Emissive polymers and devices incorporating these polymers

• US 7,393,503 B2
• Filed: 10/17/2005
• Issued: 07/01/2008
• Est. Priority Date: 05/05/1998
• Status: Expired due to Fees

• 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, Yijun
• Primary Examiner(s): Griffin; Walter D.
• Assistant Examiner(s): Mui; Christine T
• Application Number:
  US11/252,530
• Publication Number:
  US 20060120923A1
• Time in Patent Office: 988 Days
• Field of Search: 422/82, 524/492, 525/54.2, 435/6, 435/287.2
• US Class Current: 422/82
• 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 method for detecting the presence of an analyte, 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;

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

exposing the article to a medium containing an analyte and to the source of the excitation energy to cause a second emission of radiation from the article; and

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

2. A method as in claim 1, wherein the pathway includes a HOMO-LUMO gap that continually decreases in a direction along the energy migration pathway to the chromophore.

3. A method as in claim 1, wherein the article comprises at least one layer of a polymer including a chromophore.

4. A method as in claim 3, 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.

5. A method for detecting the presence of an analyte, 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;

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

exposing the article to a medium containing an analyte and to the source of the excitation energy to cause a second emission of radiation from the article; and

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

6. A method as in claim 5, wherein the polymer having reduced π

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

.

7. A method as in claim 5, wherein the polymer having reduced π

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

.

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

providing an article comprising a polymer having an energy migration pathway, wherein the polymer exhibits a quantum yield at least about 0.05 times that of a quantum yield of the polymer in solution;

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

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

exposing the article to a medium containing an analyte and to the source of the excitation energy to cause a second emission of radiation from the article; and

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

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

providing an article comprising a polymer having an energy migration pathway, wherein the polymer exhibits a quantum yield at least about 0.05 times that of a quantum yield of the polymer in solution;

exposing the article to a source of excitation energy to cause a first emission of radiation from the article;

exposing the article to a medium containing an analyte and to the source of the excitation energy to cause a second emission of radiation from the article; and

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