Semiconductor nanoparticle surface modification method

• US 20070131905A1
• Filed: 12/01/2006
• Published: 06/14/2007
• Est. Priority Date: 01/06/2005
• Status: Active Grant

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi Software Engineering Co., Ltd. (Hitachi, Ltd.)
• Inventors: Sato, Keiichi, Hattori, Shinya, Chiba, Taeko
• Granted Patent: US 8,030,784 B2
• Time in Patent Office: Days
• US Class Current: 252/301.160
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 11/02 Sulfides
• CPC Class Codes: C01G 9/08 Sulfides
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09C 1/12 Cadmium sulfoselenide
• CPC Class Codes: C09C 1/3072 Treatment with macro-molecular organic compounds
• CPC Class Codes: C09C 1/3676 Treatment with macro-molecular organic compounds
• CPC Class Codes: C09C 3/10 Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: C09K 11/565 with zinc cadmium
• CPC Class Codes: C09K 11/62 containing gallium, indium or thallium
• CPC Class Codes: C09K 11/64 containing aluminium
• CPC Class Codes: C09K 11/66 containing germanium, tin or lead
• CPC Class Codes: C09K 11/70 containing phosphorus
• CPC Class Codes: C09K 11/74 containing arsenic, antimony or bismuth
• CPC Class Codes: C09K 11/75 containing antimony
• CPC Class Codes: C09K 11/88 containing selenium, tellurium or unspecified chalcogen elements
• CPC Class Codes: C09K 2211/14 Macromolecular compounds
• CPC Class Codes: G01N 33/54346 : Nanoparticles
• CPC Class Codes: Y10S 977/773 : Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/902 : Specified use of nanostructure

Abstract

Semiconductor nanoparticles having high luminescence properties that are preferable for applications and uses of biotechnology are provided. With the use of electric charges on the surfaces of particles, the particles and selected polymers are allowed to electrostatically bind to each other, such that the surfaces of the particles are coated. The polymers are allowed to crosslink to each other, resulting in the improved durability of the particles. Further, functional groups contained in the polymers are exposed on the surfaces of the particles. Accordingly, semiconductor nanoparticles that are preferably utilized for applications such as staining and labeling of biopolymers have been synthesized.

Claims

1. A semiconductor nanoparticle, which is modified with a functional group-containing polymer that electrostatically binds to said semiconductor nanoparticle.

2. The semiconductor nanoparticle according to claim 1, wherein electron-releasing groups are arranged on the surface of said semiconductor nanoparticle and said polymer electrostatically binds to the outside of said electron-releasing groups.

3. The semiconductor nanoparticle according to claim 1, wherein said functional group-containing polymer forms a crosslinking bond via a crosslinking agent.

4. The semiconductor nanoparticle according to claim 1, wherein said functional group-containing polymer binds to the surface of the semiconductor nanoparticle via a semiconductor nanoparticle-coating compound.

5. The semiconductor nanoparticle according to claim 1, comprising said functional group-containing polymer whose functional group is one or more functional groups selected from the group consisting of —

COOH, —

OH, —

NH₂, —

SH, —

OCN, —

CNO, —

CHO, —

CH═

O, —

CH═

CH₂, and —

C≡

CH.

6. The semiconductor nanoparticle according to claim 3, wherein said crosslinking bond is one or more bonds selected from the group consisting of an ester bond, an amide bond, an imide bond, an ether bond, a urethane bond, a sulfide bond, a polysulfide bond, a carbonate bond, a thiol bond, a thioester bond, and a thiourethane bond.

7. The semiconductor nanoparticle according to claim 3, wherein said crosslinking bond results from carbon-carbon double bond or carbon-carbon triple bond polymerization.

8. The semiconductor nanoparticle according to claim 3, wherein said functional group-containing polymer is polyacrylic acid and said crosslinking agent is alkylene diamine.

9. The semiconductor nanoparticle according to claim 2, wherein said electron-releasing group is at least one electron-releasing group selected from the group consisting of —

OR, —

OCH₂R, —

OCOCH₂R, —

NHR, —

N(CH₂R)₂, —

NHCOCH₂R, —

CH₂R, and —

C₆H₄R, where R is hydrogen, a substituted hydrocarbon group, or an unsubstituted hydrocarbon group.

10. The semiconductor nanoparticle according to claim 4, wherein said semiconductor nanoparticle surface-coating compound is one or more compounds selected from the group consisting of primary amines (R₁NH₂), secondary amines (R₁R₂NH), tertiary amines (R₁R₂R₃N), and quaternary ammonium compounds (R₄R₅R₆R₇N⁺), where R₁ to R₇ are each hydrogen, a substituted hydrocarbon group, or an unsubstituted hydrocarbon group.

11. The semiconductor nanoparticle according to claim 10, wherein R₁ to R₇ comprise a substituent at a terminal opposite to an amino group or ammonium group.

12. The semiconductor nanoparticle according to claim 1, comprising a semiconductor nanoparticle whose material is one or more materials selected from the group consisting of ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdMnS, CdSe, CdMnSe, CdTe, CdMnTe, HgS, HgSe, HgTe, InP, InAs, InSb, InN, GaN, GaP, GaAs, GaSb, TiO₂, WO₃, PbS, PbSe, MgTe, AlAs, AlP, AlSb, AlS, Ge, and Si, or a semiconductor nanoparticle having a multilayer structure consisting of a core portion and a shell portion that are made of one or more members of said group.

13. The semiconductor nanoparticle according to claim 1, wherein the particle size of said semiconductor nanoparticle exhibits a deviation of less than 10% rms in diameter, thereby achieving monodispersion.

14. The semiconductor nanoparticle according to claim 1, wherein said semiconductor nanoparticle emits light in a narrow spectrum range of less than 60 nm in terms of full width at half maximum (FWHM) upon being irradiated with excitation light.

26. A fluorescent reagent comprising the semiconductor nanoparticle according to claim 1.

27. An optical device comprising the semiconductor nanoparticle according to claim 1.

15. A method of manufacturing a semiconductor nanoparticle comprising:

a process for allowing a functional group-containing polymer to electrostatically bind to the surface of the semiconductor nanoparticle;

a process for causing functional groups of said polymer to form a crosslink via a crosslinking agent.

18. The method of manufacturing a semiconductor nanoparticle according to claim 15, comprising said functional group-containing polymer whose functional group is one or more functional groups selected from the group consisting of —

COOH, —

OH, —

NH₂, —

SH, —

OCN, —

CNO, —

CHO, —

CH═

O, —

CH═

CH₂, and —

C≡

CH.

19. The method of manufacturing a semiconductor nanoparticle according to claim 15, wherein said crosslink is formed by one or more reactions selected from the group consisting of an esterification reaction, an amidation reaction, an imidation reaction, an etherification reaction, a urethanation reaction, a sulfidation reaction, a polysulfidation reaction, a carbonate reaction, a thiolation reaction, a thioesterification reaction, and a thiourethanation reaction.

20. The method of manufacturing a semiconductor nanoparticle according to claim 15, wherein said crosslink is formed by a carbon-carbon double bond or carbon-carbon triple bond polymerization reaction.

21. The method of manufacturing a semiconductor nanoparticle according to claim 15, wherein said functional group-containing polymer is polyacrylic acid and said crosslinking agent is alkylene diamine.

25. The method of manufacturing a semiconductor nanoparticle according to claim 15, comprising a semiconductor nanoparticle whose material is one or more materials selected from the group consisting of ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdMnS, CdSe, CdMnSe, CdTe, CdMnTe, HgS, HgSe, HgTe, InP, InAs, InSb, InN, GaN, GaP, GaAs, GaSb, TiO₂, WO₃, PbS, PbSe, MgTe, AlAs, AlP, AlSb, AlS, Ge, and Si, or a semiconductor nanoparticle having a multilayer structure consisting of a core portion and a shell portion that are made of one or more members of said group.

16. A method of manufacturing a semiconductor nanoparticle comprising:

a process for arranging electron-releasing groups on the surface of a semiconductor nanoparticle by adding surface-treating material that provides one or more electron-releasing groups to said semiconductor nanoparticle;

a process for allowing a functional group-containing polymer to electrostatically bind to the surface of said semiconductor nanoparticle; and

a process for causing functional groups of said polymer to form a crosslink via a crosslinking agent.

17. The method of manufacturing a semiconductor nanoparticle according to claim 16, comprising a process for coating said semiconductor nanoparticle, on which the electron-releasing groups are arranged.

22. The method of manufacturing a semiconductor nanoparticle according to claim 16, wherein said surface-treating material that provides electron-releasing groups to the semiconductor nanoparticle is at least a pure metal, and a metal compound, nitrogenated compounds selected from the group consisting of ammonia, amines, ammoniums, nitriles, and isocyanates, or oxygenated compounds selected from the group consisting of alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides.

23. The method of manufacturing a semiconductor nanoparticle according to claim 17, wherein said semiconductor nanoparticle-coating material is at least one material selected from the group consisting of primary amines (R₁NH₂), secondary amines (R₁R₂NH), tertiary amines (R₁R₂R₃N), and quaternary ammonium compounds (R₄R₅R₆R₇N⁺), where R₁ to R₇ are each hydrogen, a substituted hydrocarbon group or an unsubstituted hydrocarbon group.

24. The method of manufacturing a semiconductor nanoparticle according to claim 23, wherein R₁ to R₇ comprise a substituent at a terminal opposite to an amino group or ammonium group.