Solar cells incorporating light harvesting arrays

• US 6,596,935 B2
• Filed: 05/08/2002
• Issued: 07/22/2003
• Est. Priority Date: 07/21/2000
• Status: Expired due to Fees

• Current Assignee: North Carolina State University (University of North Carolina System)
• Original Assignee: North Carolina State University (University of North Carolina System)
• Inventors: Meyer, Gerald J., Lindsey, Jonathan S.
• Primary Examiner(s): DIAMOND, ALAN D
• Application Number:
  US10/141,654
• Publication Number:
  US 20020185173A1
• Time in Patent Office: 440 Days
• Field of Search: 136/263, 136/252, 136/256, 257/40, 257/431, 429/111
• US Class Current: 136/263
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C09B 47/00 Porphines; Azaporphines non-dyeing compounds C07D487/22
• CPC Class Codes: C09B 69/008 Dyes containing a substituent, which contains a silicium atom
• CPC Class Codes: C09B 69/108 containing a phthalocyanine dye
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H01G 9/209 Light trapping arrangements
• CPC Class Codes: H10K 30/151 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/30 Coordination compounds
• CPC Class Codes: H10K 85/361 Polynuclear complexes, i.e. complexes comprising two or more metal centers
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A solar cell incorporates a light harvesting array that comprises: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to the first electrode, each of the light harvesting rods comprising a polymer of Formula I: $\begin{array}{cc}{X}^1{—\left(X^{m+1}\right)}_m& \left(I\right)\end{array}$

wherein m is at least 1, and may be from two, three or four to 20 or more; X¹ is a charge separation group (and preferably a porphyrinic macrocycle, which may be one ligand of a double-decker sandwich compound) having an excited-state of energy equal to or lower than that of X²; and X² through X^m+1 are chromophores (and again are preferably porphyrinic macrocycles).

Claims

1. A solar cell, comprising:

(a) a first substrate comprising a first electrode;

(b) a second substrate comprising a second electrode, with said first and second substrate being positioned to form a space therebetween, and with at least one of (i) said first substrate and said first electrode and (ii) said second substrate and said second electrode being transparent;

(c) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a non-discotic backbone polymer of Formula I;

$\begin{array}{cc}{X}^1<br><br>{\mathrm{—<br><br>}\left(X^{m+1}\right)}_m& \left(I\right)\end{array}$

 

wherein;

m is at least 2;

X¹ is a charge separation group having an excited-state of energy equal to or lower than that of X²;

X² through X^m+1 are chromophores selected from the group consisting of chlorins, bacteriochlorins, isobacteriochlorins, phthalocyanines, porphyrazines, naphthalocyanines, subphthalocyanines and porphyrin isomers; and

X¹ is electrically coupled to said first electrode;

said solar cell further comprising

(d) an electrolyte in said space between said first and second substrates.

2. A solar cell according to claim 1, wherein X¹ comprises a porphyrinic macrocycle.

3. A solar cell according to claim 1, further comprising a mobile charge carrier in said electrolyte.

4. A solar cell according to claim 1, wherein said electrolyte comprises an aqueous electrolyte.

5. A solar cell according to claim 1, wherein said electrolyte comprises a non-aqueous electrolyte.

6. A solar cell according to claim 1, wherein said electrolyte comprises a polymer electrolyte.

7. A solar cell according to claim 1, wherein said electrolyte comprises a solid.

8. A solar cell according to claim 1, wherein said solar cell is devoid of liquid in said space between said first and second substrates.

9. A solar cell according to claim 1, wherein said charge separation group X¹ comprises a double-decker sandwich coordination compound.

10. A solar cell according to claim 1, wherein said light harvesting rods are oriented substantially perpendicularly to said second electrode.

11. A solar cell according to claim 1, wherein said light harvesting rods are linear.

12. A solar cell according to claim 1, wherein said light harvesting rods are not greater than 500 nanometers in length.

13. An electrical device, comprising:

(a) a solar cell according to claim 1; and

(b) a circuit electrically coupled to said solar cell.

14. An electrical device according to claim 13, wherein said circuit comprises a resistive load.

44. A solar cell according to claim 1, 15 or 30, wherein X¹ through X^m+1 each independently comprise a porphyrinic macrocycle selected from the group consisting of Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, and Formula XVII:

 

wherein;

M is selected from the group consisting of Zn, Mg, Pd, Sn and Al, or M is absent;

K¹, K², K₃, K⁴, K⁵, K⁶, K⁷, and K⁸ are independently selected from the group consisting of N, O, S, Se, Te, and CH;

S¹, S², S³, S⁴, S⁵, S⁶, S⁷, S⁸, S⁹, S¹⁰, S¹¹, S¹², S¹³, S¹⁴, S¹⁵ and S¹⁶ are each independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl;

and wherein each pair of S¹ and S², S³ and S⁴, S⁵ and S⁶, and S⁷ and S⁸, optionally independently form an annulated arene, which annulated arene is optionally unsubstituted or substituted one or more times with a substituent selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl;

and wherein S¹ through S¹⁶ optionally comprise a linking group covalently linked to an adjacent porphyrinic macrocycle of X¹ through X^m+1 or a linking group covalently linked to said first electrode.

45. A solar cell according to claim 1, 15 or 30, wherein said light-harvesting rods are intrinsic rectifiers of excited-state energy.

46. A solar cell according to claim 1, 15, or 30, wherein said light-harvesting rods are intrinsic rectifers of holes.

15. A solar cell, comprising:

(a) a first substrate comprising a first electrode;

(b) a second substrate comprising a second electrode, with said first and second substrate being positioned to form a space therebetween, and with at least one of (i) said first substrate and said first electrode and (ii) said second substrate and said second electrode being transparent;

(c) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a non-discotic backbone polymer of Formula I;

$\begin{array}{cc}{X}^1<br><br>{\mathrm{—<br><br>}\left(X^{m+1}\right)}_m& \left(I\right)\end{array}$

 

wherein;

m is at least 2;

X¹ is a charge separation group having an excited-state of energy equal to or lower than that of X²;

X² through X^m+1 are chromophores selected from the group consisting of chlorins, bacteriochlorins, isobacteriochlorins, phthalocyanines, porphyrazines, naphthalocyanines, subphthalocyanines and porphyrin isomers;

X¹ is electrically coupled to said first electrode; and

X² through X^m+1 are selected so that, upon injection of either an electron or hole from X¹ into said first electrode, the corresponding hole or electron from X¹ is transferred to at least X²;

said solar cell further comprising

(d) an electrolyte in said space between said first and second substrates; and

(e) a mobile charge carrier in said electrolyte.

16. A solar cell according to claim 15, wherein X¹ through X^m+1 are selected so that, upon injection of an electron from X¹ into said first electrode, the corresponding hole from X¹ is transferred to at least X².

17. A solar cell according to claim 15, wherein X^m+1 is bonded to said second electrode.

18. A solar cell according to claim 15, wherein X¹ comprises a porphyrinic macrocycle.

19. A solar cell according to claim 15, wherein said electrolyte comprises an aqueous electrolyte.

20. A solar cell according to claim 15, wherein said electrolyte comprises a non-aqueous electrolyte.

21. A solar cell according to claim 15, wherein said electrolyte comprises a polymer electrolyte.

22. A solar cell according to claim 15, wherein said electrolyte comprises a solid.

23. A solar cell according to claim 15, wherein said solar cell is devoid of liquid in said space between said first and second substrates.

24. A solar cell according to claim 15, wherein said charge separation group X¹ is a double-decker sandwich coordination compound.

25. A solar cell according to claim 15, wherein said light harvesting rods are oriented substantially perpendicularly to said second electrode.

26. A solar cell according to claim 15, wherein said light harvesting rods are linear.

27. A solar cell according to claim 15, wherein said light harvesting rods are not greater than 500 nanometers in length.

28. An electrical device, comprising:

(a) a solar cell according to claim 15; and

(b) a circuit electrically coupled to said solar cell.

29. An electrical device according to claim 28, wherein said circuit comprises a resistive load.

30. A solar cell, comprising:

(a) a first substrate comprising a first electrode;

(b) a second substrate comprising a second electrode, with said first and second substrate being positioned to form a space therebetween, and with at least one of (i) said first substrate and said first electrode and (ii) said second substrate and said second electrode being transparent;

(c) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a non-discotic backbone polymer of Formula I;

$\begin{array}{cc}{X}^1<br><br>{\mathrm{—<br><br>}\left(X^{m+1}\right)}_m& \left(I\right)\end{array}$

 

wherein;

m is at least 2;

X¹ is a charge separation group having an excited-state of energy equal to or lower than that of X²;

X² through X^m+1 are chromophores selected from the group consisting of chlorins, bacteriochlorins, isobacteriochlorins, phthalocyanines, porphyrazines, naphthalocyanines, subphthalocyanines and porphyrin isomers;

X¹ is electrically coupled to said first electrode; and

X^m+1 is electrically coupled to said second electrode;

said solar cell further comprising

(d) an electrolyte in said space between said first and second substrates.

31. A solar cell according to claim 30, wherein X¹ comprises a porphyrinic macrocycle.

32. A solar cell according to claim 30, wherein X¹ through X^m+1 are selected so that, upon injection of an electron from X¹ into said first electrode, the corresponding hole from X¹ is transferred to X^m+1.

33. A solar cell according to claim 30, wherein said electrolyte comprises an aqueous electrolyte.

34. A solar cell according to claim 30, wherein said electrolyte comprises a non-aqueous electrolyte.

35. A solar cell according to claim 30, wherein said electrolyte comprises a polymer electrolyte.

36. A solar cell according to claim 30, wherein said electrolyte comprises a solid.

37. A solar cell according to claim 30, wherein said solar cell is devoid of liquid in said space between said first and second substrates.

38. A solar cell according to claim 30, wherein said charge separation group a double-decker sandwich coordination compound.

39. A solar cell according to claim 30, wherein said light harvesting rods are oriented substantially perpendicularly to said second electrode.

40. A solar cell according to claim 30, wherein said light harvesting rods are linear.

41. A solar cell according to claim 30, wherein said light harvesting rods are not greater than 500 nanometers in length.

42. An electrical device, comprising:

(a) a solar cell according to claim 30; and

(b) a circuit electrically coupled to said solar cell.

43. An electrical device according to claim 42, wherein said circuit comprises a resistive load.