Emissive polymers and devices incorporating these polymers

• US 20030178607A1
• Filed: 12/18/2002
• Published: 09/25/2003
• Est. Priority Date: 05/05/1998
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Levitsky, Igor A., Kim, Jinsang, Swager, Timothy M., Lugmair, Claus G., Yang, Jye-Shane, Williams, Vance, Deans, Robert, Miao, Yi-Jun
• Granted Patent: US 7,208,122 B2
• Time in Patent Office: Days
• US Class Current: 252/582
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C08G 61/10 only aromatic carbon atoms, e.g. polyphenylenes
• CPC Class Codes: C08L 101/12 characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity liquid crystal materials or compositions C09K19/00
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 30/65 Light-sensitive field-effect devices, e.g. phototransistors
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: H10K 85/154 Ladder-type polymers
• CPC Class Codes: H10K 85/30 : Coordination compounds
• CPC Class Codes: H10K 85/615 : Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: Y02E 10/549 : Organic PV cells

Abstract

The present invention relates to a class of luminescent and conductive polymer compositions having chromophores, and particularly solid films of these compositions exhibiting increased luminescent lifetimes, quantum yields and amplified emissions. These desirable properties can be provided through polymers having rigid groups designed to prevent polymer reorganization, aggregation or π-stacking upon solidification. These polymers can also display an unusually high stability with respect to solvent and heat exposures. The invention also relates to a sensor and a method for sensing an analyte through the luminescent and conductive properties of these polymers. Analytes can be sensed by activation of a chromophore at a polymer surface. Analytes include aromatics, phosphate ester groups and in particular explosives and chemical warfare agents in a gaseous state. The present invention also relates to devices and methods for amplifying emissions by incorporating a polymer having an energy migration pathway and/or providing the polymer as a block co-polymer or as a multi-layer.

Claims

1. A sensor, comprising a film including a polymer, the polymer including a chromophore, the polymer being capable of emitting radiation with a quantum yield of at least about 0.05 times that of a quantum yield of the polymer in solution.

2. A sensor as in claim 1, wherein the polymer has a backbone including the chromophore.

3. A sensor as in claim 2, wherein the chromophore is a conjugated group.

4. A sensor as in claim 3, wherein the polymer is a conjugated polymer.

5. A sensor as in claim 4, wherein the polymer is selected from the group consisting of polyarylenes, polyarylene vinylenes, polyarylene ethynylenes and ladder polymers.

6. A sensor as in claim 2, wherein the polymer backbone has a plurality of chromophores interrupted by non-conjugated groups.

7. A sensor as in claim 6, wherein the chromophore is a conjugated group.

8. A sensor as in claim 1, wherein the polymer has a backbone and the chromophore is a pendant group.

9. A sensor as in claim 8, wherein the chromophore is a conjugated group.

10. A sensor as in claim 9, wherein the polymer backbone is non-conjugated.

11. A method for amplifying an emission, comprising:

providing an article comprising a polymer having an energy migration pathway and a chromophore;

exposing the article to a source of energy to form an excitation energy; and

allowing the excitation energy to travel through the migration pathway and to transfer to the chromophore, causing an emission that is greater than an emission resulting from a polymer free of an energy migration pathway.

12. A sensor as in claim 11, wherein the pathway includes a HOMO-LUMO gap that continually decreases in a direction along the energy migration pathway to the chromophore.

13. A method as in claim 11, wherein the article comprises at least one layer of a polymer including a chromophore.

14. A method as in claim 13, wherein the article comprises multiple layers, each layer comprising a polymer including a chromophore and the energy migration pathway being continuous throughout the multiple layers.

15. A method for amplifying an emission, comprising:

providing an article comprising a polymer having an energy migration pathway, the polymer having reduced π

-stacking;

exposing the article to a source of energy to form an excitation energy; and

allowing the excitation energy to travel through the migration pathway to cause an emission that is greater than an emission resulting from a polymer free of an energy migration pathway.

16. A method as in claim 15, wherein the polymer having reduced π

-stacking has a backbone separated from adjacent backbone at a distance of at least about 4.5 Å

.

17. A method as in claim 15, wherein the polymer having reduced π

-stacking has a backbone separated from adjacent backbone at a distance of at least about 5.0 Å

.

18. A sensor, comprising:

an article comprising at least one layer including a polymeric composition and a chromophore, the article further comprising an activation site wherein the chromophore is capable of activation by an analyte at the activation site; and

an energy migration pathway within the polymeric composition, wherein energy can be transferred between the pathway and the activation site.

19. A sensor as in claim 18, wherein the pathway includes a HOMO-LUMO gap that continually decreases in a direction along the energy migration pathway toward the activation site.

20. A sensor as in claim 18, wherein the chromophore is present in a surface of the article.

21. A sensor as in claim 18, wherein the chromophore is present in a bulk of the article.

22. A sensor as in claim 18, wherein the article comprises a first layer of a first polymer and a second layer of a second polymer, the first layer being positioned adjacent the second layer, the chromophore being present in the first and second layers and the energy migration pathway being continuous through the first and second layers.

23. A sensor as in claim 18, wherein the chromophore is capable of activation by an analyte.

24. A sensor as in claim 23, wherein a HOMO-LUMO gap of the chromophore is greater than a HOMO-LUMO gap in the pathway in the absence of activation by the analyte.

25. A sensor as in claim 23, wherein a HOMO-LUMO gap of the chromophore is less than a HOMO-LUMO gap in the pathway upon activation by an analyte.

26. A sensor comprising a polymer capable of emission, wherein the emission is variable and sensitive to a dielectric constant of a medium surrounding the sensor.

27. A sensor comprising a polymer capable of emission, wherein the emission is variable and sensitive to an electric field of a medium surrounding the sensor.

28. An amplification device, comprising:

a polymer having an energy migration pathway capable of transporting an excitation energy; and

a chromophore in electronic communication with the energy migration pathway, the chromophore being capable of emitting an enhanced radiation.

29. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms;

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

.

30. A polymeric composition as in claim 29, wherein the sum of the first and second heights is at least about 5.0 Å

.

31. A polymeric composition as in claim 29, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

32. A polymeric composition as in claim 31, wherein the film has a luminescence quantum yield of at least about 0.15 times the quantum yield of the polymeric composition in solution.

33. A polymeric composition as in claim 31, wherein the film has a luminescence quantum yield of at least about 0.2 times the quantum yield of the polymeric composition in solution.

34. A polymeric composition as in claim 31, wherein the film has a luminescence quantum yield of at least about 0.3 times the quantum yield of the polymeric composition in solution.

35. A polymeric composition as in claim 31, wherein the film has a luminescence quantum yield of at least about 0.4 times the quantum yield of the polymeric composition in solution.

36. A polymeric composition as in claim 31, wherein the film has a luminescence quantum yield of at least about 0.5 times the quantum yield of the polymeric composition in solution.

37. A polymeric composition as in claim 29, comprising a rigid three-dimensional structure such that in a first and a second optical spectrum of the composition, maxima in the first spectrum differ by no more than about 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after exposing the composition, characterized by the first spectrum, to an organic solvent that does not dissolve the composition.

38. A polymeric composition as in claim 37, wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

39. A polymeric composition as in claim 37, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

40. A polymeric composition as in claim 37, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

41. A polymeric composition as in claim 40, wherein the intensity change is less than about 15%.

42. A polymeric composition as in claim 29, comprising a rigid three-dimensional structure such that in a first and second optical spectra of the composition, maxima in the first spectrum differ by no more than 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after heating the composition to a temperature of no more than 150°

C.

43. A polymeric composition as in claim 42;

wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

44. A polymeric composition as in claim 42, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

45. A polymeric composition as in claim 42, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

46. A polymeric composition as in claim 45, wherein the intensity change is less than about 15%.

47. A polymeric composition as in claim 29, wherein the backbone is free from π

-stacking.

48. A polymeric composition as in claim 29, wherein the π

-backbone comprises the structure;

49. A polymeric composition as in claim 48, wherein E_a is attached to the π

-backbone and the polymeric composition comprises the structure;

50. A polymeric composition as in claim 49, wherein G and H may be the same or different, and each is selected from the group consisting of:

51. A polymeric composition as in claim 50, wherein A is selected from the group consisting of:

52. A polymeric composition as in claim 50, wherein at least one of G, H, I and J comprises a naphthalene group, the naphthalene group being a component of an exciplex structure.

53. A polymeric composition as in claim 49, wherein the composition is essentially rigid with respect to structural rearrangement under conditions selected from the group consisting of heating the composition to a temperature of less than about 150°

C. and exposing the composition to an organic solvent that does not dissolve the composition.

54. A polymeric composition as in claim 49, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

55. A polymeric composition as in claim 48, wherein E is selected from the group consisting of

56. A polymeric composition as in claim 48, comprising the structure:

57. A polymeric composition as in claim 48, comprising the structure:

58. A polymeric composition as in claim 48, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

59. A polymeric composition as in claim 48, comprising a rigid three-dimensional structure such that in a first and second optical spectrum of the composition, maxima in the first spectrum differ by no more than 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after exposing the composition to an organic solvent that does not dissolve the composition.

60. A polymeric composition as in claim 59, wherein the maxima in the second spectrum have an intensity of less than about 10% than the maxima in the first spectrum.

61. A polymeric composition as in claim 48, comprising a rigid three-dimensional structure such that in a first and second optical spectra of the composition, maxima in the first spectrum differ by no more than 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after heating the composition to a temperature of no more than 150°

C.

62. A polymeric composition as in claim 61, wherein the maxima in the second spectrum have an intensity of less than about 10% than the maxima in the first spectrum.

63. A polymeric composition as in claim 48, wherein the backbone has reduced π

-stacking.

64. A sensor comprising:

a polymeric composition comprising the structure;

wherein A and C are aromatic groups;

B and D are selected from the group consisting of a carbon-carbon double bond and a carbon-carbon triple bond; and

any hydrogen on aromatic group A and C can be replaced by E and F respectively, a and b being integers which can be the same or different and a=0-4, b=0-4 such that when a=0, b is nonzero and when b=0, a is nonzero, and at least one of E and F includes a bicyclic ring system having aromatic or non-aromatic groups optionally interrupted by O, S, NR¹ and C(R¹)₂ wherein R¹ is selected from the group consisting of hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy and aryl and n is less than about 10,000;

a source of energy applicable to the polymeric composition to cause emission of radiation; and

an emission detector positionable to detect the emission.

65. A sensor as in claim 64, wherein the energy is selected from the group consisting of electromagnetic radiation, electrical energy and chemical energy.

66. A sensor as in claim 64, further comprising an article positioned adjacent the polymeric composition to provide enhanced rigidity, sensitivity, selectivity, stability, and a combination thereof to the polymeric composition.

67. A sensor as in claim 66, wherein the article is selected from the group consisting of a bead, nanoparticles, a polymer fiber, a waveguide and a film.

68. A sensor as in claim 66, wherein the article is selected from the group consisting a biological species, a polymer, a ceramic, a conductor and a semiconductor.

69. A sensor as in claim 68, wherein the biological species is selected from the group consisting of a peptide, an oligonucleotide, an enzyme, an antibody, a fluorescent peptide, a fluorescent oligonucleotide and a fluorescent antibody.

70. A sensor as in claim 68, wherein the polymer is selected from the group consisting of polystyrene, polyethylene oxide, polyethylene, polysiloxane, polyphenylene, polythiophene, poly(phenylene-vinylene), polysilane, polyethylene terephthalate and poly(phenylene-ethynylene).

71. A sensor as in claim 68, wherein the semiconductor and conductor is selected from the group consisting of solids and nanoclusters.

72. A sensor as in claim 71, wherein the semiconductor is selected from the group consisting of Group II/VI semiconductors, Group III/V semiconductors and Group IV semiconductors.

73. A sensor as in claim 72, wherein the semiconductor is selected from the group consisting of CdS, CdSe, InP, GAs, Si, Ge and porous silicon.

74. A sensor as in claim 71, wherein the conductor is colloidal gold.

75. A sensor as in claim 68, wherein the ceramic is selected from the group consisting of glass, quartz, titanium oxide and indium tin oxide.

76. A method for detecting the presence of an analyte, comprising:

providing a polymeric composition comprising the structure;

wherein A and C are aromatic groups;

B and D are selected from the group consisting of a carbon-carbon double bond and a carbon-carbon triple bond; and

any hydrogen on aromatic group A and C can be replaced by E and F respectively, a and b being integers which can be the same or different and a=0-4, b=0-4 such that when a=0, b is nonzero and when b=0, a is nonzero, and at least one of E and F includes a bicyclic ring system having aromatic or non-aromatic groups optionally interrupted by O, S, NR¹ and C(R¹)₂ wherein R¹ is selected from the group consisting of hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy and aryl and n is less than about 10,000;

exposing the polymeric composition to a source of energy to cause a first emission of radiation;

exposing the polymeric composition to a medium containing an analyte, causing a second emission of radiation; and

detecting a difference between the first emission and the second emission.

77. A method as in claim 76, wherein the difference is a difference in wavelength.

78. A method as in claim 76, wherein the difference is a difference in intensity.

79. A method as in claim 76, wherein the difference is caused by an electron transfer reaction between the composition and the analyte.

80. A method as in claim 76, wherein the difference is caused by a conformation change of the composition induced by the analyte.

81. A method as in claim 76, wherein the difference is caused by an exciplex structure comprising the composition and the analyte.

82. A method as in claim 76, wherein the energy is selected from the group consisting of electromagnetic radiation, electrical energy and chemical energy.

83. A field-effect transistor, comprising:

an insulating medium having a first side and an opposing second side;

a polymeric article positioned adjacent the first side of the insulating medium;

a first electrode electrically connected to a first portion of the polymeric article and a second electrode electrically connected to a second portion of the polymeric article, each electrode positioned on the first side of the insulating medium, and the first electrode being connected to the second electrode by an electrical circuit external of the polymeric structure;

a gate electrode positioned on the second side of the insulating medium in a region directly opposite the polymeric article, the gate electrode being connected to a voltage source;

a source of electromagnetic radiation positioned to apply the electromagnetic radiation to the article; and

at least one species associated with the article, wherein the at least one species, upon exposing the polymeric article to the electromagnetic radiation, is a component of an excited state structure.

84. A field-effect transistor as in claim 83, wherein the polymeric article comprises the structure:

85. A field-effect transistor as in claim 83, wherein the first electrode is a source electrode and the second electrode is a drain electrode.

86. A field-effect transistor as in claim 85, wherein under set conditions of the electrical circuit and first conditions of exposure of the polymeric article to electromagnetic radiation a first current passes between the source and drain electrodes.

87. A field-effect transistor as in claim 86, wherein under the set conditions of the electrical circuit and second conditions of exposure of the polymeric article to electromagnetic radiation a second current passes between the source and drain electrodes.

88. A field-effect transistor as in claim 86, wherein a current between the source and drain electrodes is a second current after exposure of the polymeric article to electromagnetic radiation.

89. A field effect transistor as in claim 87, wherein the second current is greater than the first current.

91. A field-effect transistor as in claim 89, wherein the second polymeric article is a charge-injecting polymer comprising the structure:

92. A field-effect transistor as in claim 89, wherein the first electrode is a source electrode and the second electrode is a drain electrode.

93. A field-effect transistor as in claim 91, wherein under set conditions of the electrical circuit and first conditions of exposure of the second polymeric article to electromagnetic radiation a first current passes between the source and drain electrodes.

94. A field-effect transistor as in claim 92, wherein under the set conditions of the electrical circuit and second conditions of exposure of the second polymeric article to electromagnetic radiation a second current passes between the source and drain electrodes.

95. A field-effect transistor as in claim 93, wherein the second current is greater than the first current.

96. A field-effect transistor as in claim 89, wherein the first polymeric article has a charge conducting ability at least ten times a charge conducting ability of the second polymeric article.

97. A field-effect transistor as in claim 89, wherein the first polymeric article is a charge-conducting polymer.

98. A field-effect transistor as in claim 96, wherein the first polymeric article is selected from the group consisting of polythiophene, polypyrrole, polyacetylene, polyphenylene and polyaniline.

99. A field effect transistor as in claim 96, wherein the first polymeric article comprises the structure:

90. A field-effect transistor, comprising:

an insulating medium having a first side and an opposing second side;

a first polymeric article positioned adjacent the insulating medium;

a first electrode connected to a first portion of the first polymeric article and a second electrode connected to a second portion of the first polymeric article, each electrode positioned on the first side of the insulating medium, and the first electrode being connected to the second electrode by an electrical circuit external of the first polymeric article;

a gate electrode positioned on the second side of the insulating medium below the first polymeric article, the gate electrode being connected to a voltage source;

a second polymeric article positioned adjacent the first polymeric article;

a source of electromagnetic radiation applicable to the second polymeric article; and

at least one species associated with the second polymeric article, which upon exposing the second polymeric article to electromagnetic radiation, is a component of an excited state structure.