CN104650916A - Manganese/titanium-codoped alkaline earth fluoscandate luminescent material, preparation method and application thereof - Google Patents

Abstract

The invention relates to a manganese/titanium-codoped alkaline earth fluoscandate luminescent material, a chemical formula of the luminescent material is MeSc2F8: xMn<4+>, yTi<4+>, wherein x is 0.01-0.05, y is 0.01-0.08, Me is selected from at least one of magnesium element, calcium element, strontium element and barium element. In an electroluminescent spectrum of a luminescent film prepared by the manganese/titanium-codoped alkaline earth fluoscandate luminescent material, a strong luminescence peak is generated at a 650nm wavelength zone, and the manganese/titanium-codoped alkaline earth fluoscandate luminescent material can be used in a thin-film electroluminescence display. The invention also provides a preparation method and an application of the manganese/titanium-codoped alkaline earth fluoscandate luminescent material.

Description

Manganese Ti doped alkaline earth fluoscandate luminescent material, preparation method and application thereof

[technical field]

The present invention relates to a kind of manganese Ti doped alkaline earth fluoscandate luminescent material, its preparation method, manganese Ti doped alkaline earth fluoscandate 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 manganese Ti doped alkaline earth fluoscandate 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 manganese Ti doped alkaline earth fluoscandate luminescent material, its preparation method, manganese Ti doped alkaline earth fluoscandate light-emitting film, its preparation method, the membrane electro luminescent device using this manganese Ti doped alkaline earth fluoscandate luminescent material and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of manganese Ti doped alkaline earth fluoscandate luminescent material, its chemical formula is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

Described x is 0.02, y is 0.04.

A preparation method for manganese Ti doped alkaline earth fluoscandate luminescent material, comprises the following steps:

According to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element; And

Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being MeSc at 900 DEG C ~ 1300 DEG C ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate luminescent material.

A kind of manganese Ti doped alkaline earth fluoscandate light-emitting film, the chemical general formula of the material of this manganese Ti doped alkaline earth fluoscandate light-emitting film is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

A preparation method for manganese Ti doped alkaline earth fluoscandate light-emitting film, comprises the following steps:

According to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and the powder mixed is sintered 0.5 hour ~ 5 hours at 900 DEG C ~ 1300 DEG C and namely obtains target, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

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 ^-3pa ~ 1.0 × 10 ^-5pa; 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 MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate light-emitting film.

The preparation method of described manganese Ti doped alkaline earth fluoscandate light-emitting film also comprises step: by Ti doped for described manganese alkaline earth fluoscandate light-emitting film vacuum annealing process 1h ~ 3h at 500 DEG C ~ 800 DEG C.

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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

Form negative electrode on the light-emitting layer.

The preparation method of described membrane electro luminescent device, the preparation of described luminescent layer comprises the following steps:

According to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and at 900 DEG C ~ 1300 DEG C, sintering makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

Described target and described 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;

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

The preparation method of described membrane electro luminescent device, also comprises step: by Ti doped for described manganese alkaline earth fluoscandate light-emitting film vacuum annealing process 1h ~ 3h at 500 DEG C ~ 800 DEG C.

Above-mentioned manganese Ti doped alkaline earth fluoscandate luminescent material (MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺) in the electroluminescent spectrum (EL) of light-emitting film made, have very strong glow peak in 650nm 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 manganese Ti doped alkaline earth fluoscandate light-emitting film prepared by embodiment 1;

Fig. 3 is the XRD figure of manganese Ti doped alkaline earth fluoscandate 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, manganese Ti doped alkaline earth fluoscandate luminescent material, its preparation method, manganese Ti doped alkaline earth fluoscandate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.

The manganese Ti doped alkaline earth fluoscandate luminescent material of one embodiment, its chemical formula is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

Preferably, x is 0.02, y is 0.04.

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

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

Step S11, according to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element; And

Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being MeSc at 900 DEG C ~ 1300 DEG C ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate luminescent material.

In this step, preferably, x is 0.02, y is 0.04.

Step S12, the equal powder of mixing is sintered 0.5 hour ~ 5 hours and can obtain manganese Ti doped alkaline earth fluoscandate luminescent material at 900 DEG C ~ 1300 DEG C, its chemical formula is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺.

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

The manganese Ti doped alkaline earth fluoscandate light-emitting film of one embodiment, the chemical general formula of the material of this manganese Ti doped alkaline earth fluoscandate light-emitting film is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

Preferably, x is 0.02, y is 0.04.

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

Step S21, by MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and the powder mixed is sintered 0.5 hour ~ 5 hours at 900 DEG C ~ 1300 DEG C and namely obtains target, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

In this step, preferably, x is 0.02, y is 0.04, 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 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, and underlayer temperature is 250 DEG C ~ 750 DEG C; Then be filmed, obtaining chemical formula is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate light-emitting film.

Also comprise step: by Ti doped for described manganese alkaline earth fluoscandate light-emitting film vacuum annealing process 1h ~ 3h at 500 DEG C ~ 800 DEG C.

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 500 DEG C.

Refer to Fig. 1, the membrane electro luminescent device of an embodiment, this membrane electro luminescent device 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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium 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.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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, x is 0.02, y is 0.04.

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

First, by MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder 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 is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

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, 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 anode 2 is formed luminescent layer 3.

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 500 DEG C, and laser energy is 300W.

Also comprise step: by Ti doped for described manganese alkaline earth fluoscandate light-emitting film vacuum annealing process 1h ~ 3h at 500 DEG C ~ 800 DEG C.

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 MgF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.02mmol and 0.04mmol mix according to mole number, and 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, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C.The sample chemical formula obtained is MgSc ₂f ₈: 0.02Mn ⁴⁺, 0.04Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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 manganese obtained in the present embodiment Ti doped alkaline earth fluoscandate light-emitting film is MgSc ₂f ₈: 0.02Mn ⁴⁺, 0.04Ti ⁴⁺.

Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the manganese obtained Ti doped alkaline earth fluoscandate light-emitting film.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 XRD curve of manganese Ti doped alkaline earth fluoscandate light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, the diffraction peak in figure is all the peak crystallization of alkaline earth fluoscandate, does not occur the diffraction peak of doped element and other impurity, illustrates that doped element is the lattice entering alkaline earth fluoscandate, 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 5.5V 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 210cd/m ², show that device has the good characteristics of luminescence.

Embodiment 2

Select purity be 99.99% powder, by MgF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.01mmol and 0.01mmol mix according to mole number, and 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, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, and the chemical formula of the sample obtained is MgSc ₂f ₈: 0.01Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by MgF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.05mmol and 0.08mmol mix according to mole number, and 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, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtained is MgSc ₂f ₈: 0.05Mn ⁴⁺, 0.08Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by CaF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.02mmol and 0.04mmol mix according to mole number, and 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, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtained is CaSc ₂f ₈: 0.02Mn ⁴⁺, 0.04Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by CaF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.01mmol and 0.01mmol mix according to mole number, and 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, the working gas flow of argon gas 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 obtained is CaSc ₂f ₈: 0.01Mn ⁴⁺, 0.01Ti ⁴⁺⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by CaF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.05mmol and 0.08mmol mix according to mole number, and at 1150 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, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtained is CaSc ₂f ₈: 0.05Mn ⁴⁺, 0.08Ti ⁴light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by SrF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.02mmol and 0.04mmol mix according to mole number, and 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, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtained is SrSc ₂f ₈: 0.02Mn ⁴⁺, 0.04Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by SrF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.01mmol and 0.01mmol mix according to mole number, and 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, the working gas flow of argon gas 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 obtained is SrSc ₂f ₈: 0.01Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by SrF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.05mmol and 0.08mmol mix according to mole number, and 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, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtained is SrSc ₂f ₈: 0.05Mn ⁴⁺, 0.08Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by SrF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.02mmol and 0.04mmol mix according to mole number, and 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, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 DEG C, and the chemical formula of the sample obtained is SrSc ₂f ₈: 0.02Mn ⁴⁺, 0.04Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by BaF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.01mmol and 0.01mmol mix according to mole number, and 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, the working gas flow of argon gas 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 obtained is BaSc ₂f ₈: 0.01Mn ⁴⁺, 0.01Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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

Select purity be 99.99% powder, by BaF ₂, ScF ₃, MnF ₄and TiF ₄powder is that 1mmol, 2mmol, 0.05mmol and 0.08mmol mix according to mole number, and at 1150 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, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 DEG C, and the chemical formula of the sample obtained is BaSc ₂f ₈: 0.05Mn ⁴⁺, 0.08Ti ⁴⁺light-emitting film, be then 0.01Pa by the light-emitting film obtained 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 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 manganese Ti doped alkaline earth fluoscandate luminescent material, is characterized in that: its chemical formula is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

2. luminescent material according to claim 1, is characterized in that: described x is 0.02, y is 0.04.

3. a preparation method for manganese Ti doped alkaline earth fluoscandate luminescent material, is characterized in that, comprise the following steps:

According to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element; And

Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being MeSc at 900 DEG C ~ 1300 DEG C ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate luminescent material.

4. a manganese Ti doped alkaline earth fluoscandate light-emitting film, is characterized in that, the chemical general formula of the material of this manganese Ti doped alkaline earth fluoscandate light-emitting film is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

5. a preparation method for manganese Ti doped alkaline earth fluoscandate light-emitting film, is characterized in that, comprise the following steps:

According to MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and the powder mixed is sintered 0.5 hour ~ 5 hours at 900 DEG C ~ 1300 DEG C and namely obtains target, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

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 ^-3pa ~ 1.0 × 10 ^-5pa; 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 MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺manganese Ti doped alkaline earth fluoscandate light-emitting film.

6. the preparation method of manganese according to claim 5 Ti doped alkaline earth fluoscandate light-emitting film, is characterized in that, also comprise step: by Ti doped for described manganese alkaline earth fluoscandate light-emitting film vacuum annealing process 1h ~ 3h at 500 DEG C ~ 800 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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element.

8. 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 manganese Ti doped alkaline earth fluoscandate luminescent material, and the chemical formula of this manganese Ti doped alkaline earth fluoscandate luminescent material is MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

Form negative electrode on the light-emitting layer.

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 MeSc ₂f ₈: xMn ⁴⁺, yTi ⁴⁺the stoichiometric ratio of each element takes MeF ₂, ScF ₃, MnF ₄and TiF ₄powder also mixes, and at 900 DEG C ~ 1300 DEG C, sintering makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from magnesium elements, calcium constituent, at least one in strontium element and barium element;

Described target and described 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;

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

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