CN104342141A - Cerium and tin co-doped fluorphosphate luminescent material, and preparation method and application of fluorphosphate luminescent - Google Patents

Abstract

The invention discloses a cerium and tin co-doped fluorphosphate luminescent material. The chemical formula of the luminescent material is Me5-x-y(PO4)3F: x Ce<3+>, ySn<4+>, wherein x represents 0.01-0.05, y represents 0.01-0.06, and the Me represents magnesium ions, calcium ions, strontium ions or barium ions. In an electroluminescent spectrum (EL) of a luminescent film made from the cerium and tin co-doped fluorphosphate luminescent material, quite high luminescent peaks exist in a 450nm wavelength region and a 480nm wavelength region both, so the cerium and tin co-doped fluorphosphate luminescent material can be applied to a film electroluminescent member. The invention also provides a preparation method and an application of the cerium and tin co-doped fluorphosphate luminescent material.

Description

Cerium tin codoped fluorophosphate luminescent material, preparation method and application thereof

[technical field]

The present invention relates to a kind of cerium tin codoped fluorophosphate luminescent material, its preparation method, cerium tin codoped fluorophosphate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.

[background technology]

Membrane electro luminescent device (TFELD), due to its active illuminating, total solids, the advantage such as shock-resistant, reaction is fast, visual angle is large, Applicable temperature is wide, operation is simple, has caused and paid close attention to widely, and development rapidly.At present, research colour and extremely panchromatic TFELD, the material of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to the cerium tin codoped fluorophosphate luminescent material of thin-film electroluminescent displays, have not yet to see report.

[summary of the invention]

Based on this, be necessary to provide a kind of the cerium tin codoped fluorophosphate luminescent material, its preparation method, cerium tin codoped fluorophosphate light-emitting film, its preparation method, the membrane electro luminescent device using this cerium tin codoped fluorophosphate luminescent material and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of cerium tin codoped fluorophosphate luminescent material, its chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, y Sn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

A preparation method for cerium tin codoped fluorophosphate luminescent material, comprises the following steps:

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion; And

Namely described mixed powder is obtained chemical formula for 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering is Me ₂si ₆n ₁₀: xSm ³⁺cerium tin codoped fluorophosphate luminescent material.

A kind of cerium tin codoped fluorophosphate light-emitting film, the chemical general formula of the material of this cerium tin codoped fluorophosphate light-emitting film is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

A preparation method for cerium tin codoped fluorophosphate light-emitting film, comprises the following steps:

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, y Sn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa; And

Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, and the flow of working gas is 10sccm ~ 35sccm, and underlayer temperature is 250 DEG C ~ 750 DEG C, is then filmed, and obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

A kind of membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is cerium tin codoped fluorophosphate luminescent material, and the chemical formula of this cerium tin codoped fluorophosphate luminescent material is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

A preparation method for membrane electro luminescent device, comprises the following steps:

The substrate with anode is provided;

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa; And

Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, and the underlayer temperature with anode is 250 DEG C ~ 750 DEG C, then be filmed, obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, described anode prepares luminescent layer, and wherein, x is 0.01 ~ 0.05, y is 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Prepare negative electrode on the light-emitting layer, obtain described membrane electro luminescent device.

Cerium tin codoped fluorophosphate luminescent material of the present invention, adopt fluorophosphate as matrix, it has higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus produce less radiationless transition in the process of photovoltaic energy conversion, there is higher luminous efficiency.The active element of cerium tin codoped fluorophosphate luminescent material is Ce ³⁺and Sn ⁴⁺, wherein Ce is that in rare earth element, content is the highest is also the most cheap, and relative to other rare earth ions, its level structure is the simplest, at ground state 4f ¹with excited state 5d ¹between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region; And Sn is as a kind of important metal ion mixing agent, belonging to two ionization alms giver provides donor ion, can obtain higher electron carrier density, make to be doped matrix and can obtain higher specific conductivity and good field emission performance.Meanwhile, Sn doping can also change energy gap and the optical absorptive character of matrix, makes its easier exciting radiation luminous.

Above-mentioned cerium tin codoped fluorophosphate luminescent material (Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺) in the electroluminescent spectrum (EL) of light-emitting film made, have very strong glow peak in 450nm and 480nm wavelength zone, can be applied in thin-film electroluminescent displays.

[accompanying drawing explanation]

Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment;

Fig. 2 is the electroluminescent spectrogram of cerium tin codoped fluorophosphate light-emitting film prepared by embodiment 1;

Fig. 3 is the XRD figure of cerium tin codoped fluorophosphate light-emitting film prepared by embodiment 1;

Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and electric current and brightness relationship figure.

[embodiment]

Below in conjunction with the drawings and specific embodiments, cerium tin codoped fluorophosphate luminescent material, its preparation method, cerium tin codoped fluorophosphate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.

The cerium tin codoped fluorophosphate luminescent material of one embodiment, its chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

Preferably, x is 0.03, y is 0.04.

Me in this cerium tin codoped fluorophosphate luminescent material _5-x-y(PO ₄) ₃f is matrix, and cerium ion and tin ion are active elements.In the electroluminescent spectrum (EL) of the light-emitting film that this cerium tin codoped fluorophosphate luminescent material is made, there is very strong glow peak in 450nm and 480nm wavelength zone, can be applied in thin-film electroluminescent displays.

The preparation method of above-mentioned cerium tin codoped fluorophosphate luminescent material, comprises the following steps:

Step S11, according to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

In this step, preferably, x is 0.03, y is 0.04.

Step S12, namely mixed powder sinter 0.5 hour ~ 3 hours to be obtained chemical formula being Me at 900 DEG C ~ 1300 DEG C ₂si ₆n ₁₀: xSm ³⁺cerium tin codoped fluorophosphate luminescent material.

In this step, preferably at 1250 DEG C, sinter 1.5 hours.

The cerium tin codoped fluorophosphate light-emitting film of one embodiment, the chemical formula of the material of this cerium tin codoped fluorophosphate light-emitting film is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

Preferably, x is 0.03, y is 0.04.

Preferably, the thickness of cerium tin codoped fluorophosphate light-emitting film is 60nm ~ 350nm, and more preferably, the thickness of cerium tin codoped fluorophosphate light-emitting film is 130nm.

The preparation method of above-mentioned cerium tin codoped fluorophosphate light-emitting film, comprises the following steps:

Step S21, according to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, mixed powder is sintered 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C and makes target, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

In this step, preferably, x is 0.03, y is 0.04, and at 1250 DEG C, sinter 1.5 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.

Step S22, described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa;

In this step, preferably, vacuum tightness is 5 × 10 ^-4pa.

In this step, preferably, described substrate is glass or sapphire.

Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, and underlayer temperature is 250 DEG C ~ 750 DEG C, then be filmed, obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 600 DEG C.

In this step, preferred described cerium tin codoped fluorophosphate light-emitting film is at 600 DEG C of annealing 2h.

Preferably, the thickness of cerium tin codoped fluorophosphate light-emitting film is 60nm ~ 350nm, and more preferably, the thickness of cerium tin codoped fluorophosphate light-emitting film is 130nm.

Refer to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprises the substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 that stack gradually.

Substrate 1 is glass substrate.Anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.The material of luminescent layer 3 is cerium tin codoped fluorophosphate luminescent material, and the chemical formula of this cerium tin codoped fluorophosphate luminescent material is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.The material of negative electrode 4 is silver (Ag).

Preferably, the thickness of luminescent layer 3 is 60nm ~ 350nm, and more preferably, the thickness of luminescent layer 3 is 130nm.

The preparation method of above-mentioned membrane electro luminescent device, comprises the following steps:

Step S31, provide the substrate 1 with anode 2.

In present embodiment, substrate 1 is glass substrate, and anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.There is the substrate 1 priority acetone of anode 2, dehydrated alcohol and deionized water ultrasonic cleaning and carry out oxygen plasma treatment with to it.

Step S32, on anode 2, prepare luminescent layer 3, the material of luminescent layer 3 is cerium tin codoped fluorophosphate luminescent material, and the chemical formula of this cerium tin codoped fluorophosphate luminescent material is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

In present embodiment, luminescent layer 3 is obtained by following steps:

First, according to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, mixed powder is sintered 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C and makes target, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

In this step, preferably, x is 0.03, y is 0.04, and at 1250 DEG C, sinter 1.5 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.

Secondly, described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa;

In this step, preferably, vacuum tightness is 5 × 10 ^-4pa.

Then, adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, the underlayer temperature with anode is 250 DEG C ~ 750 DEG C, is then filmed, and obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, y Sn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 600 DEG C.

In this step, preferred described cerium tin codoped fluorophosphate light-emitting film is at 600 DEG C of annealing 2h.

In present embodiment, the material of negative electrode 4 is silver (Ag), and preparation method is evaporation.

Cerium tin codoped fluorophosphate luminescent material of the present invention, adopt fluorophosphate as matrix, it has higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus produce less radiationless transition in the process of photovoltaic energy conversion, there is higher luminous efficiency.The active element of cerium tin codoped fluorophosphate luminescent material is Ce ³⁺and Sn ⁴⁺, wherein Ce is that in rare earth element, content is the highest is also the most cheap, and relative to other rare earth ions, its level structure is the simplest, at ground state 4f ¹with excited state 5d ¹between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region; And Sn is as a kind of important metal ion mixing agent, belonging to two ionization alms giver provides donor ion, can obtain higher electron carrier density, make to be doped matrix and can obtain higher specific conductivity and good field emission performance.Meanwhile, Sn doping can also change energy gap and the optical absorptive character of matrix, makes its easier exciting radiation luminous.

Be specific embodiment below.

Embodiment 1

Select purity be 99.99% powder, by MgO, MgF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.93:1.5:0.03:0.04 mixes and obtains mixed powder according to mol ratio, and mixed powder being sintered at 1250 DEG C 1.5h, to form diameter be 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 ^-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and finally anneal 2h in 0.01Pa vacuum oven, and annealing temperature is 600 DEG C.Obtaining chemical formula is Mg _4.93(PO ₄) ₃f:0.03Ce ³⁺, 0.04Sn ⁴⁺light-emitting film, light-emitting film thickness is 130nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

The chemical general formula of the cerium tin codoped fluorophosphate light-emitting film obtained in the present embodiment is Mg _4.93(PO ₄) ₃f:0.03Ce ³⁺, 0.04Sn ⁴⁺, wherein Mg _4.93(PO ₄) ₃f is matrix, Ce ³⁺and Sn ⁴⁺it is active element.

Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the cerium tin codoped fluorophosphate light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 450nm and 480nm wavelength zone, can be applied in thin-film electroluminescent displays.

Refer to Fig. 3, Fig. 3 is the XRD curve of cerium tin codoped aluminate luminescent film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3 in figure X-ray diffraction peak corresponding be the characteristic peak of fluorophosphate, do not occur doped element and the relevant peak of impurity, illustrate that cerium tin dope ion enters the lattice of fluorophosphate, sample has good crystallographic property.

Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and electric current and brightness relationship figure, curve 1 is voltage and current density relation curve in figure 4, can find out that device can find out device luminescence from 5.5V, curve 2 is voltage and brightness relationship curve, and high-high brightness is 185cd/m ², show that device has the good characteristics of luminescence.

Embodiment 2

Select purity be 99.99% powder, by MgO, MgF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.98:1.5:0.01:0.01 mixes and obtains mixed powder according to mole number, and mixed powder being sintered at 900 DEG C 0.5h, to form diameter be 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, and finally anneal 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C.Obtaining chemical formula is Mg _4.98(PO ₄) ₃f:0.01Ce ³⁺, 0.01Sn ⁴⁺light-emitting film, light-emitting film thickness is 60nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 3

Select purity be 99.99% powder, by MgO, MgF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.89:1.5:0.05:0.06 mixes and obtains mixed powder according to mole number, and mixed powder being sintered at 1300 DEG C 3h, to form diameter be 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and finally anneal 3h in 0.01Pa vacuum oven, and annealing temperature is 800 DEG C.Obtaining chemical formula is Mg ₅(PO ₄) ₃f:0.05Ce ³⁺, 0.06Sn ⁴⁺light-emitting film, light-emitting film thickness is 350nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 4

Select purity be 99.99% powder, by CaO, CaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.93:1.5:0.03:0.04 mixes and obtains mixed powder according to mole number, and mixed powder being sintered at 1250 DEG C 2h, to form diameter be 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 ^-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and finally anneal 2h in 0.01Pa vacuum oven, and annealing temperature is 600 DEG C.Obtaining chemical formula is Ca _4.93(PO ₄) ₃f:0.03Ce ³⁺, 0.04Sn ⁴⁺light-emitting film, light-emitting film thickness is 200nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 5

Select purity be 99.99% powder, by CaO, CaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.98:1.5:0.01:0.01 mixes and obtains mixed powder according to mole number, and mixed powder sinters 1h at 900 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, and finally anneal 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C.Obtaining chemical formula is Ca _4.98(PO ₄) ₃f:0.01Ce ³⁺, 0.01Sn ⁴⁺light-emitting film, light-emitting film thickness is 100nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 6

Select purity be 99.99% powder, by CaO, CaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.89:1.5:0.05:0.06 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 1.5h at 1300 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and finally anneal 3h in 0.01Pa vacuum oven, and annealing temperature is 800 DEG C.Obtaining chemical formula is Ca ₅(PO ₄) ₃f:0.05Ce ³⁺, 0.06Sn ⁴⁺light-emitting film, light-emitting film thickness is 150nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 7

Select purity be 99.99% powder, by SrO, SrF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.93:1.5:0.03:0.04 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 3h at 1250 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 ^-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and finally anneal 2h in 0.01Pa vacuum oven, and annealing temperature is 600 DEG C.Obtaining chemical formula is Sr _4.93(PO ₄) ₃f:0.03Ce ³⁺, 0.04Sn ⁴⁺light-emitting film, light-emitting film thickness is 350nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 8

Select purity be 99.99% powder, by SrO, SrF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.98:1.5:0.01:0.01 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 0.5h at 900 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, and finally anneal 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C.Obtaining chemical formula is Sr _4.98(PO ₄) ₃f:0.01Ce ³⁺, 0.01Sn ⁴⁺light-emitting film, light-emitting film thickness is 60nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 9

Select purity be 99.99% powder, by SrO, SrF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.89:1.5:0.05:0.06 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 2h at 1300 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and finally anneal 3h in 0.01Pa vacuum oven, and annealing temperature is 800 DEG C.Obtaining chemical formula is Sr ₅(PO ₄) ₃f:0.05Ce ³⁺, 0.06Sn ⁴⁺light-emitting film, light-emitting film thickness is 200nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 10

Select purity be 99.99% powder, by BaO, BaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.93:1.5:0.03:0.04 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 1h at 1250 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and finally anneal 2h in 0.01Pa vacuum oven, and annealing temperature is 600 DEG C.Obtaining chemical formula is Ba _4.93(PO ₄) ₃f:0.03Ce ³⁺, 0.04Sn ⁴⁺light-emitting film, light-emitting film thickness is 100nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 11

Select purity be 99.99% powder, by BaO, BaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.98:1.5:0.01:0.01 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 2.5h at 900 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, and finally anneal 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C.Obtaining chemical formula is Ba _4.98(PO ₄) ₃f:0.01Ce ³⁺, 0.01Sn ⁴⁺light-emitting film, light-emitting film thickness is 150nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 12

Select purity be 99.99% powder, by BaO, BaF ₂, P ₂o ₅, CeO ₂and SnO ₂powder is that 4.89:1.5:0.05:0.06 mixes and obtains mixed powder according to mole number, and mixed powder is sintered 2h at 1300 DEG C, and formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and finally anneal 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C.Obtaining chemical formula is Ba ₅(PO ₄) ₃f:0.05Ce ³⁺, 0.06Sn ⁴⁺light-emitting film, light-emitting film thickness is 150nm, then evaporation one deck Ag on light-emitting film, as negative electrode.

The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a cerium tin codoped fluorophosphate luminescent material, is characterized in that, chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

2. a preparation method for cerium tin codoped fluorophosphate luminescent material, is characterized in that, comprise the following steps:

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion; And

Namely described mixed powder is obtained chemical formula for 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate luminescent material.

3. a cerium tin codoped fluorophosphate light-emitting film, is characterized in that, the chemical formula of the material of described cerium tin codoped fluorophosphate light-emitting film is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

4. cerium tin codoped fluorophosphate light-emitting film according to claim 3, is characterized in that, the thickness of described cerium tin codoped fluorophosphate light-emitting film is 60nm ~ 350nm.

5. a preparation method for cerium tin codoped fluorophosphate light-emitting film, is characterized in that, comprise the following steps:

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa; And

Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, and the flow of working gas is 10sccm ~ 35sccm, and underlayer temperature is 250 DEG C ~ 750 DEG C, is then filmed, and obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

6. the preparation method of cerium tin codoped fluorophosphate light-emitting film according to claim 5, it is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10 ^-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 DEG C.

7. a membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, it is characterized in that, the material of described luminescent layer is cerium tin codoped fluorophosphate luminescent material, and the chemical formula of this cerium tin codoped fluorophosphate luminescent material is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion.

8. membrane electro luminescent device according to claim 7, is characterized in that, the thickness of described luminescent layer is 60nm ~ 350nm.

9. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:

The substrate with anode is provided;

According to Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺the stoichiometric ratio of each element takes MeO, MeF ₂, P ₂o ₅, CeO ₂and SnO ₂powder also mixes and obtains mixed powder, and described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-5pa ~ 1.0 × 10 ^-3pa; And

Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, and the underlayer temperature with anode is 250 DEG C ~ 750 DEG C, then be filmed, obtaining chemical formula is Me _5-x-y(PO ₄) ₃f:xCe ³⁺, ySn ⁴⁺cerium tin codoped fluorophosphate light-emitting film, described cerium tin codoped fluorophosphate light-emitting film is placed in vacuum oven annealing 1 ~ 3h that vacuum tightness is 0.01Pa, annealing temperature is 500 DEG C ~ 800 DEG C, described anode prepares described luminescent layer, and wherein, x is 0.01 ~ 0.05, y is 0.01 ~ 0.06, Me is magnesium ion, calcium ion, strontium ion or barium ion;

Prepare negative electrode on the light-emitting layer, obtain described membrane electro luminescent device.

10. the preparation method of membrane electro luminescent device according to claim 9, is characterized in that, the thickness of described luminescent layer is 60nm ~ 350nm.