Doped polysilanes, compositions containing the same, methods for making the same, and films formed therefrom
View Patent ↗Doped polysilanes, inks containing the same, and methods for their preparation and use are disclosed. The doped polysilane generally has the formula H-[A a H b (DR x ) m ] q -[(A c H d R 1 e ) n ] p —H, where each instance of A is independently Si or Ge, and D is B, P, As or Sb. In preferred embodiments, R is H, -A f H f+1 R 2 f , alkyl, aryl or substituted aryl, and R 1 is independently H, halogen, aryl or substituted aryl. In one aspect, the method of making a doped poly(aryl)silane generally includes the steps of combining a doped silane of the formula A a H b+2 (DR x ) m (optionally further including a silane of the formula A c H d+2 R 1 e ) with a catalyst of the formula R 4 w R 5 y MX z (or an immobilized derivative thereof) to form a doped poly(aryl)silane, then removing the metal M. In another aspect, the method of making a doped polysilane includes the steps of halogenating a doped polyarylsilane, and reducing the doped halopolysilane with a metal hydride to form the doped polysilane. The synthesis of semiconductor inks via dehydrocoupling of doped silanes and/or germanes allows for tuning of the ink properties (e.g., viscosity, boiling point, surface tension and dopant level or concentration) and for deposition of doped silicon films or islands by spincoating, inkjetting, dropcasting, etc., with or without the use of UV irradiation.
1. A doped polysilane of the formula H-[A a H b (DR x ) m ] q -[(A c H d R 1 e ) n ] p —H, where each instance of A is independently Si or Ge; D is B, P, As or Sb; each instance of R is independently alkyl, alkylene, aralkyl, substituted aralkyl, aryl, arylene or substituted aryl, and when an instance of x=2, the two R groups may form a ring together with D; q is at least 1, but q≧2 when p=0; each of the q instances of a is independently at least 1; each of the q instances of b is independently an integer of from 1 to 2a; each of the q instances of m is an integer of from 1 to a; each of the q*m instances of x is independently 1 or 2; each instance of R 1 is independently H, -A f H f+1 R 2 f , halogen, aryl or substituted aryl; each of the p instances of n is independently at least 1; each of the p*n instances of c is independently an integer of at least 1; each of the p*n instances of d is independently an integer of from c to 2c; each of the p*n instances of e is independently an integer of from 0 to c; and the sum of the p instances of n*c≧4 when q =1.
2. The doped polysilane of claim 1 , wherein R is, alkyl or aryl.
3. The doped polysilane of claim 2 , wherein R is C 1 -C 6 alkyl, phenyl, or tolyl.
4. The doped polysilane of claim 3 , wherein R is C 1 -C 4 alkyl.
5. The doped polysilane of claim 3 , wherein a is an integer of from 2 to 6.
6. The doped polysilane of claim 3 , wherein b is (2a−2−m), (2a−2), (2a−m), or 2a.
7. The doped polysilane of claim 1 , having an average number of A atoms of at least 15 according to or as calculated from a number average molecular weight Mn of the doped polysilane.
8. The doped polysilane of claim 7 , wherein A is Si.
9. The doped polysilane of claim 1 , wherein D is B or P.
10. The doped polysilane of claim 1 , wherein p is 0.
11. The doped polysilane of claim 1 , wherein R 1 is phenyl, tolyl, Cl or H; and n*p ≧4.
12. The doped polysilane of claim 11 , wherein R 1 is phenyl or H, and n*p has an average value of at least 10.
13. The doped polysilane of claim 12 , wherein R 1 is H.
14. A composition, comprising:
a) the doped polysilane of claim 1 ; and
b) a solvent in which the doped polysilane is soluble.
15. The composition of claim 14 , wherein said solvent is selected from the group consisting of linear alkanes, cycloalkanes, polycycloalkanes, (cyclic) siloxanes, and fluoroalkanes.
16. The composition of claim 15 , wherein said solvent is selected from the group consisting of C 6 -C 12 monocycloalkanes and C 10 -C 14 di- or tricycloalkanes.
17. The composition of claim 15 , wherein said solvent is a C 6 -C 10 cycloalkane.
18. The composition of claim 14 , wherein the doped polysilane is present in the composition in an amount of from about 0.0001 to about 50% by weight or by volume.
19. The composition of claim 14 , further comprising an undoped polysilane present in an amount of from about 0.5 to about 50% by weight or by volume.
20. A doped polysilane of the formula H-[A a H b (DR x ) m ] q -[(A c H d R 1 e ) n ] p —H, where each instance of A is independently Si or Ge; D is B, P, As or Sb; each instance of R is C 1 -C 4 alkyl; q is at least 1, but q≧2 when p=0; each of the q instances of a is independently at least 1; each of the q instances of b is independently an integer of from 1 to 2a; each of the q instances of m is an integer of from 1 to a; each of the q*m instances of x is independently 1 or 2; each instance of R 1 is independently -A f H f+1 R 2 f , halogen, aryl or substituted aryl; each of the p instances of n is independently at least 1; each of the p*n instances of c is independently an integer of at least 1; each of the p*n instances of d is independently an integer of from c to 2c; each of the p*n instances of e is independently an integer of from 0 to c; and the sum of the p instances of n*c>4 when q=1.
21. The doped polysilane of claim 20 , wherein a is an integer of from 1 to 6.
22. The doped polysilane of claim 21 , wherein when x=1, b is 2a or 2a=2, and when x=2, b is 2a+1 or 2a−1.
23. The doped polysilane of claim 20 , wherein A is Si.
24. The doped polysilane of claim 20 , wherein b is 2a or 2a−1, and m=1.
25. The doped polysilane of claim 20 , wherein p is an integer of at least 1, d is 2c or 2c−2, and e=0.
26. The doped polysilane of claim 20 , having an average number of A atoms of at least 10 according to or as calculated from a number average molecular weight Mn of the doped polysilane.
27. The doped polysilane of claim 20 , wherein p is an interger of at least 1, and R 1 is phenyl, totyl, Cl or H.
28. A doped polysilane of the formula H-[A a H b (DR x ) m ] q -[(A c H d R 1 e ) n ] p —H, where each instance of A is independently Si or Ge; D is B, P, As or Sb; each instance of R is independently H, -A f H 2f+1 (where f is an interger≦4), C 1 -C 6 alkyl; phenyl, or tolyl; is at least 1, but q≧2 when p=0; each of the q instances of a is independently at least 1; each of the q instances of b is independently (2a−2−m), (2a−2), (2a−m), or 2a; each of the q instances of m is an integer of from 1 to a; each of the q*m instances of x is independently 1 or 2; each instance of R 1 is independently H, -A f H f+l R 2 f , halogen, aryl or substituted aryl; each of the p instances of n is independently at least 1 ; each of the p*n instances of c is independently an integer of at least 1; each of the p*n instances of d is independently an integer of from c to 2c; each of the p*n instances of e is independently an integer of from 0 to c; and the sum of the p instances of n*c≧4 when q=1.
29. The doped polysilane of claim 28 , wherein a is an integer of from 1 to 6.
30. The doped polysilane of claim 29 , wherein when x=1, b is 2a or 2a−2, and when x=2, b is 2a+1 or 2a−1.
31. The doped polysilane of claim 28 , having an average number of A atoms of at least 10 according to or as calculated from a number average molecular weight Mn of the doped polysilane.
32. The doped polysilane of claim 28 , wherein p is an integer of at least 1, and R 1 is phenyl, tolyl, Cl or H.
33. The doped polysilane of claim 28 , wherein A is Si.
34. The doped polysilane of claim 28 , wherein b is 2a or 2a−1, and m=1.
35. A doped polysilane of the formula H-[A a H b (DR x ) m ] q -H, where each instance of A is independently Si or Ge; D is B, P, As or Sb; each instance of R is independently H, -A f H f+l R 2 f (where R 2 is H, halogen, aryl or substituted aryl and f is an integer≦6), alkyl, alkylene, aralkyl, substituted aralkyl, halogen, aryl, arylene or substituted aryl, and when an instance of x =2, the two R groups may form a ring together with D; q is an integer≧2; each of the q instances of a is independently at least 1; each of the q instances of b is independently an integer of from 2 to 2a; each of the q instances of m is an integer of from 2 to a; and each of the q*m instances of x is independently 1 or 2.
36. The doped polysilane of claim 35 , wherein R is alkyl or aryl.
37. The doped polysilane of claim 36 , wherein R is C 1 -C 4 alkyl, phenyl or tolyl.
38. The doped polysilane of claim 35 , wherein b is (2a−2−m), (2a−2), (2a−m), or 2a.
39. The doped polysilane of claim 35 , wherein A is Si.
40. The doped polysilane of claim 35 , wherein when x=1, b is 2a or 2a−2, and when x=2, b is 2a+1 or 2a−1.
41. The doped polysilane of claim 35 , wherein R 1 is H or X.
42. A composition, comprising:
a) a doped polysilane of the formula H-[A a H b (DR x ) m ] p -[(A c H d R 1 e ) n ] p -H, where each instance of A is independently Si or Ge; D is B, P, As or Sb; each instance of R is independently H, -A f H f+l R 2 f or -A f H f R 2 f - (where R 2 is H, halogen, aryl or substituted aryl, and f is an integer≦6), alkyl, alkylene, aralkyl, substituted aralkyl, halogen, aryl, arylene or substituted aryl, and when an instance of x=2, the two R groups may form a ring together with D; q is at least 1, but q≧2 when p=0; each of the q instances of a is independently at least 1; each of the q instances of b is independently an integer of from 1 to 2a; each of the q instances of m is an integer of from 1 to a; each of the q*m instances of x is independently 1 or 2; each instance of R 1 is independently H, -A f H f+l R 2 f , halogen, aryl or substituted aryl; each of the p instances of n is independently at least 1; each of the p*n instances of c is independently an integer of at least 1; each of the p*n instances of d is independently an integer of from c to 2c; each of the p*n instances of e is independently an integer of from 0 to c; and the sum of the p instances of n*c≧4 when q=1;
b) a solvent in which the doped polysilane is soluble; and
c) an undoped polysilane present in an amount of from about 0.5 to about 50% by weight or by volume.
43. The composition of claim 42 , wherein said solvent is selected from the group consisting of linear alkanes, cycloalkanes, polycycloalkanes, (cyclic) siloxanes, and fluoroalkanes.
44. The composition of claim 43 , wherein said solvent is selected from the group consisting of C 6 -C 12 monocycloalkanes and C 10 -C 14 di- or tricycloalkanes.
45. The composition of claim 42 , wherein the doped polysilane is present in the composition in an amount of from about 0.0001 to about 50% by weight or by volume.