CN104119896A - Manganese and titanium co-doped arsenate luminescent material and preparation method and application thereof - Google Patents

Abstract

The invention discloses a manganese and titanium co-doped arsenate luminescent material with a chemical formula of Me6As2O11:xMn<4 +>, yTi<4 +>, wherein Me6As2O11 is a matrix, Mn<4 +> and Ti<4 +> ions are activating elements, x is 0.01-0.05, y is 0.005-0.03, and Me is one of magnesium, calcium, strontium, barium and zinc elements. The electroluminescent spectra (EL) of a luminescent film prepared from the manganese and titanium co-doped arsenate luminescent material has very strong luminescence peaks in the 650nm wavelength region, and the luminescent film can be applied to film electroluminescent displays. The invention also provides a preparation method and application of the manganese and titanium co-doped arsenate luminescent material.

Description

The Ti doped arsenate luminescent material of manganese, preparation method and application thereof

[technical field]

The present invention relates to the Ti doped arsenate luminescent material of a kind of manganese, its preparation method, the Ti doped arsenate light-emitting film of manganese, 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 luminous material of exploitation multiband, is the developing direction of this problem.But, can be applicable to the Ti doped arsenate luminescent material of manganese 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 Ti doped arsenate luminescent material of manganese that can be applicable to membrane electro luminescent device, its preparation method, the Ti doped arsenate light-emitting film of manganese, its preparation method, the membrane electro luminescent device that uses the Ti doped arsenate luminescent material of this manganese and preparation method thereof.

The Ti doped arsenate luminescent material of a kind of manganese, its chemical formula is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

Described x is that 0.03, y is 0.01.

A preparation method for the Ti doped arsenate luminescent material of manganese, comprises the following steps:

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element; And

The powder mixing sintering at 900 DEG C～1300 DEG C is obtained to chemical formula for 0.5 hour～5 hours is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate luminescent material of manganese.

The Ti doped arsenate light-emitting film of a kind of manganese, the chemical general formula of the material of the Ti doped arsenate light-emitting film of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

A preparation method for the Ti doped arsenate light-emitting film of manganese, comprises the following steps:

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

Described target and substrate are packed into 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; And

Adjusting 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 ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate light-emitting film of manganese.

Also comprise step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.

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 the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

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

The substrate with anode is provided;

On described anode, form luminescent layer, the material of described luminescent layer is the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

On described luminescent layer, form negative electrode.

The preparation of described luminescent layer comprises the following steps:

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes sintering at 900 DEG C～1300 DEG C and makes target in 0.5 hour～5 hours, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

Described target and described substrate are packed into 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;

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, underlayer temperature is 250 DEG C～750 DEG C, then be filmed, on described anode, form luminescent layer.

Also comprise step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.

The Ti doped arsenate luminescent material of above-mentioned manganese (Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺) in the electroluminescent spectrum (EL) of the light-emitting film made, there is very strong glow peak in 650nm wavelength zone, can be applied in thin-film electroluminescent displays.

[brief description of the drawings]

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

Fig. 2 is the electroluminescent spectrogram of the Ti doped arsenate light-emitting film of manganese prepared of embodiment 1;

Fig. 3 is the Raman spectrum of the Ti doped arsenate light-emitting film of manganese prepared of embodiment 1;

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

[embodiment]

Below in conjunction with the drawings and specific embodiments, the Ti doped arsenate luminescent material of manganese, its preparation method, the Ti doped arsenate light-emitting film of manganese, its preparation method, membrane electro luminescent device and preparation method thereof are further illustrated.

The Ti doped arsenate luminescent material of manganese of one embodiment, its chemical formula is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

Preferably, x is that 0.03, y is 0.01.

In the electroluminescent spectrum (EL) of the light-emitting film that the Ti doped arsenate luminescent material of this manganese is made, there is very strong glow peak in 650nm wavelength zone, can be applied in thin-film electroluminescent displays.

The preparation method of the Ti doped arsenate luminescent material of above-mentioned manganese, comprises the following steps:

Step S11, according to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element; And

The powder mixing sintering at 900 DEG C～1300 DEG C is obtained to chemical formula for 0.5 hour～5 hours is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate luminescent material of manganese.

In this step, preferred, x is that 0.03, y is 0.01.

Step S12, by mix equal powder sintering at 900 DEG C～1300 DEG C within 0.5 hour～5 hours, can obtain the Ti doped arsenate luminescent material of manganese, its chemical formula is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺.

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

The Ti doped arsenate light-emitting film of manganese of one embodiment, the chemical general formula of the material of the Ti doped arsenate light-emitting film of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

Preferably, x is that 0.03, y is 0.01.

The preparation method of the Ti doped arsenate light-emitting film of above-mentioned manganese, comprises the following steps:

Step S21, press Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

In this step, preferred, x is that 0.03, y is 0.01, and at 1250 DEG C, 3 hours one-tenth diameters of sintering are 50mm, the ceramic target that thickness is 2mm.

Step S22, the target obtaining in step S21 and substrate are packed into 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, preferred, vacuum tightness is 5 × 10 ^-4pa.

Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 DEG C～750 DEG C; Then be filmed, obtaining chemical formula is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate light-emitting film of manganese.

Also comprise step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.

In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 DEG C.

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 the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.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.The substrate 1 with anode 2 is successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning and use it is carried out to oxygen plasma treatment.

Step S32, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

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

First, by Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes sintering at 900 DEG C～1300 DEG C and makes target in 0.5 hour～5 hours, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

Secondly, target and substrate are packed into 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, preferred, 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, underlayer temperature is 250 DEG C～750 DEG C, is then filmed, and forms luminescent layer 3 on anode 2.

In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 DEG C, and laser energy is 300W.

Also comprise step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.

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

Selecting purity is 99.99% powder, by the MgO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.03mmol ₂tiO with 0.01mmol ₂powder, after even mixing, at 1250 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C.The sample chemical formula obtaining is Mg ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 600 DEG C, anneal 2h, then evaporation one deck Ag on light-emitting film, as negative electrode.

The chemical general formula of the Ti doped arsenate light-emitting film of manganese obtaining in the present embodiment is Mg ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺.

Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the Ti doped arsenate light-emitting film of the manganese obtaining.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 650nm wavelength zone, can be applied in thin-film electroluminescent displays.

Refer to Fig. 3, Fig. 3 is the Raman spectrum of the Ti doped arsenate light-emitting film of manganese prepared of embodiment 1, Raman peaks in figure is depicted as arsenate characteristic peak, does not occur the peak of doped element and other impurity, illustrates that doped element and substrate material have formed good bonding.

Refer to Fig. 4, Fig. 4 is the graph of relation between voltage and current density and voltage and the brightness of the membrane electro luminescent device prepared of embodiment 1, curve 1 is voltage and current density relation curve, can find out that this device starts luminous from voltage 5.5V, curve 2 is voltage and brightness relationship curve, and the high-high brightness that can find out this device is 148cd/m ², show that device has the good characteristics of luminescence.

Embodiment 2

Selecting purity is 99.99% powder, by the MgO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.01mmol ₂tiO with 0.005mmol ₂powder, after even mixing, at 900 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, and the chemical formula of the sample obtaining is Mg ₆as ₂o ₁₁: 0.01Mn ⁴⁺, 0.005Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 500 DEG C, anneal 1h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 3

Selecting purity is 99.99% powder, by the MgO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.05mmol ₂tiO with 0.03mmol ₂powder, after even mixing, at 1300 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtaining is Mg ₆as ₂o ₁₁: 0.05Mn ⁴⁺, 0.03Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 800 DEG C, anneal 3h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 4

Selecting purity is 99.99% powder, by the CaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.03mmol ₂tiO with 0.01mmol ₂powder, after even mixing, at 1250 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtaining is Ca ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 600 DEG C, anneal 2h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 5

Selecting purity is 99.99% powder, by the CaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.01mmol ₂tiO with 0.005mmol ₂powder, after even mixing, at 900 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, laser energy 500W.The chemical formula of the sample obtaining is Ca ₆as ₂o ₁₁: 0.01Mn ⁴⁺, 0.005Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 500 DEG C, anneal 1h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 6

Selecting purity is 99.99% powder, by the CaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.05mmol ₂tiO with 0.03mmol ₂powder, after even mixing, at 1300 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtaining is Ca ₆as ₂o ₁₁: 0.05Mn ⁴⁺, 0.03Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 800 DEG C, anneal 3h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 7

Selecting purity is 99.99% powder, by the SrO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.03mmol ₂tiO with 0.01mmol ₂powder, after even mixing, at 1250 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtaining is Sr ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 600 DEG C, anneal 2h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 8

Selecting purity is 99.99% powder, by the SrO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.01mmol ₂tiO with 0.005mmol ₂powder, after even mixing, at 900 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, laser energy 500W.The chemical formula of the sample obtaining is Sr ₆as ₂o ₁₁: 0.01Mn ⁴⁺, 0.005Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 500 DEG C, anneal 1h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 9

Selecting purity is 99.99% powder, by the SrO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.05mmol ₂tiO with 0.03mmol ₂powder, after even mixing, at 1300 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtaining is Sr ₆as ₂o ₁₁: 0.05Mn ⁴⁺, 0.03Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 800 DEG C, anneal 3h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 10

Selecting purity is 99.99% powder, by the BaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.03mmol ₂tiO with 0.01mmol ₂powder, after even mixing, at 1250 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtaining is Ba ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 600 DEG C, anneal 2h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 11

Selecting purity is 99.99% powder, by the BaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.01mmol ₂tiO with 0.005mmol ₂powder, after even mixing, at 900 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, laser energy 500W.The chemical formula of the sample obtaining is Ba ₆as ₂o ₁₁: 0.01Mn ⁴⁺, 0.005Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 500 DEG C, anneal 1h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 12

Selecting purity is 99.99% powder, by the BaO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.05mmol ₂tiO with 0.03mmol ₂powder, after even mixing, at 1300 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtaining is Ba ₆as ₂o ₁₁: 0.05Mn ⁴⁺, 0.03Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 800 DEG C, anneal 3h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 13

Selecting purity is 99.99% powder, by the ZnO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.03mmol ₂tiO with 0.01mmol ₂powder, after even mixing, at 1250 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump ^-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtaining is Zn ₆as ₂o ₁₁: 0.03Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 600 DEG C, anneal 2h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 14

Selecting purity is 99.99% powder, by the ZnO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.01mmol ₂tiO with 0.005mmol ₂powder, after even mixing, at 900 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C, laser energy 500W.The chemical formula of the sample obtaining is Zn ₆as ₂o ₁₁: 0.01Mn ⁴⁺, 0.005Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 500 DEG C, anneal 1h, then evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 15

Selecting purity is 99.99% powder, by the ZnO of 6mmol, and the As of 1mmol ₂o ₅, the MnO of 0.05mmol ₂tiO with 0.03mmol ₂powder, after even mixing, at 1300 DEG C, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump ^-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtaining is Zn ₆as ₂o ₁₁: 0.05Mn ⁴⁺, 0.03Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtaining vacuum tightness in vacuum tightness, annealing temperature is 800 DEG C, anneal 3h, then evaporation one deck Ag on light-emitting film, as negative electrode.

The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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. the Ti doped arsenate luminescent material of manganese, is characterized in that: its chemical formula is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

2. luminescent material according to claim 1, is characterized in that: described x is that 0.03, y is 0.01.

3. a preparation method for the Ti doped arsenate luminescent material of manganese, is characterized in that, comprises the following steps:

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element; And

The powder mixing sintering at 900 DEG C～1300 DEG C is obtained to chemical formula for 0.5 hour～5 hours is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate luminescent material of manganese.

4. the Ti doped arsenate light-emitting film of manganese, is characterized in that, the chemical general formula of the material of the Ti doped arsenate light-emitting film of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

5. a preparation method for the Ti doped arsenate light-emitting film of manganese, is characterized in that, comprises the following steps:

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

Described target and substrate are packed into 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; And

Adjusting 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 ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the Ti doped arsenate light-emitting film of manganese.

6. the preparation method of the Ti doped arsenate light-emitting film of manganese according to claim 5, is characterized in that, also comprises step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.

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 the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element.

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

The substrate with anode is provided;

On described anode, form luminescent layer, the material of described luminescent layer is the Ti doped arsenate luminescent material of manganese, and the chemical formula of the Ti doped arsenate luminescent material of this manganese is Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺, Me ₆as ₂o ₁₁matrix, Mn ⁴⁺and Ti ⁴⁺ion is active element, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

On described luminescent layer, form negative electrode.

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

According to Me ₆as ₂o ₁₁: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeO, As ₂o ₅, MnO ₂and TiO ₂powder also mixes sintering at 900 DEG C～1300 DEG C and makes target in 0.5 hour～5 hours, and wherein, x is that 0.01～0.05, y is that 0.005～0.03, Me is the one in magnesium elements, calcium constituent, strontium element, barium element and zinc element;

Described target and described substrate are packed into 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;

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, underlayer temperature is 250 DEG C～750 DEG C, then be filmed, on described anode, form luminescent layer.

10. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, also comprises step: the vacuum annealing at 500 DEG C～800 DEG C of Ti doped described manganese arsenate light-emitting film is processed to 1h～3h.