CN109943338B

CN109943338B - Preparation method of near-infrared luminescent rare earth doped indium selenide nanosheet

Info

Publication number: CN109943338B
Application number: CN201910203507.XA
Authority: CN
Inventors: 白功勋; 刘源; 潘二; 徐时清
Original assignee: China Jiliang University
Current assignee: China Jiliang University
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2021-12-28
Anticipated expiration: 2039-03-18
Also published as: CN109943338A

Abstract

The invention provides a preparation method of near-infrared luminescent rare earth doped indium selenide nanosheets. Weighing a certain amount of indium selenide and rare earth ion fluoride, and putting the indium selenide and the rare earth ion fluoride into an agate mortar for full grinding. Then putting the mixture into a tubular furnace, introducing gas, and carrying out solid-phase sintering treatment. And then putting a certain amount of the fired powder into a centrifuge tube, adding a certain amount of NMP, and then putting the centrifuge tube into an ultrasonic instrument for ultrasonic treatment. And finally, placing the ultrasonically treated substance into a centrifugal machine for centrifugal treatment, and collecting an upper clear solution which is a rare earth doped indium selenide nanosheet solution. The rare earth doped indium selenide nanosheets prepared by adjusting parameters such as a tubular furnace temperature system, an ultrasonic system of an ultrasonic instrument, a centrifugal system of a centrifugal machine and the like have the advantages of simple preparation process, high yield, controllable preparation and the like, and have very important functions in the fields of low-dimensional nanometer devices, non-contact temperature probes, biological nerve imaging and the like.

Description

Preparation method of near-infrared luminescent rare earth doped indium selenide nanosheet

Technical Field

The invention belongs to the field of preparation of low-dimensional nano materials, and particularly relates to preparation of rare earth doped indium selenide nanosheets.

Background

The research and development of new materials play an important role in the production and life of people, and in the research and development process, the dimension of the materials becomes an important parameter for adjusting the structural characteristics of the materials. Materials are usually three-dimensional structures, and when the materials are changed from three-dimensional structures to two-dimensional structures, the physicochemical properties of the materials are changed quite remarkably. Indium selenide is a semiconductor material whose different crystalline phases typically have band widths (bandgaps): 1.3ev, 1.5ev or 1.9ev, the layers are stacked together by van der waals force, and after the three-dimensional structure is changed into a two-dimensional structure, the organic silicon solar cell has important application in many aspects such as low-dimensional nanometer devices, biological nerve imaging, solar cell thin films, high-efficiency photocatalysts and the like.

The 4f electron orbit of the rare earth element has rich energy levels, and the luminescence phenomenon is transition between the energy levels, so that absorption and emission from an ultraviolet region to a near infrared region can be realized. In addition, the rare earth ions have high quantum yield, narrow energy band width, long luminescence life and good stability in luminescence, so the rare earth ions are widely applied to the field of luminescence. Rare earth elements are doped into the indium selenide semiconductor material to be made into a two-dimensional layered material, and the two advantages can be combined, so that the two-dimensional layered material plays an important role in photoelectric application. At present, compared with the extensive research on two-dimensional semiconductor materials such as molybdenum disulfide, tungsten disulfide, molybdenum diselenide and the like, the research on the preparation and application of rare earth-doped indium selenide two-dimensional semiconductors needs to be further enhanced.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a preparation method of a near-infrared luminescent rare earth doped indium selenide nanosheet, which adopts the following technical scheme:

a preparation method of near-infrared luminescent rare earth doped indium selenide nanosheets comprises the following specific preparation processes:

a) weighing a certain amount of indium selenide and rare earth ion fluoride, and fully grinding in an agate mortar;

b) putting the ground powder into a tubular furnace, adjusting the temperature system of the tubular furnace, introducing gas, and performing solid-phase sintering treatment;

c) putting the sintered powder into an agate mortar for fully grinding again, putting the ground powder into a centrifugal tube, and adding NMP (N-methyl pyrrolidone) for dispersing;

d) putting the NMP and powder mixture obtained in the step c) into an ultrasonic instrument, adjusting parameters such as power and time of the ultrasonic instrument, and carrying out ultrasonic treatment;

e) putting the NMP mixture subjected to ultrasonic treatment into a centrifuge, adjusting parameters such as the rotating speed and time of the centrifuge and the like, and performing centrifugal treatment;

f) and collecting the supernatant clear brown solution after centrifugal treatment, and observing the rare earth doped indium selenide nanosheets under an electron microscope.

The mole percentage of the doping amount of the rare earth ion fluoride in the step a) is as follows: 0.01 to 10 percent.

The temperature system in the step b) is as follows: the rate of temperature increase from room temperature to firing temperature was: 1-50 ℃/min; the firing temperature is as follows: 500-1000 ℃; the firing time is as follows: 1 to 10 hours.

The weight of the ground powder in the step c) is as follows: 1 mg to 100 mg; the volume of NMP added was: 1 ml to 100 ml.

The ultrasonic treatment time in the step d) is 1-48 h.

The centrifugal rate of the centrifugal machine in the step e) is as follows: 1000 r/min-20000 r/min.

The rare earth doped indium selenide nanosheets prepared by the solid-phase sintering method and the liquid-phase stripping method have the following advantages:

1. the preparation process is simple. The method is prepared by a solid-phase sintering method and a liquid-phase stripping method, and the two methods are simple and mature to operate.

2. The crystallinity is good. The method prepares the rare earth doped indium selenide by a solid-phase sintering method, and the prepared doped indium selenide powder has excellent crystallinity.

3. The yield of the nano-sheets is high. The method prepares rare earth doped indium selenide nanosheets by a liquid phase stripping method, and can prepare a large number of nanosheets by adjusting parameters such as ultrasonic time, power and the like.

4. The prepared indium selenide nanosheet has good luminous performance and water solubility.

Drawings

Fig. 1 is a TEM image of neodymium ion doped indium selenide nanoplates.

Fig. 2 is an XRD pattern of indium selenide doped with neodymium ions.

Fig. 3 is a photoluminescence map of indium selenide doped with neodymium ions.

Detailed Description

The invention will be further explained with reference to the drawings.

Example 1

Step 1, weighing 14.935g of indium selenide and 0.065g of neodymium fluoride raw materials, and fully grinding the raw materials in an agate mortar to uniformly mix the raw materials.

Step 2, placing the ground powder into a tube furnace, introducing atmosphere, and setting a temperature system as follows: heating to 300 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1 hour, then heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 4 hours, and finally naturally cooling to room temperature and taking out.

And 3, putting the fired powder into an agate mortar for re-grinding, putting 20 mg of powder into a centrifuge tube, and adding 10ml of NMP to disperse the powder.

And 4, putting the centrifuge tube into an ultrasonic instrument, adjusting the power of the ultrasonic instrument to be 100, adjusting the ultrasonic time to be 12 hours, and keeping the water bath temperature to be below 10 ℃.

And 5, putting the mixture of NMP and powder after ultrasonic treatment into a centrifuge, and setting a centrifugation system as follows: the mixture is firstly centrifuged for 4 min at a centrifugation speed of 3000 r/min, and then centrifuged for 10 min again at a centrifugation speed of 4000 r/min.

And 6, collecting the upper clear brown solution, and observing the rare earth doped indium selenide nanosheets under an electron microscope. Example 2

Step 1, 14.9270g of indium selenide and 0.0730g of thulium fluoride raw material are weighed and put into an agate mortar for full grinding, so that the raw materials are uniformly mixed.

Step 2, putting the fully ground powder into a tube furnace, introducing atmosphere, and setting the temperature system as follows: raising the temperature from room temperature to 300 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1 hour, then raising the temperature to 550 ℃ at the heating rate of 10 ℃/min, preserving the heat for 6 hours, and finally naturally cooling to room temperature and taking out.

And 3, putting the fired powder into an agate mortar for grinding again, taking 10 mg of powder into a centrifuge tube, and adding 10ml of NMP to disperse the powder.

And 4, putting the centrifugal tube into an ultrasonic instrument, adjusting the power of the ultrasonic instrument to be 100, adjusting the ultrasonic time to be 12 hours, and keeping the water bath temperature to be below 10 ℃ for ultrasonic treatment.

And 5, putting the mixture of the NMP and the powder after the ultrasonic treatment into a centrifuge, and setting a centrifugation system as follows: the mixture is firstly centrifuged for 5 min at the centrifugation speed of 2000 r/min and then centrifuged for 10 min again at the centrifugation speed of 4000 r/min.

And 6, collecting the upper clear brown solution, and observing the rare earth doped indium selenide nanosheets under an electron microscope.

Example 3

Step 1, 14.9639g of indium selenide and 0.0361g of erbium fluoride raw material are weighed and then put into a mortar for full grinding, so that the raw materials are uniformly mixed.

Step 2, putting the ground powder into a tube furnace, introducing atmosphere, and setting the temperature system of the tube furnace as follows: raising the temperature from room temperature to 300 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1 hour, raising the temperature to 500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 6 hours, and finally naturally cooling to room temperature and taking out.

And 3, putting the fired powder into an agate mortar for secondary grinding, putting 10 mg of the powder into a centrifuge tube, and adding 10ml of NMP at the same time.

And 4, placing the centrifugal tube in an ultrasonic instrument, adjusting the power of the centrifugal tube to be 100, keeping the time to be 12 hours, and carrying out ultrasonic treatment while ensuring the water bath temperature to be below 10 ℃.

Step 5, putting the mixture of NMP and powder after ultrasonic treatment into a centrifuge, and adjusting the centrifuge system as follows: the mixture is firstly centrifuged for 5 min at a centrifugation speed of 2000 r/min, and then centrifuged for 10 min again at a centrifugation speed of 5000 r/min.

Claims

1. A preparation method of near-infrared luminescent rare earth doped indium selenide nanosheets is characterized by comprising the following steps:

a) weighing a certain amount of indium selenide and rare earth ion fluoride, and fully grinding in an agate mortar; the rare earth ions are Nd, Tm or Er;

b) putting the ground powder into a tubular furnace, adjusting the temperature system of the tubular furnace, introducing gas, and performing solid-phase sintering treatment; the firing temperature is as follows: 500-650 ℃; the firing time is as follows: 1 h-10 h;

d) putting the NMP and powder mixture obtained in the step c) into an ultrasonic instrument, adjusting power and time parameters of the ultrasonic instrument, and carrying out ultrasonic treatment;

e) putting the NMP mixture subjected to ultrasonic treatment into a centrifuge, adjusting the rotating speed and time parameters of the centrifuge, and performing centrifugal treatment;

f) collecting the upper layer of clear brown solution after centrifugal treatment, and observing rare earth doped indium selenide nanosheets under an electron microscope;

the mole percentage of the doping amount of the rare earth ions in the step a) is as follows: 0.1 to 10 percent.

2. The method for preparing near-infrared luminescent rare earth doped indium selenide nanosheets of claim 1, wherein: the solid phase sintering process parameters in the step b) are as follows: the rate of temperature increase from room temperature to firing temperature was: 1-50 ℃/min.

3. The method for preparing near-infrared luminescent rare earth doped indium selenide nanosheets of claim 1, wherein: the weight of the ground powder in the step c) is as follows: 1 mg to 100 mg; the volume of NMP added was: 1 ml to 100 ml.

4. The method for preparing near-infrared luminescent rare earth doped indium selenide nanosheets of claim 1, wherein: the ultrasonic time in the step d) is as follows: 1 to 48 hours.

5. The method for preparing near-infrared luminescent rare earth doped indium selenide nanosheets of claim 1, wherein: the centrifugal rate of the centrifugal machine in the step e) is as follows: 1000 r/min-20000 r/min.