WO1997014176A1 - Suspension colloidale de nanoparticules semi-conductrices - Google Patents

Suspension colloidale de nanoparticules semi-conductrices Download PDF

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Publication number
WO1997014176A1
WO1997014176A1 PCT/US1996/015286 US9615286W WO9714176A1 WO 1997014176 A1 WO1997014176 A1 WO 1997014176A1 US 9615286 W US9615286 W US 9615286W WO 9714176 A1 WO9714176 A1 WO 9714176A1
Authority
WO
WIPO (PCT)
Prior art keywords
colloidal suspension
capping agent
produce
nanoparticles
semiconductor
Prior art date
Application number
PCT/US1996/015286
Other languages
English (en)
Inventor
Douglas L. Schulz
Martin Pehnt
Calvin J. Curtis
David S. Ginley
Original Assignee
Midwest Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Midwest Research Institute filed Critical Midwest Research Institute
Priority to AU73705/96A priority Critical patent/AU7370596A/en
Publication of WO1997014176A1 publication Critical patent/WO1997014176A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites

Definitions

  • the present invention relates to a substantially stable colloidal suspension of semiconductor nanoparticles capped with a volatile capping agent and to the preparation of the colloidal suspension.
  • An exemplified colloidal suspension is cadmium telluride nanoparticles capped with acetonitrile, whereby the cadmium telluride nanoparticles can be employed through the deposition thereof onto a suitable substrate in the production of a substantially carbon-free cadmium telluride semiconductor film.
  • Semiconductor nanoparticles have scientific and research functionalities due to novel properties such as quantum size effects, size-dependent chemical reactivity, optical nonlinearity, efficient photoelectron emission and melting point reduction.
  • One particular application utilizing semiconductor nanoparticles is found in the production of semiconductor films as described in co-pending and commonly assigned United States Patent Application Serial No.08/536,348, incorporated herein in its entirety by reference.
  • semiconductor nanoparticles such as cadmium telluride can be deposited onto a substrate whose surface temperature after nanoparticle deposition thereon is sufficient to thereby cause simultaneous fusion of the nanoparticles to thereby coalesce with each other and effectuate film growth.
  • Relatively non-volatile capping agents such as trioctylphophine (boiling point 29°C/50mm Hg) and trioctylphosphineoxide (boiling point 201-202°C/2mm Hg) are taught.
  • these agents tend to decompose rather than volatilize, and therefore cause the inco ⁇ oration of carbon into the nanoparticle-derived semiconductor films. While such inco ⁇ oration is not fatal to film production, a greater degree of purity generally results in the production of a more efficient and effective semiconductor film
  • a primary object of the present invention is to provide a substantially stable colloidal suspension comprising semiconductor nanoparticles capped with a volatile capping agent such that the suspension can be employed for growing semiconductor films.
  • Another object of the present invention is to provide a process for the preparation of a substantially stable nanoparticle colloidal suspension wherein volatile capping agents are employed.
  • Yet another object of the present invention is to provide a substantially stable colloidal suspension wherein the capping agent employed is a volatile coordinating Lewis base.
  • the present invention is a substantially stable colloidal suspension comprising semiconductor nanoparticles capped with a volatile capping agent, and the preparation thereof.
  • a colloidal suspension so defined can be employed, for example, as a source of substantially carbon-free semiconductor nanoparticles to be deposited onto a substrate whose surface temperature after nanoparticle deposition thereon is sufficient to cause simultaneous fusion ofthe nanoparticles which thereby coalesce with each other and effectuate film growth.
  • Such freedom from carbon impurities is achieved because of the volatility of the capping agent which, instead of breaking down and introducing carbon to the suspension, volatilizes away during nanoparticle deposition to thereby leave a substantially carbon-free nanoparticle deposition.
  • volatile is defined as having a boiling point less than about 200°C at ambient pressure.
  • the capping agent preferably is chosen from volatile coordinating Lewis bases species such as aromatics, O-coordinating alkyl ethers, N-coordinating amines and nitriles, and P- and O-coordinating alkyl phosphines and phosphine oxides.
  • Preparation of the colloidal suspension comprises providing two salts reactable with each other to produce a semiconductor and reacting these two salts to produce a semiconductor nanoparticle precipitate.
  • Introduction of the volatile capping agent can occur either during nanoparticle synthesis or after nanoparticle synthesis by appropriate exposure to and treatment of the nanoparticles by the volatile capping agent.
  • the two salts are reacted in the presence of a volatile capping agent at a temperature and time sufficient to produce a precipitate.
  • the precipitate is mixed with 7/14176 PC17US96/15286
  • additional volatile capping agent to produce a mixture which is subjected to sonication and centrifugation for a time sufficient to produce a concentrated colloidal suspension.
  • This concentrated suspension is diluted with additional volatile capping agent in an amount sufficient to produce a colloidal suspension suitable for deposition in the formation of a semiconductor film.
  • the two salts are reacted to form a nanoparticle precipitate. Thereafter, this precipitate is mixed with a volatile capping agent to produce a mixture which is subjected to sonication and centrifugation for a time sufficient to produce a concentrated colloidal suspension.
  • the present invention is a substantially stable colloidal suspension comprising a plurality of semiconductor nanoparticles each capped with a volatile capping agent, and the preparation thereof.
  • the following Examples speak toward the preparation of a preferred embodiment thereof comprising a substantially stable colloidal suspension of cadmium telluride nanoparticles capped with acetonitrile.
  • Example I introduces a volatile capping agent during nanoparticle synthesis;
  • Example II introduces a volatile capping agent after nanoparticle has occurred.
  • Example I A colloidal suspension was prepared by adding 0.516 g cadmium iodide (1.41 mmol) to a 500 ml side-arm round bottom flask fitted with a Teflon-coated stir bar, and adding 0.267 g sodium telluride (1.54 mmol) to a 250 ml side-arm round bottom flask fitted with a Teflon-coated stir bar in an inert atmosphere glove box. After attaching each of these flasks to a Schlenk vacuum line, 200 ml freshly distilled and deoxygenated acetonitrile was added to the cadmium iodide flask.
  • the remaining dark red precipitate slurry along with remaining liquid was divided into two equal portions and each portion was transferred to a respective 40 ml centrifuge tube and centrifuged for 15 minutes at 4,000 r.p.m. to thereby remove additional supernatant which was decanted and discarded. Thereafter, acetonitrile was added to fill each tube and the resulting mixture was subjected to sonication for 15 minutes (to disperse the nanoparticles) and subsequent centrifugation for 15 minutes at 4,000 r.p.m At the completion of centrifugation, the resulting supernatant was dark red, indicative of the formation of a colloidal suspension.
  • Example II A colloidal suspension was prepared by adding 1.033 g cadmium iodide (2.82 mmol) to a 500 ml side-arm round bottom flask fitted with a Teflon-coated stir bar, and adding 0.502 g sodium telluride (2.89 mmol) to a 250 ml side-arm round bottom flask fitted with a Teflon-coated stir bar in an inert atmosphere glove box. After attaching each of these flasks to a Schlenk vacuum line, 250 ml freshly distilled and deoxygenated methanol was added to the cadmium iodide flask and 30 ml freshly distilled and deoxygenated methanol was added to the sodium telluride flask.
  • each of the flasks were stirred, the flasks were cooled to -78 °C by employing dry ice/isopropanol baths over a period of 25 minutes.
  • a small gauge cannula then was employed to transfer the sodium telluride/methanol solution to the cadmium iodide/methanol mixture, at which time a dark red precipitate slurry formed. The precipitate was allowed to settle and the colorless supernatant was decanted and discarded. The remaining dark red precipitate slurry was divided into two equal portions and each portion was transferred to a respective 40 ml centrifuge tube. Each tube was filled with methanol and sonicated for 15 minutes to solubilize any remaining sodium iodide.

Abstract

Suspension colloïdale sensiblement stable comprenant une pluralité de nanoparticules semi-conductrices coiffées chacune par un agent de coiffe volatil, ainsi que sa préparation. On peut utiliser cette suspension colloïdale en tant que source de nanoparticules sensiblement exemptes de carbone servant à effectuer la croissance de couches semi-conductrices. La préparation de cette suspension colloïdale consiste à mettre en réaction deux sels afin de produire des nanoparticules semi-conductrices. On peut introduire l'agent de coiffe volatil pendant ou après la synthèse des nanoparticules au moyen de l'exposition appropriée audit agent et du traitement des nanoparticules par ledit agent. On mélange le précipité obtenu de nanoparticules avec l'agent de coiffe volatil, afin d'obtenir un mélange qu'on soumet à un traitement ultrasonique et à une centrifugation pendant une durée suffisante pour obtenir une suspension colloïdale concentrée, qu'on dilue ensuite afin qu'elle se dépose ultérieurement pendant le processus de formation d'une couche semi-conductrice.
PCT/US1996/015286 1995-09-29 1996-09-24 Suspension colloidale de nanoparticules semi-conductrices WO1997014176A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73705/96A AU7370596A (en) 1995-09-29 1996-09-24 Semiconductor nanoparticle colloids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53598195A 1995-09-29 1995-09-29
US08/535,981 1995-09-29

Publications (1)

Publication Number Publication Date
WO1997014176A1 true WO1997014176A1 (fr) 1997-04-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/015286 WO1997014176A1 (fr) 1995-09-29 1996-09-24 Suspension colloidale de nanoparticules semi-conductrices

Country Status (4)

Country Link
AR (1) AR003732A1 (fr)
AU (1) AU7370596A (fr)
WO (1) WO1997014176A1 (fr)
ZA (1) ZA968079B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1066418A1 (fr) * 1998-01-27 2001-01-10 Midwest Research Institute Synthese de solutions de nanoparticules de chalcogenures metalliques melangees et depot par pulverisation de films precurseurs
WO2003003982A2 (fr) * 2001-07-02 2003-01-16 Board Of Regents, University Of Texas System Nanoparticules electroluminescentes et procede de production correspondant
WO2004008550A2 (fr) * 2002-07-15 2004-01-22 Advanced Research And Technology Institute, Inc. Synthese rapide, a basse temperature, de points quantiques
US6846565B2 (en) 2001-07-02 2005-01-25 Board Of Regents, The University Of Texas System Light-emitting nanoparticles and method of making same
US7850933B2 (en) * 2006-04-12 2010-12-14 Nanomas Technologies, Inc. Nanoparticles, methods of making, and applications using same
US8618595B2 (en) 2001-07-02 2013-12-31 Merck Patent Gmbh Applications of light-emitting nanoparticles

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5215631A (en) * 1982-06-25 1993-06-01 Cel Systems Corporation Electrolytic preparation of tin, other metals, alloys and compounds
US5262357A (en) * 1991-11-22 1993-11-16 The Regents Of The University Of California Low temperature thin films formed from nanocrystal precursors

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5215631A (en) * 1982-06-25 1993-06-01 Cel Systems Corporation Electrolytic preparation of tin, other metals, alloys and compounds
US5262357A (en) * 1991-11-22 1993-11-16 The Regents Of The University Of California Low temperature thin films formed from nanocrystal precursors

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
APPLIED PHYSICS A., 1993, Vol. 56, MULLENBORN M., "Characterization of Solution-Synthesized CdTe and HgTe", pages 317-321. *
APPLIED PHYSICS LETTERS, October 1995, Vol. 67, No. 15, PEHNT M., "Nanoparticle Precursor Route to Low-Temperature Spray Deposition of CdTe thin Films", pages 2176-2178. *
MATERIALS RESEARCH SOCIETY SYMPOSIUM, 1993, Vol. 272, JARVIS R.F., "Solution Synthesis and Photoluminescence of Small Crystallites of Cadmium Telluride", pages 229-235. *
ULTRASONICS, September 1989, Vol. 27, GUTIERREZ M., "Preparation of Colloidal Semiconductor Solutions of MoS2 and WSe2 via Sonication", pages 259-261. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1066418A1 (fr) * 1998-01-27 2001-01-10 Midwest Research Institute Synthese de solutions de nanoparticules de chalcogenures metalliques melangees et depot par pulverisation de films precurseurs
EP1066418A4 (fr) * 1998-01-27 2001-05-23 Midwest Research Inst Synthese de solutions de nanoparticules de chalcogenures metalliques melangees et depot par pulverisation de films precurseurs
WO2003003982A2 (fr) * 2001-07-02 2003-01-16 Board Of Regents, University Of Texas System Nanoparticules electroluminescentes et procede de production correspondant
WO2003003982A3 (fr) * 2001-07-02 2003-07-10 Univ Texas Nanoparticules electroluminescentes et procede de production correspondant
US6846565B2 (en) 2001-07-02 2005-01-25 Board Of Regents, The University Of Texas System Light-emitting nanoparticles and method of making same
US8618595B2 (en) 2001-07-02 2013-12-31 Merck Patent Gmbh Applications of light-emitting nanoparticles
WO2004008550A2 (fr) * 2002-07-15 2004-01-22 Advanced Research And Technology Institute, Inc. Synthese rapide, a basse temperature, de points quantiques
WO2004008550A3 (fr) * 2002-07-15 2004-12-23 Advanced Res & Tech Inst Synthese rapide, a basse temperature, de points quantiques
US7850933B2 (en) * 2006-04-12 2010-12-14 Nanomas Technologies, Inc. Nanoparticles, methods of making, and applications using same

Also Published As

Publication number Publication date
AU7370596A (en) 1997-04-30
AR003732A1 (es) 1998-09-09
ZA968079B (en) 1997-04-21

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