Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G15/00—Compounds of gallium, indium or thallium
  • C01G15/006—Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the invention relates to a copper indium sulfide semiconductor nano particle and a preparation method thereof. Background technique
• nanomaterial science has become an indispensable and important field in the development of materials science.
• the progress of nanomaterial research is bound to push many disciplines such as physics, chemistry and biology to a new level, and it will also bring new opportunities for technological research in the 21st century.
• solar cells have attracted worldwide attention as a renewable and clean energy source.
• the application of nanomaterials and technologies to solar cells is likely to greatly increase the conversion efficiency of existing solar cells, reduce the production cost of solar cells, and promote the development of new solar cells. In this case, developing nanomaterials that can be used in solar cells has become a new challenge.
• CuInS 2 belongs to the im-vi 2 semiconductor compound material, has a chalcopyrite structure, has a forbidden band width of 1.50 eV, has a large absorption coefficient, and is a good solar energy because CuInS 2 does not contain any toxic components. Battery material.
• the conversion efficiency of the thin film solar cell based on CuInS 2 has reached 14.4%.
• the main processes for preparing such solar cells are chemical vapor deposition, magnetron sputtering, electrochemical deposition and the like. However, these methods have higher requirements on conditions, complicated preparation processes, and higher costs.
• the synthesis of CuInS 2 nanoparticles, the process of film formation by spin coating, and then sintering will be a good solution to the industrialization of CuInS 2 solar cells.
• the exciton radius of the CuInS 2 semiconductor obtained by theoretical calculation is 4. l nm, so it is expected that when the size of the semiconductor nanoparticle of CuInS 2 is equivalent to the exciton radius, it exhibits a strong quantum confinement effect. Should.
• the preparation method of the copper indium sulfide semiconductor nanoparticle of the invention comprises the following steps: a) adding a copper salt, an indium salt and an alkyl mercaptan to a non-polar organic solvent, and then heating, stirring and dissolving under an inert atmosphere; Until a dark red colloidal solution is obtained;
• step b) The colloidal solution obtained in the step a) is cooled to room temperature, a polar solvent is added, and copper indium sulfide semiconductor nanoparticles are obtained by centrifugation; further, the copper indium sulfide semiconductor nanoparticle powder can be obtained by washing and vacuum drying.
• the copper indium sulfide semiconductor nanoparticles are tetragonal and have a particle size of 2 to 10 nm. Its emission spectrum is in the near infrared region of 600 ⁇ 800 nm.
• Figure 1 Absorption and fluorescence spectra of CuInS 2 nanoparticles obtained at different reaction times at a temperature of 240 ° C in Example 1 of the present invention; wherein la is the absorption spectrum and Figure lb is the fluorescence spectrum.
• FIG. 2 TEM images CuInS 2 nanoparticles prepared in Example 1 of the present invention, Figure 2;
• Figure 2a is a TEM of the reaction CuInS 2 nanoparticles prepared for 2 hours at a temperature of 240 ° C, the temperature in FIG. 2b
• Fig. 3 is an X-ray diffraction chart of a CuInS 2 nanoparticle powder prepared by reacting at a temperature of 240 ° C for 2 hours in Example 1 of the present invention. detailed description
• the method for preparing the scale copper indium sulfide semiconductor nano particles of the invention adopts low cost copper salt, indium salt and alkyl mercaptan as raw materials, and prepares a ternary particle size controllable by simple solution reaction and heating pyrolysis method.
• the method has the advantages of simple preparation process, low cost, non-toxicity, large amount of preparation, easy control and the like.
• the preparation method of the copper indium sulfide semiconductor nanoparticles of the invention comprises the following steps:
• step b) The colloidal solution obtained in the step a) is cooled to room temperature, a polar solvent is added, and copper indium sulfide semiconductor nanoparticles are obtained by centrifugal sedimentation; the copper indium sulfide semiconductor nanoparticle powder can be further obtained by washing and vacuum drying.
• the yield of the preparation process of the invention is as high as 90%.
• the copper indium sulfide semiconductor nanoparticles of the invention have a tetragonal crystal shape with a particle size of 2 to 10 nm, and the emitted light is in the near infrared region of 600 to 800 nm.
• the copper indium sulfide semiconductor nanoparticles of the present invention have a spherical, triangular, sheet-like and/or rod-like morphology,
• the molar ratio of the copper salt to the indium salt is preferably from 1 to 2: 1 - 2 , and the molar ratio of the alkyl alcohol is preferably greater than the molar content of the copper salt or the indium salt, preferably mole.
• the ratio is 100 to 1. 5: 1, more preferably 50 to 2: 1, particularly preferably 12 to 3:1.
• the temperature of the heating and agitation described in the step a) is preferably between 100 ° C and 350 ° C, more preferably between 200 ° C and 300 ° C, particularly preferably between 240 ° C and 270 ° C, and the time is preferably 10 Between 30 minutes and more preferably between 20 minutes and 6 hours, particularly preferably between 1 hour and 2 hours.
• the cleaning is performed by dispersing the obtained copper indium sulfide semiconductor nanoparticles in a solvent of n-hexane, chloroform or terpene, and then adding sterol to perform centrifugal sedimentation, and the cleaning may be repeated until the desired copper indium sulfide semiconductor is obtained. Nanoparticles.
• the copper salt may be cuprous acetate, copper acetate, copper chloride, cuprous chloride, copper sulfate or any mixture thereof.
• the indium salt may be indium acetate, indium chloride, indium sulfate, indium nitrate or any mixture therebetween.
• the alkyl mercaptan may be a thiol having one or more mercapto functional groups or a mixture of the mercaptans having one or more mercapto functional groups.
• the thiol having a mercapto functional group is preferably an octyl mercaptan, an isooctyl alcohol, a dodecyl mercaptan, a hexadecyl mercaptan or an octadecyl mercaptan.
• the thiol having one or more mercapto functional groups is preferably 1,8-octanedithiol or 1,6-octanedithiol or the like.
• the nonpolar organic solvent is preferably octadecene, paraffin, diphenyl ether, dioctyl ether, octadecane or any mixed solvent therebetween.
• the polar solvent is preferably decyl alcohol, ethanol, isopropanol, acetone or any mixed solvent therebetween.
• the inert gas is preferably argon or nitrogen or the like.
• the copper indium sulfide semiconductor nanoparticles obtained by the preparation method of the invention can be applied to the fields of biomarkers, light emitting diodes, thin film solar cells, polymer solar cells and the like.
• the invention has the following characteristics:
• the present invention does not require the preparation of a precursor containing any toxic substance in advance, but uses an inexpensive copper salt and an indium salt and an alkyl mercaptan to carry out the reaction, and has a simple preparation process, is easy to control, and is easy to realize mass production.
• the ternary semiconductor copper indium sulfide (CuInS 2 ) nanoparticles obtained in the present invention have a fluorescence quantum efficiency close to 10% and an emission spectrum in the near-infrared region. This nanoparticle can be dissolved into the aqueous phase by ligand exchange.
• the ternary semiconductor copper indium sulfide (CuInS 2 ) nanoparticles obtained in the present invention can be dispersed in a non-polar solvent for a long period of time, and the copper indium sulfide semiconductor nanoparticle powder obtained by vacuum drying can be dispersed again into a non-polar solvent. .
• a mixture of cuprous acetate, indium acetate and dodecyl mercaptan and 50 ml of octadecene were added to a 100 ml three-necked flask in which the molar ratio of cuprous acetate, indium acetate and dodecyl mercaptan was 1 : 1: 10, argon or nitrogen for 30 minutes to remove the air, at 240 ° C
• the mixture was heated and stirred to obtain a clear pale yellow solution, and then the mixed solution was continuously heated at 240 ° C.
• the color of the colloidal solution gradually changed from light yellow to deep red, and the total heating reaction time was 2 hours.
• the colloidal solution obtained by the above reaction was cooled to room temperature, 100 ml of acetone was added, and the mixture was centrifuged to remove the upper layer solution to obtain copper indium sulfide semiconductor nanoparticles. through
• the specific conditions are shown in Table 1).
• the absorption and fluorescence spectroscopy tests show that the absorption and fluorescence spectra of the obtained CuInS 2 semiconductor nanoparticles are modulatable (the absorption and fluorescence spectra are shown in Figure la, lb, respectively).
• the precipitate was redissolved in toluene, and decyl alcohol, which is 3 times the volume of benzene, was added, and then sedimented by centrifugation, and the above process was repeated three times. Finally, the cleaned precipitate was vacuum dried to obtain a powder of black copper indium sulfide nanoparticles. The yield was 90%.
• the mixture copper acetate, indium acetate, and hexadecyl mercaptan and 50 ml of octadecene were added to 2 5 0 ml three-necked flask, in which copper acetate, indium acetate, and hexadecyl mercaptan was 1 molar ratio of : 1: 100, argon or nitrogen for 30 minutes to remove the air, at 240. Stirring under C gave a clear, pale yellow solution which was then constant at 240.
• the copper-indium-sulfur semiconductor having an average particle diameter of 3.5 nm was obtained by centrifugation to obtain a copper-indium-sulfur semiconductor having an average particle diameter of 3.5 nm.
• a mixture of cuprous chloride, indium acetate and dodecyl mercaptan and 50 ml of octadecene were added to a 50 ml three-necked flask in which the molar ratio of cuprous chloride, indium acetate and dodecyl mercaptan was For 1: 1:10, remove the air by argon or nitrogen for 30 minutes at 240. Stirring under C gave a clear, pale yellow solution which was then constant at 240. The mixed solution was further heated at C, and the total heating reaction time was 2 hours. The obtained colloidal solution was cooled to room temperature, 100 ml of acetone was added, and copper indium sulfide semiconductor nanoparticles having an average particle diameter of 2.5 nm were obtained by centrifugal sedimentation.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Nanotechnology (AREA)
• Organic Chemistry (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Composite Materials (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Luminescent Compositions (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Photovoltaic Devices (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=39918722

Family Applications (1)

Country Status (7)

Cited By (2)

Families Citing this family (28)

Citations (3)

Family Cites Families (6)

• 2008
  • 2008-03-06 CN CNA200810101428XA patent/CN101234779A/zh active Pending
• 2009
  • 2009-03-06 EP EP09718518.5A patent/EP2263977A4/en not_active Withdrawn
  • 2009-03-06 CN CN200980107584XA patent/CN102105400A/zh active Pending
  • 2009-03-06 KR KR1020107022221A patent/KR20100124802A/ko not_active Withdrawn
  • 2009-03-06 US US12/920,665 patent/US20110039104A1/en not_active Abandoned
  • 2009-03-06 JP JP2010549003A patent/JP2011513181A/ja active Pending
  • 2009-03-06 WO PCT/CN2009/000237 patent/WO2009109110A1/zh not_active Ceased
• 2010
  • 2010-08-26 IL IL207814A patent/IL207814A0/en unknown

Patent Citations (3)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events