CN104449680A - Fluorine/copper-codoped alkaline earth sulfide light-emitting material, and preparation method and application thereof - Google Patents

Abstract

The invention provides a fluorine/copper-codoped alkaline earth sulfide light-emitting material of which the chemical formula is MeS:xCu<2+>,yF<->, wherein x is 0.01-0.05, y is 0.01-0.06, and Me is zinc ion, magnesium ion, calcium ion, strontium ion or barium ion. In the electroluminescent spectrum (EL) of the light-emitting film prepared from the fluorine/copper-codoped alkaline earth sulfide light-emitting material, the 430nm-wavelength region has strong light-emitting peak, and thus, the fluorine/copper-codoped alkaline earth sulfide light-emitting material can be applied to film electroluminescent displays. The invention also provides a preparation method and application of the fluorine/copper-codoped alkaline earth sulfide light-emitting material.

Description

Fluorine copper codope alkaline earth sulfide luminescent material, preparation method and application thereof

[technical field]

The present invention relates to a kind of fluorine copper codope alkaline earth sulfide luminescent material, its preparation method, fluorine copper codope alkaline earth sulfide light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.

[background technology]

Thin-film electroluminescent displays (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 fluorine copper codope alkaline earth sulfide 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 fluorine copper codope alkaline earth sulfide luminescent material, its preparation method, fluorine copper codope alkaline earth sulfide light-emitting film, its preparation method, the membrane electro luminescent device using this fluorine copper codope alkaline earth sulfide luminescent material and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of fluorine copper codope alkaline earth sulfide luminescent material, its chemical formula is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

A preparation method for fluorine copper codope alkaline earth sulfide luminescent material, comprises the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also mixes, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion; And

Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being MeS:xCu at 900 DEG C ~ 1300 DEG C ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

A kind of fluorine copper codope alkaline earth sulfide light-emitting film, the chemical general formula of the material of this fluorine copper codope alkaline earth sulfide light-emitting film is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

A preparation method for fluorine copper codope alkaline earth sulfide light-emitting film, comprises the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-3pa ~ 1.0 × 10 ^-5pa; And

Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, and operating pressure is 0.5Pa ~ 5Pa, and working gas flow is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80W ~ 300W, is then filmed, and obtaining chemical formula is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In a preferred embodiment, the vacuum tightness of described vacuum cavity is 5.0 × 10 ^-4pa, operating pressure is 3Pa, and working gas flow is 20sccm, and base target spacing is 60mm, and underlayer temperature is 500 DEG C, and laser energy is 150W.

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 fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, 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;

Described anode forms luminescent layer, and the material of described luminescent layer is fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Form negative electrode on the light-emitting layer.

In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Described target and described substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-3pa ~ 1.0 × 10 ^-5pa;

Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, and operating pressure is 0.5Pa ~ 5Pa, and working gas flow is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80W ~ 300W, is then filmed, and obtaining chemical formula is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide light-emitting film, described anode forms luminescent layer.

Above-mentioned fluorine copper codope alkaline earth sulfide luminescent material (MeS:xCu ²⁺, yF ^-) in the electroluminescent spectrum (EL) of light-emitting film made, have very strong glow peak in 430nm 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 fluorine copper codope alkaline earth sulfide light-emitting film prepared by embodiment 1;

Fig. 3 is the XRD figure of fluorine copper codope alkaline earth sulfide light-emitting film prepared by embodiment 1;

Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and current density and the graph of relation between voltage and brightness.

[embodiment]

Below in conjunction with the drawings and specific embodiments, fluorine copper codope alkaline earth sulfide luminescent material, its preparation method, fluorine copper codope alkaline earth sulfide light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.

The fluorine copper codope alkaline earth sulfide luminescent material of one embodiment, its chemical formula is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

Preferably, x is 0.02, y is 0.03.

In this fluorine copper codope alkaline earth sulfide luminescent material, MeS is matrix, Cu ²⁺and F ^-ion is active element.In the electroluminescent spectrum (EL) of the light-emitting film that this fluorine copper codope alkaline earth sulfide luminescent material is made, there is very strong glow peak in 430nm wavelength zone, can be applied in thin-film electroluminescent displays.

The preparation method of above-mentioned fluorine copper codope alkaline earth sulfide luminescent material, comprises the following steps:

Step S11, according to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferably, x is 0.02, y is 0.03.

Step S12, the equal powder of mixing is sintered 0.5 hour ~ 5 hours and can obtain fluorine copper codope alkaline earth sulfide luminescent material at 900 DEG C ~ 1300 DEG C, its chemical formula is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferably at 1250 DEG C, sinter 3 hours.

The fluorine copper codope alkaline earth sulfide light-emitting film of one embodiment, the chemical general formula of the material of this fluorine copper codope alkaline earth sulfide light-emitting film is MeGa ₂o ₄: xCe ³⁺, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

Preferably, x is 0.02, y is 0.03.

The preparation method of above-mentioned fluorine copper codope alkaline earth sulfide light-emitting film, comprises the following steps:

Step S21, by MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferably, x is 0.02, y is 0.03, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.

Step S22, the target that obtains in step S21 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 ^-3pa ~ 1.0 × 10 ^-5pa.

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

Step S23, adjustment pulsed laser deposition coating process parameter are: base target spacing is 45mm ~ 95mm, and operating pressure is 0.5Pa ~ 5Pa, and working gas flow is 10sccm ~ 40sccm, and underlayer temperature is 250 DEG C ~ 750 DEG C; Laser energy is 80W ~ 300W, is then filmed, and obtaining chemical formula is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferred base target spacing is 60mm, and operating pressure is 3Pa, and working gas flow is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150W.

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 fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.The material of negative electrode 4 is silver (Ag).

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, form luminescent layer 3, the material of luminescent layer 3 is fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

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

First, by MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

In this step, preferably, x is 0.03, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.

Secondly, 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 ^-3pa ~ 1.0 × 10 ^-5pa.

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

Then, adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure is 0.5Pa ~ 5Pa, working gas flow is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80W ~ 300W, is then filmed, and anode 2 is formed luminescent layer 3.

In this step, preferred base target spacing is 60mm, and operating pressure is 3Pa, and working gas flow is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150W.

Step S33, on luminescent layer 3, form negative electrode 4.

In present embodiment, the material of negative electrode 4 is silver (Ag), is formed by evaporation.

Be specific embodiment below.

Embodiment 1

Select purity be 99.99% powder, by MgS, CuS and MgF ₂according to mol ratio be 1:0.02:0.03 after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 20sccm, and pressure is adjusted to 3Pa, and underlayer temperature is 500 DEG C, laser energy 150W.The sample chemical formula obtained is MgS:0.02Cu ²⁺, 0.03F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

The chemical general formula of the fluorine copper codope alkaline earth sulfide light-emitting film obtained in the present embodiment is MgS:0.02Ce ³⁺, 0.03Tb ³⁺, wherein MgS is matrix, Cu ²⁺and F ^-ion is active element.

Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the fluorine copper codope alkaline earth sulfide light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 430nm wavelength zone, can be applied in thin-film electroluminescent displays.

Refer to Fig. 3, Fig. 3 is the XRD curve of fluorine copper codope alkaline earth sulfide light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, diffraction peak is depicted as the peak crystallization of alkaline earth sulfide, does not occur the diffraction peak of doped element and other impurity, illustrates that the product that this preparation method obtains has good crystalline quality.

Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and current density and the graph of relation between voltage and brightness, curve 1 is voltage and current density relation curve, the luminescence from voltage 5.0V of this device can be found out, curve 2 is voltage and brightness relationship curve, can find out that the high-high brightness of this device is 118cd/m ², show that device has the good characteristics of luminescence.

Embodiment 2

Select purity be 99.99% powder, by MgS, CuS and MgF ₂according to mol ratio be 1:0.01:0.01 after Homogeneous phase mixing, at 900 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80W.The chemical formula of the sample obtained is MgS:0.01Cu ²⁺, the light-emitting film of 0.01F-, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 3

Select purity be 99.99% powder, by MgS, CuS and MgF ₂according to mol ratio be 1:0.05:0.06 after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 40sccm, and pressure is adjusted to 5Pa, and underlayer temperature is 750 DEG C, laser energy 300W.The chemical formula of the sample obtained is MgS:0.05Cu ²⁺, 0.06F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 4

Select purity be 99.99% powder, by CaS, CuS and CaF ₂according to mol ratio be 1:0.02:0.03 after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 20sccm, and pressure is adjusted to 3Pa, and underlayer temperature is 500 DEG C, laser energy 150W.The sample chemical formula obtained is CaS:0.02Cu ²⁺, 0.03F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 5

Select purity be 99.99% powder, by CaS, CuS and CaF ₂according to mol ratio be 1:0.01:0.01 after Homogeneous phase mixing, at 900 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80W.The chemical formula of the sample obtained is CaS:0.01Cu ²⁺, 0.01F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 6

Select purity be 99.99% powder, by CaS, CuS and CaF ₂according to mol ratio be 1:0.05:0.06 after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 40sccm, and pressure is adjusted to 5Pa, and underlayer temperature is 750 DEG C, laser energy 300W.The chemical formula of the sample obtained is CaS:0.05Cu ²⁺, 0.06F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 7

Select purity be 99.99% powder, by SrS, CuS and SrF ₂according to mol ratio be 1:0.02:0.03 after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 20sccm, and pressure is adjusted to 3Pa, and underlayer temperature is 500 DEG C, laser energy 150W.The sample chemical formula obtained is SrS:0.02Cu ²⁺, 0.03F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 8

Select purity be 99.99% powder, by SrS, CuS and SrF ₂according to mol ratio be 1:0.01:0.01 after Homogeneous phase mixing, at 900 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80W.The chemical formula of the sample obtained is SrS:0.01Cu ²⁺, 0.01F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 9

Select purity be 99.99% powder, by SrS, CuS and SrF ₂according to mol ratio be 1:0.05:0.06 after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 40sccm, and pressure is adjusted to 5Pa, and underlayer temperature is 750 DEG C, laser energy 300W.The chemical formula of the sample obtained is SrS:0.05Cu ²⁺, 0.06F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 10

Select purity be 99.99% powder, by BaS, CuS and BaF ₂according to mol ratio be 1:0.02:0.03 after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 20sccm, and pressure is adjusted to 3Pa, and underlayer temperature is 500 DEG C, laser energy 150W.The sample chemical formula obtained is BaS:0.02Cu ²⁺, 0.03F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 11

Select purity be 99.99% powder, by BaS, CuS and BaF ₂according to mol ratio be 1:0.01:0.01 after Homogeneous phase mixing, at 900 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80W.The chemical formula of the sample obtained is BaS:0.01Cu ²⁺, 0.01F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 12

Select purity be 99.99% powder, by BaS, CuS and BaF ₂according to mol ratio be 1:0.05:0.06 after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 40sccm, and pressure is adjusted to 5Pa, and underlayer temperature is 750 DEG C, laser energy 300W.The chemical formula of the sample obtained is BaS:0.05Cu ²⁺, 0.06F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 13

Select purity be 99.99% powder, by ZnS, CuS and ZnF ₂according to mol ratio be 1:0.02:0.03 after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 20sccm, and pressure is adjusted to 3Pa, and underlayer temperature is 500 DEG C, laser energy 150W.The sample chemical formula obtained is ZnS:0.02Cu ²⁺, 0.03F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 14

Select purity be 99.99% powder, by ZnS, CuS and ZnF ₂according to mol ratio be 1:0.01:0.01 after Homogeneous phase mixing, at 900 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80W.The chemical formula of the sample obtained is ZnS:0.01Cu ²⁺, 0.01F ^-light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 15

Select purity be 99.99% powder, by ZnS, CuS and ZnF ₂according to mol ratio be 1:0.05:0.06 after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into 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, working gas is oxygen, and the flow of work gas is 40sccm, and pressure is adjusted to 5Pa, and underlayer temperature is 750 DEG C, laser energy 300W.The chemical formula of the sample obtained is ZnS:0.05Cu ²⁺, 0.06F ^-light-emitting film, 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 (9)

1. a fluorine copper codope alkaline earth sulfide luminescent material, is characterized in that: its chemical formula is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

2. a preparation method for fluorine copper codope alkaline earth sulfide luminescent material, is characterized in that, comprise the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also mixes, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion; And

Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being MeS:xCu at 900 DEG C ~ 1300 DEG C ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material.

3. a fluorine copper codope alkaline earth sulfide light-emitting film, is characterized in that, the chemical general formula of the material of this fluorine copper codope alkaline earth sulfide light-emitting film is MeS:xCu ²⁺, yF ^-, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

4. a preparation method for fluorine copper codope alkaline earth sulfide light-emitting film, is characterized in that, comprise the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-3pa ~ 1.0 × 10 ^-5pa; And

Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, and operating pressure is 0.5Pa ~ 5Pa, and working gas flow is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80W ~ 300W, is then filmed, and obtaining chemical formula is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide light-emitting film, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

5. the preparation method of fluorine copper codope alkaline earth sulfide light-emitting film according to claim 4, it is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10 ^-4pa, base target spacing is 60mm, and operating pressure is 3Pa, and working gas flow is 20sccm, and pulsed laser deposition underlayer temperature is 500 DEG C, and laser energy is 150W.

6. 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 fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion.

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

The substrate with anode is provided;

Described anode forms luminescent layer, and the material of described luminescent layer is fluorine copper codope alkaline earth sulfide luminescent material, and the chemical formula of this fluorine copper codope alkaline earth sulfide luminescent material is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide luminescent material, wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Form negative electrode on the light-emitting layer.

8. the preparation method of membrane electro luminescent device according to claim 7, is characterized in that, the preparation of described luminescent layer comprises the following steps:

According to MeS:xCu ²⁺, yF ^-the stoichiometric ratio of each element takes MeS, CuS and MeF ₂powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y be 0.01 ~ 0.06, Me is zine ion, magnesium ion, calcium ion, strontium ion or barium ion;

Described target and described substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 ^-3pa ~ 1.0 × 10 ^-5pa;

Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, and operating pressure is 0.5Pa ~ 5Pa, and working gas flow is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80W ~ 300W, is then filmed, and obtaining chemical formula is MeS:xCu ²⁺, yF ^-fluorine copper codope alkaline earth sulfide light-emitting film, described anode forms luminescent layer.

9. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, described x is 0.02, y is 0.03.