Films of dithiolene complexes in gas-detecting microsensors

• US 4,992,244 A
• Filed: 09/27/1988
• Issued: 02/12/1991
• Est. Priority Date: 09/27/1988
• Status: Expired due to Fees

• Current Assignee: the united states of america as represented by the secretary of the navy
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Grate, Jay W.
• Primary Examiner(s): Hill, Jr., Robert J.
• Assistant Examiner(s): Collins, Laura E.
• Application Number:
  US07/250,004
• Time in Patent Office: 868 Days
• Field of Search: 422/98, 422/90, 549/3, 338/34, 340/633, 340/634, 427/51
• US Class Current: 422/98
• CPC Class Codes: G01N 27/126 comprising organic polymers

Abstract

Chemical microsensors are fabricated by applying dithiolene transition metal complexes as thin films to chemiresistor devices using the Langmuir-Blodgett technique. The thin films interact with ambient gases and change electrical conductivity upon exposure to a particular gas or vapor. The film material determines the chemical sensitivity and selectivity. The degree of current change depends on the particular gas or vapor and its concentration. These compounds are different in structure and electrical conductive response to gas or vapors than previous materials used for chemical microsensors. This invention is particularly suited for hydrazine detection.

Claims

1. A chemical microsensor for detection of gases and vapors, comprising:

a. an insulating substrate;

b. a film comprising a dithiolene complex of a transition metal covering the substrate wherein a measurable physical property of the film changes upon exposure to gases and vapors;

c. a sensing element to detect any change in physical properties of the film.

2. A chemical microsensor as recited in claim 1 wherein the film comprises a bis(dithiolene) complex of the following formula:

##STR6## wherein M is a divalent metal and R1, R2, R3 and R4 are chosen from the group consisting of hydrogen, alkyl, aryl, a substituted alkyl and a substituted aryl.

3. A chemical microsensor as recited in claim 1 wherein the film comprises a tris(dithiolene) complex of a transition metal of the following formula:

##STR7## wherein M is a trivalent metal and R1, R2, R3, R4, R5 and R6 are chosen from the group consisting of hydrogen, alkyl, aryl, a substituted alkyl and a substituted aryl.

4. A chemical microsensor as recited in claim 1 wherein the film comprises a polymer with the repeating unit of the formula:

##STR8## wherein M is a divalent metal and n is an integer greater than one.

5. A chemical microsensor comprising

a. a substrate of insulating material;

b. a conductive material microfabricated in a pattern on the substrate; and

c. a film covering the substrate and the conductive material wherein the electrical conductivity of the film changes upon exposure to gases and vapors and wherein the film is a bis(dithiolene) complex of a transition metal of the following formula;

##STR9## wherein M is a divalent metal and R1, R2, R3 and R4 are chosen from the group consisting of hydrogen, alkyl, aryl, a substituted alkyl and a substituted aryl;

d. a sensing element to detect any change in electrical conductivity.

6. A chemiresistor for detection of gases and vapors chosen from the group consisting of water, ammonia, nitrogen dioxide, sulfur dioxide, dimethylmethylphosphonate, diethylsulfide, hydrazine and substituted hydrazine compounds in which the electrical conductivity changes upon exposure to the gases and vapors, comprising:

a. a substrate of insulating material;

b. a conductive material microfabricated in a pattern on the substrate; and

c. a film covering the conductive material wherein the electrical conductivity of the film changes upon exposure to gases and vapors and wherein the film comprises a bis(dithiolene) complex of a transition metal of the following formula;

##STR10## wherein M is a divalent metal and R1, R2, R3 and R4 are chosen from the group consisting of hydrogen, alkyl, aryl, a substituted alkyl and a substituted aryl;

d. a sensing element to detect any change in electrical conductivity.

7. A chemiresistor as recited in claim 6 wherein the film is 0.5 to 5 micron thick.

8. A chemiresistor as recited in claim 6 wherein the divalent metal is chosen from the group consisting of nickel, palladium, and platinum.

9. A chemiresistor as recited in claim 8 wherein R₁ -R₄ are chosen from the group consisting of hydrogen, an alkyl with 20 carbons atoms or less, an aryl, or an aryl, substituted with an alkyl, an alkoxy or a tertiary amino group.

10. A chemiresistor as recited in claim 9 wherein the film comprises bis(diethylaminodithiobenzil)nickel of the following formula:

##STR11##

11. A chemiresistor as recited in claim 10 wherein the film is a film in the range of three to thirty-three layers.

12. A chemiresistor as recited in claim 11 wherein the film is a film of five layers.

13. A chemiresistor as recited in claim 12 wherein the substrate is quartz.

14. A chemiresistor as recited in claim 13 wherein the conductive material comprises at least one pair of gold interdigitated electrodes.

15. A surface acoustic wave device for detection of gases and vapors, comprising:

a. a substrate;

b. a film covering the substrate wherein the mass and/or electrical conductivity of the film changes upon exposure to gases and vapors resulting in a detectable change in frequency and wherein the film is a bis(dithiolene) complex of a transition metal of the following formula;

##STR12## wherein M is a divalent metal and R1, R2, R3 and R4 are chosen from the group consisting of hydrogen, alkyl, aryl, a substituted alkyl and a substituted aryl.

d. a sensing element to detect any change in electrical conductivity and mass.