CN112028477A - Quantum dot luminescent glass and preparation method and application thereof - Google Patents

Abstract

The invention relates to quantum dot luminescent glass and a preparation method and application thereof, wherein the glass comprises the following components: SiO 2₂ 60％～65％，Al₂O₃ 15％～25％，B₂O₃ 0.1％～5％，Na₂O 10％～20％，P₂O₅0.1-5 percent of magnesium oxide, 0.1-5 percent of MgO and 0.1-5 percent of SnO; the quantum dots comprise 5-15% of ZnO, 1-5% of CdS and 1-5% of Se. The preparation method comprises obtaining CdS from quantum dot components_xSe_1‑xa/ZnS powder; then adding CdS_xSe_1‑xthe/ZnS powder and the glass powder are uniformly mixed to obtain quantum dot luminescent glass powder, the quantum dot luminescent glass powder is dissolved and poured to obtain a glass block body, and finally annealing treatment is carried out, and then the temperature is reduced to room temperature to obtain the quantum dot luminescent glass.

Description

Quantum dot luminescent glass and preparation method and application thereof

Technical Field

The invention belongs to the technical field of glass materials, and particularly relates to quantum dot luminescent glass and a preparation method and application thereof.

Background

Due to quantum confinement effect and quantum size effect, the semiconductor quantum dot has the characteristics of wide excitation spectrum, narrow half-peak width and adjustable wavelength, so that the nano quantum dot material is widely concerned. The nanometer quantum dot glass is a luminescent glass with high transparency, chemical stability, thermal stability, short response time and high third-order nonlinear polarizability, and has strong advantages in the aspects of practicality of photonic switches and devices, improvement of existing optical devices and the like.

When the semiconductor quantum dot mainly comprises II-VI group elements (such as CdSe, CdTe, CdS, ZnS and the like) and III-V group elements (such as lnP, lnAs and the like), glass can provide a good growth environment for the quantum dot nano cluster, and a semiconductor consisting of the II-VI group elements can grow in a glass substrate and has good optical stability, so that the quantum dot luminescent glass can provide a new method for further preparing an LED luminescent material, but no related report exists at present.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides quantum dot luminescent glass and a preparation method and application thereof, wherein the melting method is simple and effective in preparation, cheap and easily available in raw materials and easy to popularize, and the prepared quantum dot luminescent glass has an obvious quantum size effect, good luminescent performance and good application prospect.

The invention is realized by the following technical scheme:

a quantum dot luminescent glass comprises a glass component and a quantum dot component;

the glass component comprises the following components in percentage by mol: SiO 2₂ 60％～65％，Al₂O₃15％～25％，B₂O₃0.1％～5％，Na₂O 10％～20％，P₂O₅ 0.1％～5％，MgO0.1％～5％，SnO 0.1％～5％；

The quantum dot component comprises, by weight, 5% -15% of ZnO, 1% -5% of CdS and 1% -5% of Se.

A method for preparing the quantum dot luminescent glass comprises the following steps:

step 1, obtaining CdS from quantum dot components by a hot melting method_xSe_1-xa/ZnS powder;uniformly mixing the glass components to obtain glass powder;

step 2, CdS_xSe_1-xThe preparation method comprises the following steps of uniformly mixing/ZnS powder and glass powder to obtain quantum dot luminescent glass powder, and pouring after dissolving the quantum dot luminescent glass powder to obtain a glass block body;

and 3, annealing the glass block at 300-600 ℃, and cooling to room temperature to obtain the quantum dot luminescent glass.

Further, in the step 1, the quantum dot components are pretreated at the temperature of 150-450 ℃ to obtain CdS_xSe_1-xa/ZnS powder.

And further, pretreating the quantum dot component for 1-5 hours at the temperature.

Further, in the step 2, the quantum dot luminescent glass powder is dissolved at 1200-1500 ℃.

And further, after the quantum dot luminescent glass powder is dissolved at the temperature, preserving the heat for 3-6 h.

Further, in the step 3, annealing the glass block body for 6-12 hours at the temperature.

A quantum dot luminescent glass obtained by the method for preparing quantum dot luminescent glass described in any one of the above.

The quantum dot luminescent glass is applied to electronic equipment, display equipment or preparation of LED luminescent materials.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention relates to quantum dot luminescent glass, which is prepared from SiO₂The content of the glass skeleton is more than 60% and less than 65%, so that the requirements of melting, chemical durability and mechanical strength can be satisfied; 15 to 25 percent of Al₂O₃Can increase the viscosity of the glass melt, reduce the devitrification tendency of the glass, Al³⁺Non-bridge oxygen can be captured to form an aluminum-oxygen tetrahedron to enter a silicon-oxygen network, and broken nets are reconnected to enable the glass structure to be more compact; 0.1 to 5 percent of B₂O₃The low-temperature viscosity can be improved, and the dielectric constant of the glass can be increased; 10 to 20 percent of Na₂O can reduce the melting of the glassThe melting temperature and the liquidus temperature, thereby reducing the softening point of the glass and greatly reducing the viscosity of the glass; p₂O₅Belongs to a glass network former, and 0.1 to 5 percent of P₂O₅The glass structure becomes loose by adding the (B) so as to be beneficial to the distribution of quantum dots. The addition of MgO can improve the stability of the glass, reduce the crystallization tendency of the glass and improve the melting performance of the glass composition; SnO₂The glass component is added as a clarifying agent, the addition amount of the clarifying agent is usually 0.1-5%, and bubbles in glass melt can be eliminated; 5% -15% of ZnO doped in the glass can effectively improve the crystallization process of the glass, and when the free oxygen is enough, ZnO forms [ ZnO₄]The CdS and Se are mainly used for synthesizing quantum dot powder with a core-coated structure, CdSe is arranged in the glass, CdSe is coated by the CdSe, and the CdS can be finally obtained through a hot melting method, dissolution, pouring and annealing treatment_xSe_1-xthe/ZnS quantum dot luminescent glass has an obvious quantum size effect, can be excited at a position of 360-520 nm to generate fluorescence, has good luminescent performance, and can provide a new mode for a green LED.

The invention relates to a preparation method of quantum dot luminescent glass, which comprises the steps of firstly obtaining CdS from quantum dot components by a hot melting method_xSe_1-x/ZnS powder, mixing glass components uniformly to obtain glass powder, and then CdS_xSe_1-xthe/ZnS powder and the glass powder are mixed uniformly, dissolved and poured, and finally the stress of the glass can be eliminated through annealing treatment to obtain the CdS_xSe_1-xthe/ZnS quantum dot luminescent glass has an obvious quantum size effect, can be excited at a position of 360-520 nm to generate fluorescence, has good luminescent performance, and can provide a new mode for a green LED. CdS is synthesized by adopting a melting method_xSe_1-xthe/ZnS quantum dot luminescent glass does not need to react in an anhydrous environment, has mild reaction, easily controlled crystal nucleus quality and good experimental reproducibility, simplifies the preparation process, and simultaneously has higher luminescent property and better stability. By passingThe quantum dot luminescent glass with thermal stability and mechanical property meeting the requirements can be obtained through reasonable component design.

The quantum dot luminescent glass is suitable for electronic equipment or display equipment and for preparing LED luminescent materials, and can remarkably improve the optical performance of LEDs.

Drawings

FIG. 1 is CdS_xSe_1-xThe excitation spectrum of the/ZnS quantum dot luminescent glass.

FIG. 2 is CdS_xSe_1-xEmission spectrum of/ZnS quantum dot luminescent glass.

FIG. 3 is CdS_xSe_1-xThe absorption spectrum of the/ZnS quantum dot luminescent glass.

Detailed Description

The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.

The invention relates to a CdS_xSe_1-xthe/ZnS quantum dot luminescent glass comprises the following raw material components in percentage by mol: SiO 2₂60％～65％，Al₂O₃ 15％～25％，B₂O₃ 0.1％～5％，Na₂O10％～20％，P₂O₅ 0.1％～5％，MgO 0.1％～5％，SnO 0.1％～5％。

In the quantum dot component, ZnO, CdS and Se account for 5-15 percent of ZnO, 1-5 percent of CdS, 1-5 percent of Se and CdS according to the percentage of the total mass of the raw materials_xSe_1-xX in/Zn depends on the specific content of Se.

The above CdS are discussed below_xSe_1-xThe function and specific content of each component in the/ZnS quantum dot luminescent glass are all mole percentage content.

SiO₂：60％～65％。

SiO₂Is an essential component for constituting the glass skeleton. When SiO in glass₂At a lower concentration of (A), the chemical durability of the resulting glass is low, but if SiO is contained in the glass₂Too high concentration of (A) can reduce the forming energy of the glassForce due to too high SiO₂The concentration increases the difficulty of melting the glass, which adversely affects the glass forming ability. When the content is 60% or more and 65% or less, the melting, chemical durability and mechanical strength can be satisfied at the same time.

Al₂O₃：15％～25％。

Al₂O₃Is an intermediate oxide and is used as a glass network forming agent. Al (Al)₂O₃The viscosity of the glass melt can be increased and the tendency of the glass to devitrify can be reduced because it is predominantly tetrahedrally coordinated in the glass melt formed from the glass. Al (Al)³⁺Can capture non-bridge oxygen to form aluminum-oxygen tetrahedron to enter into silicon-oxygen network, and reconnect broken network to make glass structure more compact. But if Al is present₂O₃When the content is too large, it is difficult to obtain a glass having a long glass quality. Al (Al)₂O₃The content of (b) is 15% to 25%, the viscosity of the glass melt is not excessively high.

B₂O₃：0.1％～5％。

B₂O₃Can improve the low-temperature viscosity of the glass and can be used as a cosolvent, but when the alkali metal oxide Na is used₂When O is excessive, B₂O₃The presence of (A) increases the high temperature coefficient of thermal expansion, but by balancing Al₂O₃And Na₂The concentration of O is 0.1 to 5 percent of B₂O₃Can improve low-temperature viscosity and increase the dielectric constant of the glass.

Na₂O：10％～20％。

Adding Na to glass₂O lowers the melting temperature and liquidus temperature of the glass, lowers the softening point of the glass, and greatly lowers the viscosity of the glass, but Na₂The concentration of O is equal to that of Al₂O₃Is balanced otherwise it affects the high temperature coefficient of thermal expansion of the glass, so 10% -20% Na₂O can meet the requirement.

P₂O₅：0.1％～5％。

P₂O₅Belonging to the network formers of glass, but becauseOne phosphorus-oxygen double bond in phosphorus-oxygen tetrahedron is easy to break, so its network is lamellar structure, and the bond length of phosphorus-oxygen bond is greater than that of silicon-oxygen bond, and the volume of phosphorus-oxygen tetrahedron is greater than that of silicon-oxygen tetrahedron, so that 0.1% -5% of P is₂O₅The glass structure becomes loose by adding the (B) so as to be beneficial to the distribution of quantum dots.

MgO：0.1％～5％。

The addition of MgO to the glass can improve the stability of the glass, reduce its tendency to crystallize, and improve the melting properties of the glass composition.

SnO₂：0.1％～5％。

SnO₂The glass is used as a clarifying agent and added into the glass component, the content of the clarifying agent is 0-5%, and bubbles in glass melt can be eliminated.

ZnO 5％～15％。

ZnO doped in glass can effectively improve the crystallization process of the glass, and ZnO is generally [ ZnO ]₆]Located in the glass, but when there is sufficient free oxygen, ZnO forms [ ZnO₄]The CdS and CdSe mainly exist in the glass as ZnS and ZnSe after the ZnO is excessive, so that the requirement is met by adopting 5-15% of ZnO.

CdS 1％～5％，Se 1％～5％。

CdS and Se are mainly used for synthesizing quantum dot powder, a core-shaped structure can be obtained by the CdS and Se through a hot melting method, CdSe is arranged inside the core-shaped structure, and CdSe is wrapped by the CdS.

CdS of the invention_xSe_1-xThe production process of the/ZnS quantum dot luminescent glass comprises the following steps:

firstly, ZnO, CdS and Se powder are uniformly mixed, and are pretreated for 1-5 hours at the temperature of 150-450 ℃, namely CdS is obtained by a hot melting method_xSe_1-xa/ZnS powder.

Then weighing SiO according to the specified mol percentage₂、Al₂O₃、B₂O₃、Na₂O、P₂O₅The MgO and the SnO are mixed evenly,obtaining glass powder, and adding the above CdS_xSe_1-xUniformly mixing/ZnS powder in glass powder to obtain mixed powder, dissolving the mixed powder at 1200-1500 ℃, preserving heat for 3-6 hours, pouring by using a pouring mold to obtain a glass block, ensuring the use of later-stage glass slices, transferring the glass block to a muffle furnace, annealing at 300-600 ℃ for 6-12 hours to eliminate the stress of the glass, ensuring the integrity of the glass in the cooling process, and then cooling to room temperature along with the furnace to obtain CdS_xSe_1-xthe/ZnS quantum dot luminescent glass.

In the specific operation, the formulations of 7 examples are determined according to the oxide proportions listed in table 1, then a certain amount of quartz sand is weighed according to the proportions in table 1, the purity of the quartz sand can be 99.8%, the content of Fe is below 100ppm, the granularity is below 100 meshes, and chemically pure aluminum oxide, chemically pure boric acid, chemically pure sodium carbonate, chemically pure aluminum metaphosphate, chemically pure magnesium oxide, chemically pure tin oxide, chemically pure zinc oxide, chemically pure cadmium sulfide and chemically pure selenium are prepared according to the parameters in table 2.

Table 1: formula and fluorescence wavelength of CdSxSe1-x/ZnS quantum dot light-emitting glass

Table 2: formula and fluorescence wavelength of CdSxSe1-x/ZnS quantum dot light-emitting glass

7 CdS were prepared according to the above data_xSe_1-xThe resulting fluorescence emission wavelengths are shown in Table 1 and are based on the above most preferred data for the ranges of glass composition and quantum dot compositionReasonable expansion is achieved, and optimized data are adopted for dissolution of the mixed powder and subsequent annealing treatment. The excitation spectrogram, the emission spectrogram and the absorption spectrogram are respectively tested by using an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer, such as figure 1, figure 2 and figure 3. Therefore, the quantum dot luminescent glass can be excited to generate a fluorescence effect, and can be excited to emit green light by blue light emitted by the LED wafer, so that the quantum dot luminescent glass can be used in the preparation of LED luminescent materials, and can be sliced, flat ground and polished at the later stage so as to be used conveniently.

Claims (9)

1. The quantum dot luminescent glass is characterized by comprising a glass component and a quantum dot component;

the glass component comprises the following components in percentage by mol: SiO 2₂ 60％～65％，Al₂O₃15％～25％，B₂O₃0.1％～5％，Na₂O 10％～20％，P₂O₅ 0.1％～5％，MgO 0.1％～5％，SnO 0.1％～5％；

The quantum dot component comprises, by weight, 5% -15% of ZnO, 1% -5% of CdS and 1% -5% of Se.

2. A method for preparing the quantum dot luminescent glass of claim 1, comprising the steps of:

step 1, obtaining CdS from quantum dot components by a hot melting method_xSe_1-xa/ZnS powder; uniformly mixing the glass components to obtain glass powder;

step 2, CdS_xSe_1-xThe preparation method comprises the following steps of uniformly mixing/ZnS powder and glass powder to obtain quantum dot luminescent glass powder, and pouring after dissolving the quantum dot luminescent glass powder to obtain a glass block body;

and 3, annealing the glass block at 300-600 ℃, and cooling to room temperature to obtain the quantum dot luminescent glass.

3. The method of claim 2 for preparing a quantum dot luminescent glassThe method is characterized in that in the step 1, the quantum dot components are pretreated at the temperature of 150-450 ℃ to obtain CdS_xSe_1-xa/ZnS powder.

4. The method for preparing the quantum dot luminescent glass according to claim 3, wherein the quantum dot component is pretreated at the temperature for 1-5 h.

5. The method for preparing quantum dot luminescent glass according to claim 2, wherein the quantum dot luminescent glass powder is dissolved at 1200-1500 ℃ in the step 2.

6. The method for preparing the quantum dot luminescent glass according to claim 5, wherein the quantum dot luminescent glass powder is dissolved at the temperature and then is subjected to heat preservation for 3-6 hours.

7. The method for preparing the quantum dot luminescent glass according to claim 2, wherein the glass block is annealed at the temperature for 6-12 h in the step 3.

8. A quantum dot luminescent glass obtained by the method for preparing quantum dot luminescent glass according to any one of claims 2 to 7.

9. The application of the quantum dot luminescent glass as claimed in claim 8 in electronic devices, display devices or the preparation of LED luminescent materials.

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