CN112110851A - Copper-based hybrid red luminescent semiconductor material and application of light conversion film - Google Patents

Copper-based hybrid red luminescent semiconductor material and application of light conversion film Download PDF

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CN112110851A
CN112110851A CN202011037141.2A CN202011037141A CN112110851A CN 112110851 A CN112110851 A CN 112110851A CN 202011037141 A CN202011037141 A CN 202011037141A CN 112110851 A CN112110851 A CN 112110851A
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copper
tpt
light conversion
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许让栋
刘广宁
蔡瑞芸
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University of Jinan
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Abstract

The invention discloses a zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material and a preparation method thereof. SaidThe molecular structural formula of the luminescent semiconductor is Cu6(TPT)6The hybrid material is represented as a hybrid zero-dimensional gear-like structure with an organic ligand and an inorganic component connected through coordination bonds. The specific structure is characterized in that three copper ions and sulfur atoms of three organic ligands are alternately connected to form a six-membered ring, the copper ions in the ring respectively form coordinate bonds with nitrogen atoms in the other three organic ligands, each organic ligand fixes two six-membered rings in parallel under the action of bridging, and the organic ligands with trifluoromethyl groups are uniformly distributed around the six-membered ring in a zigzag manner to form a gear-shaped structure. The compound Cu is obtained by selecting cuprous iodide, 2-mercapto-5- (trifluoromethyl) pyridine, potassium iodide, water, acetonitrile and hydriodic acid as reaction raw materials under the condition of solvothermal6(TPT)6The single crystal of (2) can be used in the field of light conversion thin film materials.

Description

Copper-based hybrid red luminescent semiconductor material and application of light conversion film
Technical Field
The invention relates to the field of luminescent materials, in particular to a zero-dimensional copper-based inorganic-organic hybrid red luminescent semiconductor material Cu6(TPT)6And the application of the light conversion material thereof, wherein TPT is 2-mercapto-5- (trifluoromethyl) pyridine.
Background
The composite fluorescent film is used as a light conversion material with excellent performance and widely applied to devices such as solar concentrators, white light LEDs and the like. In recent years, quantum dot luminescent materials have been successfully applied to backlight modules of liquid crystal displays, so that the color gamut level of the liquid crystal displays is improved, and the quantum dot luminescent materials have great advantages in color reduction. The development of new light conversion materials and the research of the preparation method of the composite fluorescent film have important social and economic significance.
At present, the most important realization modes of quantum dot luminescent materials and their applications include two main categories: the first type is light pipe technology mainly based on QD Vision in the United states, which is mainly based on CdSe quantum dot luminescent materials; the second category is the technology of light conversion films, including InP quantum dot-based light conversion films from Samsung, and QDEF quantum dot-enhanced film series based on CdSe quantum dots from 3M. However, most of these materials are Rare Earth (RE) elements, which may face serious supply shortage, lack of recyclability and damage to the environment, and the technology of the light conversion film is complicated, high in cost and low in yield. Luminescent metal-based hybrid materials are a class of materials with broad application prospects. The copper-based hybrid luminescent semiconductor material has been paid attention to by many researchers because of stable properties, cheap and easily available raw materials, mild synthesis conditions and excellent light conversion performance.
In the invention, cuprous iodide is used as a reactant to be combined with an organic ligand to form a zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material, belonging to a non-rare earth pollution-free hybrid semiconductor material; the material can be excited by ultraviolet to emit red light, shows excellent light conversion performance and has important value in the field of light conversion film material research.
Disclosure of Invention
The invention aims to provide a zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material; the method overcomes the defects of high cost of the rare earth element luminescent material, environment-unfriendliness of the rare earth element luminescent material and the like at the present stage, and has the advantages of simple condition, low cost of synthetic raw materials, easy obtainment, no toxicity, no harm and good light conversion performance; after the material is dispersed in PMMA (polymethyl methacrylate), the material has excellent luminescence, strong processability and good stability.
The technical scheme of the invention comprises the following contents:
1. zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material Cu6(TPT)6TPT in the formula represents 2-mercapto-5- (trifluoromethyl) pyridine. The compound is monoclinic system, and is crystallized in a C2/C space group, and the unit cell parameters are a = 26.2 (2) A, b = 9.6 (2) A, C =18.9 (3) A, α =90 degrees, β =101.0(2) degrees, and γ =90 degrees. The crystal color of the material is yellow, and the material is represented as a hybridized zero-dimensional gear-like structure formed by connecting an organic ligand and an inorganic component through a coordination bond. The specific structure is characterized in that three copper ions and sulfur atoms of three organic ligands are alternately connected to form a six-membered ring, the copper ions in the ring respectively form coordinate bonds with nitrogen atoms in the other three organic ligands, each organic ligand fixes two six-membered rings in parallel under the action of bridging, and the organic ligands with trifluoromethyl groups are uniformly distributed around the six-membered ring in a zigzag manner to form a gear-shaped structure.
2. The method for preparing a zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material according to item 1, characterized in that: weighing the components in a molar ratio of 20: 17: 100 cuprous iodide, 2-mercapto-5- (trifluoromethyl) pyridine and potassium iodide, dissolved in volumeThe ratio is 3: 3: 1, water, acetonitrile and hydriodic acid under the condition of solvothermal to obtain a yellow crystalline product, namely Cu6(TPT)6。
3. Use of the zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material according to item 1, characterized in that: the material has excellent light conversion performance and is used as a candidate material of a light conversion film.
The invention has the advantages that the synthesis conditions of the product are simple and easy to control and have no pollution; the material has excellent light conversion performance and high stability, and can be used for manufacturing a light conversion film.
Drawings
FIG. 1 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The molecular structure of (1), hydrogen atoms are omitted.
FIG. 2 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The spatial packing pattern of molecules within the unit cell along the c-axis, ignoring the hydrogen atoms.
FIG. 3 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The as-synthesized powder diffraction patterns all completely matched the simulated single crystal diffraction results.
FIG. 4 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6An infrared spectrum of (1).
FIG. 5 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6Band gap diagram of (1).
FIG. 6 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6Fluorescence excitation emission profile of (a).
FIG. 7 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The photoluminescence color coordinates of (a).
FIG. 8 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The light conversion film is prepared.
FIG. 9 shows an inorganic-organic hybrid luminescent semiconductor Cu6(TPT)6The luminescence spectrum of the light conversion film is prepared.
Detailed Description
(1) Compound Cu6(TPT)6Synthesis of (2)
Placing 0.038 g of CuI, 0.249 g of KI and 0.031 g of 2-mercapto-5- (trifluoromethyl) pyridine into a 25 mL polyfluoroethylene propylene reaction bag in a polytetrafluoroethylene liner, adding 1 mL of hydroiodic acid, 3 mL of water and 3 mL of acetonitrile, placing the polytetrafluoroethylene liner into a stainless steel reaction kettle, screwing, heating in a 140 ℃ oven, keeping the temperature for three days, cooling to room temperature, washing with ethanol to obtain yellow blocky crystals, namely the compound Cu6(TPT)6. The purity and yield of the crystal obtained under the reaction conditions are high.
(2) Production of light conversion film
5mg of fully ground Cu6(TPT)6Adding the powder into 10ml of acetonitrile, adding 1g of PMMA in the magnetic stirring process until the PMMA is completely dissolved to form uniformly dispersed colloid, sucking 0.5ml of colloid solution, dripping the colloid solution on a glass slide, placing the glass slide in a culture dish, protecting a preservative film, airing and taking down the preservative film, namely obtaining the light conversion film.

Claims (2)

1. A zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material with light conversion performance is characterized in that: the structural formula of the hybrid material is Cu6(TPT)6TPT in the formula represents 2-mercapto-5- (trifluoromethyl) pyridine; the copper-based hybrid luminescent semiconductor material is crystallized in a monoclinic system C2A/c space group, unit cell parameters a = 26.2 (2), b = 9.6 (2), c =18.9 (3), a =90 °, β =101.0(2), γ =90 °; the crystal color of the material is yellow, and the hybrid material is represented as a hybrid zero-dimensional gear-shaped structure formed by connecting an organic ligand and an inorganic component through a coordination bond; the specific structure is characterized in that three copper ions are alternately connected with sulfur atoms of three TPT organic ligands to form (Cu)3S3) A six-membered ring, wherein copper ions form coordination bonds with nitrogen atoms of three other organic ligands respectively, i.e. each organic ligand further bridges two (Cu) in a N, S double-tooth manner3S3) The six-membered rings are fixed in parallel, the organic ligands with trifluoromethyl groups being distributed uniformly in a zigzag pattern around the six-membered ringsForming a gear-like structure.
2. Use of the zero-dimensional copper-based inorganic-organic hybrid red light-emitting semiconductor material according to claim 1, wherein: the material has excellent optical performance and high stability, and can be used for manufacturing a light conversion film.
CN202011037141.2A 2020-09-28 2020-09-28 Copper-based hybrid red luminescent semiconductor material and application of light conversion film Pending CN112110851A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201328A (en) * 2021-04-12 2021-08-03 华中科技大学 Single-matrix dual-band white light emitting material and preparation method and application thereof
CN113999168A (en) * 2021-10-22 2022-02-01 济南大学 Organically modified copper-sulfur two-dimensional semiconductor material and application thereof
CN114561208A (en) * 2021-11-30 2022-05-31 闽都创新实验室 Inorganic-organic hybrid compound crystal [ K10(CuI)9L10]xH2O and preparation method and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201328A (en) * 2021-04-12 2021-08-03 华中科技大学 Single-matrix dual-band white light emitting material and preparation method and application thereof
CN113999168A (en) * 2021-10-22 2022-02-01 济南大学 Organically modified copper-sulfur two-dimensional semiconductor material and application thereof
CN114561208A (en) * 2021-11-30 2022-05-31 闽都创新实验室 Inorganic-organic hybrid compound crystal [ K10(CuI)9L10]xH2O and preparation method and application thereof
CN114561208B (en) * 2021-11-30 2023-08-04 闽都创新实验室 Inorganic-organic hybrid compound crystal [ K ] 10 (CuI) 9 L 10 ]xH 2 O and preparation method and application thereof

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Application publication date: 20201222