CN104342137A - Ce-doped trivalent vanadium silicate light-emitting film as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a Ce-doped trivalent vanadium silicate light-emitting film having a chemical formula of Me3VSi3O13:xCe<3+>, wherein x is not less than 0.01 and is not more than 0.05, Me3VSi3O13 is a matrix, Ce element is an active element, Me is Al, Ga, In or Tl. In the electroluminescence (EL) spectrum of the Ce-doped trivalent vanadium silicate light-emitting film, strong luminescence peaks appear in a 620nm-wavelength area; so that the Ce-doped trivalent vanadium silicate light-emitting film can be applied to a thin film electroluminescence device. The invention also provides a preparation method and application of the Ce-doped trivalent vanadium silicate light-emitting film.

Description

Cerium dopping three races vanadium silicate light-emitting film, preparation method and application thereof

[technical field]

The present invention relates to a kind of cerium dopping three races vanadium silicate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.

[background technology]

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

[summary of the invention]

Based on this, be necessary to provide a kind of the cerium dopping three races vanadium silicate light-emitting film, this cerium dopping three races vanadium silicate light-emitting film electroluminescent device of its preparation method and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of cerium dopping three races vanadium silicate light-emitting film, its chemical formula is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

Preferably, the thickness of cerium dopping three races vanadium silicate light-emitting film is 80nm ~ 300nm.

A preparation method for cerium dopping three races vanadium silicate light-emitting film, comprises the following steps:

Substrate is provided;

Substrate is loaded in 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, adopts the carrier of argon stream, according to Me ₃vSi ₃o ₁₃: xCe ³⁺dipivaloylmethane alkaline earth salt, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber by the stoichiometric ratio of each element, and

Then pass into oxygen, carrying out chemical vapour deposition, to obtain cerium dopping three races its chemical formula of vanadium silicate light-emitting film be Me ₃vSi ₃o ₁₃: xCe ³⁺cerium dopping three races vanadium silicate light-emitting film, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

Dipivaloylmethane alkaline earth salt, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium mol ratio are 3:1:3:(0.01 ~ 0.05);

Preferably, argon stream amount is 5 ~ 15sccm, and oxygen flow amount is 10 ~ 200sccm.

A kind of membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

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

The substrate with anode is provided; Described 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 the substrate temperature with anode to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, adopts argon stream as carrier, according to Me ₃vSi ₃o ₁₃: xCe ³⁺the stoichiometric ratio of each element is by dipivaloylmethane alkaline earth salt ((DPM) ₃me), triethoxy vanadium oxide, silane and four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium passes in reaction chamber, and wherein, argon stream amount is 5 ~ 15sccm;

Then pass into oxygen, oxygen flow amount is 10 ~ 200sccm; On described anode, deposit film obtains luminescent layer, and the film of described luminescent layer is cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl;

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

Cerium dopping three races of the present invention vanadium silicate luminescent material, matrix three races vanadium silicate its there is higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus less radiationless transition is produced in the process of photovoltaic energy conversion, there is higher luminous efficiency.For dopant ion, Ce is that in rare earth element, content is the highest is also the most cheap, and relative to other rare earth ions, its level structure is the simplest, at ground state 4f ¹with excited state 5d ¹between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region.

Above-mentioned cerium dopping three races vanadium silicate light-emitting film (Me ₃vSi ₃o ₁₃: xCe ³⁺) electroluminescent spectrum (EL) in, have very strong glow peak in 620nm wavelength zone, can be applied in thin-film electroluminescent displays.

[accompanying drawing explanation]

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

Fig. 2 is the electroluminescent spectrogram of cerium dopping three races vanadium silicate light-emitting film prepared by embodiment 1;

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

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

[embodiment]

Below in conjunction with the drawings and specific embodiments, cerium dopping three races vanadium silicate light-emitting film, its preparation method and membrane electro luminescent device and preparation method thereof are illustrated further.

The cerium dopping three races vanadium silicate light-emitting film of one embodiment, its chemical formula is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

Preferably, the thickness of cerium dopping three races vanadium silicate light-emitting film is 80nm ~ 300nm, x is 0.03.

Me in this cerium dopping three races vanadium silicate light-emitting film ₃vSi ₃o ₁₃be matrix, Ce elements is active element.In the electroluminescent spectrum (EL) of this cerium dopping three races vanadium silicate light-emitting film, there is very strong glow peak in 620nm wavelength zone, can be applied in thin-film electroluminescent displays.

The preparation method of above-mentioned cerium dopping three races vanadium silicate light-emitting film, comprises the following steps:

Step S11, provide substrate; Substrate is loaded in 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 the 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.

Step S12, by substrate 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.

Step S13, adjustment substrate temperature are 250 DEG C ~ 650 DEG C, and rotating speed is 50 revs/min ~ 1000 revs/min, adopts the carrier of argon stream, according to Me ₃vSi ₃o ₁₃: xCe ³⁺the stoichiometric ratio of each element is by (DPM) ₃me, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber;

Described dipivaloylmethane alkaline earth salt ((DPM) ₃me), triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium mol ratio be 3:1:3:(0.01 ~ 0.05);

Preferably, described substrate temperature is preferably 500 DEG C, and the rotating speed of substrate is preferably 300 revs/min, and argon stream amount is 5 ~ 15sccm;

Preferred, described argon stream amount is 10sccm;

Step S14, then pass into oxygen, carrying out chemical vapour deposition, to obtain cerium dopping three races its chemical formula of vanadium silicate light-emitting film be Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

Preferably, described oxygen flow amount is 10 ~ 200sccm, x is 0.03.

More preferably oxygen flow amount is 120sccm.

Stop passing into (DPM) after step S15, deposition ₃me, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium and helium, continue to pass into oxygen and make the temperature of cerium dopping three races vanadium silicate light-emitting film be down to 40 ~ 100 DEG C.

Be appreciated that step S12 and step S15 can omit.

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

Substrate 1 is glass substrate.Anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.The material of luminescent layer 3 is cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.The material of negative electrode 4 is silver (Ag).

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

Step S21, 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.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; 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 S22, the substrate 1 with anode 2 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 the temperature with the substrate 1 of anode 2 to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, adopts argon stream as carrier, according to Me ₃vSi ₃o ₁₃: xCe ³⁺the stoichiometric ratio of each element is by dipivaloylmethane alkaline earth salt ((DPM) ₃me), triethoxy vanadium oxide, silane and four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium passes in reaction chamber, and wherein, argon stream amount is 5 ~ 15sccm;

Then pass into oxygen, oxygen flow amount is 10 ~ 200sccm; On described anode, deposit film obtains luminescent layer 3, and the film of described luminescent layer 3 is cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl;

In preferred embodiment, by substrate 700 DEG C of thermal treatments 10 minutes ~ 30 minutes.Also can without the need to this step.

In a preferred embodiment, (DPM) ₃me, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium mol ratio are 3:1:3:(0.01 ~ 0.05);

In a preferred embodiment, substrate temperature is preferably 500 DEG C, and the rotating speed of substrate is preferably 300 revs/min, and argon stream amount is 5 ~ 15sccm;

In more preferred embodiment, argon stream amount is 10sccm;

In preferred embodiment, the flow of oxygen is preferably 10 ~ 200sccm;

In more preferred embodiment, oxygen flow amount is 120sccm.

In preferred embodiment, stop after deposition passing into (DPM) ₃me, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium and helium, continue to pass into oxygen and make the temperature of cerium dopping three races vanadium silicate light-emitting film be down to 40 ~ 100 DEG C.

Step S23, on luminescent layer 3, prepare negative electrode 4.

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

Cerium dopping three races of the present invention vanadium silicate luminescent material, matrix three races vanadium silicate its there is higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus less radiationless transition is produced in the process of photovoltaic energy conversion, there is higher luminous efficiency.For dopant ion, Ce is that in rare earth element, content is the highest is also the most cheap, and relative to other rare earth ions, its level structure is the simplest, at ground state 4f ¹with excited state 5d ¹between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region.

Be specific embodiment below.

Embodiment 1

Substrate is ito glass, 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 organic source (DPM) ₃al, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.03, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 Al ₃vSi ₃o ₁₃: 0.03Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

The chemical general formula of the cerium dopping three races vanadium silicate light-emitting film obtained in the present embodiment is Al ₃vSi ₃o ₁₃: 0.03Ce ³⁺, wherein Al ₃vSi ₃o ₁₃be matrix, Ce elements is active element.

Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the cerium dopping three races vanadium silicate light-emitting film that embodiment 1 obtains.As seen from Figure 2, the electroluminescent spectral curve of cerium dopping three races vanadium silicate light-emitting film that embodiment 1 obtains has very strong glow peak can be applied in thin-film electroluminescent displays in 620nm wavelength zone.

Refer to Fig. 3, Fig. 3 is the XRD curve of cerium dopping three races vanadium silicate light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3 in figure X-ray diffraction peak corresponding be the characteristic peak of three races's vanadium silicate, do not occur doped element and the relevant peak of impurity, illustrate that cerium dopping ion enters the lattice of three races's vanadium silicate, sample has good crystallographic property.

Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and electric current and brightness relationship figure, curve 1 is voltage and current density relation curve in figure 4, can find out that device can find out device luminescence from 6.0V, curve 2 is voltage and brightness relationship curve, and high-high brightness is 170cd/m ², show that device has the good characteristics of luminescence.

Embodiment 2

Substrate is ito glass, 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 machine source (DPM) ₃al, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 40 DEG C, takes out sample Al ₃vSi ₃o ₁₃: 0.05Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 3

Substrate is ito glass, 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 organic source (DPM) ₃al, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.01, gas of carrier gas is argon gas, and argon stream amount is 5sccm.Pass into oxygen, oxygen flow amount 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 50 DEG C, takes out sample Al ₃vSi ₃o ₁₃: 0.01Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 4: substrate is ito glass, 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 organic source (DPM) ₃ga, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.03, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 60 DEG C, takes out sample Ga ₃vSi ₃o ₁₃: 0.03Ce ³⁺finally evaporation one deck Ag on light-emitting film, as negative electrode.

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 machine source (DPM) ₃ga, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 Ga ₃vSi ₃o ₁₃: 0.05Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

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 organic source (DPM) ₃ga, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.01, gas of carrier gas is argon gas, and argon stream amount is 15sccm.Pass into oxygen, oxygen flow amount 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 80 DEG C, takes out sample Ga ₃vSi ₃o ₁₃: 0.01Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

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 organic source (DPM) ₃in, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.03, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 90 DEG C, takes out sample In ₃vSi ₃o ₁₃: 0.03Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

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 organic source (DPM) ₃in, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 85 DEG C, takes out sample In ₃vSi ₃o ₁₃: 0.05Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 9: 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 machine source (DPM) ₃in, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 75 DEG C, takes out sample In ₃vSi ₃o ₁₃: 0.01Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 10: 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 machine source (DPM) ₃tl, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.03, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 Tl ₃vSi ₃o ₁₃: 0.03Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 11: 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 machine source (DPM) ₃tl, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 65 DEG C, takes out sample Tl ₃vSi ₃o ₁₃: 0.05Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

Embodiment 12: 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 machine source (DPM) ₃tl, triethoxy vanadium oxide (C ₆h ₁₅o ₄v), silane (SiH ₄) and the mol ratio of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium be 3:1:3:0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount 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 95 DEG C, takes out sample Tl ₃vSi ₃o ₁₃: 0.01Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode.

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

Claims (10)

1. a cerium dopping three races vanadium silicate light-emitting film, is characterized in that, the chemical formula of the material of described cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

2. cerium dopping three races according to claim 1 vanadium silicate light-emitting film, is characterized in that, the thickness of described cerium dopping three races vanadium silicate light-emitting film is 80nm ~ 300nm.

3. a preparation method for cerium dopping three races vanadium silicate light-emitting film, is characterized in that, comprise the following steps:

Substrate is provided;

Described substrate is loaded in 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, adopts the carrier of argon stream, according to Me ₃vSi ₃o ₁₃: xCe ³⁺dipivaloylmethane alkaline earth salt, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber by the stoichiometric ratio of each element; And

Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical formula be Me ₃vSi ₃o ₁₃: xCe ³⁺cerium dopping three races vanadium silicate light-emitting film, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

4. the preparation method of cerium dopping three races according to claim 3 vanadium silicate light-emitting film, is characterized in that, the thickness of described cerium dopping three races vanadium silicate light-emitting film is 80nm ~ 300nm.

5. the preparation method of cerium dopping three races according to claim 3 vanadium silicate 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 cerium dopping three races according to claim 3 vanadium silicate light-emitting film, is characterized in that, after described substrate is loaded described reaction chamber, by described substrate 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 cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

8. 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 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;

The substrate temperature described in adjustment with anode is 250 DEG C ~ 650 DEG C, and rotating speed is 50 revs/min ~ 1000 revs/min, adopts argon stream as carrier, according to Me ₃vSi ₃o ₁₃: xCe ³⁺dipivaloylmethane alkaline earth salt, triethoxy vanadium oxide, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber by the stoichiometric ratio of each element, and wherein, argon stream amount is 5 ~ 15sccm;

Then pass into oxygen, oxygen flow amount is 10 ~ 200sccm; On described anode, deposit film obtains luminescent layer, and the film of described luminescent layer is cerium dopping three races vanadium silicate light-emitting film, and the chemical formula of this cerium dopping three races vanadium silicate light-emitting film is Me ₃vSi ₃o ₁₃: xCe ³⁺, wherein, 0.01≤x≤0.05, Me is Al, Ga, In or Tl;

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

10. the preparation method of membrane electro luminescent device according to claim 9, is characterized in that, the thickness of described luminescent layer is 80nm ~ 300nm.