ( 102 ) by chemisorption or covalently.

8. The electronic switching device ( 100 ) according to claim 1 , wherein the molecular layer ( 103 ) is a molecular monolayer.

9. An electronic component comprising one or more switching devices ( 100 ) according to claim 1 .

10. The electronic component according to claim 9 , 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.

11. The electronic component according to claim 9 , 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.

12. The electronic component according to claim 9 , wherein the component is a resistive memory device, a sensor, a field-effect transistor or a Josephson junction.

13. A method for operating an electronic component according to claim 9 , wherein one or more of the switching devices ( 100 ) of the electronic component is switched into a state of high electrical resistance by setting a corresponding first electrode ( 102 ) to a first electrical potential and setting a corresponding second electrode ( 104 ) to a second electrical potential, where the 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, a switching device ( 100 ) of the electronic component is switched into a state of low electrical resistance by setting a corresponding first electrode ( 102 ) to a third electrica

Assignees

• Merck Patent Gmbh

Inventors

• Kirsch Peer
• Resch Sebastian
• Seim Henning
• Lieberman Itai
• Arai Shintaro
• Tornow Marc
• Kamiyama Takuya
• Dlugosch Julian
• Moinpour Mansour

Classifications

• H10K30/671

  Organic radiation-sensitive molecular electronic devices · CPC title

• H10K19/202 Primary

  Integrated devices comprising a common active layer · CPC title

• H10K10/82

  Electrodes · CPC title

• H10K85/6576

  comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene · CPC title

• H10K85/6574

  comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes · CPC title