Modified hybrid sol-gel solutions and compositions formed from such solutions
Provided are modified hybrid sol-gel precursor solutions and coatings formed from such solutions. A modified hybrid sol-gel precursor solution includes an inorganic precursor, cross-linkable inorganic-organic precursor, cross-linkable organic precursor, protic solvent, and aprotic solvent. The inorganic precursor may include a metal or metalloid and two or more hydrolysable groups. The cross-linkable inorganic-organic precursor may include a metal, hydrolysable group, and organic molecule. The cross-linkable organic precursor has another organic molecule with two or more second cross-linking groups. A combination of protic and aprotic solvents in the same solution may be used to control properties of the solutions, thermodynamics, and other processing aspects. The solution may also include nanoparticles. The nanoparticles may include functionalized surface to form covalent bonds with one or more precursors of the solution, such as a plasma treated surface. The nanoparticles may be sized to fit into the sol-gel network without substantially disturbing this network.
1. A modified hybrid sol-gel precursor solution comprising
an inorganic precursor comprising two or more first hydrolysable groups and one of a first metal or a first metalloid,
wherein the one of the first metal or the first metalloid is covalently bonded to the two or more first hydrolysable groups;
a cross-linkable inorganic-organic precursor comprising a second metal, a second hydrolysable group, and a first organic molecule,
wherein the second metal is covalently bound to the second hydrolysable group and is covalently bound to the first organic molecule,
wherein the first organic molecule comprises a first cross-linking group;
a cross-linkable organic precursor comprising a second organic molecule,
wherein the second organic molecule comprises two or more second cross-linking groups;
a protic solvent; and
an aprotic solvent,
wherein a weight ratio of the protic solvent and the aprotic solvent in the modified hybrid sol-gel precursor solution is selected to achieve a gelation rate of the inorganic precursor, the cross-linkable inorganic-organic precursor, and the cross-linkable organic precursor,
wherein the first metalloid is selected from the group consisting of boron, germanium, arsenic, antimony, tellurium, bismuth, and polonium, and
wherein the first metal is selected from the group consisting of transition metals, lanthanides, actinides, alkaline earth metals, and Group IIIA through Group VA metals.
2. The modified hybrid sol-gel precursor solution of claim 1 , wherein the inorganic precursor has structural Formula (I):
M-(O—R 1 ) e (I)
where
M is the first metal or the first metalloid,
(O—R 1 ) or U is one of the two or more first hydrolysable groups such that
e is 2-6,
O is oxygen,
R 1 is one of alkyl, substituted alkyl, or heteroalkyl, and.
3. The modified hybrid sol-gel precursor solution of claim 1 , wherein the cross-linkable inorganic-organic precursor is represented by structural Formula (II):
—(U-L 1 ) f -M′-(O—R 2 ) g — (II)
where
M′ is the second metal selected from the group consisting of Si, Ge, and Sn,
(U-L 1 ) is the first organic molecule such that
f is 1 or 2,
U is the first cross-linking group, and
L 1 is one of alkyldiyl, substituted alkydiyl, fluoroalkydiyl, or heteroalkydiyl,
(O—R 2 ) is the second hydrolysable group such that
g is 2-5,
O is oxygen, and
R 2 is an alkyl, substituted alkyl, or heteroalkyl.
4. The modified hybrid sol-gel precursor solution of claim 3 , wherein U is one of a bond, —O—, —N(R 5 )—, —N(H)—, —S—, —S—S—, C(O)N(R 5 )—, —N(R 5 )C(O)—, —N(R 5 )S(O 2 )—, —S(O) 2 N(R 5 )—, —OC(O)—, —OC(O)N(R 5 )—, —N(R 5 )C(O)O—, —N(R 5 )C(O)N(R 6 )—, —N(R 5 )S(O 2 )N(R 6 ), —C(H 2 )C(H 2 )—, —C(H 2 )C(H)(OH)—, —C(H 2 )C(H)(COOR)—, —C(H 2 )C(Me)(COOR)—, and —C 6 H 10 (OH)—O—, wherein each one of R, R 5 and R 6 is one of an alkyl, an aryl, a substituted alkyl, a substituted aryl, a heteroalkyl, a heteroaryl, or a cycloalkyl.
5. The modified hybrid sol-gel precursor solution of claim 1 , wherein the cross-linkable organic precursor is represented by structural Formula (III):
—V-L 2 -(V) h — (III)
where
V-L 2 -(V) h is the second organic molecule,
L 2 is one of alkyl, substituted alky, heteroalkyl, cycloalkyl, silsesquioxane, or polydimethysiloxane,
V is one of the two or more second cross-linking groups such that h is 1-7.
6. The modified hybrid sol-gel precursor solution of claim 5 , wherein V is one of a bond, —O—, —N(R 5 )—, —N(H)—, —S—, —S—S—, C(O)N(R 5 )—, —N(R 5 )C(O)—, —N(R 5 )S(O 2 )—, —S(O) 2 N(R 5 )—, —OC(O)—, —OC(O)N(R 5 )—, —N(R 5 )C(O)O—, —N(R 5 )C(O)N(R 6 )—, —N(R 5 )S(O 2 )N(R 6 ), —C(H 2 )C(H 2 )—, —C(H 2 )C(H)(OH)—, —C(H 2 )C(H)(COOR)—, —C(H 2 )C(Me)(COOR)—, and —C 6 H 10 (OH)—O—, wherein each one of R, R 5 and R 6 is one of an alkyl, an aryl, a substituted alkyl, a substituted aryl, a heteroalkyl, a heteroaryl, or a cycloalkyl.
7. The modified hybrid sol-gel precursor solution of claim 1 , wherein the protic solvent is selected from the group of propanol and acetic acid.
8. The modified hybrid sol-gel precursor solution of claim 1 , wherein the aprotic solvent is selected from the group of dimethylformamide (DMF), acetonitrile (MeCN), tetrahydrofuran (THF), and rthyl acetate (EtOAc).
9. The modified hybrid sol-gel precursor solution of claim 1 , wherein each of the protic solvent and the aprotic solvent has a molecular weight less than 100 g/mol.
10. The modified hybrid sol-gel precursor solution of claim 1 , wherein a weight ratio of the protic solvent and the aprotic solvent is between about 1:1 to 1000:1.
11. The modified hybrid sol-gel precursor solution of claim 1 , wherein a weight ratio of the protic solvent and the aprotic solvent is between about 10:1 to 100:1.
12. The modified hybrid sol-gel precursor solution of claim 1 , further comprising an additional protic solvent different from the protic solvent.
13. The modified hybrid sol-gel precursor solution of claim 1 , further comprising nanoparticles.
14. The modified hybrid sol-gel precursor solution of claim 13 , wherein the nanoparticles have functionalized surfaces configured to form covalent bonds with one or more of the inorganic precursor, the cross-linkable inorganic-organic precursor, or the cross-linkable organic precursor.
15. The modified hybrid sol-gel precursor solution of claim 14 , wherein the functionalized surfaces of the nanoparticles are plasma treated surfaces.
16. The modified hybrid sol-gel precursor solution of claim 13 , wherein the nanoparticles are selected from the group consisting of carbon nanoparticles, fullerene nanoparticles, metal oxi-nitride particles, and metal halide particles.
17. The modified hybrid sol-gel precursor solution of claim 13 , wherein the nanoparticles have an average size of between about 1 nanometer to about 20 nanometers.
18. A method of forming a solid thin film layer, the method comprising:
applying a modified hybrid sol-gel precursor solution onto a surface of a substrate,
the modified hybrid sol-gel precursor solution comprising:
an inorganic precursor comprising two or more first hydrolysable groups and one of a first metal or a first metalloid,
wherein the one of the first metal or the first metalloid is covalently bonded to the two or more first hydrolysable groups;
a cross-linkable inorganic-organic precursor comprising a second metal, a second hydrolysable group, and a first organic molecule,
wherein the second metal is covalently bound to the second hydrolysable group and is covalently bound to the first organic molecule,
wherein the first organic molecule comprises a first cross-linking group;
a cross-linkable organic precursor comprising a second organic molecule,
wherein the second organic molecule comprises two or more second cross-linking groups;
a protic solvent; and
an aprotic solvent,
wherein a weight ratio of the protic solvent and the aprotic solvent in the modified hybrid sol-gel precursor solution is selected to achieve a gelation rate of the inorganic precursor, the cross-linkable inorganic-organic precursor, and the cross-linkable organic precursor; and
curing the modified hybrid sol-gel precursor solution on the surface thereby forming the solid thin film layer
wherein the first metalloid is selected from the group consisting of boron, germanium, arsenic, antimony, tellurium, bismuth, and polonium, and
wherein the first metal is selected from the group consisting of transition metals, lanthanides, actinides, alkaline earth metals, and Group IIIA through Group VA metals.