Method for producing an electronic component which includes a self-assembled monolayer
The invention relates to a process for the production of an electronic component comprising a self-assembled monolayer (SAM) using compounds of the formula I R 1 -(A 1 -Z 1 ) r —(B 1 ) n —(Z 2 -A 2 ) s -Sp-G (I) in which the groups occurring have the meanings defined in Claim 1 ; the present invention furthermore relates to the use of the components in electronic switching elements and to compounds for the production of the SAM.
1. A process for production of a component, comprising:
(1) providing a substrate having a substrate surface,
(2) applying a solution comprising one or more compounds of the formula I to the substrate surface,
(3) heating the substrate to a temperature in the range from 60° C. to 300° C.,
where formula I is defined as follows:
R 1 -(A 1 -Z 1 ) r —(B 1 ) n —(Z 2 -A 2 ) s -Sp-G (I)
in which
R 1 denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH 2 groups in these radicals may each be replaced, independently of one another, by —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, in addition, one or more H atoms may each be replaced by halogen, CN, SCN or SF 5 ,
R 0 , R 00 denote, identically or differently, an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, 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 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 1 to 12 C atoms,
B 1 denotes
where the groups may be oriented in both directions,
L 1 to L 5 denote, independently of one another, F, Cl, Br, I, CN, SF 5 , CF 3 , or OCF 3 , where L 3 alternatively may 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 —, —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 —SO 2 OR V , —OP(O)(OR V ) 2 , —PO(OR V ) 2 , —C(OH)(PO(OR V ) 2 ) 2 , or —COOR V ,
R V denotes secondary or tertiary alkyl having 3 to 20 C atoms,
r and s, independently of one another, denote 0, 1, 2 or 3,
where r+s≤4, and
n denotes 0 or 1.
2. The process according to claim 1 , where the substrate consists of a material selected from glass, metal oxide, metal nitride, metal oxynitride, element semiconductors, group III-V compound semiconductors, group II-VI compound semiconductors, metals, and conductive, oxidic materials.
3. The process according to claim 1 , where the substrate consists of a material selected from Si, Ge, C, Sn, Se, GaAs, InAs, InP, GaSb, TaN, TiN, MoN, WN, GaN, CdSe, ZnS, Au, Ag, Cu, Al, W, Ta, Ti, Co, Mo, Pt, Ru, Mg, ITO, IGO, IGZO, AZO, FTO, glass, SiO 2 , Al 2 O 3 , TiO 2 , HfO 2 , ZrO 2 Si 3 N 4 , TaN x , TiN x TiN x O y , or TaN x O y .
4. The process according to claim 1 , where the substrate surface has a coating consisting of a different material from the substrate.
5. The process according to claim 4 , where the coating of the substrate surface consists of an oxide and/or nitride of one or more metals or semi-metals.
6. The process according to claim 1 , where the solvent is removed by means of a stream of inert gas after application of the solution to a substrate.
7. The process according to claim 1 , where at least one of the steps is carried out at a pressure below 1000 hPa.
8. The process according to claim 1 , where the application of the solution to a substrate is carried out by spin coating.
9. The process according to claim 1 , where n in formula I denotes 1.
10. A process for production of a component, the wherein production is carried out by deposition of one or more compounds of the formula I according to claim 1 from the gas phase.
11. The process according to claim 10 , where the deposition is carried out at a pressure of less than 500 hPa.
12. A component for use in an electronic element containing a self-assembled monolayer, formed and set up for adoption of two switching states, where the component is produced by the process according to claim 1 , with the proviso that the self-assembled monolayer is produced using one or more compounds of formula IA
R 1 -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp-G (IA)
wherein
R 1 denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH 2 groups in these radicals may each be replaced, independently of one another, by, —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, in addition, one or more H atoms may each be replaced by halogen, CN, SCN or SF 5 ,
R 0 , R 00 denote, identically or differently, an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, 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 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 1 to 12 C atoms,
B 1 denotes
where the groups may be oriented in both directions,
L 1 to L 5 denote, independently of one another, F, Cl, Br, I, CN, SF 5 , CF 3 , or OCF 3 , where L 3 alternatively may 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 —, —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 —SO 2 OR V , —OP(O)(OR V ) 2 , —PO(OR V ) 2 , —C(OH)(PO(OR V ) 2 ) 2 , or —COOR V ,
R V denotes secondary or tertiary alkyl having 3 to 20 C atoms,
r and s, independently of one another, denote 0, 1, 2 or 3, and
where r+s<4.
13. The component according to claim 12 , where the one or more compounds of the formula IA are selected from the compounds of the formulae
R 1 -B 1 -Sp-G
IAa
R 1 -(A 1 -Z 1 )-B 1 -Sp-G
IAb
R 1 -(A 1 -Z 1 ) 2 -B 1 -Sp-G
IAc
R 1 -B 1 -(Z 2 -A 2 )-Sp-G
IAd
R 1 -B 1 -(Z 2 -A 2 ) 2 -Sp-G
IAe
R 1 -(A 1 -Z 1 )-B 1 -(Z 2 -A 2 -)-Sp-G
IAf
in which R 1 , A 1 , A 2 , B 1 , Z 1 , Z 2 , Sp and G have the meanings indicated in claim 12 .
14. The component according to claim 13 , where the one or more compounds of the formula IA are selected from the compounds of the formulae IAa, IAb, and IAd.
15. The component according to claim 12 ,
where the material for production of the self-assembled monolayer comprises one or more compounds of the formula Ig
R 2 -G Ig
in which
R 2 has the meaning indicated for R 1 in claim 12 and
G has the meaning indicated in claim 12 .
16. The component according to claim 15 ,
where the one or more compounds of the formula Ig are selected from the compounds of the formulae Ig-1 to Ig-3
CH 3 (CH 2 ) r -G Ig-1
CF 3 (CF 2 ) s CH 2 CH 2 -G Ig-2
in which
G denotes —PO(OR V ) 2 or —SO 2 OR V ,
R V denotes secondary or tertiary alkyl having 3 to 20 C atoms,
r denotes an integer from 1 to 20,
s denotes an integer from 1 to 18, and
t denotes an integer from 1 to 4.
17. A memristive electronic switching element comprising the component according to claim 12 .
18. A compound of formula IA
R 1 -(A 1 -Z 1 ) r —B 1 —(Z 2 -A 2 ) s -Sp-G (IA)
in which
R 1 denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, 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, in addition, one or more H atoms may each be replaced by halogen, CN, SCN or SF 5 ,
R 0 , R 00 denote, identically or differently, an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, 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 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 1 to 12 C atoms,
B 1 denotes
where the groups may be oriented in both directions,
L 1 to L 5 denote, independently of one another, F, Cl, Br, I, CN, SF 5 , CF 3 , or OCF 3 , where L 3 alternatively may 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 —, 13 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 —SO 2 OR V , —OP(O)(OR V ) 2 , —PO(OR V ) 2 , —C(OH)(PO(OR V ) 2 ) 2 , or —COOR V ,
R V denotes secondary or tertiary alkyl having 3 to 20 C atoms,
r and s, independently of one another, denote 0, 1, 2 or 3,
where r+s<4.
19. The compound according to claim 18 , in which
G denotes —SO 2 OR V or —PO(OR V ) 2 , and
R V denotes an isopropyl or tert-butyl radical.
20. The compound according to claim 18 , wherein said compound is selected from the following compounds: