CN110894425A

CN110894425A - Rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and preparation method thereof

Info

Publication number: CN110894425A
Application number: CN201911180132.6A
Authority: CN
Inventors: 颜晓红; 李哲; 王祥夫; 笪海霞; 刘青
Original assignee: Nanjing University of Posts and Telecommunications
Current assignee: Nanjing University of Posts and Telecommunications
Priority date: 2019-11-27
Filing date: 2019-11-27
Publication date: 2020-03-20

Abstract

The invention discloses a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and a preparation method thereof, wherein the phosphor is prepared from the following synthetic raw materials: NaCO₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99%), MgO (A.R.), SrO (A.R.). The preparation method of the technical scheme is simple, and the rare earth and metal ion doped phosphor prepared by the technical scheme has good thermal stability, chemical stability and optical property and has precise light and temperature sensing performance. The Yb is³⁺‑Er³⁺With Mg²⁺，Sr²⁺The doped phosphor material can excite tunable narrow-band green and red lights and can be monitored by Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25The temperature measurement is realized by the temperature-variable spectrum.

Description

Rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and preparation method thereof

Technical Field

The invention relates to a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and a preparation method thereof, which can be used in the technical field of light temperature sensing.

Background

A common method of measuring temperature in life is to measure temperature by directly contacting the surface of an object. The method is suitable for occasions where the surface of an object is easy to contact and the measuring process is safer for human beings. However, in some special situations, such as high-voltage environment, coal mine, and interior of microelectronic devices, it is inconvenient to use a contact temperature measurement method, so a new non-contact temperature measurement method needs to be explored, and a non-contact temperature sensor for monitoring temperature based on detecting the change of fluorescence spectrum of a light-emitting object with temperature in high-temperature environment is a new temperature measurement method.

In recent years, rare earth ion-doped phosphors have attracted much attention because of their excellent luminescent properties of narrow fluorescence spectrum width, pure emission chromaticity, wide emission wavelength distribution, long fluorescence lifetime, and high efficiency. The material fits a change function of the fluorescence emission intensity of the adjacent thermal coupling energy levels of the rare earth ions and the temperature through the relationship of the fluorescence emission intensity and the temperature, and the temperature is calculated through the fluorescence intensity. However, because the adjacent thermal coupling energy levels of the rare earth ions are close to each other, errors are sometimes caused by interference, and the accuracy of temperature measurement is not high. There is therefore a need to improve the accuracy of the measurement by methods of doping with Mg after taking into account the important influence of the crystal structure on the luminescent properties of the phosphor²⁺，Sr²⁺Regulation of the crystal field by metal ions, using Yb³⁺，Er³⁺The luminous intensity of the phosphor is controlled, and the light temperature sensing sensitivity is better. Novel Mg²⁺Doped rare earth phosphors may be a good light and temperature sensing material.

Disclosure of Invention

The present invention is directed to solve the above problems in the prior art, and provides a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and a method for preparing the same.

The purpose of the invention is realized by the following technical scheme: a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions is prepared from the following raw materials: NaCO₃，CaCO₃，BaCO₃， NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99％)，MgO(A.R.)，SrO(A.R.)，

The chemical expression of the phosphor is:

Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x(x＝0.05，0.1，0.15，0.2，0.25，0.3，0.4，0.5)，

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25，0.3，0.4，0.5)，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x(x＝0.05，0.1，0.15，0.2，0.25)，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25)。

preferably, the phosphor has the chemical expression: na (Na)₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25。

The invention also discloses a preparation method of the rare earth and metal ion doped phosphor with the functions of light temperature sensing and multiband light emission, which comprises the following steps:

s1: preparation of Na by high-temperature solid-phase method₂BaCa_0.89P₂O₈Er_0.01Yb_0.1

According to the mol ratio of Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99%) by mass, weighing the required raw materials by an electronic balance, putting the raw materials into a mortar for grinding for a certain time, adding a proper amount of absolute ethyl alcohol for grinding for half an hour, finally putting the raw materials into a corundum crucible, keeping the temperature of the corundum crucible in a high-temperature furnace for 4 hours, cooling the corundum crucible to room temperature, and grinding the mixture uniformly again to obtain a synthetic sample Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1；

S2: preparation of Mg by high-temperature solid-phase method²⁺，Sr²⁺Doping with Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1

At S1 step Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Doping Mg with different concentrations on the basis of successful preparation and synthesis²⁺，Sr²⁺To the phosphor, in terms of molar ratio:

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25)

calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99%), MgO (A.R), and SrO (A.R.) by weight, grinding the raw materials in a mortar for a certain time, adding a proper amount of absolute ethyl alcohol for grinding for half an hour, finally putting the mixture in a corundum crucible, keeping the temperature in a high-temperature furnace for 4 hours, cooling to room temperature, and grinding uniformly again to obtain a synthetic sample:

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x。

preferably, in the step S1, the mixture is put into a mortar for grinding for 10 minutes, then 2ml of absolute ethyl alcohol is added for grinding for half an hour, and finally the mixture is put into a corundum crucible and is kept at a constant temperature for 4 hours in a high-temperature furnace,

preferably, in the step S1, the corundum crucible is finally loaded into a high-temperature furnace at 1150 ℃ for 4 hours.

Preferably, in the step S2, after the required raw materials are weighed by an electronic balance, the raw materials are put into a mortar for grinding for 10 minutes, then 2mL of absolute ethyl alcohol is added for grinding for half an hour, and finally the raw materials are put into a corundum crucible and are kept at the constant temperature for 4 hours in a high-temperature furnace.

Preferably, in the step S2, the corundum crucible is finally loaded into a high-temperature furnace at 1150 ℃ for 4 hours.

Compared with the prior art, the invention adopting the technical scheme has the following technical effects: the preparation method of the technical scheme is simple and is suitable for industrial batch production. The phosphor doped with the rare earth and the metal ions prepared by the technical scheme has good thermal stability, chemical stability and optical property, and the phosphor doped with the rare earth and the metal ions has precise light and temperature sensing performance.

The Yb is³⁺-Er³⁺With Mg²⁺，Sr²⁺The doped phosphor material can excite tunable narrow-band green and red lights and can be monitored by Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25The temperature measurement is realized by the temperature-variable spectrum.

Drawings

FIG. 1 shows Er of the present invention³⁺-Yb³⁺Doping with Na₂BaCaP₂O₈X-ray diffraction pattern of (a).

FIG. 2 shows Na of the present invention₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The spectrum of (a).

FIG. 3 shows Na of the present invention₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) of the upconverted luminescence spectrum.

FIG. 4 shows Na of the present invention₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm.

FIG. 5 shows Na of the present invention₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) of the upconverted luminescence spectrum.

FIG. 6 shows Na of the present invention₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm.

FIG. 7 shows Na of the present invention₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x(x＝0.05，0.1，0.15，0Upconversion emission spectrum of 2, 0.25, 0.3, 0.4, 0.5).

FIG. 8 shows Na of the present invention₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm.

FIG. 9 shows Na of the present invention₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) of the upconverted luminescence spectrum.

FIG. 10 shows Na of the present invention₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm.

FIG. 11 shows the presence of Na under 980nm excitation₂BaCa_0.89P₂O₈Er_0.01Yb_0.1A variable temperature spectrogram.

FIG. 12 shows the presence of Na under 980nm excitation₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25A variable temperature spectrogram.

FIG. 13 shows the presence of Na under 980nm excitation₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25A variable temperature spectrogram.

FIG. 14 shows the presence of Na under 980nm excitation₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2A variable temperature spectrogram.

FIG. 15 shows the presence of Na under 980nm excitation₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1The temperature-variable spectrogram of (1).

FIG. 16 shows Na of the present invention₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The fluorescence intensity ratio of the phosphor is plotted against temperature.

FIG. 17 shows Na of the present invention₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25The fluorescence intensity ratio of (a) with temperature.

FIG. 18 shows Na of the present invention₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1The fluorescence intensity ratio of the phosphor is plotted against temperature.

FIG. 19 shows Na of the present invention₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25， Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25，Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2，Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1Error value map of (2).

FIG. 20 shows Na of the present invention₂Ca_0.89P₂O₈Er_0.01Yb_0.1Is a graph of the change of LnFIR with 1/T.

FIG. 21 shows Na of the present invention₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25Is a graph of the change of LnFIR with 1/T.

FIG. 22 shows Na of the present invention₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2，Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1Is a graph of the change of LnFIR with 1/T.

FIG. 23 shows Na of the present invention₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.2， Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.2，Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2，Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1Schematic diagram of relative sensitivity of (c).

Detailed Description

Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.

The invention discloses a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions, which is synthesized from the following raw materials: NaCO₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)， Er₂O₃(99.99％)，MgO(A.R.)，SrO(A.R.)，

The chemical expression of the phosphor is:

Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，

the chemical expression of the phosphor is: na (Na)₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25。

According to the mol ratio of Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99%) by mass, weighing the required raw materials by an electronic balance, putting the raw materials into a mortar for grinding for a certain time, adding a proper amount of absolute ethyl alcohol for grinding for half an hour, finally putting the raw materials into a corundum crucible, keeping the temperature of the corundum crucible in a high-temperature furnace for 4 hours, cooling the corundum crucible to room temperature, and grinding the mixture uniformly again to obtain a synthetic sample Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1。

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25)

calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)， Er₂O₃(99.99%), MgO (A.R), and SrO (A.R.) by weight, grinding the raw materials in a mortar for a certain time, adding a proper amount of absolute ethyl alcohol for grinding for half an hour, finally putting the mixture in a corundum crucible, keeping the temperature in a high-temperature furnace for 4 hours, cooling to room temperature, and grinding uniformly again to obtain a synthetic sample:

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x。

in the step S1, the mixture was put into a mortar and ground for 10 minutes, then 2ml of absolute ethanol was added and ground for half an hour, and finally the mixture was put into a corundum crucible and kept at a constant temperature in a high-temperature furnace for 4 hours, and in the step S1, the mixture was finally put into a corundum crucible and kept at a constant temperature in a high-temperature furnace for 4 hours at 1150 ℃.

In the step S2, after the required raw materials are weighed by an electronic balance, the raw materials are put into a mortar for grinding for 10 minutes, then 2mL of absolute ethyl alcohol is added for grinding for half an hour, and finally the raw materials are put into a corundum crucible and are kept at the constant temperature for 4 hours in a high-temperature furnace. In the step S2, the corundum crucible is finally loaded into a high-temperature furnace at 1150 ℃ for 4 hours.

Preparation of Na by high-temperature solid-phase method₂BaCa_0.89P₂O₈Er_0.01Yb_0.1According to the molar ratio of Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)， Yb₂O₃(A.R.)，Er₂O₃(99.99%) in mass, respectively:

NaCO₃	CaCO₃	BaCO₃	NH₄H₂PO₄	Yb₂O₃	Er₂O₃
						1.9422g	2.34g	2.3049g	2.691g	0.2867g	0.0223g

weighing the required raw materials by an electronic balance, putting the raw materials into a mortar for grinding for 10 minutes, then adding 2ml of absolute ethyl alcohol for grinding for half an hour, and finally putting the raw materials into a corundum crucible and keeping the temperature of the corundum crucible at 1150 ℃ for 4 hours. After cooling to room temperature, grinding uniformly again to obtain a synthetic sample Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1。

(b) Preparing Mg by a high-temperature solid-phase method²⁺，Sr²⁺Doping with Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1

In Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Based on the successful preparation and synthesis, Mg with different concentrations is doped²⁺，Sr² ⁺Into the phosphor.

According to the molar ratio:

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25)

calculating NaCO used for the experiment₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)， Er₂O₃(99.99%), MgO (A.R.), SrO (A.R.) by mass:

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x

NaCO₃

CaCO₃

BaCO₃

NH₄H₂PO₄

Yb₂O₃

Er₂O₃

MgO

X＝0.05

1.7762g

0.9523g

2.003g

2.461g

0.2622g

0.0204g

0.0216g

X＝0.1

1.7928g

0.9612g

1.9148g

2.484g

0.2646g

0.0206g

0.0435g

X＝0.15

1.8094g

0.9701g

1.8252g

2.507g

0.2671g

0.0208g

0.0659g

X＝0.2

1.8426g

0.9879g

1.7494g

2.553g

0.2720g

0.0212g

0.0895g

X＝0.25

1.8592g

0.9968g

1.6548g

2.576g

0.2744g

0.0214g

0.1128g

X＝0.3

1.8924g

1.0146g

1.5721g

2.622g

0.2793g

0.0218g

0.1378g

X＝0.4

1.9422g

1.0413g

1.3829g

2.691g

0.2867g

0.0223g

0.1886g

X＝0.5

1.992g

1.068g

1.182g

2.76g

0.294g

0.0229g

0.2418g

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x

NaCO₃

CaCO₃

BaCO₃

NH₄H₂PO₄

Yb₂O₃

Er₂O3

SrO

X＝0.05

1.9505g

1.0458g

2.199g

2.7025g

0.2879g

0.0224g

0.0609g

X＝0.1

1.9621g

1.0520g

2.0957g

2.7186g

0.2896g

0.0226g

0.1225g

X＝0.15

1.9737g

1.0582g

1.9910g

2.7347g

0.2913g

0.0227g

0.1848g

X＝0.2

1.9854g

1.0644g

1.8849g

2.7508g

0.293g

0.0228g

0.2478g

X＝0.25

1.9986g

1.0716g

1.7789g

2.7692g

0.295g

0.023g

0.3118g

X＝0.3

2.0086g

1.0769g

1.6686g

2.783g

0.2966g

0.0231g

0.3761g

X＝0.4

2.0352g

1.0911g

1.4491g

2.8198g

0.3004g

0.0234g

0.5081g

X＝0.5

2.06g

1.1045g

1.222g

2.8543g

0.3040g

0.0237g

0.6428g

weighing the required raw materials by an electronic balance, putting the raw materials into a mortar for grinding for 10 minutes, adding 2mL of absolute ethyl alcohol for grinding for half an hour, finally putting the raw materials into a corundum crucible, keeping the temperature of the corundum crucible at 1150 ℃ for 4 hours, cooling the corundum crucible to room temperature, and grinding the mixture uniformly again to obtain a synthetic sample:

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x，

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x。

the experimental results are as follows:

FIG. 1 shows Er³⁺-Yb³⁺Doping with Na₂BaCaP₂O₈The abscissa is angle and the ordinate is intensity. The XRD of the sample regulated by adding the metal ions is also tested in a relevant way, and is compared with the standard card Na₂BaCaP₂O₈And comparing, and finding that doping does not cause impurity, and no impurity peak is generated, so that the sample synthesis is successful.

FIG. 2 shows Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The abscissa of the spectrum of (a) is wavelength and the ordinate is emission intensity. Under the excitation of 980nm near infrared light, Na₂BaCaP₂O₈The photoluminescence spectrum of the phosphor comprises green and red emission bands, and the emission peaks are 525nm, 540nm and 650 nm.

FIG. 3 is Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1Mg_x(x is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) and fig. 4 is Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm. In FIG. 3, the abscissa is wavelength and the ordinate is emission intensity, in the case of Mg doping²⁺The position of an emission peak is not changed before and after the transition, and the main transition is Er³⁺4I15/2 → 4H11/2 (525nm), 4I15/2 → 4S3/2(546nm), 4I15/2 → 4F9/2(659 nm).

The study of the optical temperature sensing performance is mainly based on the study between thermal coupling energy levels, so that Na is used₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The two green bands are primarily explored in this series of phosphorsThe strength of the originating thermal coupling energy levels H11/2 and 4S3/2 varies. FIG. 4 with doped Mg on the abscissa²⁺The molar concentration and the ordinate are the emission intensity, and Mg doping is found in the experimental process²⁺It will affect its spectrum and enhance the intensity of the green and red light. Na (Na)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Doping with Mg²⁺After that, the peak shift of the emission band is unchanged. In Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1Mg_xIn (2) when Mg²⁺When the doping amount is 0.25 mol%, the fluorescence intensity of two green bands is strongest.

FIG. 5 shows Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1The up-conversion emission spectrum of Srx (x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5), and fig. 6 is Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1Spectral intensity plots of the 25nm and 540nm emission bands for Srx (x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5). In FIG. 5, the abscissa represents wavelength and the ordinate represents emission intensity, in the case of Sr doping²⁺The position of an emission peak is not changed before and after the transition, and the main transition is Er³⁺4I15/2 → 4H11/2 (525nm), 4I15/2 → 4S3/2(546nm), 4I15/2 → 4F9/2(659 nm).

FIG. 6 shows doped Sr on the abscissa²⁺The molar concentration and the ordinate are the emission intensity, and the doped Sr is found in the experimental process²⁺It will affect its spectrum and enhance the intensity of the green and red light. Na (Na)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Doped with Sr²⁺After that, the peak shift of the emission band is unchanged. In Na₂Ba_1-xCaP₂O₈Er_0.01Yb_0.1Sr_xIn (2) when Mg²⁺When the doping amount is 0.25 mol%, the fluorescence intensity of two green bands is strongest.

FIG. 7 shows Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) of the upper transitionsAnd converting the emission spectrogram. FIG. 8 shows Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x(x ═ 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5) spectral intensity plots of the emission bands at 525nm and 540 nm. In Er³⁺-Yb³⁺Doped Na₂BaCaP₂O₈Changing Ca in phosphor²⁺Molar ratio of elements, doping with Mg in different concentrations²⁺，Sr²⁺To change the crystal field. In fig. 7, the abscissa represents wavelength and the ordinate represents emission intensity. In the doping of Mg²⁺The positions of the emission peaks are not changed before and after, but the emission intensities of the green light and the red light are adjusted. As shown in FIG. 8, the abscissa is doped Sr²⁺Molar concentration, ordinate is emission intensity. In Na₂BaCa_0.89- _xP₂O₈Er_0.01Yb_0.1Mg_xIn the case of doping with 0.2 mol% Mg²⁺The two green bands have the greatest spectral intensity.

FIG. 9 shows Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5.) upconverted emission spectrum fig. 10 is Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x is the spectral intensity of the emission bands at 525nm and 540nm at 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5. in FIG. 9, the abscissa is the wavelength and the ordinate is the emission intensity²⁺The positions of the emission peaks are not changed before and after, but the emission intensities of the green light and the red light are adjusted. As shown in FIG. 10, the abscissa is doped Sr²⁺Molar concentration, ordinate is emission intensity. In Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_xIn the formula, 0.1 mol% of Sr is selected²⁺When the red fluorescent powder is used, two green light spectrums of 525nm and 546nm are strongest, but the fluorescent intensity effect is obviously lower than that of undoped Sr²⁺Na of (2)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1。

FIG. 11, FIG. 12, FIG. 13, FIG. 14 and FIG. 15 are each Na not doped with a metal ion₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Phosphor, Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25Phosphor, Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25Phosphor, Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2Phosphor and Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1Temperature change spectra of phosphors over a temperature range of 298K to 623K. In fig. 11, 12, 13, 14, and 15, the X-axis represents wavelength, the Y-axis represents temperature, and the Z-axis represents spectral intensity.

The position of the emission peak of the fluorescence spectrum at different temperatures does not change, but the intensity of the fluorescence spectrum changes with increasing temperature. Er³⁺The two thermal coupling energy levels have obvious spectral contrast change, the fluorescence intensity of 4I15/2 → 4H11/2 (525nm) is greatly enhanced along with the temperature rise, and the fluorescence intensity of 4I15/2 → 4S3/2(546nm) is less changed, so that the fluorescence intensity contrast between the two thermal coupling energy levels is obvious, and the thermal coupling energy levels are suitable for the research of the light and temperature sensing performance.

In fig. 16, 17, and 18, the horizontal axis is temperature, the vertical axis is fluorescence intensity ratio, the measurement in the optical temperature sensing aspect is generally explored by the fluorescence intensity ratio of two thermal coupling energy levels, and the energy difference Δ E of the thermal coupling energy levels is calculated by performing operation fitting on spectral intensity data points at different temperatures. As shown in FIG. 16, Na was found by data fitting₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The experimental data of the fluorescence intensity ratio of (a) are well matched with the formula. Similarly, as shown in FIGS. 17 and 18, Mg is doped at different concentrations²⁺Or Sr²⁺Thereafter, the experimental data were successfully fitted. Na (Na)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1As the temperature increasesThe experimental value of Delta E is about 628.43cm^-1。

Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25And Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25Δ E experiment value ratio of (A) to (B) Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1High, 925.47cm-1 and 927.43cm-1 respectively. Na (Na)₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2The experimental value of (a) is relatively large and is 775.92. Description of doping with Mg²⁺，Sr²⁺The light-temperature sensing properties of the primary phosphor can be adjusted, but also result in different Δ Ε values.

FIG. 19 is Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25，Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2， Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1The error map is fitted to the data. To evaluate the accuracy of light-temperature sensing of the samples, the delta values of the above five phosphors were calculated. The calculation formula is as follows: Δ ═ Δ E_f-ΔE_m|/ΔE_mΔ Ef is the theoretical energy difference between thermally coupled energy levels, Δ E_mIs the energy difference obtained experimentally.

Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1Delta of (D) is about 27.4%, Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25Delta of (3) is about 6.9%, Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25Delta of (d) is about 7.1%, Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2Delta of (d) is about 10.4%, Na₂BaCa_0.79P₂O₈Er_0.01Yb_0.1Sr_0.1Is about 33.6%. It can be seen that there is a large error in the study of optical temperature sensing purely using the FIR of the above formula. Therefore, improvement on the above fluorescence intensity ratio is required, a new calculation method is explored, and a method of taking the logarithm of the FIR and then adding a correction term is adopted to improve the precision.

In FIGS. 20, 21 and 22, the abscissa represents the logarithm of the fluorescence intensity ratio, and the ordinate represents the reciprocal 1/T of the temperature. The relationship between the fluorescence intensity ratio and the temperature was expressed as: LnFIR ═ Δ E/KT + C, where C is the correction factor and Δ E is the energy difference between thermally coupled energy levels 2H11/2 and 4S 3/2. And obtaining an expression of LnFIR through data fitting, and reflecting the function relation of the fluorescence peak value ratio and the temperature.

In fig. 23, the horizontal axis represents temperature and the vertical axis represents relative sensitivity, and the light-temperature sensitivity needs to be calculated in consideration of the actual use of the light-temperature sensor. The relative sensitivity SR is an important parameter in reflecting the accuracy of the phosphor for light temperature measurement. The formula for calculating the relative sensitivity is: s_R＝dFIR/dT＝FIR*ΔEm/KT²。

As shown in FIG. 23, Mg was doped at different concentrations²⁺，Sr²⁺Na of (2)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The relative sensitivity of the phosphor, which increases and then decreases as the temperature increases, has a maximum between 298K and 623K absolute temperatures.

Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25，Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Sr_0.25，Na₂BaCa_0.69P₂O₈Er_0.01Yb_0.1Mg_0.2Relative sensitivity of the sampleNa being more than undoped metal ion₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The sensitivity of (2) is high. Na (Na)₂BaCa_0.89P₂O₈Er_0.01Yb_0.1The relative sensitivity of the phosphor reaches a maximum of 0.0025K at 395K^-1. In the presence of Mg²⁺，Sr²⁺Then, the relative sensitivity reaches the maximum value of 0.0030K at 395K^-1The temperature detection range is not changed, but the sensitivity is improved; so that the total amount of Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1In phosphor series, all are suitable for light and temperature sensing measurement at medium and low temperature. Wherein, Na₂Ba_0.7 ₅Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25The relative sensitivity of (2) is the highest, and reaches 0.0030K at 395K^-1. Thus Na₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25Is the most suitable phosphor for light and temperature sensing measurement in the whole series.

The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.

Claims

1. A rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission, characterized by: the phosphor is synthesized by the following raw materials: NaCO₃，CaCO₃，BaCO₃，NH₄H₂PO₄(A.R.)，Yb₂O₃(A.R.)，Er₂O₃(99.99％)，MgO(A.R.)，SrO(A.R.)，

The chemical expression of the phosphor is:

Na₂BaCa_0.89P₂O₈Er_0.01Yb_0.1，

2. the rare earth and metal ion doped phosphor with optical temperature sensing and multiband light emission function of claim 1, wherein: the chemical expression of the phosphor is: na (Na)₂Ba_0.75Ca_0.89P₂O₈Er_0.01Yb_0.1Mg_0.25。

3. A method for preparing a rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions is characterized in that: the method comprises the following steps:

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x(x＝0.05，0.1，0.15，0.2，0.25)

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Mg_x

Na₂Ba_1-xCa_0.89P₂O₈Er_0.01Yb_0.1Sr_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Mg_x，

Na₂BaCa_0.89-xP₂O₈Er_0.01Yb_0.1Sr_x。

4. the method of claim 2, wherein the phosphor doped with rare earth and metal ions has functions of light temperature sensing and multiband light emission, and comprises: in the step S1, the mixture was ground in a mortar for 10 minutes, then ground for half an hour by adding 2ml of absolute ethanol, and finally placed in a corundum crucible and kept at a constant temperature for 4 hours in a high temperature furnace.

5. The method of claim 2, wherein the phosphor doped with rare earth and metal ions has functions of light temperature sensing and multiband light emission, and comprises: in the step S1, the corundum crucible is finally loaded into a high-temperature furnace at 1150 ℃ for 4 hours.

6. The method of claim 2, wherein the phosphor doped with rare earth and metal ions has functions of light temperature sensing and multiband light emission, and comprises: in the step S2, after the required raw materials are weighed by an electronic balance, the raw materials are put into a mortar for grinding for 10 minutes, then 2mL of absolute ethyl alcohol is added for grinding for half an hour, and finally the raw materials are put into a corundum crucible and are kept at the constant temperature for 4 hours in a high-temperature furnace.

7. The method of claim 2, wherein the phosphor doped with rare earth and metal ions has functions of light temperature sensing and multiband light emission, and comprises: in the step S2, the corundum crucible is finally loaded into a high-temperature furnace at 1150 ℃ for 4 hours.