CN104277834A - Bis-alkaline-earth phosphate light-emitting film as well as preparation and application thereof - Google Patents

Abstract

The invention discloses a bis-alkaline-earth phosphate light-emitting film with a chemical formula of (AyB(1-y))2P2O7:xMn<2+>, wherein (AyB(1-y))2P2O7 is matrix, x is not smaller than 0.01 and not greater than 0.08, y is not smaller than 0.1 and not greater than 0.5, A and B are Mg, Ca, Sr or Ba, and the A and the B are different. In electroluminescence spectra of the bis-alkaline-earth phosphate light-emitting film, the electroluminescence peak is very strong in a 655nm-wavelength region, and thus, the bis-alkaline-earth phosphate light-emitting film can be applied to a film electroluminescence display. The invention further provides a preparation method and application of the bis-alkaline-earth phosphate light-emitting film.

Description

Two alkaline earth phosphate light-emitting film, preparation method and application thereof

Technical field

The present invention relates to a kind of two alkaline earth phosphate 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 film of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to two alkaline earth phosphate light-emitting films 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 two alkaline earth phosphate light-emitting films, its preparation method, the electroluminescent device using this pair of alkaline earth phosphate light-emitting film and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of two alkaline earth phosphate light-emitting film, the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In a preferred embodiment, the thickness of two alkaline earth phosphate light-emitting film is 80nm ~ 300nm.

A preparation method for pair alkaline earth phosphate light-emitting film, comprises the following steps:

Substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa;

Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺the stoichiometric ratio of each element is by ((C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃pass in reaction chamber with the luxuriant manganese of methyl two; And

Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical general formula be (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺two alkaline earth phosphate light-emitting films, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In a preferred embodiment, described substrate is indium tin oxide glass, fluorine doped tin oxide glass, mixes the zinc oxide of aluminium or mix the zinc oxide of indium.

In a preferred embodiment, described argon stream amount is 5 ~ 15sccm, and described oxygen flow amount is 10 ~ 200sccm.

In a preferred embodiment, described substrate to be loaded after described reaction chamber first by described substrate 200 ~ 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.

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 two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In a preferred embodiment, the thickness of described luminescent layer is 80nm ~ 300nm.

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 two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical; And

Form negative electrode on the light-emitting layer.

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

Substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa;

Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺the stoichiometric ratio of each element is by ((C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃pass in reaction chamber with the luxuriant manganese of methyl two, argon stream amount is 5 ~ 15sccm;

Pass into oxygen, carry out chemical vapour deposition and form luminescent layer on described anode, the chemical general formula of luminescent layer is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

Above-mentioned couple of alkaline earth phosphate light-emitting film ((A _yb _1-y) ₂p ₂o ₇: xMn ²⁺) electroluminescent spectrum (EL) in, doped element Mn is the active element in luminescence system, structure composition in enter P ⁵⁺the lattice of ion, has very strong glow peak in 655nm 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 two alkaline earth phosphate light-emitting films prepared by embodiment 1;

Fig. 3 is the XRD figure of two alkaline earth phosphate light-emitting films prepared by embodiment 1.

Embodiment

For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.

Two alkaline earth phosphate light-emitting films of one embodiment, the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In two alkaline earth phosphate light-emitting film, doped element Mn is the active element in luminescence system, is enter P in structure composition ⁵⁺the lattice of ion.

The thickness of this pair of alkaline earth phosphate light-emitting film is 80nm ~ 300nm.

Preferably, x is 0.03, and thickness is 150nm.

Above-mentioned pair of alkaline earth phosphate light-emitting film, (A _yb _1-y) ₂p ₂o ₇be matrix, doped element Mn is the active element in luminescence system, in structure composition, enter P ⁵⁺the lattice of ion, serves as main luminescence center in the film, and obtaining, in the electroluminescence spectrum (EL) of film, has very strong glow peak in 655nm position.

The preparation method of above-mentioned pair of alkaline earth phosphate light-emitting film, comprises the following steps:

Step S11, substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa.

In present embodiment, substrate is indium tin oxide glass (ITO), is appreciated that in other embodiments, can be also fluorine doped tin oxide glass (FTO), mixes the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium.

Substrate priority toluene, acetone and EtOH Sonicate clean 5 minutes, then clean with distilled water flushing, the air-dry rear feeding reaction chamber of nitrogen.

Preferably, the vacuum tightness of reaction chamber is 4.0 × 10 ^-3pa.

In present embodiment, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa.

Step S12, adjustment substrate temperature are 250 DEG C ~ 650 DEG C, and rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺the stoichiometric ratio of each element is by (C ₅h ₅) ₂a, (C ₅h ₅) ₂b, phosphuret-(t)ed hydrogen (PH ₃) and the luxuriant manganese of methyl two (MCp) pass in reaction chamber.

Preferably, substrate to be loaded after reaction chamber first by described substrate 200 ~ 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.

In this step, argon stream amount is 5 ~ 15sccm.Be preferably 10sccm.

In present embodiment, 0.01≤x≤0.08,0.1≤y≤0.5.Preferably, x is 0.05, y is 0.4.

Preferably, the rotating speed of substrate is 300 revs/min.

Step S13, then pass into oxygen, carrying out chemical vapour deposition, to obtain two its chemical general formula of alkaline earth phosphate light-emitting film be (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In two alkaline earth phosphate light-emitting film, doped element Mn is the active element in luminescence system, is enter P in structure composition ⁵⁺the lattice of ion.

In this step, oxygen flow amount is 10 ~ 200sccm.Be preferably 120sccm.

Stop after step S14, two alkaline earth phosphate luminescent thin-film deposition passing into (C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃with the luxuriant manganese of methyl two and nitrogen, continue to pass into oxygen and make the temperature of two alkaline earth phosphate light-emitting film be down to 60 DEG C ~ 100 DEG C.

Be understandable that, step S14 can omit.

Refer to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprises the substrate 10, anode 20, luminescent layer 30 and the negative electrode 40 that stack gradually.

Substrate 10 is glass substrate.Anode 20 is for being formed at the tin indium oxide (ITO) in glass substrate.The material of luminescent layer 30 is two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.The material of negative electrode 40 is silver (Ag).

In two alkaline earth phosphate light-emitting film, doped element Mn is the active element in luminescence system, is enter P in structure composition ⁵⁺the lattice of ion.

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

Step S21, provide the substrate 10 with anode 20.

In present embodiment, substrate 10 is glass substrate, and anode 20 is for being formed at the tin indium oxide (ITO) in glass substrate.Be appreciated that in other embodiments, can be also fluorine doped tin oxide glass (FTO), mix the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium.

Substrate priority toluene, acetone and EtOH Sonicate clean 5 minutes, then clean with distilled water flushing, the air-dry rear feeding reaction chamber of nitrogen.

Preferably, the vacuum tightness of reaction chamber is 4.0 × 10 ^-3pa.

In present embodiment, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa.

Step S22, on anode 20, form luminescent layer 30, the material of luminescent layer 30 is two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In two alkaline earth phosphate light-emitting film, doped element Mn is the active element in luminescence system, is enter P in structure composition ⁵⁺the lattice of ion.

In present embodiment, luminescent layer 30 is obtained by following steps:

First, substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa.

Then, regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺the stoichiometric ratio of each element is by (C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃pass in reaction chamber with the luxuriant manganese of methyl two.

Preferably, substrate to be loaded after reaction chamber first by described substrate 200 ~ 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.

In this step, argon stream amount is 5 ~ 15sccm.Be preferably 10sccm.

In present embodiment, 0.01≤x≤0.08,0.1≤y≤0.5.Preferably, x is 0.05, y is 0.4.

Preferably, the rotating speed of substrate is 300 revs/min.

Then, pass into oxygen, carry out chemical vapour deposition film and form luminescent layer on described anode, the chemical general formula of luminescent layer is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇the active element that to be host doped element M n be in luminescence system is enter P in structure composition ⁵⁺the lattice of ion, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

In this step, oxygen flow amount is 10 ~ 200sccm.Be preferably 120sccm.

Finally, stop after two alkaline earth phosphate luminescent thin-film deposition passing into (C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃with the luxuriant manganese of methyl two and nitrogen, continue to pass into oxygen and make the temperature of two alkaline earth phosphate light-emitting film be down to 60 DEG C ~ 100 DEG C.It should be noted that, this step can be omitted.

Step S23, on luminescent layer 30, form negative electrode 40.

In present embodiment, the material of negative electrode 40 is silver (Ag), is formed by evaporation.

Be specific embodiment below.

Embodiment 1

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into (C ₅h ₅) ₂mg, (C ₅h ₅) ₂ca, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, molar flow is than being 0.8:1.2:2:0.05, and pass into oxygen, flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 100 DEG C, takes out sample Mg _0.8ca _1.2p ₂o ₇: 0.05Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Refer to Fig. 2, Fig. 2 is the electroluminescence spectrum (EL) of two alkaline earth phosphate light-emitting films that the present embodiment obtains.As seen from Figure 2, two alkaline earth phosphate light-emitting films that the present embodiment obtains have very strong glow peak in 655nm wavelength zone, can be applied in thin-film electroluminescent displays.

Refer to Fig. 3, Fig. 3 is the XRD figure that the present embodiment obtains two alkaline earth phosphate light-emitting film.Reference standard PDF card, is the peak crystallization of two alkaline earth phosphate, does not occur the diffraction peak of doped element and other impurity, proves that doped element is the lattice entering two alkaline earth phosphate, does not occur phase-splitting.

Embodiment 2

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into (C ₅h ₅) ₂mg, (C ₅h ₅) ₂sr, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, the molar flow of three provenances is than being 0.4:1.6:2:0.01, and pass into oxygen, flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 60 DEG C, takes out sample Mg _0.4sr _1.6p ₂o ₇: 0.01Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 3

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into (C ₅h ₅) ₂mg, (C ₅h ₅) ₂ba, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, the molar flow of three provenances is than being 0.9:1.1:2:0.08, and pass into oxygen, flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 65 DEG C, takes out sample Mg _0.9ba _1.1p ₂o ₇: 0.08Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 4

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into (C ₅h ₅) ₂ca, (C ₅h ₅) ₂sr, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, molar flow is than being 1.3:0.7:2:0.05, and pass into oxygen, flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 80 DEG C, takes out sample Ca _1.3sr _0.7p ₂o ₇: 0.05Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 5

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into (C ₅h ₅) ₂ca, (C ₅h ₅) ₂ba, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, the molar flow of three provenances is than being 1.5:0.5:2:0.01, and pass into oxygen, flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 70 DEG C, takes out sample Ca _1.5ba _0.5p ₂o ₇: 0.01Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 6

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into (C ₅h ₅) ₂sr, (C ₅h ₅) ₂ca, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, the molar flow of three provenances is than being 0.3:1.7:2:0.08, and pass into oxygen, flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 90 DEG C, takes out sample Sr _0.3ca _1.7p ₂o ₇: 0.08Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 7

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into (C ₅h ₅) ₂sr, (C ₅h ₅) ₂mg, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, molar flow is than being 0.8:1.2:2:0.05, and pass into oxygen, flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 95 DEG C, takes out sample Sr _0.8mg _1.2p ₂o ₇: 0.05Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

Embodiment 8

Substrate is the ito glass that Nan Bo company buys, and successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10 ^-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into (C ₅h ₅) ₂ba, (C ₅h ₅) ₂ca, PH ₃with the carrier gas Ar gas of the luxuriant manganese of methyl two (MCp), flow is 10sccm.Wherein, the molar flow of three provenances is than being 0.6:1.4:2:0.01, and pass into oxygen, flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical oxygen, temperature drops to 75 DEG C, takes out sample Ba _0.6ca _1.4p ₂o ₇: 0.01Mn ²⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

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 two alkaline earth phosphate light-emitting film, it is characterized in that, the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

2. according to claim 1 pair of alkaline earth phosphate light-emitting film, is characterized in that, the thickness of described pair of alkaline earth phosphate light-emitting film is 80nm ~ 300nm.

3. a preparation method for two alkaline earth phosphate light-emitting film, is characterized in that, comprise the following steps:

Substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa;

Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ³⁺the stoichiometric ratio of each element is by (C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃pass in reaction chamber with the luxuriant manganese of methyl two; And

Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical general formula be (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺two alkaline earth phosphate light-emitting films, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

4. the preparation method of according to claim 3 pair of alkaline earth phosphate light-emitting film, is characterized in that, described substrate is indium tin oxide glass, fluorine doped tin oxide glass, mix the zinc oxide of aluminium or mix the zinc oxide of indium.

5. the preparation method of according to claim 3 pair of alkaline earth phosphate light-emitting film, is characterized in that, described argon stream amount is 5 ~ 15sccm, and described oxygen flow amount is 10 ~ 200sccm.

6. the preparation method of according to claim 3 pair of alkaline earth phosphate light-emitting film, is characterized in that, described substrate to be loaded after described reaction chamber first by described substrate 200 ~ 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.

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 two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.

8. the preparation method of membrane electro luminescent device according to claim 7, is characterized in that, the thickness of described luminescent layer is 80nm ~ 300nm.

9. 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 two alkaline earth phosphate light-emitting films, and the chemical general formula of this pair of alkaline earth phosphate light-emitting film is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇matrix, 0.01≤x≤0.08,0.1≤y≤0.5, wherein, A and B is Mg, Ca, Sr or Ba, and A and B is not identical; And

Form negative electrode on the light-emitting layer.

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

Substrate is loaded the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10 ^-2pa ~ 1.0 × 10 ^-3pa;

Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺the stoichiometric ratio of each element is by ((C ₅h ₅) ₂a, (C ₅h ₅) ₂b, PH ₃pass in reaction chamber with the luxuriant manganese of methyl two; And

Pass into oxygen, carry out chemical vapour deposition and form luminescent layer on described anode, the chemical general formula of luminescent layer is (A _yb _1-y) ₂p ₂o ₇: xMn ²⁺, wherein (A _yb _1-y) ₂p ₂o ₇be matrix, 0.01≤x≤0.08,0.1≤y≤0.5, A and B is Mg, Ca, Sr or Ba, and A and B is not identical.