CN104277829A - Cerium doped indium silicate luminescent thin film and preparation method and application thereof - Google Patents

Abstract

The invention relates to a cerium doped indium silicate luminescent thin film. The cerium doped indium silicate luminescent thin film has the chemical general formula of MeIn2Si2O8:xCe<3+>, wherein MeIn2Si2O8 is a matrix, x is not smaller than 0.01 and is not greater than 0.05, and Me is Al, Ga, In or Tl. In an electroluminescent (EL) spectrum of the cerium doped indium silicate luminescent thin film, luminescent peaks in the wavelength region of 620nm are very strong, so that the cerium doped indium silicate luminescent thin film can be applied to a thin-film electroluminescent display. The invention further provides a preparation method and application of the cerium doped indium silicate luminescent thin film.

Description

Cerium dopping indium silicate light-emitting film, preparation method and application thereof

Technical field

The present invention relates to a kind of cerium dopping indium silicate 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 the cerium dopping indium 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 indium silicate light-emitting film, its preparation method, the electroluminescent device using this cerium dopping indium silicate light-emitting film and preparation method thereof that can be applicable to membrane electro luminescent device.

A kind of cerium dopping indium silicate light-emitting film, the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl;

The thickness of this cerium dopping indium silicate light-emitting film is 80nm ~ 300nm.

A preparation method for cerium dopping indium silicate 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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by (DPM) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber; And

Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical general formula be MeIn ₂si ₂o ₈: xCe ³⁺cerium dopping indium silicate light-emitting film, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

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 300 DEG C ~ 700 DEG C 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 cerium dopping indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

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 cerium dopping indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl; 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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by (DPM) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber, and 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 MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

Above-mentioned cerium dopping indium silicate light-emitting film (MeIn ₂si ₂o ₈: xCe ³⁺) electroluminescent spectrum (EL) in, doped element Ce is the active element in luminescence system, structure composition in enter In ³⁺the lattice of ion, has 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 indium silicate light-emitting film prepared by embodiment 1;

Fig. 3 is the XRD figure of cerium dopping indium silicate light-emitting film 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.

The cerium dopping indium silicate light-emitting film of one embodiment, the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl.

In cerium dopping indium silicate light-emitting film, doped element Ce is the active element in luminescence system, in structure composition, enter In ³⁺the lattice of ion.

The thickness of this cerium dopping indium silicate light-emitting film is 80nm ~ 300nm.

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

The preparation method of above-mentioned cerium dopping indium silicate 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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by beta diketone hydrochlorate ((DPM) ₂me), beta diketone indium ((DPM) ₃in), silane (SiH ₄) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD) ₄) pass in reaction chamber.

Preferably, substrate to be loaded after reaction chamber first by described substrate 300 DEG C ~ 700 DEG C thermal treatments 10 minutes ~ 30 minutes.

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

In present embodiment, 0.01≤x≤0.05.

Step S13, then pass into oxygen, carrying out chemical vapour deposition, to obtain its chemical general formula of cerium dopping indium silicate light-emitting film be MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

In cerium dopping indium silicate light-emitting film, doped element Ce is the active element in luminescence system, in structure composition, enter In ³⁺the lattice of ion.

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

In this step, preferably, x is 0.03.

Stop passing into DPM after step S14, cerium dopping indium silicate light-emitting film deposition) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium and nitrogen, continue to pass into oxygen and make the temperature of cerium dopping indium silicate 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 cerium dopping indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl.The material of negative electrode 40 is silver (Ag).

In cerium dopping indium silicate light-emitting film, doped element Ce is the active element in luminescence system, in structure composition, enter In ³⁺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 cerium dopping indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl.

In cerium dopping indium silicate light-emitting film, doped element Ce is the active element in luminescence system, in structure composition, enter In ³⁺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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by dipivaloylmethane hydrochlorate ((DPM) ₂me), beta diketone indium ((DPM) ₃in), silane (SiH ₄) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD) ₄) pass in reaction chamber.

Preferably, substrate to be loaded after reaction chamber first by described substrate 300 DEG C ~ 700 DEG C thermal treatments 10 minutes ~ 30 minutes.

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

In present embodiment, 0.01≤x≤0.05.

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 MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

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

In this step, preferably, x is 0.03.

Finally, stop passing into DPM after cerium dopping indium silicate light-emitting film deposition) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium and nitrogen, continue to pass into oxygen and make the temperature of cerium dopping indium silicate 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 (DPM) ₂mg, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.03, 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 MgIn ₂si ₂o ₈: 0.03Ce ³⁺.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 the cerium dopping indium silicate light-emitting film that the present embodiment obtains.As seen from Figure 2, the cerium dopping indium silicate light-emitting film that the present embodiment obtains has very strong glow peak in 620nm 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 cerium dopping indium silicate light-emitting film.Test comparison standard P DF card, diffraction peak is all the peak crystallization that indium silicate is relevant, does not occur the diffraction peak of doped element and other impurity.

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 300 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 (DPM) ₂mg, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.06, 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 MgIn ₂si ₂o ₈: 0.06Ce ³⁺.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 400 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 (DPM) ₂mg, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.01, 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 70 DEG C, takes out sample MgIn ₂si ₂o ₈: 0.01Ce ³⁺.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 (DPM) ₂ca, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.03, 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 CaIn ₂si ₂o ₈: 0.03Ce ³⁺.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 500 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 (DPM) ₂ca, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.06, 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 90 DEG C, takes out sample CaIn ₂si ₂o ₈: 0.06Ce ³⁺.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 650 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 (DPM) ₂ca, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.01, 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 70 DEG C, takes out sample CaIn ₂si ₂o ₈: 0.01Ce ³⁺.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 550 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 (DPM) ₂sr, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.03, 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 SrIn ₂si ₂o ₈: 0.03Ce ³⁺.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 (DPM) ₂sr, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.06, 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 SrIn ₂si ₂o ₈: 0.06Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

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 450 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 (DPM) ₂sr, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.01, 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 SrIn ₂si ₂o ₈: 0.01Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

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 (DPM) ₂ba, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.03, 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 BaIn ₂si ₂o ₈: 0.03Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

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 350 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 (DPM) ₂ba, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.06, 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 BaIn ₂si ₂o ₈: 0.06Ce ³⁺.Finally evaporation one deck Ag on light-emitting film, as negative electrode, obtains membrane electro luminescent device.

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 (DPM) ₂ba, (DPM) ₃in, silane (SiH ₄) and the carrier gas Ar gas of four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium, flow is 10sccm.Wherein, the molar flow of four provenances is than being 1:2:2:0.01, 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 100 DEG C, takes out sample BaIn ₂si ₂o ₈: 0.01Ce ³⁺.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 cerium dopping indium silicate light-emitting film, is characterized in that, the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl.

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

3. a preparation method for cerium dopping indium silicate light-emitting film, is characterized in that, 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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by (DPM) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber; And

Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical general formula be MeIn ₂si ₂o ₈: xCe ³⁺cerium dopping indium silicate light-emitting film, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.

4. the preparation method of cerium dopping indium silicate light-emitting film according to claim 3, 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 cerium dopping indium silicate light-emitting film according to claim 3, 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 indium silicate light-emitting film according to claim 3, is characterized in that, described substrate to be loaded after described reaction chamber first by described substrate 300 DEG C ~ 700 DEG C 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 indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl.

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 cerium dopping indium silicate light-emitting film, and the chemical general formula of this cerium dopping indium silicate light-emitting film is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈matrix, 0.01≤x≤0.05, wherein, Me is Al, Ga, In or Tl; 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 MeIn ₂si ₂o ₈: xCe ³⁺the stoichiometric ratio of each element is by (DPM) ₂me, (DPM) ₃in, silane and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium pass in reaction chamber; And

Pass into oxygen, carry out chemical vapour deposition and form luminescent layer on described anode, the chemical general formula of luminescent layer is MeIn ₂si ₂o ₈: xCe ³⁺, wherein MeIn ₂si ₂o ₈be matrix, 0.01≤x≤0.05, Me is Al, Ga, In or Tl.