Siloxanes, doped siloxanes, methods for their synthesis, compositions containing the same, and films formed therefrom
View Patent ↗In one aspect, the present invention provides undoped and doped siloxanes, germoxanes, and silagermoxanes that are substantially free from carbon and other undesired contaminants. In a second aspect, the present invention provides methods for making such undoped and doped siloxanes, germoxanes, and silagermoxanes. In still another aspect, the present invention provides compositions comprising undoped and/or doped siloxanes, germoxanes, and silagermoxanes and a solvent, and methods for forming undoped and doped dielectric films from such compositions. Undoped and/or doped siloxane compositions as described advantageously provide undoped and/or doped dielectric precursor inks that may be employed in forming substantially carbon-free undoped and/or doped dielectric films.
1. A method of making a siloxane, germoxane, or silagermoxane compound, comprising:
a) mixing a linear, branched, cyclic or caged silane, germane, or silagermane containing at least three A atoms comprising units of the formula =(AH)—, -(AH 2 )—, -(AH 3 ), -(c-A q H 2q-1 ) and/or -(c-A q H 2q-x )—, where each instance of A is independently Si or Ge, each instance of q is independently an integer from 3 to 12, and each instance of x is independently an integer from 0 to q, with a solvent; and
b) reacting said silane, germane, or silagermane compound with an oxygen source selected from the group consisting of sulfur-based oxidants, alkali metal-based oxidants, alkaline earth metal-based oxidants, transition metal-based oxidants, lanthanide metal-based oxidants and/or actinide metal-based oxidants and that contains substantially no carbon atoms to form said siloxane, germoxane, or silagermoxane.
2. The method of claim 1 , wherein said linear, branched, cyclic or caged silane, germane, or silagermane consists essentially of silicon and hydrogen.
3. The method of claim 1 , wherein said linear, branched, cyclic or caged silane, germane, or silagermane further comprises one or more units of the formula of the formula DR 1 p , where each instance of D is independently Sb, As, P or B, each instance of p is independently an integer from 0 to 2, and each instance of R 1 is independently alkyl, aryl, aralkyl, H, or AR 2 3 , where R 2 is H, or -A y H 2y+1 , and y is an integer from 1 to 4.
4. The method of claim 3 , wherein D is P or B.
5. The method of claim 1 , further comprising adding one or more dopant and/or dopant precursor compounds to said linear, branched, cyclic or caged silane, germane, or silagermane and said solvent prior to said reacting step to form a mixture.
6. The method of claim 5 , wherein said one or more dopant and/or dopant precursor compounds are present in an amount providing from 0.0001 at % to 20 at % of dopant atoms in the mixture.
7. A method of making a polysiloxane, comprising:
a) mixing a linear, branched, cyclic or caged silane, germane, or silagermane containing at least three A atoms comprising units of the formula =(AH)—, -(AH 2 )—, -(AH 3 ), -(c-A q H 2q-1 ) and/or -(c-A q H 2q-x )—, where each instance of A is independently Si or Ge, each instance of q is independently an integer from 3 to 12, and each instance of x is independently an integer from 2 to q, with a solvent; and
b) adding one or more dopant and/or dopant precursor compounds to said linear, branched, cyclic or caged silane, germane, or silagermane and said solvent to form a mixture; and
c) after said adding step, reacting said silane, germane, or silagermane with an oxygen source that contains substantially no carbon atoms to form said polysiloxane.
8. The method of claim 7 , wherein the oxygen source is selected from the group consisting of sulfur-based oxidants, alkali metal-based oxidants, alkaline earth metal-based oxidants, transition metal-based oxidants, lanthanide metal-based oxidants and/or actinide metal-based oxidants.
9. The method of claim 7 , wherein the oxygen source is selected from the group consisting of air, O 2 , O 3 and H 2 O 2 .
10. The method of claim 7 , wherein said linear, branched, cyclic or caged silane, germane, or silagermane consists essentially of silicon and hydrogen.
11. The method of claim 7 , wherein said one or more dopant and/or dopant precursor compounds comprises a compound of the formula D a R 1 b , where D is Sb, As, P or B or Al; a is from 1 to 20; b is an integer corresponding to the number of binding sites available on the a instances of D; each of the b instances of R 1 is independently H, alkyl, aryl, aralkyl, a halogen, O, OR 2 , NR 2 2 or AR 2′ 3 ; where R 2 is hydrogen, alkyl, aryl, aralkyl, F, Cl, Br, or I; R 2′ is hydrogen, alkyl, aryl, aralkyl or A y H 2y+1 ; and y is an integer of from 1 to 4.
12. The method of claim 11 , wherein said one or more dopant and/or dopant precursor compounds comprises one or more soluble organoboranes, (organo)azaboranes, organoborates, boron oxides, BX 3 , an adduct and/or salt of BF 3 , white or red phosphorous, a phosphorous oxide, an organophosphines, an organophosphine oxide, an organophosphite, an organophosphate, a meta- or polyphosphate, an organophosphazenes, an organooxophosphazene, PX 3 , PX 5 , POX 3 , P(NR 2 ) 3 , O═P(NR 2 ) 3 , or P(═NR)X 3 , where X is a halogen and R is alkyl or aryl.
13. The method of claim 7 , wherein said one or more dopant and/or dopant precursor compounds are present in an amount providing from 0.0001 at % to 20 at % of dopant atoms in the mixture.
14. A method of making a polysiloxane, comprising:
a) mixing a polysilane containing at least 15 silicon atoms consisting essentially of units of the formula ═(SiH)—, —(SiH 2 )—, —(SiH 3 ), -(c-Si q H 2q-1 )— and/or -(c-Si q H 2q-x )—, where each instance of q is independently an integer from 3 to 12, and each instance of x is independently an integer from 2 to q, with a solvent; and
b) reacting said polysilane with an oxygen source that contains substantially no carbon atoms to form said polysiloxane.
15. The method of claim 14 , wherein the oxygen source is selected from the group consisting of sulfur-based oxidants, alkali metal-based oxidants, alkaline earth metal-based oxidants, transition metal-based oxidants, lanthanide metal-based oxidants and/or actinide metal-based oxidants.
16. The method of claim 14 , wherein the oxygen source is selected from the group consisting of air, O 2 , O 3 and H 2 O 2 .
17. The method of claim 14 , wherein said linear, branched, cyclic or caged silane, germane, or silagermane further comprises one or more units of the formula of the formula DR 1 p , where each instance of D is independently Sb, As, P or B, each instance of p is independently an integer from 0 to 2, and each instance of R 1 is independently alkyl, aryl, aralkyl, H, or AR 2 3 , where R 2 is H, or -A y H 2y+1 , and y is an integer from 1 to 4.
18. The method of claim 14 , further comprising adding one or more dopant and/or dopant precursor compounds to said linear, branched, cyclic or caged silane, germane, or silagermane and said solvent prior to said reacting step.
19. The method of claim 18 , wherein said one or more dopant and/or dopant precursor compounds comprises a compound of the formula D a R 1 b , where D is Sb, As, P or B or Al; a is from 1 to 20; b is an integer corresponding to the number of binding sites available on the a instances of D; each of the b instances of R 1 is independently H, alkyl, aryl, aralkyl, a halogen, O, OR 2 , NR 2 2 or AR 2′ 3 ; where R 2 is hydrogen, alkyl, aryl, aralkyl, F, Cl, Br, or I; R 2′ is hydrogen, alkyl, aryl, aralkyl or A y H 2y+1 ; and y is an integer of from 1 to 4.
20. The method of claim 18 , wherein said one or more dopant and/or dopant precursor compounds are present in an amount providing from 0.0001 at % to 20 at % of dopant atoms in the mixture.