US4371883A
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Current controlled bistable electrical organic thin film switching device
Assignee: Johns Hopkins University
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Filing: 1980-03-14
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Granted: 1983-02-01
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Expires: 2000-03-14
Abstract
Abstract A current-controlled, bistable threshold or memory switch comprises a polycrystalline metal-organic semiconductor sandwiched between metallic electrodes. Films of either copper or silver complexed with TNAP, DDQ, TCNE, TCNQ, derivative TCNQ molecules, or other such electron acceptors provides switching between high and low impedance states with combined delay and switching times on the order of 1 nanosecond. Switching behavior of a complex of the present invention is related to the reduction potential of the acceptor molecule.
Inventors
- 👤 Richard S. Potember
- 👤 Theodore O. Poehler, Jr.
- 👤 Dwaine O. Cowan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 19:40
CPC Classifications
B; B82; B82Y; B82Y10/00; G; G11; G11C; G11C13/00; G11C13/0002; G11C13/0009; G11C13/0014; H; H10; H10K; H10K10/00; H10K85/00; H10K85/60; H10K85/611; Y; Y10; Y10S; Y10S438/00; Y10S438/90
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
145 words
An electric, current-controlled device for providing stable, reproducible switching comprising: a thin film which comprises: a metal wherein the metal is a material selected from the group consisting of copper and silver, and an electron acceptor combined with the metal wherein the electron acceptor is a material selected from the group consisting of tetracyanoquinodimethane (TCNQ), tetracyanonapthoquinodimethane (TNAP), and any of the TCNQ derivatives defined by the notation: ##STR2## wherein R 1 =H, R 2 =--H; R 1 =CH 3 , R 2 =--H; R 1 =--OCH 3 , R 2 =--H; or R 1 =F, R 2 =--F; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said thin film.
Claim 2
Dependent Claim
145 words
An electric, current-controlled device for providing stable, reproducible switching comprising: a thin film which comprises: a metal wherein the metal is a material selected from the group consisting of copper and silver, and an electron acceptor combined with the metal wherein the electron acceptor is a material selected from the group consisting of tetracyanoquinodimethane (TCNQ), tetracyanonapthoquinodimethane (TNAP), and any of the TCNQ derivatives defined by the notation: ##STR2## wherein R 1 =H, R 2 =--H; R 1 =CH 3 , R 2 =--H; R 1 =--OCH 3 , R 2 =--H; or R 1 =F, R 2 =--F; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said thin film.
Claim 3
Dependent Claim
31 words
A device, as in claim 1, further comprising: two electrodes and wherein the thin film comprises a charge-transfer complex which is sandwiched between and is electrically connected to the two electrodes.
Claim 4
Dependent Claim
15 words
A device, as in claim 1, wherein the thin film is a polycrystalline semiconducting film.
Claim 5
Dependent Claim
30 words
A device, as in claim 1, wherein the metal:electron acceptor ratio in the bulk of the thin film is 1:1 when the device is in its high impedance switching state.
Claim 6
Dependent Claim
37 words
A device, as in claim 1, wherein said electron acceptor is chosen from a class of weak electron acceptors having a low reduction potential thereby providing threshold switching from one impedance to state to another impedance state.
Claim 7
Dependent Claim
36 words
A device, as in claim 1, wherein said electron acceptor is chosen from a class of strong electron acceptors having a high reduction potential thereby providing memory switching from one impedance state to another impedance state.
Claim 8
Independent Claim
87 words
A device for switching between a high impedance state and a low impedance state comprising: a film comprising a metal charge-transfer salt selected from the group consisting of CuTCNQ(OMe) 2 , CuTCNQ(Me) 2 , CuTCNQ, CuTNAP, and CuTCNQF 4 , and means for applying an electric field across the film, said applied field being sufficient to induce a solid-state reversible electrochemical reaction in the film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a high to a low impedance state in the film.
Claim 9
Independent Claim
87 words
A device for switching between a high impedance state and a low impedance state comprising: a film comprising a metal charge-transfer salt selected from the group consisting of CuTCNQ(OMe) 2 , CuTCNQ(Me) 2 , CuTCNQ, CuTNAP, and CuTCNQF 4 , and means for applying an electric field across the film, said applied field being sufficient to induce a solid-state reversible electrochemical reaction in the film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a high to a low impedance state in the film.
Claim 10
Dependent Claim
30 words
A device, as in claim 7, further comprising: means for removing the electric field, wherein said removal of the field results in returning the film to a high impedance state.
Claim 11
Dependent Claim
30 words
A device, as in claim 8, wherein the return to a high impedance state occurs following a delay and wherein the delay is proportional to the thickness of the film.
Claim 12
Dependent Claim
33 words
A device, as in claim 8 or 9, wherein the return to a low impedance state occurs following a delay and wherein the delay is proportional to the duration of the applied field.
Claim 13
Dependent Claim
23 words
A device, as in claim 7, wherein the film, upon removal of the electric field, provides a small emf as an electrochemical cell.
Claim 14
Dependent Claim
29 words
A device, as in claim 7, wherein the film enters the low impedance state when the applied field is at a value between 1000 to 10,000 volts per centimeter.
Claim 15
Dependent Claim
50 words
A device, as in claim 7, wherein the ratio of the low impedance state to the high impedance state is approximately 1:10,000 and wherein the applied field is between 1000 and 50,000 volts per centimeter across a film having a thickness which can range from 1 μm to 10 μm.
Claim 16
Dependent Claim
27 words
A device, as in claim 7, wherein the combined switching and delay time from the high impedance state to the low impedance state is approximately 1 nanosecond.
Claim 17
Dependent Claim
20 words
A device, as in claim 7, wherein the switching characteristics of the film are insensitive to ambient moisture and light.
Claim 18
Dependent Claim
22 words
A device, as in claim 7 or 15, wherein the switching characteristics of the film are unaffected over a large temperature range.
Claim 19
Dependent Claim
19 words
A device, as in claim 7, wherein the applied field may have any direction and polarity across the film.
Claim 20
Dependent Claim
60 words
An electrical switch comprising: a solid, organic film comprising a metal complexed with tetracyanoethylene (TCNE); and, an electric field applied across said film, said applied field being sufficient to induce a solid-state reversible electrochemical reaction in said film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 21
Dependent Claim
60 words
An electrical switch comprising: a solid, organic film comprising a metal complexed with tetracyanoethylene (TCNE); and, an electric field applied across said film, said applied field being sufficient to induce a solid-state reversible electrochemical reaction in said film wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 22
Dependent Claim
20 words
An electrical switch, as in claim 18, wherein the metal is selected from the group consisting of silver and copper.
Claim 23
Dependent Claim
28 words
An electrical switch, as in claim 17, wherein the switch has two terminals and exhibits a negative resistance I-V characteristic symmetric about the origin of the I-V characteristic.
Claim 24
Dependent Claim
63 words
An electrical switch comprising: a solid semiconducting film comprising a metal complexed with 2, 3 dichloro-5,6-dicyano-1,4 benzoquinone (DDQ); and, an electric field applied across said film, said applied field being sufficient to induce a solid statereversible electrochemical reaction in said film wherein said electrical reaction causes a detectable switching in electrical impedance from a first to a second impendance state in said film.
Claim 25
Dependent Claim
63 words
An electrical switch comprising: a solid semiconducting film comprising a metal complexed with 2, 3 dichloro-5,6-dicyano-1,4 benzoquinone (DDQ); and, an electric field applied across said film, said applied field being sufficient to induce a solid statereversible electrochemical reaction in said film wherein said electrical reaction causes a detectable switching in electrical impedance from a first to a second impendance state in said film.
Claim 26
Dependent Claim
20 words
An electrical switch, as in claim 2, wherein the metal is selected from the group consisting of silver and copper.
Claim 27
Dependent Claim
107 words
An electrical diode comprising: a thin film comprised of: a metal selected from the group consisting of silver and copper and an electron acceptor complexed with the metal wherein the electron acceptor is selected from the group consisting of: TCNQ(OMe) TCNQ(OMe) 2 TCNQ(OMe)(OEt) TCNQ(OMe)(O-I-Pr) TCNQ(OMe)(O-i-Bu) TCNQ(O-i-C 2 H 5 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQBr TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 TNAP TCNE DDQ and two electrodes wherein one consists of a metal selected from the group consisting of platinum, gold, and, magnesium, wherein the thin film is sandwiched between and is electrically connected to the two electrodes.
Claim 28
Dependent Claim
107 words
An electrical diode comprising: a thin film comprised of: a metal selected from the group consisting of silver and copper and an electron acceptor complexed with the metal wherein the electron acceptor is selected from the group consisting of: TCNQ(OMe) TCNQ(OMe) 2 TCNQ(OMe)(OEt) TCNQ(OMe)(O-I-Pr) TCNQ(OMe)(O-i-Bu) TCNQ(O-i-C 2 H 5 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQBr TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 TNAP TCNE DDQ and two electrodes wherein one consists of a metal selected from the group consisting of platinum, gold, and, magnesium, wherein the thin film is sandwiched between and is electrically connected to the two electrodes.
Claim 29
Dependent Claim
135 words
A multiterminal device comprising: a substrate made of a first metal selected from the group consisting of copper and silver; a plurality of films formed on the surface of the substrate, wherein each film comprises a portion of the first metal complexed with an electron acceptor selected from the group consisting of: TCNQ(OMe) TCNQ(OMe) 2 TCNQ(OMe) (OEt) TCNQ(OMe) (O-i-Pr) TCNQ(OMe) (O-i-Bu) TCNQ(O-i-C 2 H 5 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQBr TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 TNAP TCNE DDQ; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film, wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 30
Dependent Claim
135 words
A multiterminal device comprising: a substrate made of a first metal selected from the group consisting of copper and silver; a plurality of films formed on the surface of the substrate, wherein each film comprises a portion of the first metal complexed with an electron acceptor selected from the group consisting of: TCNQ(OMe) TCNQ(OMe) 2 TCNQ(OMe) (OEt) TCNQ(OMe) (O-i-Pr) TCNQ(OMe) (O-i-Bu) TCNQ(O-i-C 2 H 5 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQBr TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 TNAP TCNE DDQ; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film, wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 31
Dependent Claim
21 words
A multiterminal device, as in claim 24, further comprising: a plurality of contacts each being electrically connected across a corresponding film.
Claim 32
Dependent Claim
99 words
An electrical switch comprising: a solid, organic film comprising a metal complexed with an electron acceptor selected from the group consisting of: TCNQ(OMe) TCNQ(OMe)(OEt) TCNQ(OMe) (O-i-Pr) TCNQ(OMe) (O-i-Bu) TCNQ(O-i-C 2 H 2 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 ; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film, wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 33
Dependent Claim
99 words
An electrical switch comprising: a solid, organic film comprising a metal complexed with an electron acceptor selected from the group consisting of: TCNQ(OMe) TCNQ(OMe)(OEt) TCNQ(OMe) (O-i-Pr) TCNQ(OMe) (O-i-Bu) TCNQ(O-i-C 2 H 2 ) TCNQ(OEt)(SMe) TCNQCl TCNQBr TCNQClMe TCNQBrMe TCNQIMe TCNQCl TCNQI TCNQ(OMe)(OCH 3 ) 2 TCNQ(CN) 2 TCNQ(Me) TCNQ(Et) TCNQ(i-Pr) TCNQ(i-Pr) 2 ; and, an electric field applied across said film, said applied field being sufficient to induce a solid state reversible electrochemical reaction in said film, wherein said electrochemical reaction causes a detectable switching in electrical impedance from a first to a second impedance state in said film.
Claim 34
Dependent Claim
27 words
A device, as in claim 1, 18, 21, or 26, wherein said film, upon removal of said electric field, provides a small emf as an electrochemical cell.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1986-01-31 | 1986-08-02 | 1987-02-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-01-31 | 1990-08-02 | 1991-02-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-01-31 | 1994-08-02 | 1995-02-01 | $7700.00 | Window Closed / Lapsed |