Self-assembled organic monolayer hybrid materials and methods thereof

Patent metadata

Field	Value
Publication number	US-9478361-B2
Application number	US-201414477344-A
Country	US
Kind code	B2
Filing date	Sep 4, 2014
Priority date	Sep 4, 2013
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

Abstract

Self-assembled monolayer hybrid materials having a modified carboxylic acid deposited from the gas-phase onto a metal oxide substrate, methods of using targeted α-carbon modified carboxylic acids to rapidly deposit activated organic molecules into a self-assembled monolayer on metal oxide substrates, and the self-assembled monolayer hybrid materials capable of being used in various industries, such as optoelectronics and separation science.

First claim

We claim:

1. A method of forming a self-assembled monolayer hybrid material, the method comprising:
providing an inorganic oxide substrate in a reaction chamber, the inorganic oxide material having at least one surface;
providing a reactant in the reaction chamber, the reactant comprising at least one α-carbon modified carboxylic acid having an electron withdrawing functional group on the α-carbon to the carboxylate;
heating the inorganic oxide substrate and the reactant in the chamber to a temperature to allow evaporation or sublimation of the reactant into a gas-phase; and
depositing the reactant in the gas-phase onto at least a portion of the at least one surface of the inorganic oxide substrate for a period of time to form a self-assembled monolayer of the reactant covalently bound to the portion of the at least one surface of the inorganic oxide substrate.

2. The method of claim 1 , wherein the reactant is provided as a liquid, solid, solution or suspension.

3. The method of claim 1 , wherein the electron withdrawing functional group on the α-carbon to the carboxylate is a nitrile.

4. The method of claim 1 , wherein the at least one α-carbon modified carboxylic acid comprises a structure of Formula 1A and/or Formula 1B:

wherein R 1 in Formula 1A and Formula 1B is the electron withdrawing functional group on the α-carbon to the carboxylate, the electron withdrawing functional group chosen from a nitrile, nitro, halogen, hydroxyl, sulfonic acid, NR a R′ a , SR b , COR c , and COOR d ;
wherein R a and R′ a may be each chosen from the group consisting of H, O, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R b is chosen from the group consisting of H, Cd, Hg, As, Zn, Na 2 , Pb, O 3 —H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R c is chosen from the group consisting of H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R d is chosen from the group consisting of H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R f , R g , and R h may be each independently a halo, NR a R′ a , SR b , COR c , COOR d , CR e , C 0-20 hydroxyl, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 halocycloalkyl, C 1-20 haloheterocycl, CO—(C 1-20 alkyl), C 1-20 alkyl, C 1-20 cycloalkyl, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, C 1-20 aryl, and C 1-20 heteroaryl; and
wherein R e is chosen from the group consisting of H 3 , F 3 , Cl 3 , N, C 0-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl.

5. The method of claim 1 , wherein the period of time of depositing the reactant in the gas-phase onto the at least one surface of the inorganic oxide substrate to form the self-assembled monolayer of the reactant covalently bound to the at least one surface of the inorganic oxide substrate is between about 10 minutes and about 45 minutes.

6. The method of claim 1 , wherein the period of time of depositing the reactant in the gas-phase onto the at least one surface of the inorganic oxide substrate to form the self-assembled monolayer of the reactant covalently bound to the at least one surface of the inorganic oxide substrate is between about 15 minutes and about 40 minutes.

7. The method of claim 1 , wherein the temperature is held below a thermal degradation point of the reactant.

8. The method of claim 1 , wherein the inorganic oxide substrate comprises a metal oxide chosen from silicon dioxide, zinc oxide, titanium dioxide, aluminum oxide, an iron oxide, tin oxide, indium oxide, indium doped tin oxide, copper oxide, tungsten oxide, silver oxide, palladium oxide, chromium oxide, manganese oxide, thallium oxide, vanadium oxide, antimony oxide, and combinations thereof.

9. The method of claim 1 , wherein the metal oxide has a surface that is nanoporous.

10. A method of forming a self-assembled monolayer hybrid material, the method comprising:
providing an inorganic oxide substrate in a reaction chamber, the inorganic oxide material having at least one surface;
providing a reactant in a gas-phase in the reaction chamber, the reactant comprising at least one α-carbon modified carboxylic acid having an electron withdrawing functional group on the α-carbon to the carboxylate; and
depositing the reactant in the gas-phase onto at least a portion of the at least one surface of the inorganic oxide substrate for a period of time to form a monolayer of the reactant covalently bound to the portion of the at least one surface of the inorganic oxide substrate.

11. The method of claim 10 , wherein the electron withdrawing functional group on the α-carbon to the carboxylate is a nitrile.

12. The method of claim 10 , wherein the at least one α-carbon modified carboxylic acid comprises a structure of Formula 1A and/or Formula 1B:

wherein R 1 in Formula 1A and Formula 1B is the electron withdrawing functional group on the α-carbon to the carboxylate, the electron withdrawing functional group chosen from a nitrile, nitro, halogen, hydroxyl, sulfonic acid, NR a R′ a , SR b , COR c , and COOR d ;
wherein R a and R′ a may be each chosen from the group consisting of H, O, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R b is chosen from the group consisting of H, Cd, Hg, As, Zn, Na 2 , Pb, O 3 —H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R e is chosen from the group consisting of H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R d is chosen from the group consisting of H, C 1-20 hydroxyl, C 1-20 alkyl, CO—(C 1-20 alkyl), C 1-20 alkane, C 1-20 alkene, C 1-20 conjugated alkene, C 1-20 heterocycl, C 1-20 conjugated heterocycl, an asymmetric carbon atom of CR f R g R h , C 1-20 aryl, and C 1-20 heteroaryl;
wherein R f , R g , and R h may be each independently a halo, NR a R′ a , SR b , COR c , COOR d , CR e , C 0-20 hydroxyl, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 halocycloalkyl, C 1-20 haloheterocycl, CO—(C 1-20 alkyl), C

Assignees

• South Dakota Board Of Regents

Inventors

• Logue Brian A
• Farrakh Baroughi Mahdi
• Mallam Venkataiah

Classifications

• B05D1/60

  Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00) · CPC title

• Y02E10/542

  Dye sensitized solar cells · CPC title

• C23C16/4485

  by evaporation without using carrier gas in contact with the source material (C23C16/4486 takes precedence) · CPC title

• H01G9/2059 Primary

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title

• C23C14/12

  Organic material · CPC title